The Pesticides Monitoring Journal is published quarterly under the auspices of the FEDERAL WORKING GROUP ON PEST MANAGEMENT (responsible to the Council on Environmental Quality) and its Panel on Pesticide Monitoring as a source of information on pesticide levels relative to man and his environment. The WORKING GROUP is comprised of representatives of the U. S. Departments of Agricul- ture; Commerce; Defense; the Interior; Health. Education, and Welfare; State; and Transporta- tion; and the Environmental Protection Agency. The Pesticide Monitoring Panel consists of representatives of the Agricultural Research Service, Consumer and Marketing Service. Extension Service. Forest Service, Department of Defense, Fish and Wildlife Service, Geological Survey, Food and Drug Administration. Environmental Protection Agency. National Marine Fisheries Service, National Science Foundation, and Tennessee Valley Authority. Publication of the Pesticides Monitoring Journal is carried out by the Division of Pesticide Community Studies of the Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies repre- sented on the Pesticide Monitoring Panel which participate in operation of the national pesti- cides monitoring network, are expected to be the principal sources of data and interpretive articles. However, pertinent data in summarized jorm, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institu- tions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Manuscripts received for publication are reviewed by an Editorial Advisory Board established by the Monitoring Panel. Authors are given the benefit of review comments prior to publication. Editorial Advisory Board members are: Reo E. Duggan, Food and Drug Administration, Chairman Anne R. Yobs, Environmental Protection Agency William F. Durham, Environmental Protection Agency Thomas W. Duke, Environmental Protection Agency William F. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Paul F. Sand, Agricultural Research Service Mention of trade names or commercial sources in the Pesticides Monitoring Journal is for identification only and does not represent endorsement by any Federal agency. Address correspondence to: Mrs. Sylvia P. O'Rear Editorial Manager PESTICIDES MONITORING JOURNAL Environmental Protection Agency 4770 Buford Highway, Bldg. 29 Chamblee. Georgia 30341 CONTENTS Volume 6 June 1972 Number 1 Page PESTICIDES IN PEOPLE DDT and DDE residues in blood from children, South Carolina — 1970_ Julian E. Keil, William Weston, III, C. Boyd Loadholt, Samuel H. Sandifer, and James J. Colcolough Organochlorine pesticide residue levels in human milk — Victoria, Australia — 1970 K. G. Newton and N. C. Greene Organochlorine pesticide levels in human serum and adipose tissue, Utah— fiscal years 1967-71 9 Stephen L. Wamick RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mirex and DDT residues in wildlife and miscellaneous samples in Mississippi — 1970 . 14 Karl P. Baetcke, Jimmie D. Cain, and William E. Poe Chemical residues in Lake Erie fish — 1970-71 . 23 Richard L. Carr, Charles E. Finsterwalder, and Michael J. Schibi Mercury and lead residues in starlings — 1970 27 William E. Martin Organochlorine residues in starlings — 1970. 33 William E. Martin and Paul R. Nickerson The occurrence of mirex in starlings collected in seven southeastern states— 1970 : 41 John C. Oberheu Organochlorine pesticide residues in commercially caught fish in Canada— 1970 43 J. Reinke, J. F. Uthe, and D. Jamieson Residues of organochlorine pesticides, polychlorinated biphenyls, and mercury in bald eagle eggs and changes in shell thickness — 7969 and 1970 50 Stanley N. Wiemeyer, Bernard M. Mulhern, Frank J. Ligas, Richard J. Hensel. John E. Mathisen, Fred C. Robards, and Sergej Postupalsky PESTICIDES IN WATER Organochlorine pesticide residues in water, sediment, algae, and fish, Hawaii— 1970-71 56 Arthur Bevenue, John W. Hylin, Yoshihiko Kawano, and Thomas W. Kelley PESTICIDES IN SOIL DDT residues in forest floor and soil after aerial spraying, Oregon— 1965-68 65 R. F. Tarrant, D. G. Moore, W. B. Bollen, and B. R. Loper GENERAL Decay of parathion and endosulfan residues on field-treated tobacco. South Carolina— 1971 73 Julian E. Keil, C. Boyd Loadholt, Bob L. Brown. Samuel H. Sandifer, and Wayne R. Sitterly APPENDIX Chemical names of compounds discussed in this issue 76 PESTICIDES IN PEOPLE DDT and DDE Residues in Blood From Children, South Carolina — 7970 Julian E. Keil,' William Weston, III,= C. Boyd Loadholt." Samuel H. Sandifer,' and James J. Colcolough * I ABSTRACT DDT and DDE residue levels in blood plasma jrom 192 children in South Carolina, ages 6-9 years, indicated that Negro children had levels two to three times higher than white children. DDT residues averaged 18.4 ppb in Negroes and 6.7 ppb in whites; DDE values for these two races were 55.6 ppb and 24.8 ppb. respectively. White males in this group also had significantly higher levels of both compounds than white females. From the data in this study, baseline levels for a high-risk pediatric group, usually prone to pesticide poisoning, were established. Introduction In 1969, the S. C. Community Pesticide Study measured pesticide residues in plasma from 800 persons in Charles- ton County; the subjects had been selected by sex, race, residence, and 10-year age groupings (6). The out- standing findings of this study were: (1) Negroes had much higher levels of DDT and its metabolites than whites, and (2) children between the ages of 5 and 10 years had significantly higher DDT DDE levels than the rest of the population studied and. in some instances, as high as DDT formulators. The present study, partially reported here, was begun with several purposes in mind: (I) to confirm earlier findings of the South Carolina investigators of higher DDT and DDE levels among children and Negroes; (2) to establish new baselines for young children who are prone to poisoning, because analytical methods have changed since the earlier work; and (3) to explore ^ Department of Preventive Medicine. The Medical University of South Carolina, Charleston. S. C. 29401. " Department of Pediatrics. The Medical University of South Carolina. Charleston, S. C 29401. ~ Department of Biometry. The Medical University of South Carolina. Charleston, S. C. 29401. ' South Carolina State Board of Health. Sullivan's Island, S. C. 29482. Vol. 6, No. 1, June 1972 reasons for the age and racial differences previously reported. This last endeavor is still under study. Sampling Methods A total of 192 apparently healthy children, ages 6-9 years from public and private schools in Charleston, S. C, were stratified by race (nonwhites were almost exclusively Negro), sex, residence, and 1-year age spans. After approval by school authorities, written parental permission was obtained for blood sampling of the children. Venous blood samples were collected in heparinized vacutainers. Residue values for this group were compared with those of control subjects of the S. C. Community Pesticide Study. Analytical Procedures Plasma extraction was carried out by a modified method of Dale, Curley, and Cueto (/), as recommended by the Perrine Primate Research Branch Laboratory in Perrine, Fla. Two milliliters of plasma were placed in a 16 X 125 mm round-bottom culture tube fitted with screw caps, size 15-415 with Teflon-faced liners; 6 ml of nanograde hexane were added; and the mixture was rotated on a slow speed rotating mixer at 50 rpm for 2 hours. The formation of emulsions was infrequent; when they did occur, centrifugation was used to sep- arate the layers. Following the 2-hour rotation period, a 5-ml aliquot of the hexane layer was quantitatively transferred to a 1 0-ml graduated concentrator tube. The degree of concentration or dilution that was neces- sary was determined by a preliminary analysis of the 5-ml aliquot. If concentration was necessary, one 3-mm glass bead was added, and a modified micro-Snyder column was attached. The extract was evaporated on a steam bath to a volume of about 200 ijlI. The tubes 1 were allowed to cool for about 5 minutes, the micro- Snyder column was removed, and the sides of the tube and column joint were rinsed down with hexane. The final volume was adjusted to 500 /nl for subsequent analysis. No celanup procedure was required or utilized. A 5 /nl portion was then injected into a MicroTek 220 gas chromatograph equipped with a tritium foil electron capture detector. All injections were ofT-column injec- tions. All samples were analyzed on the OV-17/QF-1 column, and the residues were confirmed on the SE- 30/QF-l column. It was necessary in almost all cases to run several sample extract chromatograms of various concentrations to achieve reasonable approximation of peak sizes with those of the standard mixture. The samples were stoppered and mixed on a Vortex mixer for about 30 seconds after each dilution before injection. GAS-LIQUID CHROMATOGRAPHY The operating parameters for gas chromatographic analysis were as follows: Columns: 1.5% OV-17 and 1.95% QF-1 on Chromosorb W, DMCS, HP. 100/ 120 mesh; 4% SE-30 and 6% QF-1 on Chromosorb W, DMCS, HP, 100/120 mesh FIGURE l.—Mean plasma levels of p.p'-DDT and p,p'-DDE in a pediatric group and adult reference group by race. South Carolina — 1970 Temperatures: Injection chamber 225° C Column 200° C Transfer block 235° C Detector 205° C Nitrogen flow: OV-17/ QF-1 60 ml/min SE-30/ QF-1 80 ml/min All qualitative retention times were based on the reten- tion time of aldrin. Quantitation of pesticide residues was based on ative peak areas which were supplied by an Infotronics Chromatograph Integrator Model CRS-101. Recovery, based on the addition of a known quantity of p.p'-DDE and p.p'-YiDT. ranged from 95.0 to 98.6%. Residue results were not corrected for re- covery. The minimum reporting limit for p.p'-DDE was 1.0 ppb and for p.p'-DDT, 2.0 ppb. No polychlorinated biphenyls were detected in any of the samples analyzed. A least squares analysis was used to estimate and test differences between strata means. Resi4lts and Discussion Results of previous studies indicating unusually high DDT/DDE levels in preadolescents were not confirmed. As shown in Fig. 1, children in the 6-9 age group had lower levels than did their adult counterparts (control subjects of the S. C. Community Pesticide Study). This is at variance with earlier work by Finklea et al. (6), but consistent with results reported by Watson et al. (7). Improvements in analytical techniques since the IB 5 [Al DDT DD€ Ages 6-9 DDT DDE Reference Adult Population Mean Age 40 earlier study (6) may have reduced variances in riesults and accounted for the lower levels. DDT and DDE were two to three times higher in the Negro than in the white group. This difference was evident in the juvenile cohorts as well as in the adult reference group ( Fig. I ) . This study confirms racial differences in DDT/ DDE residue levels between whites^ and nonwhites reported by Davis (2,3). Edmundson (4.5), and Finklea (6). White males had significantly higher levels of both com- pounds than white females (Table 1). No significant differences in levels of DDT or DDE were apparent when sex and race were evaluated according to the place of residence of subjects (Table 2); thus, values in Table I may be used to estimate "normal" ranges for this high-risk pediatric age group, unusually prone to pesti- cide poisoning. Table 3 lists DDT and DDE levels by 1-year age groups and indicates no significant increase or decrease in levels with age. TABLE 1. — DDT and DDE residue levels in plasma frorr, 192 children, ages 6-9 years, by race and sex. South Carolina — 7970 White* NONWHITE Compound Male Female (N=50) (N=46) SDi Male Female (N=45) (N=51) SO' DDT (ppb) DDE (ppb) 8.5 4.8 29.9 19.2 6.5 14.2 16.9 19.7 11.0 55.2 55.9 29.5 • Pooled standard deviation for sex within races. • Differences between levels in white males and females significant at Pesticides Monitoring Journai TABLE 2. — DDT and DDE residue levels in plasma from 192 children, ages 6-9 years, by residence, race, and sex. South Carolina — 1970 Mean Residue Levels (ppb) Urban Rural Race and Sex DDT DDE DDT DDE White Males 7.8 (N=27) 28.2 8.9 (N=23) 31.0 White Females 4.8 (N=24) 16.9 4.7 (N=22) 21.8 Nonwhite MaJes 16.5 (N=25) 54.5 17.7 (N=20) 54.5 Nonwhite Females 19.1 (N=27) 49.2 20.5 (N=24) 63.5 TABLE 3. — DDT and DDE residue levels in plasma by age of 192 school children, Charleston County, S. C. — 1970 Mean Residue Levels (ppb) (Years) DDT DDE 6 (N=35) 7 (N=35) 8 (N=42) 9 (N=70) 14.5 13.4 11.9 11.7 41.5 43.4 38.1 38.5 See Appendix for chemical names of compounds discussed in thi; paper. This study was supported by EPA contracts PH21-2017 and NEG 68- 03-0045 and by the Department of Pediatrics of the Medical University of South Carolina. LITERATURE CITED (1) Dale, W. E., A. Curley, and C. Cueto. 1966. Hexane extractable chlorinated insecticides in human blood. Life Sci. 5:47-54. (2) Davies. J. £.. ti'. F. Edmundson. A. Maceo. A. Barquet, and J. Cassady. 1969. An epidemiologic application of the study of DDE levels in whole blood. Am. J. Public Health 59:435-441. (3) Davies, J. E. 1971 . The role of social class in human pesticide pollution. Am. J. Epidemol. In press. (4) Edmundson. W. F.. J. E. Davies, G. A. Nachman, and R. L. Roeth. 1969. p,p'-DDT and p.p'-DDE in blood samples of occupationally exposed workers. Public Health Rep. 84:53-58. {5) Edmundson. W. F.. J. E. Davies, A. Maceo, and C. Mor- gade. 1970. Drug and environmental effects on DDT residues in human blood. South. Med. J. 63:1440-1441. I6) Finklea, J. F.. J. E. Keil, L. E. Priester. W. Weston, S. H. Sandifer, and R. H. Gadsden. 1969. Plasma chlorinated hydrocarbon residues in workers and the general popula- tion: another hazard for negro children? Abstract, APHA, Philadelphia. (7) Watson, M., W. Benson, and J. Gabica. 1970. Serum organochlorine pesticide levels in people in southern Idaho. Pestic. Monit. J. 4(2):47-50. Vol. 6, No. 1, June 1972 Organochlorine Pesticide Residue Levels in Human Milk — Victoria, Australia — 7970 ' K. G. Newton and N. C. Greene ABSTRACT Samples of human milk were collected in 1970 from 39 rural and 28 urban donors in Victoria, Australia, and were an- alyzed for organochlorine pesticides using electron capture gas chromatography. All samples contained DDT, DDE, and HCB. Twenty-nine contained dieldrin (mean 0,006 ppm), 12 contained DDD {mean 0.007 ppm). and 3 contained both dieldrin and DDD. Total DDT averaged 0.139 ppm for rural 0.145 ppm for urban donors, and HCB averaged 0.042 ppm and 0.063 ppm. respectively. Introduction The Australian State of Victoria has a population of 3.4 million, 2.2 million of whom live in the capital city of Melbourne. The State is self-sufficient in food pro- duction; its agriculture, sophisticated and in parts in- tensive, supplies centralized common markets which distribute food throughout the metropolis. The use of DDT, aldrin, dieldrin, and other common organochlorine pesticides is restricted to those situations where no suitable alternative is available, and tolerance limits set by State health regulations are low. Over the past 10 years, greater use has been made of the less persistent organophosphate and carbamate pesticides. In an effort to determine organochlorine pesticide residue levels in human milk, a small survey involving 23 participants (13 rural and 10 urban) was carried out in April 1970. The rural donors lived on or near fruit orchards in Shepparton, the center for a district which produces under irrigation large quantities of tree fruits for the local and export markets. The donors were asked to collect milk during one or more feedings until about From the Stale Health Laboratory, 5 Parliament Place, Melbourne. Victoria, Australia 3002; permission to publish this paper was granted by the Chief Health Officer of Victoria, 2 ounces was obtained. Simple details on past exposure to pesticides were considered desirable but are not in- cluded with the results in Table 2, since efforts to obtain reliable information were unsuccessful. Differences in the levels of total DDT between the two groups were apparent; however, it was determined that further sampling of other rural areas should be under- taken and that, to maintain parity, more metropolitan samples should be analyzed before valid conclusions could be drawn regarding such differences. A second survey consisting of 26 rural and 18 urban donors was undertaken in December 1970. These donors were se- lected with on consideration of age, race, weight, medical history, or age of baby. Resources sufficient to guarantee an accurate history of pesticide exposure and uniform sample collection from each donor were not available. Thus, no exposure infor- mation was requested, and the mothers were relied on to collect their own samples according to a designated procedure which was simple enough to ensure coopera- tion and yet provide a representative sample. This procedure was established after a preliminary study using one donor to obtain a limited check on variability in fat content of milk during the suckling period. In this study the mother collected a small amount of milk from several feedings at three intervals during each feeding, the beginning, middle, and end. Individual samples taken at each of these intervals were composited by group to provide three samples for analysis, and the results are shown in Table I. These figures are not included in the general results. Sampling Procedure t Based on results of the preliminary tests to assess varia bility in fat content of the milk, the sampling procedure Pesticides Monitoring Journai TABLE 1. — Organochlorine pesticide residue levels in human milk from one donor obtained at three intervals during each of several feedings Time During Percent Fat Organochlorine Pesticide Residue Levels (PPM) Total DDT HCB DiELDRIN Whole Milk Fat Basis Whole Milk Fat Basis Whole Milk Fat Basis Jeginning tliddle ■nd 1.8 1.2 5.1 0.014 0.007 0.066 0.78 0.58 1.29 0.005 0.003 0.024 0.25 0.25 0.47 0.002 0.001 0.006 0.11 0.08 0.12 lescribed below was followed. Written instructions were ;iven to the volunteers asking them to combine over four 0 six feedings small quantities of milk taken alternately t the beginning and end of each feeding and to store he samples under refrigeration. A composite milk ample was obtained only once from each donor. Clean lass bottles with aluminum foil-lined caps, preprinted ibels, and insulated packing cartons were supplied. Analytical Procedure ill samples were received in a fresh condition, frigeze- ored until ready for analysis, and then thawed at room ;mperature. The milk was well mixed before aliquots ere withdrawn. II solvents were redistilled in glass before use and tested 1 conjunction with the other chemical standards for vtraneous peaks. The unactivated Florisii used in imple cleanup was "1200 F" Florisii, from supplier's ocks, stored under room conditions. This Florisii was ;tivated by heating at 650° C for 1 hour and stored 130° C. at was determined by the Gerher method (S) on a ■parate 1 1.O-ml aliquot. Chlorinated hydrocarbon pesti- de residues were determined by modified procedures Giuffrida et at. (6) for separating the fat and Mills al. (7) for the cleanup. spending on the amount of milk available, 20 to 50 g as weighed into a 350-ml glass-stoppered flask, 100 ml ' acetone and 20 g of celite were added, the contents iiaken well, and then suction-filtered through a coarse iper. The retained milk solids and celite were returned ' the flask and shaken with 100 ml of hexane and re- tered. The combined filtrates were transferred to a liter separating funnel and shaken for 30 seconds; 10 ml of water and 10 ml of saturated NaCI were en added and the funnel shaken again for I minute, he aqueous layer was discarded, and the dried hexane- t solution evaporated to 5-10 ml and used to evenly lat. by stirring, 10 g of unactivated Florisii contained a small beaker. Stirring was maintained to give a y, free-flowing, fat-coated powder. OL. 6, No. 1, June 1972 This was then poured onto a I -inch layer of unactivated Florisii in an 18-mm diameter column and eluted with 70 ml of 10% water in acetonitrile; the eluate was col- lected in a I -liter separating funnel containing 100 ml of hexane. From this point the procedures were the same as de- scribed in references (6) and (7), except that only one 200-ml elution at 5 ml/minute with 8% ether in hexane was used to remove all organochlorine pesticides, in- cluding dieldrin. from the final activated Florisii cleanup column used by Mills et a!. (7). The removal of dieldrin with a single elution, however, would not have been possible if the Florisii had been made too active by prolonged healing. Eluates were concentrated to about 0.5 ml and then transferred to glass-stoppered tubes, using hexane, to give a final volume of 2.0 ml. Aliquots from this solution were analyzed on a Varian Aerograph Model 1200 chromato- graph equipped with a 250 mc tritium electron capture detector. Operating conditions were: Column: Pyrex glass, 5' x '/s", packed with an equal mixture of \0% DC-200 and 15% QF-1 on individually coated 80/100 mesh Gas Chrom Q. A t'ass liner was used in the injec- tion port. Temperatures: Oven 180° C Detec r foil 185° C Inlet 210° C Carrier gas: Nitrogen at 35 cc per minute Injection volumes were held between 2 and 5 fj.\ by sample dilution where necessary. The amounts of pesti- cides injected were kept within the linear range of the detector. A hexane solution containing lindane, aldrin, dieldrin, DDD, DDE, and DDT, each at 0.1 ng//j,l, was used as a standard. HCB (hexachlorobenzene) and BHC standard solutions were also used at 0.5 ng/ fj.\. Injections of these standards were interspersed with samples during chromatography to provide peak height calibration graphs for quantitation. All samples were chromatographed on a second column, packed with 12% QF-1 on Gas Chrom Q, to provide qualitative, and a small degree of quantitative, confirma- tion. Thin layer chromatography with AgNOa-UV visualiza- tion, as described by Abbott et al. (2), was also used to confirm about one-half of the samples. Additional confirmation of HCB was carried out on four samples by scraping the developed and UV-exposed HCB spot from the plate, extracting the alumina with hexane, and injecting the concentrated extract onto the first column. Human milk samples spiked with chlorinated hydro- carbon pesticides to levels between 0.2 and 0.4 ppm gave the following recoveries when carried through the full analytical procedure: HCB and lindane — 73-77%; al- drin, p.r'-DDD. ^./^'-DDE, and /^.p'-DDT— 80-90%: and dieldrin — 83%. The data presented in this report do not include recovery corrections. The lower limit of sensitivity was 0.001 ppm for 50 g of whole milk. Results I Total DDT shown in the results is the sum, withoui molecular weight adjustment, of the DDE, DDD, ano DDT found. As stated, the collection of samples occurred in twci parts, separated by a period of 7 months. All of the 1 rural samples in the first collection were from one fruit-growing district, whereas the 26 rural samples ir the second collection were from 10 other disparate rurai areas. The directions given to obtain a representative milk sample from the donors also varied slightly bei tween the two collections. Table 2 shows the combined results in order to preseni the information in a unified form. Table 3 presents foi total DDT and HCB only, the separate residue leveli from the two surveys. TABLE 2. — Percent fat and organochlorine residues in milk from 67 human donors. Victoria, Australia, 1970 Number of Compound Samples with Detectable Residues ARITHMETIC Mean Range Geometric Mean SD SE PERCENT FAT IN WHOLE MILK Rural 36 3.7 1.0-5.6 _ 1.24 0.21 Urban 26 4.2 2.5-7.2 — 1.18 0.23 Total '62 3.95 1.0-7.2 — 1.25 0.16 ORGANOCHLORINE RESIDUES IN WHOLE MILK (PPM) HCB Rural 39 0.042 0.005-0.17 0.031 0.033 0.005 Urban 28 0,063 0.002-0,33 0.040 0.065 0.012 Total 67 0.051 0.002-0.33 0.035 0.050 0.006 Dieldrin Rural 14 0.008 0,002-0.029 — — — Urban 15 0.004 0.001-0.014 — — — Total 29 0.006 0,001-0,029 — — — DDE Rural 39 0.100 0,022-0,45 — 0.088 0,012 Urban 28 0.112 0,012-0,29 — 0.070 0.013 Total 67 0.105 0.012-0.45 — 0.081 0.010 DDD Rural 4 0,008 0.006-0.014 — — — Urban 8 0.006 0.003-0.010 — — — Total 12 0.007 0.003-0.014 — — — DDT Rural 39 0.038 0,007-0,16 — 0,033 0.005 Urban 28 0.034 0,007-0,12 — 0.022 0.004 Total 67 0.036 0,007-0.16 — 0.029 0.004 Total DDT Rural 39 0.139 0.033-0.58 0.109 0.119 0.019 Urban 28 0,145 0.015-0.40 0.118 0.089 0.017 Total 67 0,141 0.015-0,58 0,112 0.107 0.013 Total DDT (Fat Basis) Rural 36 4.63 0.81-25.35 3.22 5.21 0.87 Urban 26 3.73 1.11- 6.88 3.29 1.78 0.35 Total '52 4.25 0.81-25.35 3.25 4.16 0.53 'Insufficient sample in five cases for a fat determination. Pesticides Monitoring Journai TABLE 3. — Total DDT and HCB residues in human milk from rural and urban donors by survey Sample Group Residues in PPM Total DDT HCB Arithmetic Mean Geometric Range Mean Arithmetic Mean Range Geometric Mean APRIL 1970 Rural (13 samples) Urban (10 samples) 0.208 0.142 0.045- 0.58 0.015- 0.40 0.145 0.105 0.039 0.040 0.010- 0.080 0.002- 0.090 0.031 0.025 DECEMBER 1970 Rural (26 samples) Urban (18 samples) 0.104 0.147 0.033- 0.20 0.051- 0.31 0.095 0.125 0.043 0.076 0.005- 0.17 0.016- 0.33 0.031 0.052 iince the distribution of the levels is skew, geometric neans are shown, and as the results for some pesticides •over a wide range, standard deviation and standard ■rror of the mean have been included where considered ippropriate. In this present study total DDT in human milk, on a fat basis, ranged from 0.81 to 25.35 ppm, with a geometric mean of 3.25 ppm. The ratio of DDE to DDT based on arithmetic means was 2.7 for rural donors. 3.3 for urban, and 2.9 overall. ~lve samples were too meager to determine the fat content. The total DDT in each was 0.033. 0.015. 0.10. ).072. and 0.058 ppm, all below the mean. However in he absence of fat determinations, it is difficult to assess he effect of their exclusion on the mean concentration jf total DDT calculated on a fat basis. Forty-three donors supplied the age of their baby at :he time of the survey: these ages ranged from 2 to 46 vveeks. Discussion All samples contained HCB. It is possible that HCB entered the food chain of Victorians from the improper channeling of HCB-treated seed wheat into the local poultry and stock food industries following a series of severe reductions in wheat acreage during the period of worldwide wheat over-production in the past decade. All samples contained DDT and its first metabolite DDE, but only 12 had the second metabolite DDD. Total DDT ranged from 0.015 to 0.58 ppm, with a mean of 0.141 ppm. These results may be considered in respect to other research findings. Egan et al. (5) reported total DDT in the range of 0.075 to 0.170 ppm with a mean of 0.126 ppm for 19 human milks in England. Curley and Kimbrough (4) determined total DDT in the milk of five U.S. women at three stages during a period of from 3 to 96 days postpartum. Although the range was small. 0.05 to 0.15 ppm. two subjects showed an increase in levels, two a decrease, and one a steady state over this period. Vol. 6, No. 1, June 1972 Abbott ct al. ( / ). in a study in the United Kingdom on postmortem human fat from 91 female subjects over 3 years of age, found total DDT to range from 0.21 to 8.10 ppm, with a geometric mean of 2.2 ppm. For their 248 male and female postmortem samples grouped according to sex. age. and district, they noted a fairly constant ratio for the groupings of I part of DDT to 2,6 parts DDE. Bick (5), in a survey in Victoria using biopsy specimens of human body fat collected from 23 adult males and 30 adult females, found for total DDT a geometric mean of 2.00 ppm for the males, 1 .68 ppm for the females, and a combined range of 0.48 to 6.35 ppm. These figures are on a fresh-tissue basis; mention is made that the lipid content of biopsy specimens is variable. In this study, the mean levels of total DDT in human milk exceeded 0.05 ppm, the limit for total DDT in cow's milk proposed by the FAO WHO and the tolerance set by the U. S. Food and Drug Administration. These limits are based in part on the fact that DDT is now widespread in the biosphere and on the expectation that an individual will consume milk in his diet for a lifetime. They do not provide for residues resulting from the deliberate use of DDT on dairy farms. The results reported here thus pose a difficult problem for those who are responsible for advising mothers on the feeding of their newborn babies. A cknowledgment We thank Miss Christine Hartshorne for her assistance in the chemical analysis and officers of the Maternal and Child Welfare Branch of the State Department of Health, Victoria, for obtaining the samples. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Abbott, D. C, R. Goulding. and J. OG. Tatton. 1968. Organochlorine pesticide residues in human fat in Great Britain. Br. Med. J. 3:146-149. (2) Abbott, D. C. J. O'G. Tatton, and N. F. Wood. 1969. A screening method for organochlorine pesticide residues using thin-layer chromatography. J. Chromatogr. 42:83- 88. (3) Bick, M. 1967. Chlorinated hydrocarbon residues in human body fat. Med. J. Aust. June:1127-1130. (4) Curley, A., and R. Kimbrough. 1969. Chlorinated hydro- j carbon insecticides in plasma and milk of pregnant and ' lactating women. Arch. Environ. Health 18:156-164. (5) Egan, H., R. Goulding, J. Roburn, and J. O'G. Tatton. 1965. Organochlorine pesticide residues in human fat and . human milk. Br. Med. I. 2:66-69. (6) Giuffrida, L., D. C. Bostwick, and N. F. Ives. 1966. Rapid cleanup techniques for chlorinated pesticide resi- dues in milk fats and oils. J. Assoc. Off. Anal. Chem. 49:634-638. (7) Mills, P. A., J. H. Onley, and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in non-fatty foods. J. Assoc. Off. Anal. Chem. 46:186-191. (8) Williams, K. A. 1966. Oils, fats, and fatty foods. 4th edition. J. A. Churchill, Ltd., London, p. 438. Pesticides Monitoring Journai Organochlorine Pesticide Levels in Human Serum and Adipose Tissue, Utah — Fiscal Years 1967-71 ' Stephen L. Warnick ABSTRACT Organochlorine pesticide residue levels were determined in 1,417 serum and 103 adipose samples collected during fiscal years 1967-71 from residents of Utah: levels agreed closely with values reported for persons from other parts of the United States. The results supported previous evidence of no increase in pesticide storage in the general population since 1951 and a tendency towards decreased storage since 1966. Specific findings from the Utah samples included the following: (I) Significantly higher organochlorine levels were found in samples from persons occupationally exposed to pesti- cides than in those from the general population. 12) Significantly higher levels of DDE were found in serum samples from persons 21 years of age and older than in those from persons under 21. (3) Although residue levels were higher in males than in females, the difference was not significant. 14) Mean values of total DDT in adipose tissue for the years in which these samples were obtained were 9.0 ppm in 1968, 7.2 ppm in 1969, and 5.3 ppm in 1970. indicating a decrease in storage levels. (5) Lastly, results from studies of the relation between resi- due levels in serum and adipose tissue, between levels in serum and food, and between serum and household dust, indicated no significant correlations. However, the latter two correlations closely approximated a significant re- lationship, and the results suggested that the respiratory route of exposure to pesticides may be as significant as dietary intake in maintaining an individual's body burden of pesticides. ' From the Utah Community Pesticide Study, State of Utah Depart- ment of Social Services. Division of Health. 44 Medical Drive. Salt Lake City. Utah 84113. Vol. 6, No. 1, June 1972 Introduction A chief concern regarding pesticides is the relationship between pesticide residues in human tissues and human health. Although current evidence indicates that present levels of pesticides in man's environment, food, and body are not adversely affecting human health, it is prudent to ascertain the body burden of pesticides. Numerous studies on pesticide levels in people have been reported (1,3,5-8). including two recently completed studies in Arizona (2) and Idaho (4). Utah is one of 14 States under contract with the Federal Environmental Protection Agency to investigate the effect of pesticides on human health. One aspect of these studies is to determine levels of pesticides in the environ- ment and human population of each project State. Since the projects are widely scattered throughout the contigu- ous United States and Hawaii, pooling results from these studies provides up-to-date representative information for the whole countrv. This paper reports the results of 5 years' analyses for the presence of organochlorine pesticides in serum and adipose tissue samples from Utah residents. Residue levels are presented according to sex, age, race, and ex- posure of residents; method of sample analysis; and year of sampling. Results of studies correlating pesticide levels between serum and adipose tissue, between serum and food, and between serum and house dust are also reported. The discussion in this paper is limited to residues of p,p'-DDT, p,p'-DDE, total DDT (including DDT, DDE, and DDD), and dieldrin, although several other residues were present in both serum and adipose tissue samples. Sampling Methods and Analytical Procedures A total of 1,417 blood samples (fresh serum rather than whole blood) and 103 adipose tissue samples from the population of Utah were collected and analyzed for pesticide residues during the 5-year period, fiscal years 1967-71. The blood samples included 970 from the general population and 447 from persons occupationally exposed to pesticides. Sample extraction, cleanup, and analyses were performed according to methods prescribed for the Community Pesticide Studies Laboratories. These included the Radomski (21) and the Mills, Onley, and Gaither (22) methods for analyzing adipose tissue; the Dale, Curley, and Cueto (23) method for blood; and modifications of the Mills method for adipose and the Dale method for serum as described in the "Manual of Analytical Methods" (9), prepared by the Primate Research Lab- oratories, Environmental Protection Agency, Perrine, Fla. The Perrine Laboratory also provided the pesticide standards used in this study and carried out a quality control program in which the Utah Laboratory partici- pated. The MicroTek 220 gas chromatograph equipped with a Ni'''' detector was used for identifying pesticides, and a two-column gas chromatographic system was used routinely for confirmation. Recovery studies have shown that, for the pesticides reported, recovery is routinely greater than 90%. Results Table 1 presen._ values from the literature for p.p'-DDT, r.p'-BDE, DDT + DDE, and dieldrin levels in people from various areas of the United States for comparison with levels in the general population of Utah. Residue levels in Utah residents compared closely with results from other areas of the country despite considerable differences in quantities of pesticides used. Table 2 is a summary of organochlorine pesticide resi- due levels in blood of Utah residents according to sex, age, race, and exposure; method of analysis; and year of sampling. Table 3 presents organochlorine residue levels in adipose tissue, collected at autopsy from Utah resi- dents who died in accidents; these data are given ac- cording to the residents' sex, age, race, and year of sampling. TABLE 2. — Average organochlorine pesticide residue levels in human serum, Utah — fiscal years 1967-71 No. OF Sam- Residues INPPB Total p,p'-DDE p,p'-DDT DDT> Dieldrin Total 1,417 19.8 6.2 28.3 1.8 Sex Male 1,003 21.9 6.9 31.5 2.1 Female 414 14.6 4.3 20.5 0.9 Year FY 1967 72 19.5 9.8 32.8 4.5 FY 1968 237 15.4 7,2 24.7 2.1 FY 1969 267 20.8 7.9 31.2 1.6 FY 1970 439 18.7 4.3 25.1 1.6 FY 1971 402 22.9 5.7 31.2 1.4 Method of Analysis Method 1 172 15.2 8,4 26.1 3.4 (Single Extract) Method 2 843 19.3 5.9 27.4 1.6 (Triple Extract) Method 3 (2-hour 402 22.9 5.7 31.2 1.4 Roto-rack Ext.) Exposure Group Exposed Workers 447 24.7 11. 1 38.9 3.7 General Population 970 17.6 3.8 23.4 0.9 Age <21 202 13.4 3.6 18,5 0.6 >21 1,215 20.9 6.6 29,9 2.0 Race Caucasian 1.347 19.8 6.0 28,1 1.8 Negro 4 14.3 4,8 20,8 0.8 Oriental 22 35.6 18.6 58,4 1.0 Indian 43 14.0 4,4 20,1 0.5 Mexican I 16.0 3.0 21,0 I.O 'Total DDT = DDT -t- 1.114 (DDE -f- DDD), formula used to for differences in molecular weight. -Mean organochlorine pesticide concentrations in human blood and adipose tissue from Utah and levels reported for other areas of the United Slates UTAH CHICAGO' ARIZONA^ FLORIDA^ IDAHO' UTAH- Compound Blood (PPB) N=970 Adipose (PPM) N=103 Blood (PPB) Adipose (PPM) N=959 Blood (PPB) Adipose (PPM) N=70 Blood (PPB) N = 119 Adipose (PPM) N=159 Blood (PPB) N=I00 Adipose (PPM) Blood (PPB) Adipose (PPM) N=89 p.p'-DDT 3,8 1.5 2,4 1,5 7.0 4.3 4,7 4.7 1.3 P.P'-DDE 17.6 5.0 6,4 4,6 11,3 7.0 22,0 22.5 4.5 DDT + DDE 21,4 6.5 8,8 6,1 11.3 26.7 27,2 5.8 DIELDRIN 0.90 0.17 0,14 (N=22I) 0,14 0.5 0,04 1 Hoffman el al.. 1967, -Morgan and Roan, 1970, sDavies et al., 1968, * Watson e! al.. 1970, = Casarett el al.. 1968, Pesticides Monitoring Journal TABLE 3. — Average organochlorine pesticide residue levels in human adipose tissue, Utah — fiscal years 1967-71 No. OF Samples Residues in fpb p.p'-DDE p,p'-DDT Total DDT' DiELDRIN Total 103 5.03 1.53 7.31 0.17 Sex Male 71 5.36 1.68 7.85 0.19 Female 32 4.31 1.20 6.10 0.14 Year FY 1968 48 5.95 2.13 9.01 0.20 FY 1969 15 4.81 1.51 7.15 0.15 FY 1970 40 4.02 0.83 5.33 0.15 FY 1971 samples ana Age <21 15 4.11 1.25 5.97 0.09 >21 88 5.19 1,58 7.54 0.19 Race Caucasian 96 4.75 1.32 6.76 0.16 Negro 4 7.90 3.70 12.70 0.20 Oriental 1 14.40 11.50 29.60 0.80 Indian 1 4.80 1.50 7.10 0.30 Mexican 1 11.40 3.10 16.40 0.30 'Total DDT = DDT + 1.114 (DDE + DDD), formula used to adjust for differences in molecular weight. Discussion There is no evidence of increased storage of organochlo- rine pesticides in the general population since 1951 (13). and. further, this study and others show a tendency to- ward decreasing levels since 1966. The fact that there has not been progression in storage can probably be attributed to regulations that base maintained low dietary residues. The question of changes in pesticide levels with time is interesting but complicated by the need for standardized analytical methodology. Improved methods of analysis the past few years have offset the very subtle changes that may have taken place in tissue stores as related to changing patterns of pesticide usage. In comparing total DDT in the blood of Utah people as related to sex, the overall average for males was 31.5 ppb and 20.5 ppb for females. Total DDT in adipose was 7.8 ppm for males and 6.1 ppm for females. In both cases, the levels in males were higher, but the difference was not found to be statistically significant. In comparing total DDT in the blood as related to age, levels in persons 21 years of age and older averaged 29.9 ppb. and levels in those under 21 years averaged 18.5 ppb. In adipose tissue persons 21 years of age and older had average levels of 7.5 ppm. while those under 21 years had 6.0 ppm. In both cases the levels of total DDT in people over 21 years were higher but not significantly so. Of the individual compounds, only for levels of serum DDE was the difference according to age significant. Vol. 6, No. 1, June 1972 In comparing total DDT in the blood as related to exposure, results showed that the general population had an average level of 23.4 ppb, while a group of occupationally exposed workers averaged 38.9 ppb; this difference is significant at (P <0.059'f ). Adipose tissue was obtained only from the general population; the average level for total DDT was 7.3 ppm. In comparing total DDT in the blood by method of analysis, residues determined using the single hexane extraction method averaged 26.1 ppb; the triple hexane extraction method, 27.4 ppb; and the 2-hour roto-rack hexane extraction method, 31.2 ppb. The last two methods significantly increased DDE recovery, but not DDT. These more efficient analytical methods may have offset a decline in storage levels of DDE in blood during years 1969, 1970, and 1971. There were some changes in the method for adipose analysis, but the changes did not affect pesticide recovery significantly. Comparison of total DDT found in the blood by year, is difficult due to changes in analytical methodology, but levels for 1967, 1969, and 1971 were higher than levels in 1968 and 1970. An interesting trend was noted in the adipose samples which averaged 9.0 ppm in 1968, 7.1 ppm in 1969, and 5.3 ppm in 1970. This decrease may have been related to a 157c reduction in the use of DDT in Utah during this same period. A budget cut in fiscal year 1971 prevented collection of adipose tissue this year, so it was not determined if the downward trend continued. An insufficient number of samples made a comparison of DDT in the blood and adipose as related to race invalid, except perhaps in the case of American Indians. A total of 43 blood samples were obtained from Amer- ican Indians; these averaged 20.1 ppb compared to 28.1 ppb for Caucasians, perhaps reflecting less exposure for the Indians. Although many studies have investigated the mechanics of DDT storage and metabolism, even after two decades the process is not completely understood. There does ap- pear to be a direct relationship between the daily intake of DDT and levels in the fat achieved at equilibrium. Hayes (14) reached this conclusion by feeding DDT to human volunteers for 1 8 months and showing that even when doses were 200 times as much as found in the daily diet. DDT and DDE concentration in the fat leveled off in about a year. Other studies have supported his finding. When DDT is ingested, carbon-14 studies (15) have shown that a good portion is not absorbed, but excreted directly in the feces. As much as 19% is also excreted 11 in the feces and urine as DDA. The remainder is in equilibrium between storage in the fat and circulation in the blood where it is gradually metabolized and excreted. Recent studies have shown that pesticide storage is affected by other pesticides, certain drugs, and diet deficiencies {16-19). A study in Arizona {20) in which human volunteers were given DDT showed that DDT ingestion does not markedly increase DDE storage, indicating that the body burden of DDE is ingested as DDE. Only about 8% of the stored DDE came from the ingested DDT. There was no attempt in this paper to relate pesticide levels to pathology; but other studies (1,2,10-12) have shown no correlation between levels similar to those found in Utah residents and abnormalities in human health. On this basis, it can be assumed that present levels of organochlorine pesticides in Utah people are not a threat to the health of the community. CORRELATION STUDIES A study was done on 40 people supplying both adipose tissue and serum samples to determine if a significant correlation existed between pesticide levels in adipose and serum. The correlation coefficients (r) were 0.22 for [>.p'-DDT and 0.06 for p.p'-DDE. To be significant at P <5% for 40 samples, the correlation coefficient must be r = 0.32, thus no statistically significant rela- tionship was found between levels in the two types of samples. Another part of the research by the Utah Community Pesticide Study is to determine environmental pesticide levels in food, water, air, house dust, soil, wildlife, etc. To accomplish this, total diet food samples and vacuum cleaner dust samples are collected from selected homes and analyzed for pesticide residues. A study was done to see if DDT levels in the serum correlated with either DDT levels in food or DDT levels in house dust. Ten homes representing the minimally exposed general pop- ulation were chosen. Blood samples were also collected from the male head-of-household and analyzed for pesticides. The following correlation coefficients were then determined for total DDT residues between serum and food, r = 0.41 and between serum and house dust, r = 0.47. To be significant at P <5% for a sample of 10, the correlation coefficient would have to be r = 0.52, thus neither of these relationships was statistically sig- nificant. It is interesting to note, however, that the cor- relation is greater between serum and house dust than between serum and food. This is reasonable based on the fact that the mean level of total DDT in house dust was 1000 times greater than in food (5120 ppb 12 house dust; 6.13 ppb food). This does indicate that the respiratory route of exposure may be as significant as diet in maintaining a person's body burden of pesticides. Additional samples are being collected and analyzed in an attempt to confirm this theory. A cknowledgment Pesticide analyses were performed with the assistance of Lynn Thomas, and data analyses were done by Tom Whitley. See Appendix for chemical names of compounds discussed in ttiis paper. The Utah Community Studies Pesticides Project was supported under contract by the Division of Pesticide Community Studies, Office of Pesticides Programs, Environmental Protection Agency through the Utah State Division of Health. LITERATURE CITED (1) Hoffman William S., H. Adler. W. I. Fishbein, and F. C. Bauer. 1967. Relation of pesticide concentrations in fat to pathological changes in tissue. Arch. Environ. Health 15:758-765. (2) Morgan, Donald P.. and Clifford C. Roan. 1970. Chlo- rinated hydrocarbon pesticide residue in human tissues. Arch. Environ. Health 20:452-457. 13) Davie:. John E.. Waller F. Edmundson. Nathan J. Schnieder, and Janel C. Cassady. 1968. Problems of prevalence of pesticide residues in humans. Pestic. Monit. J. 2(2):80-85. (4) War.u>n. Michael, W. W. Benson, and Joe Gabica. 1970. Senini organochlorine pesticide levels in people in southern Idaho. Pestic. Monit. J. 4(2):47-50. (5) Ca.sarett. L. J., G. C. Fryer. W. L. Yauger. Jr., and H. W. Klemmer. I96S. Organochlorine pesticide residues in human tissues — Hawaii. Arch. Environ. Health 17: 306-311. (6) Quinby, G. £., W. J. Haves, Jr.. J. F. Armstrong, and W. F. Durham. 1965. DDT storage in the U. S. popula- tion. J. Am. Med. Assoc. 191:175-179. (7) Fiserova-Bergerova, V.. J. L. Radomski. J. E. Davies, and J. H. Davis. 1967. Levels of chlorinated hydro- carbon pesticides in human tissues. Ind. Med. Surg. 36(0:65-70. (8) Brown. J. R. 1967. Organo-chlorine pesticide residues in human depot fat. Can. Med. Assoc. J. 97:367-373. (9} Thompson. J. F.. editor. 1971. Manual of analytical methods. Prepared for the Community Studies Projects by the Perrine Primate Research Laboratories, Environ- mental Protection Agency, Perrine, Fla. (lOt Hayes. Wayland J.. Jr., W. E. Dale, and C. I. Pirkle. 1971 . Evidence of safety of long-term, high oral doses of DDT for man. Arch. Environ. Health 22:1 19-135. (11) Echohichon. D. J. 1971. Chlorinated hydrocarbon in- secticides— recent animal data of potential significance for man. Can. Med. Assoc. J. 103(7):71 1-715. (12) Durham. William F. 1969. Body burden of pesticides in man. N. Y. Acad. Sci. 160:183-195. (13) Laug, E. P.. F. M. Kunze. and C. .S. Prickett, 1951. Occurrence of DDT in human fat and milk. AMA Arch. Ind. Hyg. 3:245-246. 114) Hayes. W. J., Jr.. G. E. Quinby. K. C. Walker. J. W. Elliot, and W. M. Upholt. 1958. Storage of DDT and DDE in people with different degrees of exposure to DDT. AMA Arch. Ind. Health 18:398-406. Pesticides Monitoring Journal '5) Jensen. J. A., C. Cueto, W. E. Dale, C. F. Rothe. G. W. Pearce, and A. M. Matlson. 1957. Metabolism of in- secticides: DDT metabolites in feces and bile of rats. J. Agric. Food Chem. 5:919-925. '6) Street, J. C, and Adrian D. Blau. 1966. Insecticide in- teractions affecting residue accumulation in animal tis- sues. Toxicol. Appl. Pharmacol. 8:497-504, \7} Diechmann, W. B.. W. E. MacDonald. and D. A. Cubit. 1971. DDT tissue retention: sudden rise induced by the addition of aldrin to u fixed DDT intake. Science 172 (3980):275-276. ^8) Edmundson. W. F., J. E. Davies, A. Maceo, and C. Morgade. 1970. Drug and environmental effects on DDT residues in human blood. South. Med. J. 63(12): 1440-1441. (19) Street, J. C. 1969. Nutritional parameters in the bio- chemistry of organochlorine pesticides. Utah State Di- vision of Health, Community Pesticide Study, Quarterly Report No. 8. Salt Lake City, Utah. (20) Roan, Clifford C. 1971. Feeding of small doses of chlorinated hydrocarbon pesticides to human subjects, Arizona Community Studies Pesticide Project Annual Rep. No. 4, University of Arizona, Tucson. I2l) Radomski, S. L.. and Vera Fiserova-Bergerova. 1965. The determination of pesticides in tissues without prior clean-up. Ind. Med. Surg. 34:934-939. (22) Mills. P A.. J. H. Onley. and R. A. Gaitlier. 1967. Rapid method for chlorinated pesticide residues in non- fatty foods. J. Assoc. Agric. Chem. 46:186-191. (23) Dale. W. E.. A. Curley. and C. Cueto. 1966. Hexane extractable chlorinated insecticides in human blood. Life Sci. 5:47-54. v^OL. 6, No. 1, JuNt; 1972 13 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mirex and DDT Residues in Wildlife and Miscellaneous Samples in Mississippi — 1970' Karl P. Baetcke, Jimmie D. Cain, and William E. Poe ABSTRACT Samples of wildlife and a few miscellaneous samples, such as beef, were collected in Mississippi in 1970 and analyzed for the presence of mirex and DDT and its analogs. Levels of mirex residues were found to range from 0 ppm to a high of about 104 ppm; residues of DDT and its metabolites (DDTR = DDT + DDE + DDD) were found to range from^"n for jxtraction and cleanup of mirex. the pesticide of specific merest in this study, as well as DDT were already well ;stablished although recovery rates for mirex were not ivailable. Recovery rates for both mirex and DDT and ts analogs were determined for this study. Electron ;apture gas-liquid chromatography was utilized in the determinative step. Thin layer chromatography and infrared spectroscopy were utilized js confirmatory pro- cedures in selected samples. Fish and birds were dissected and the liver, ? '.pose, and brain tissues were analyzed separately by the procedure described in the Pesticide Analytical Manual, Vol. Ill (/); however, adipose tissue Vol. 6, No. 1, June 1972 was not obtained from all avian species because of an apparent depletion of fat reserves. Only adipose tissue was selected from beef and deer for analysis, using the same procedures as that for fish and bird tissue analysis. However, because of the varia- tion in the state of the deer samples which included fresh tissues, dehydrated tissues, and. in extreme cases, partially decomposed tissues, meaningful comparisons of residue values based on fresh weights were not possible. There- fore, in order to make the deer fat samples more com- parable, the samples were ground in a Duall tissue grinder with petroleum ether (b.p. 30-60" C). the ether evaporated on a 60" C water bath, and sampling for residue analysis made on the resulting petroleum ether soluble lipids according to Enos et iil. (/). Residues in cows' milk were determined on a fat basis utilizing the procedure described in the Pesticide An- alytical Manual. Vol. I (2) for the extraction of fat. Cleanup of the milk fat prior to GLC analysis was ac- complished by the procedure of Langlois, Stemp. and Liska (3) with the following modification: Instead of incorporating fluid milk into the top Florisil layer, 1 g or less of extracted butterfat contaned in about 25 ml of 30-60" C petroleum ether was incorporated into Florisil (deactivated with 5'^c water) to form the top layer. This modification extends the usefulness of this cleanup method making it applicable to a wide variety of plant and animal tissue extracts. Extraction of resi- dues from silage and fescue samples was handled es- sentially as described by Mills. Onley. and Gaither {4). This was followed by cleanup as previously described for milk fat. Extraction and cleanup of cattle egret and little blue heron eggs were accomplished according to Cummings el al. (5); no problems were encountered during subse- quent gas chromatography. Arthropods and earthworms were composited by maceration in a Duall tissue grinder, and the micromethod of Enos et al. (I) was used for the extraction, cleanup, and residue determination on the composite. Primary identification and quantification of the pesti- cides were accomplished on a MicroTek NT-220 gas chromatograph. Two columns having different resolu- tion characteristics were utilized on every sample. Instru- ment parameters were as follows: Columns: Detector: (A) Borosilicate glass, 6' x 'A", packed with 1. 57c OV-17, 1.95% QF-1 on 80/100 mesh Supelcoport (B) Borosilicate glass. 6' x '4 ". packed with 4% SE-30. 69c QF-1 on 80/100 mesh Suplecoport Electron capture, having 130 mc tritium ionizing source 15 Temperatures: Injector 235° C Column 195'^ C Detector 210= C Carrier gas: Prepurified nitrogen flowing at 90 ml/min (Column A) and 60 ml/ min (Column B) RECOVERY RATES To establish recovery rates, adipose, liver, and brain tissues collected from chickens were spiked with known amounts of o,p'-DDT, p.p'-DDT, [>,p'-T>DE. and mirex, and the tissues were then analyzed for these residues utilizing the procedures ^escribed above. Recoveries on each tissue were based on three unspiked samples and two levels of fortification with DDTR (DDT and its analogs) and mirex, each consisting of three replicates. The first level consisted of 0.21 ppm DDTR (0.10 ppm p,p'-DDE + 0.10 ppm p.p'-DDT + 0.01 ppm o.p'- DDT) and 0.10 ppm mirex; the second level consisted of 21.00 ppm DDTR (10.00 ppm p.p'-DDE + 10 ppm p.p'-DDT + 1.00 ppm o.p'-DDT) and 10.00 ppm mirex. Percent recoveries at the first level averaged 1 10%, 88%, and 98% for DDTR and 71%, 81%, and 110% for mirex in adipose, liver, and brain tissue, respectively. At the second level, recoveries were 93%, 85%, and 102% for DDTR and 82%, 91%. and 102%^ for mirex in adipose, liver, and brain tissue, respectively. Efficiency of the analytical technique utilized on arthro- pods was determined by grinding 1 0 crickets and dividing the material into four 500 mg samples consisting of three spiked samples and one blank. The spike consisted of 1.0 ppm p.p'-DDT. 1.0 ppm p.p'-DDE, 0.1 ppm o.p'- DDT, and 1.0 ppm mirex. Based on one level of fortifi- cation and three replicates, percent recovery averaged 86% for DDTR and 92% for mirex. None of the data presented herein were corrected on the basis of recovery rates. Confirmation of the presence of mirex was made by thin layer chromatography of six samples (two brown thrash- ers, two bluejays. one channel catfish, and one robin), on Brinkmann-Silica Gel-G plates and developed with n-heptane solvent. Retention values for the mirex stand- ard and for the mirex extracted from samples both aver- aged .75, thus confirming the identification of the ex- tracted compound as mirex. Further confirmation of the presence of mirex was obtained from infrared spectra of two samples (the channel catfish and one blue jay); however, additional infrared spectra could not be ob- tained due to insufficient quantities of mirex in the remaining four samples. Confirmation of DDT and its analogs was accomplished by extraction p-values in some similar wildlife samplings carried out prior to the experiments relating to this study. Many confirmations by this technique have been made in the past, and to date, polychlorinated biphenyls have not been found to be present in quantities sufficient to 16 I interfere with DDT calculations. It is true that PCB's when present at high enough concentrations, interfen with identification of p.p'-DDE, p.p'-DDD, o,p'-DDT p.p'-DDT, and others. However, PCB's, notably Aroclc 1254 and Aroclor 1248, also exhibit tell-tale electroi capture responses in regions of the chromatogram botl earlier and later than that occupied by DDT and analogs None of these patterns were observed in any samples ir this study. This fact does not, of course, preclude the presence or absence of PCB's. It does show, however that they were not present in high enough concentration: to interfere with the identification and quantitation o DDT and its analogs under the conditions of thes* experiments. Results and Discussion The results of the analyses for mirex residues are giver in Tables 1-4. Each table also shows the amount O! DDTR (the sum of p.p'-DDT, o.p'-DDT, p.p'-DDl and p.p'-DDD) found in each sample analyzed. Mire: residues were found to range from 0 ppm to a high o about 104 ppm; DDT and its metabolites (DDTR DDT + DDE + DDD) were found to range from <0.001 ppm to 126 ppm. By analyzing for DDT residues, in addition to mire: residues, it was possible to make some general com parisons between residues representing a pesticide whicl has been employed primarily in local situations ver recently (mirex) and one which has had long-terr widespread usage (DDT). Data are presented on ir dividual samples in the tables in order that more corr TABLE I. — Mirex and DDT residues in adipose tissue c deer collected in Noxubee, Olitibbeha, and Monroe Counties, Mississippi — 7970 Residues in ppm 1 Deer Sample Number W Q Q "a. D Q Q "o. Q 'a. Q s 1 0.015 0.010 — 0.096 0.121 — 2 0.015 0.010 — 0.107 0.132 — 3 0.025 0.014 0.011 0.059 0.109 0.09 4 0.035 0.029 — 0.178 0.242 0.17 5 0.023 0.013 0.007 0.102 0.145 — 6 — 0.014 — 0.057 0.070 0.28 7 0.033 0.014 O.0O7 0.094 0.148 — 8 0.105 0.316 — 1.290 1.711 — 9 0.038 0.015 — 0.083 0.135 — 10 0.059 0.029 — 0,359 0.447 — 11 0.055 0.022 — 0.188 0.265 — 12 0.051 0.034 — 0.128 0.213 0.30 13 0.022 0.016 0.007 0.101 0.146 0.06- 14 0.006 0.008 — 0,063 0.077 — 15 0.114 0.035 — 0.405 0.554 — 16 0.098 0.074 — 0.428 0.600 — 17 0.025 0.007 0.009 0.080 0.121 0.04: 18 0.032 0.024 0.009 0.112 0.177 0.12 19 0.036 0.025 0.012 0.187 0.270 -: NOTE: — indicates none detected; all results on lipid basis. Pesticides Monitoring Journai ilete comparisons can be made between DDTR residues ind mirex residues. rhe results of the current investigation demonstrate videspread occurrence of mirex in wildlife in the reated area. Of 19 deer adipose samples from the hill irea of Mississippi, 7 contained mirex (Table 1). Mirex vas not found in any of 5 1 samples collected from deer n the Delta where mirex use had been sporadic and very ocalized. Data pertaining to the Delta deer samples are not presented in the tables since the main purpose of this report is to compare levels of mirex with levels of DDT. as well as to show to what extent mirex is present in samples from the treated area. Of 42 individual birds representing 9 species analyzed for the presence of mirex. mirex was found present in one or more tissues of 41 birds (Tables 2a-2d). Mirex was not found in any tissue of one turkey (Tables 2a- 2c). Of all fish from the hill area analyzed for mirex. TABLE 2a. — Mirex and DDT icxidues in liver tissue of fish and birds collected in Oktibbeha. Noxubee, and Lowndes Counties, Mississippi — 1970 Residues in ppm Sample Number i Specimen P,P'-DDE p,p'-DDD o.p'-DDT p,p'-DDT DDTR Mirex Fisli 1 0.046 O.OIl T 0.012 0.069 0.281 Channel catfish 2 0.004 0.004 0.023 3(2) 0.089 0.044 0.046 0.048 0.227 0.337 4(2) 0.121 — 0.052 0.024 0.197 0.674 5 0.023 0.028 0.047 0.060 0.158 = 6 0.054 0.063 0.061 0.068 0.246 = 7 0.024 0.052 0.056 0.021 0.153 _ Birds Chicken 1 0.823 0.047 0.024 0.150 1.044 0.550 Bobwhite quail 1 0.404 _ _ 0.006 0.410 0.013 2 0.389 0.003 0.012 0.007 0.411 0.027 3 0.101 T T T O.IOI 4 0.421 T T T 0.421 5 0.400 T T T 0.400 6 0.156 T T T 0.156 0.014 7 0.281 T T 0.018 0.299 0.052 8 0.459 T 0.015 T 0.474 0.016 9 0.270 0.005 0.012 0.017 0.304 0.077 10 0.144 0.004 — 0.009 0.157 11 0.487 T 0.016 T 0.503 0.031 12 0.303 T T T 0.303 0.027 13 0.057 T T T 0.057 0.026 14 0.371 T T T 0.371 0.147 15 0.021 T T T 0.021 0.034 16 0.254 — — — 0.254 0.034 17 0.194 T T T 0.194 0.209 18 0,339 T — T 0.339 0.216 19 0.161 — — — 0.161 0.050 20 0.111 — — — O.Ill 0.295 Brown thrasher 1 1.369 _ 0.029 0.026 1.424 0.456 2 1.519 — — 0.118 1.637 1.811 3 4.228 — 0.046 0.119 4.393 1.838 4 1.725 — 0.015 0.045 1.785 1.242 Blue jay 1 0.499 0.013 0.046 0.558 1.434 2 0.415 — — — 0.415 0.350 3 0.514 — — 0.023 0.537 1.506 Meadow lark 1 1.312 0.010 0.014 0.233 1.569 7.564 2 1.348 0.007 0.011 0.095 1.461 3.744 Turkey 1 3 0.090 — - T 0.090 0.076 4 5 1.130 0.010 o.oio 0.026 1.176 0.206 6 0.329 T T 0.033 0.362 0.475 Eastern kingbird 1 5.462 0.077 0.154 0.308 6.001 0.131 Robin 1 _ _ 2 13.879 5.042 0.206 0.158 19.285 0.724 3 13.332 4.220 0.174 0.255 17.951 0.298 4 0.583 0.062 0.039 0.089 0.773 1.443 5 1.683 0.151 0.044 0.086 1.964 0.694 Barred owl 1 4.046 0.012 - 0.052 4.110 4.072 TOTE: Blank = sample not analyzed; — indicates none detected; T = trace = <0.002 ppm i Numbers in parentheses indicate composite of two or more fish or birds. Samples collected in the Delta. /OL. 6, No. 1, June 1972 lirex; all results on fresh-weight basis. 17 4 of 5 channel catfish samples were found to contain the pesticide (Tables 2a, 2b, 2d) and 2 of 2 green sunfish (bream) samples were found to contain the pesticide (Table 2b). Of 25 individual and composite samples of arthropods analyzed for pesticides, 10 were found to contain niirex. It should be pointed out that all of the samples containing mirex, with the exception of two robins, were collected from the area that had been treated relatively recently with mirex. Among the few miscellaneous samples collected, thcl significant findings were that mirex was present in the] two milk samples and the three beef samples (adipose} tissue) collected (Table 4). One milk fat sample con- tained 0.007 ppm of mirex and the other contained 0.016 J ppm. The values for mirex in the three beef fat samples^ were 0.012, 0.113, and 0.042 ppm. The results of th£| analyses for mirex in beef fat and milk, in addition tci results concerning the deer samples, suggest that thifj TABLE 2b.— Mirex ai (/ DDT residues in adipose tissue of fisli and birds collected in Oktibbeha, Noxubee, and Lowndes Counties, Mississippi — 1970 Sample Residues in ppm Specimen Number 1 P,p'-DDE p,P'-DDD o,p'-DDT p,p'-DDT DDTR Mirex Fish Green sunflsh (Bream) 1 0.086 0.010 T 0.016 0,112 0.138 2 0.068 0.008 0.009 0.024 0.109 0.105 Channel catfish 1 0.579 0.088 0.013 0.087 0.767 11.252 2 0.211 0.076 0.036 0.058 0.381 5.978 3(2) 1.170 0.399 0.112 0.559 2.240 3.760 4(2) 2.382 0.659 0.309 0.783 4.133 2.479 5 1.953 2.421 1.371 2.189 7.934 — = 6 3.579 2.935 0.753 2.885 10.152 — -1 1.968 2.021 1.296 2.402 7.687 — Birds Chicken I 0.067 0.004 - 0.030 0.101 0.087 Bobwhite quail 1 0.073 0.073 0.252 2 T — — — T — 3 0.014 — — — 0.014 0.016 4 0.141 — — T 0.141 0.072 5 0.074 T T 0.046 0.120 0.038 6 0.063 T T T 0.063 0.036 7 0.085 — — — 0.085 1.047 8 0.050 — — T 0.050 0.410 9 0.071 — — — 0.098 0.147 10 0.017 — — — 0.017 0.177 11 0.290 T T 0.038 0.328 T 12 0.908 0.015 0.023 0.032 0.987 3.148 13 0.580 0.015 0.036 0.060 0.515 0.691 14 0.511 T T 0.863 1.374 0.843 15 0.840 0.010 — 0.037 0.887 2.755 16 0.291 T T 0.040 0.331 0.292 17 0.398 0.014 T 0.042 0.454 0.907 18 0.763 0.024 0.043 0.071 0.901 1.610 19 0.407 T T 0.072 0.479 0.717 20 0.758 T T 0.092 0.850 1.843 Brown thrasher 1 17.732 0.261 T 1.390 19.122 53.563 2 28.380 0.176 0.197 2.589 31.342 59.925 3 60.086 0.337 0.167 4.677 65.267 25.432 4 33.629 T T 1.990 35.619 19.978 Blue jay , 29.779 T T 2.963 32.742 104.386 2 8.388 0.077 0.153 0.481 9.029 5.104 3 50.38! T T 2.607 52.988 35.720 Turkey 1 0.889 0.036 0.025 0.593 1.543 1.614 2 2.936 0.110 0.084 2.290 5.420 0.156 ,■( 0.091 T T 0.074 0.165 0.014 4 0.053 0.005 T 0.099 0.157 — 5 0.471 — — 0.099 0.570 0.098 6 0.436 — — 0.128 0.564 1.207 Eastern kingbird 1 8.068 0.190 T 0.351 8.609 0.436 Robin \ 0.677 0.062 0.030 0.047 0.816 1.002 3 4 17.976 0.220 0.559 2.815 21.570 35.138 5 96.341 1.840 0.924 26.829 125.934 56.536 NOTE: Blank = saniple not analyzed; — indicates none detected; T = trace = <0.001 ppm DDT or <0.002 ppm mire i; all results on fresh-weigh basis. 'Numbers in parentheses indicate composite of two or more fish or bi ds. = Samples collected in the Delta. 18 Pesticides MONITORINC JOURNA pesticide may have entered the food chain of human leings. However, additional data involving larger num- jers of samples must be collected before any definite itatements can be made concerning mirex residues in 'ood products since the possibility of misleading informa- ion exists when the number of samples is so small. .Vhen mirex values are compared with DDTR values, it ■an be seen from Tables 1-4 that in many cases, mirex esidue values were found to exceed DDTR values. \mong all birds sampled, mirex residues exceeded DDTR residues in 20 of 38 adipose tissues (Table 2b), 10 of 39 liver tissues (Table 2a), and 10 of 37 brain issues (Table 2c); in fish, mirex values exceeded DDTR /alues in 4 of 9 adipose samples (Table 2b), in 4 of 7 liver samples (Table 2a), and 1 of 5 muscle samples (Table 2d); similarly, in 6 of 25 arthropod samples (Table 3), mirex values exceeded DDTR values. Addi- tional comparisons between DDTR and mirex values can be made from the information presented in the tables, but the above data are sufficient to illustrate the point that mirex has indeed become a prominent pesti- cide residue in some wildlife, at least in Mississippi. The existence of some mirex levels which exceed DDTR levels is somewhat surprising since the mirex has been applied at rates which represent grams of toxicant per acre, whereas DDT has been applied at a rate of several pounds per acre, although not necessarily in the area studied. DDT has also been used for a much longer period of time than mirex. TABLE 2c. — Mirex and DDT residues in brain tissue of birds collected in Oktibbeha. Noxubee, and Lowndes Counties, Mississippi — 1970 Sample Number Residues in ppm ),p'-DDT p,p'-DDT Chicken Bobwhite quail Brown thrasher Blue jay Meadow lark Turkey Eastern kingbird Robin 0.014 0.028 0.009 0.010 0.226 0.010 0.015 0.008 0.008 0.012 0.036 0.029 0.008 0.008 0.017 0.019 0.019 0.595 0.244 1.256 0.281 0.486 0.118 0.396 0.080 0.338 1.381 9.819 0.171 1.057 1.651 0.002 0.003 0.698 1.238 0.032 0.033 0.010 0.010 n.003 0.078 0.138 0.015 0.013 0.086 0.022 0.011 0.030 0.016 0.031 0.008 0.071 0.031 0.180 0.049 0.002 0.014 0.053 0.022 0.010 0.278 0.010 0.015 0.008 0.008 0.012 0.036 0.029 0.008 0.008 0.017 0.019 0.019 0.638 0.244 1.342 0.303 0.486 0.129 0.436 0.101 0.369 4.354 13.716 0.234 1.309 1.703 0.067 0.318 0.429 1.057 n.374 1.195 0.099 1.513 0.462 0.524 0.028 0.029 0.197 0.172 0.404 0.572 1.820 NOTE: Blank = samples not analyzed; — indicates none detected: T = trace =<0.00! ppm DDT or <0.002 ppm mirex: all results on fresh-weight basis. Vol. 6, No. 1, June 1972 19 TABLE 2d.- -Mirex and DDT residues in heart and muscle tissue of fish and birds collected in Oktibbeha, Noxubee, and Lowndes Counties, Mississippi — 1970 Sample Number ' Tissue Residues in ppm | * Specimen p,p'-DDD p,p'-DDE o,p'-DDT p,p'-DDT DDTR Mirex Fish Channel catfish 3(2) 4(2) 5 26 27 Muscle Muscle Muscle Muscle Muscle 0.118 0.121 0.327 0.016 0.024 0.105 0.219 0.251 0.026 0.083 0.037 0.289 0.030 0.142 0.160 0.449 0.072 0.024 0.448 0.537 1.316 0.060 0.079 Birds Meadow lark 1 2 Heart Heart 0.004 T 0.113 0.911 0.005 T 0.041 0.045 0.163 0.956 1.058 1.931 Turkey 5 6 7 Heart Heart Heart — 0.018 0.636 0.029 0.002 0.010 0.117 T 0.030 0.753 0.029 0.020 0.127 0.229 Barred owl 1 Muscle 0.005 1.036 - 0.020 1.061 0.934 NOTE: —indicates none detected; T = trace = <0.(X)l ppm DDT or <0.002 ppm mirex; all results on fresh-weight basis. 1 Numbers in parentheses indicate composite of two or more samples, 2 Samples collected in the Delta. TABLE 3. — Mirex and DDT residues in arthropods collected in Oktibbeha County, Mississippi — 1970 Specimen Number of Individuals per Sample Residues in ppm P,p'-DDD p,p'-DDE o.p'-DDT p,p'-DDT DDTR Mirex Praying mantis 3 0.001 0.008 0.003 0.010 0.022 0.008 Walking sticks 4 0.002 0.003 0.004 0.006 0.015 0.021 Stink bugs 19 0.004 0.061 0.018 0.048 0.131 — Lady bugs 15 0.012 0.692 0.039 0.052 0.793 — Beetles 17 0.003 0.033 0.020 0.048 0.131 — Spiders 5 0.040 0.368 0.336 0.308 1.052 1.219 Spider 1 — 0.017 0.019 0.013 0.049 0.065 Spider 1 — 0.010 0.014 0.016 0.040 0.267 Spider 1 — 0.015 0.020 0.029 0.064 0.189 Katydid 2 — 0.011 0.019 0.029 0.059 — Katydid 2 — 0.007 0.019 0.017 0.043 — Cricket 2 — 0.013 0.016 0.052 0.081 0.008 Cricket 2 0.049 0.049 0.013 0.240 0.351 0.030 Cricket 2 0.007 0.010 0.016 0.022 0.055 — Cricket 2 — 0.012 0.011 0.031 0.054 — Cricket 2 — 0.012 0.042 0.042 0.075 0.026 Cricket 2 — — _ 0.075 Cricket 2 — 0.005 0.022 0.017 0.044 — Cricket 2 — — — _ _ Cricket 2 — 0.006 0.009 — 0.015 — Cricket 2 0.007 0.012 — — 0.019 — Grasshopper 1 — — 0.034 0.033 0.067 — Grasshopper 2 — — 0.010 0.019 0.029 — Grasshopper 2 0.021 — 0.030 0.019 0.049 — Grasshopper 4 0.077 0.011 0.012 0.015 0.038 - NOTE: — indicates none detected; all results on fresh-weight basis. It is difficult at the present time to assess the imphca- be 365 mg/kg for adult female rats. The 90-dose LD50. tions of the results reported in the present paper. Lacking the amount daily given in a single dose for 90 days in most reports to date is any information pertaining to which will result in 50% mortality, was reported to be the buildup of mire.x in animals following treatment with 6 mg/kg. Earlier. Gaines (7) found that when corn oil mire.x and what toxic effects, if any. can be expected at various tissue levels. A number of LD.,,, values have been established for mirex and these values indicate that mirex is rather low in its toxicity to animals. Gaines and Kimbrough (6). for example, in a study of the was used as the carrier, the oral LD-,,, for mirex in male and female rats was 740 and 600 mg/kg, re- spectively. Mirex administered in a peanut oil solution resulted in a LD.-„ value greater than 3.000 mg/kg, in males and females alike. The pronounced difference in the LD.,,, values found, based on which carrier was toxicity of mirex to rats found the single dose LD-,,, to used, has not been explained. 20 Pesticides Monitoring Journal TABLE 4. — Mirex and DDT residues in miscellaneous samples collected in Lowi des and Oktibbeha Counties, Mississippi — 1970 Residues in ppm Sample Specimen Number 1 P,p'-DDD p,p'-DDE o,p'-DDT p,p'-DDT DDTR Mirex Cattle egret eggs 1 0.056 0.759 0.017 0.089 0.921 1.555 2 0.011 0.834 0.013 0.044 0.902 0.035 3 0.012 1.944 — 0.014 2.070 0.285 4 0.024 1.769 0.014 0.353 2.160 0.055 5 0.068 2.605 0.042 0.230 2.945 0.277 6 0.006 0.655 0.011 0.036 0.708 0.618 7 0.018 0.302 0.022 0.139 0.481 0.073 Blue heron eggs , 0.084 1.561 0.031 0.605 2.281 0.051 2 0.049 0.511 0.097 0.239 0.896 0.166 3 0.053 3.479 0.406 0.517 4.455 0.316 4 0.012 0.220 0.017 0.062 0.311 T 5 0.010 0.369 0.017 0.059 0.455 0.083 6 0.075 1.139 0.098 0.562 1.874 0.694 Cow's milk (lipid basis) 1 0.003 0.013 T 0.007 0.023 0.007 2 — 0.007 — — 0.007 0.016 3 0.056 0.291 — 0.054 0.401 — Earthworms 1 0.005 _ _ 0.005 0.030 2(10) 0.005 0.005 T 0.008 0.018 0.076 Beef adipose 1 0.013 0.134 _ 0.067 0.214 0.012 2 0.023 0.118 — 0.074 0.215 — 3 0.035 0.868 — 0.068 0.971 0.113 4 0.021 0.227 — 0.055 0.303 0.042 5 0.156 1.324 0.019 0.410 1.909 — Silage (dry weight) 1 0.015 0.011 -^ _ 0.026 _ 2 0.016 0.011 — — 0.027 — Fescue (dry weight) 1 0.003 0.010 0.012 0.037 0.062 - oJOTE: — indicates none detected; T = trace= <0.00l ppm DDT or <0.(X)2 ppm mirex: all results on fresh-weight basis unless otherwise noted. Numbers in parentheses indicate composite of two or more samples SVare and Good (S) found that a rather low level of and 8'"f of a group of cowbirds fed 500 ppm of mirex mirex in the diet (10 ppm) of mice resulted in \00'"r died after M) days. mortality by 60 days. This report also showed that 5 ppm of mirex increased parent mortality and decreased In addition to mortality data, it has been shown that litter size. when mirex (600 ppm) was fed to laying hens over a 16-week period, the hens lost weight and the hatcha- ,.,,.. ... ,. bilitv of eges and survival of chicks was reduced (10). In addition to mortalitv data on mammalian species. r. ■ u i_- i_ c ■ ■ j u . , , , ■ Based on the high amounts of mirex required to reach some evidence has been accumulated which sueeests that , r^ . " j ■ «■ . •. u • „ , ... . '7 ,. . ill LD-„ or to produce toxic effects, it would not appear toxic effects can be produced in mammals following .u . .u i i f • u i • • i i j ^ . , , that the levels of mirex observed in animals sampled mirex ingestion. Gaines and Kimhroueh tound that fe- . ., .-.•.• . .• i u j "^ , ,^ , . ,.,.',. , in the current investigation represent a potential hazard. male rats fed 25 ppm of mirex exhibited ultrastructural changes in liver tissue (6). Also, some offsprinc from _^, , ,. . , ,■ rr , 1 r 1 -,£■ r ,^-. J . , . ' The most re evant information reported reeardme effects females fed 25 ppm for 102 davs developed cataracts; ^ . . .^ u • u ■,,,.,,,, f. , ,,. ., . ., , ,. : , , . , . of mirex in fish IS that provided bv Van Valin er f». (//). the incidence of cataracts at this level, which correspond _, , , ,,.'..,, , , . , , r - - ... These workers showed that lesions in Bills and kidnevs to an average intake of Z.i mg/kg/da\ . was 4b Vr. of so dfish occurre d followine f sedine of mir ex. Tissue In relating the findings reported for avian species in the current report to previous work, one must rely on amounts of mirex reported which cause mortality. Toxicity data on a number of different species of birds are given in Circular 199 of the Fish and Wildlife Service (9). Data in that publication show that 12% mortality was produced in quail fed 300 ppm for 111 days; young mallards fed a diet containing 500 ppm of mirex experienced a maximum of 81 ^J- mortality in 30 days; 20% mortality was observed in pheasants fed a diet which contained 200 ppm of mirex for 30 days: Vol. 6, No. 1, June 1972 levels of mirex in goldfish at completion of the experi- ment ranged from 0 to 1.350 ppm in liver tissue and ranged from 20.8 to 232 ppm in muscle tissue. These fish had been exposed to 1 .0 ppm mirex in water for 224 days. The levels reported by Van Valin et al. which resulted in histological changes in fish are considerably higher than the values for mirex residues found for the same tissues in the limited number of fish samples in the current investigations. To summarize the above discussion, it appears that for the most part mirex is low in its toxicity to animals based on LDr.d values. However, rather low amounts of this material in the diet of some animals, mice for example, can produce mortality. Because of the lack of informa- tion regarding tissue levels of mirex encountered with the feeding of LD-,,, dosages, it is not possible to interpret the meaning of the levels observed in samples discussed in this report, although some previous data on fish indicate that the values reported in the current study do not represent toxic levels. A cknowledgment The authors are indebted to Mr. Burton S. Webster and the staff of the Noxubee Wildlife Refuge for the assist- ance given in obtaining samples. Special thanks is extended to the many technicians who assisted in the pesticide analyses. See Appendix for chemical names of compounds discussed in tfiis paper. This work was supported in part by funds provided by the Public Health Service, Food and Drug Administration, Department of Health, Education, and Welfare, under contract FDA 71-6. LITERATURE CITED (1) Biros. F. 1970. Pesticide Analytical Manual, Vol. Ill, Sec. HE 212.1. Food and Drug Admin., U. S. Dep. Health, Educ. and Welfare, Washington, D. C. 20204. (2) Barry, H. C, J. G. Hundley, and L. Y. Johnson. 1963. (Revised 1964, 1965). Pesticide Analytical Manual, Vol. I, Sec. 2.21. Food and Drug Admin., U. S. Dep. Health, Educ. and Welfare, Washington, D. C. 20204. (3) Langlois, B. £., A. R. Stemp, and B. J. Liska. 1964. Rapid clean-up of dairy products for chlorinated in- secticide residue analysis. J. Agric. Food Chem. 12:243. (4) Mills. P. A.. J. H. Onlcy. and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in non- fatty foods. J. Assoc. Off. Anal. Chem. 46(2);186-191. (5) Ciimmings, J. G., K. T. Zee, V. Turner, and F. Quinn. 1966. Residues in eggs from low level feeding of five chlorinated hydrocarbon insecticides to hens. J. Assoc. Off. Anal. Chem. 49(2);354-364. (6) Gaines, T. B.. and R. D. Kimbrough. 1970. Oral toxicity of mirex in adult and suckling rats. Arch. Environ. Health 21:7-14. (7) Gaines, T. B. 1969. Acute toxicity of pesticides. Toxicol. Appl. Pharmacol. 14:515-534. (5) Ware, G. W.. and E. E. Good. 1967. Effects of insecti- cides on reproduction in the laboratory mouse:II. mirex, telodrin, and DDT. Toxicol. Appl. Pharmacol. 10:54-61. (9) Stickel, L. 1964. Wildlife studies, Patuxent Wildlife Research Center, p. 77-116. In Pesticide-Wildlife Studies, 1963. A Review of Fish and Wildlife Service Investiga- tions During the Calendar Year. U. S. Dep. of the Inter., Fish and Wildlife Serv. Circ. 199. (10} Naber, E. C, and G. W. Ware. 1965. Effect of Kepone and mirex on reproductive performance in the laying hen. Poult. Sci. 44:875-880. (//) Van Valin, C. C, A. K. Austin, and L. L. Eller. 1968. Some effects of mirex on two warm-water fishes. Trans. Am. Fish Soc. 97:185-196. 22 Pesticides Monitoring Journal I Chemical Residues in Lake Erie Fish — 1970-71 ' Richard L. Carr. Charles E. Finsterwalder. and Michael J. Schibi ABSTRACT Wellow perch, colio salmon, carp, channel catfish, jreshwater drum, and white bass from the Ohio shore of Lake Erie were analyzed during 1970-71 for residues of chloriiuiteil pesticides (DDE, TDE. DDT, and dieldriii). polyclilorinaled biphenyls (PCB's), and mercury. All but I of the 80 samples analyzed contained DDT and/or its metabolites: PCB's were found in all samples. Fifty-three of the SO .samples were analyzed for mercury, and all were found positive. Average levels of residues for the species sampled rangeil from 0.06 to 0.42 ppm for DDE: 0.07 lo 0.52 ppm. TDE: 0.03 to 0.25 ppm, DDT: 0.18 to 0.90 ppm. total DDT: 0.01 to 0.07 ppm, dieldrin: 0.08 to 4.4 ppm. PCBs: and 0.12 to 0.64 ppm, mercury. The highest average residue levels of total DDT were in coho salmon and channel catfish. Average levels of PCB's were significantly higher in channel catfish. and levels of mercury were significantly higher in white bass. Introduction 'In the spring of 1970 the Cincinnati District of the U. S. Food and Drug Administration began monitoring yellow perch {Pcrca fiavescetts) and. in cooperation with the Ohio Department of Natural Resources. Division of Wildlife, coho salmon (Oncorhynchus kisuich) to de- termine the extent of pesticide contamination in these species in Lake Erie. The next spring (1971) monitor- ing was broadened to include white bass ( Roccus chrysops) , freshwater drum (Aplodinotus grunniens). channel catfish (Ictalunis pitnctatiis). and carp {Cyprin- inus carpio). These six species were selected because they had the greatest commercial significance and/or greatest potential for residues due to their predatory eating habits and size. The investigation of these species was limited to the Ohio shore of Lake Erie, since this was the legal boundary of Cincinnati District of FDA. Prior to the expansion of the program ( 1970), the coho From the U. S. Food and Drug Adminislration, 1141 Central Park- way, Cincinnati. Ohio 45202. Vol. 6, No. 1, June 1972 salmon and yellow perch (15 and 12 samples, respec- tively) were analyzed for DDT and its isomers and metabolites, dieldrin, and PCB's (calculated as Aroclor'^ 1254): after the expansion (1971). all species were analyzed for mercury as well. Sampling Procedures The coho salmon, collected by the Ohio Division of Wildlife, were random samples and represented catches from almost the entire Ohio shore of Lake Erie (Fig. 1): the other species were collected by Food and Drug inspectors at commercial fisheries in Ohio. The coho salmon represent catches on a year-round basis, while the other species were obtained during the fishing season on Lake Erie, a period from latter March to early October. Each coho sample consisted of 1 or 2 fish and the other samples consisted of 5 to 10 fish. On collection, the samples were frozen and shipped to the laboratory in Cincinnati. At the laboratory, the samples were thawed, and the heads, viscera, and scales removed. The rest of the fish was then thoroughly ground and mixed in a meat grinder. A nalylical Procedures ORG.ANOCHLORINES AND PCB'S The method employed for extraction and cleanup of samples to determine DDT residues, dieldrin, and PCB's was that described by Porter, Young, and Burke (6). The procedure involved dehydrating the sample with sodium sulfate and then isolating the fat by blending 50 g of the sample three times with petroleum ether. The fat was partitioned with acetonitrile and the residues isolated by a Florisil column, eluted with 6% and 159?- ethyl petroleum ether. The 15 9r eluate which contained any residues of dieldrin was additionally cleaned up using alkaline saponification (-7). PCB residues in the 23 FIGURE 1. — Map of Ohio Shore of Lake Erie showing collection points of fish samples analyzed — 1970-71 MICHIGAN OHIO y^ TOLEDO CRANE CREEK. BEACH SANDUSKY BAY HURON RIVER 6% eluate were isolated from DDT residues by using the silicic acid column method described by Armour and Burke ( /). A Barber-Coleman Model 10 gas-liquid chromatograph (GLC), equipped with a 150-mc tritium electron cap- ture detector, was used for all quantitative assays (4). Two columns were used; ( 1 ) 10% DC-200 on Chromo- sorb W/HP and (2) a 1 to I mixture of 10% DC-200 and 15% QF-1 on Chromosorb W/HP. Parameters were those given in the FDA Pesticide Analytical Manual (3). Confirmation tests for the chlorinated pesticide residues consisted of thin layer chromatography (J) of 10 ran- domly selected samples. PCB residues were confirmed by their stability to alkaline saponification and by micro- coulometric GLC using a chlorine specific detector (3). Quantitation of pesticide residues was accomplished using peak height. PCB residues in the fish had a pattern most similar to Aroclor* 1254 and were calculated by comparing the entire area of the PCB pattern with the area of Aroclor'" 1254. Standards were supplied by the FDA Pesticide Reference Standard Section. Recovery data for the above procedure provided by Carr in a collaborative study (2) were p.p'-DDE, 87.5 ± 13.5%: p.p'-TDE. 88.6 ± 11.4%: p.p'-DDT, 90.6 ± 9.7%- and dieldrin 82.2 ± 25.4%. MERCURY Mercury was determined using the method described and collaborated by Munns and Holland (5). The method employs a perchloric acid digestion and subsequen determination by "cold vapor" atomic absorption. The instrument was a Perkin-Elmer Model 303 AA with i 17-cm cell length in a closed system. The 2533 A ab sorption line was used. The average recovery for sample: fortified with methyl mercury chloride was 85.4%. Results Table I lists the individual residue levels for each fisl sample in the study by species: Table 2 summarize these results. These data were not corrected for percen recovery, and the minimum level recorded in all de terminations was 0.01 ppm: all residues are reportet on a wet-weight basis. Average residues of total DDT were highest in coho salmon (0.90 ppm) and catfisl (0.89 ppm): however, none of the samples approachec the FDA guideline of 5 ppm. Average dieldrin residue: were highest in coho salmon (0.07 ppm), although agair the levels were low. Polychlorinated biphenyl residue were significantly higher in channel catfish (average 4.4 ppm). White bass continued the highest average level of mercury with residues in five of the six white bass samples examined in excess of FDA's 0.5 pprr guideline. In general, the species lowest in the fooc chain, yellow perch, and the "rougher" fish (fish that are not sport fish or of significant food value), carp anc freshwater drum contained the lowest amounts of chem ical residues. See Appendix for chemical names of compounds discussed in thi paper. Pesticides Monitoring Journal TABLE 1. — Chemical residue levels in six species of fisi , Lake Erie- -1970-71 Location of Catch Date Collected ' Residues in ppm DDE TDE DDT TOTAL DDT DiELDRIN PCB's Mercury COHO SALMON ^andusky Bay (I) 4/1/70 0.39 0.15 0.25 0.79 0.06 1.6 Sandusky Bay (M) 4/1/70 0.38 0.28 — 0.66 0.06 1.7 landusky Bay (I) 4/1/70 0.34 0.10 0.31 0.75 0.05 1.6 vJNW Toledo (M) 5/18/70 0.32 0.28 0.18 0.78 0.07 1.3 MNW Toledo (M) 5/18/70 0.32 0.15 0.37 0.84 0.06 1.0 MNW Toledo (M) 5/18/70 0.43 _ 0.67 1.10 0.08 2.2 East Pelee Island (M)- 6/10/70 0.62 0.45 0.23 1.30 0.08 2.6 East Pelee Island (M) 6/10/70 0.53 0.32 0.23 1.09 0.06 1.6 Soulheast Shoal 6/30/70 0.72 0.21 0.38 1.31 0.06 3.2 Southeast Shoal 6/30/70 0.64 0.25 0.50 1.39 0.06 3.2 Southeast Shoal (I) 6/30/70 0.55 0.42 0.11 1.08 0.05 4.3 ME Erieau Ontario (M) 7/28/70 0.39 0.25 0.04 0.68 0.05 1.5 NE Erieau Ontario (M) 7/28/70 0.88 0.50 0.07 1.45 0.15 3.1 NE Erieau Ontario (M) 7/28/70 0.60 0.42 0.15 1.17 0.10 3.S W Erieau Ontario (M) 7/30/70 0.90 0.30 0.49 1.69 0.14 3.2 NE Fairport Harbor (M) 8/1/70 0.53 0.23 0.50 1.26 0.07 2.2 0.42 NE Fairport Harbor (M) 8/11/70 0.27 0.20 0.24 0.71 0.06 1.6 0.59 NE Fairport Harbor (M) 8/11/70 0.31 0.18 0.06 0.55 0.03 1.3 0.39 N Conneaut (M) 9/2/70 0.04 0.46 0.13 0.63 0.09 3.8 0.58 N Conneaut (M) 9/2/70 0.06 0.25 0.61 0.91 0.06 1.5 0.21 N Ashtabula (I) 9/2/70 0.17 0.17 0.44 0.78 0.05 1.10 O.ll N Conneaut (I) 9/3/70 — 0.10 0.11 0.21 0.04 1.2 0.14 W Huron (M) 10/12/70 0.46 0.20 0.08 0.74 0.03 1.3 0.47 W Huron (M) 10/12/70 0.42 0.24 0.11 0.78 0.04 1.9 0.36 W Huron (M) 10/12/70 0.47 0.16 0.26 0.89 0.03 1.2 0.20 Huron River Dam (M) 11/4/70 0.47 0.22 O.IO 0.79 0.04 29 0.35 Huron River Dam (M) 12/8/70 0.37 (1.21 0.07 0.65 0.03 2.6 0.41 Sandusky Bay (I) 4/1/71 0.28 0.16 0.11 0.53 0.07 I.I 0.24 Bono (M) 4/23/71 0.50 _ 0.50 1.00 0.10 1.4 0.12 ■ Middle Island (M) 6/14/71 0.21 0.22 0.07 0.50 0.07 2.6 0.36 YELLOW PERCH North of Cleveland 4/13/70 0.04 0.03 _ 0.09 0.02 0.5 North of Fairport 4/19/70 - - _ _. _ 0.26 Sandusky Bay 4/30/70 0.05 0.05 0.05 0.15 0.02 0.6 Catawba Island 5/13/70 0.08 0.06 _ 0.14 _ 1.1 ENE of Toledo 5/16/70 0.08 0.06 0.07 0.21 0.8 Crane Creek-Toledo 5/17/70 0.09 0.07 — 0.16 _ 1.2 NW Conneaut 5/18/70 0.17 0.05 0.13 0.35 _ 0.8 NE Cleveland 5/18/70 0.08 0.05 0.11 0.24 _ 0.8 East of Conneaut 6/15/70 0.09 0.03 0.05 0.17 _ 0.5 North of Cleveland 6/16/70 0.10 0.08 0.06 0.24 — 0.8 East of Reno Beach 6/16/70 0.10 0.11 — 0.21 — 1.3 East of Reno Beach 7/14/70 0.14 0.15 0.05 0.34 0.02 0.9 East of Cedar Point 8/18/70 0.02 0.04 — 0.09 — 0.2 0.15 North of Conneaut 8/26/70 0.06 0.08 0.20 0.34 — 0.5 0.22 East of Toledo 9/15/70 — 0.19 0.11 0.30 — 2.4 0.37 NW of Vermillion 10/5/70 0.06 0.05 0.04 0.15 0.02 0.6 0.25 Ashtabula 10/7/70 0.04 0.05 0.07 0.16 0.02 0.2 0.16 East of Toledo 10/8/70 0.08 0.10 O.02 0.20 0.01 0.9 0.40 Grand River 11/18/70 0.03 0.04 — 0.07 — 0.7 0.13 Sandusky Bay 3/29/71 0.05 0.07 0.02 0.14 0.01 0.8 0.25 ENE of Toledo 3/30/71 0.06 0.10 0.01 0.17 0.01 0.8 0.45 Conneaut 5/11/71 0.02 0.04 0.03 0.09 0.01 0.4 0.16 Vermillion 5/13/71 0.05 0.03 0.03 0.11 0.01 0.5 0.19 WHITE BASS Cedar Point 8/11/70 0.24 0.27 0.13 0.64 0.06 2.1 0.62 East of Toledo 9/15/70 0.02 0.30 0.05 0.37 0.03 3.5 0.70 Sandusky Bay 9/23/70 0.26 0.30 0.31 0.87 0.03 1.9 0.60 East of Toledo 10/12/70 0.11 0.22 0.10 0.43 0.03 1.4 0.58 Vermillion 3/29/71 0.33 0.34 0.06 0.73 0.06 2.4 0.86 ENE of Toledo 3/30/71 0.11 0.21 0.02 0.34 0.03 1.6 0.45 Vol. 6, No. 1, June 1972 25 TABLE 1. — Chemical residue levels in six species of fish, Lake Erie — 1970-7 J — Continued Location of Catch Date Collected! Residues in ppm Total DDT East of Cedar Point 8/18/70 0.04 0.08 _ 0.12 0.4 0 07 East of Toledo 9/15/70 0.02 0.06 0.02 0.10 _ 0.3 0 11 Sandusky Bay 9/23/70 — 0.39 0.12 0.51 0.02 0.9 East of Toledo 10/8/70 0.14 0.24 0.04 0.38 0.05 4.3 0.08 Vermillion 3/13/71 0.61 0.26 0.04 0.91 0.06 5.3 0.13 Vermillion 3/20/71 0.11 0.21 — 0.32 0.04 1.1 0.17 ENE of Toledo 3/30/71 0.13 0.32 - 0.45 0.04 2.3 0.12 CHANNEL CATFISH East of Cedar Point East of Toledo Sandusky Bay East of Toledo ENE of Toledo Sandusky Bay Vermillion 8/18/70 9/15/70 9/23/70 10/8/70 3/30/71 4/23/71 5/12/71 0.53 0.07 0.04 0.43 0.28 0.38 0.66 0.85 0.09 0.65 0.46 0.33 0.59 0.26 0.09 0.13 0.06 0.06 0.15 1.41 1.18 0.22 0.77 0.74 0.10 0.05 0.01 0.07 0.07 0.04 0.04 0.31 0.45 0.14 0.72 0.48 0.32 0.49 FRESHWATER DRUM Cedar Point 8/18/70 0.08 0.11 _ 0.19 0.8 0.40 East of Toledo 9/15/70 0.12 0.19 0.09 0.40 _ 1.4 0.45 Sandusky Bay 9/23/70 — 0.08 0.02 0.10 0.02 0.6 0.21 East of Toledo 10/8/70 0.17 0.18 0.12 0.47 0.02 1.3 0.37 Vermillion 3/29/71 0.08 0.10 0.04 0.22 0.04 0.8 0.24 ENE of Toledo 3/30/71 0.09 0.15 0.02 0.26 0.03 1.2 0.43 Vermillion 5/12/71 0.17 0.11 0.15 0.43 0.05 1.5 0.29 NOTE: — := not detected; blank = not analyzed. CM) — Mature fish; (I) r= Immature fish. ' Although the monitoring program was not expanded to include carp, channel catfish, freshwater analyses were done on samples collected in 1970. - Although sample was found to be a chinook salmon, it was not eliminated from the study. nd white bass until 1971. some of th TABLE 2. — Average and range of chemical residue levels in six species of fish, Lake Erie — 1970-71 Number OF Samples Re sidues IN PPM Species DDE Ave. Range Ave. TDE Range AVG. DDT Range Total DDT Ave. Range DlELDRlN Ave. Range AVG. PCB's Range Mercury AvG. Rang Coho salmon 30/15 1 0.42 0.04-0.90 0.24 0.00-0.50 0.25 0.00-0.67 0.90 0.21-1.69 0.07 0.03-0.15 2.1 1.0-4.3 0.32 0.11-0.5 Yellow perch 23/11 ' 0.06 0.00-0.17 0.07 0.00-0.19 0.05 0.00-0.20 11.18 0.07-0.35 0.01 0.00-0.02 0.8 0.2-2.4 0.25 0.13-0.1 White bass 6 0.18 0.02-0.33 0.27 0.21-0.34 0.11 0.02-0.3 1 0.56 0.34-0.87 0.04 0.03-0.06 2.1 1.4-3.5 0.64 0.45-0.8 Carp 7 0.15 0.00-0.61 0.22 0.06-0.39 0.03 0.00-0.12 0.40 0.10-0.91 0.04 0.00-0.06 2.0 0.3-5.3 0.12 0.07-0.1 Channel catfish 7 0.25 0.00-0.53 0.52 0.09-0.85 0.12 0.06-0.26 0.89 0.22-1.31 0.05 0.01-0.10 4.4 1.4-7.8 0.42 0.14-0.' Freshwater drum 7 0.10 0.00-0.17 0.13 0.08-0.19 0.06 0.00-0.15 0.30 0.10-0.47 0.02 0.00-0.05 1.1 0.6-1.5 0.34 0.21-0.4 ' Total samples/samples analyzed for mercury. LITERATURE CITED (I) Aimour. J. A., and J. A. Burke. 1970. Method for sep- arating polychlorinated biphenyls from DDT and its analogs. J. Assoc. Off. Anal. Cheni. 53:761-768. 12) Carr, R. L. 1971. Collaborative study of a method for multiple chlorinated pesticide residues in fish. J. Assoc. Off. Anal. Chem. 54:525-527. (S) Food and Drug Adniinislralion. U. S. Department of Health, Education, and Welfare. 1970. Pesticide An- alytical Manual, Vol. 1. Washington, D. C. 20204. 26 (4} Horwitz, W., editor. 1970. Methods of analysis. 1 1th e Assoc. Off. Anal. Chem. p. 478. 481. (5) Muiins. R. K.. and D. C. Holland. 1971. Determinatit of mercury in fish by flameless atomic absorption collaborative studv. J. Assoc. Off. Anal. Chem. 54:20 205- i6) Porter. M. L., S. J. V. Young, and J. A. Burke. 1970 method for the analysis of fish, animal, and poult tissue for chlorinated pesticide residues. J. Assoc. O Anal. Chem. 5.3:1300-1303. Pesticides Monitoring Jourw I'oi Mercury and Lead Residues in Starlings — 1970 ' William H. Martin ABSTRAn 'tarlinn (Sturnus vulgaris) sampler fmni 125 randomly se- eded sites were iinalyzed for mercury residues. Except for lirec locations, cdl samples had residues well below 0.5 ppni. Lead residues were identified in all samples from 23 survey iites that had been tentatively selected to evaluate use of Uarlinf's as a biological measure of envirotimeiual coiitam- nation by lead. Residues of lead ranged from 0.4 to 13.3 ppni mill a mean of 3.18 ppm and a standard error of 0.62 ppm. Introdiiclion The starling (Sturnus viili;ciris) has been used since 1967 by the Bureau of Sport Fisheries and Wildlife as an indicator species for measuring occurrence and rel- ative amounts of selected persistent environmental contaminants. The overall wildlife monitoring scheme, the randomized nationwide sampling design, and an- alytical methods used for determining residue levels of persistent organochlorine insecticides, mercury, and lead in starling tissue are described by Dustman ct al. ( / ) and Martin (2). Determination of mercury residues in starlings is con- ducted to aid in evaluation of the relative distribution of this element in terrestrial fauna other than game birds. Concern over possible widespread environmental contamination by lead provided the impetus for the preliminary survey of lead residues in starlings. The starling was selected because it is present throughout the contiguous States in both urban and rural areas, it is omnivorous in its feeding habits, and normalh is not exposed to lead shotgun pellets. This report presents lead and mercury residue data gathered from starling monitoring collections made during November and December 1970. ' From the Pesticide Appraisal and Monitoring Branch. Divii Wildlife Services, Bureau of Sport Fisheries and Wildlife. U. partment of the Interior. Washington, D. C. 20240. Vol. 6, No. 1, June 1972 Samplini; Procedures MERCURY A randomized, nationwide sampling design was used to obtain birds for mercury analysis. This standard design allows for sampling at up to four randomly selected sites within each of 40 five-degree blocks drawn from 24" to 49 latitude and 64 to 124 longitude, as shown in Fig. 1 . Sampling locations are identified by a row number, a column letter, and a site number; e.g.. the site near Tacoma. Wash., is designated 1-A-I. Tissues used for mercury analysis in the study reported here were taken from the same bird samples used for persistent organochlorine insecticide analyses reported separately by Martin and Nickerson (3). Collections were success- ful at 125 of the planned 1.^9 sites (Table 1). A total of 25 sampling sites were selected to reflect the degree of lead residues expected from man's activities and related pollution sources, such as a high incidence of industrialization, heavy automobile traffic, etc. Samples were not obtained from two critical preselected locations — Los Angeles. Calif., a site which was ex- pected to reflect relatively high lead residue, and Carls- bad, N. Mex., predicted to reflect relatively low lead residues. Selected sampling sites are listed in Table 2 with results of lead analyses. As described by Martin and Nickerson {3). each sample normally consisted of a "pool" of 10 birds. "Pools" containing fewer than 10 birds are indicated by footnote in the appropriate tables. Birds analyzed for mercury residues had been either trapped or shot. Star- lings collected for lead analysis were taken by means other than lead shot or poison. The bird "pools" were wrapped in aluminum foil, placed in polyethylene bags, and frozen immediately for later laboratory analyses. 27 FIGURE 1. — Starling monitoring sites — 1970 TABLE 1. — Mercury and lead sampling site locations, 1970 Sampling Sampling State City or Site State City or Site County Number '■= County Number '■= Alabama Marion 3-H-l Georgia Pike 4-H-4 Talladega 4-H-3 Wayne Atlanta (Lead) 4-1-2 19 Arizona Navajo 3-C-3 Yavapi 3-C^ Idaho Nezperce 1-B-l Maricopa 4-C-l Owyhee 2-B-l Graham 4-C-2 Franklin 2-C-3 Plioenix (Lead) 7 Minidoka Boise (Lead) 2-C-4 5 Arkansas Yell/Pope Lonoke/Pulaski Stuttgart (Lead) 3-G-2 3-G-3 16 Illinois Stephencon Sangamon Cook 2-G-l 2-G-3 2-H-2 California Colusa Shasta 2-A.l 2-A-2 Chicago (Lead) 13 Modoc 2-A-3 Indiana Henry 2-H-3 Ventura 3-A-l Iowa Pottawattamie 2-F-3 Stanislaus 3-A-2 Polk 2-G-2 Monterey 3-A-3 Butler 2-G-4 Inyo 3-B-l Kern 3-B-4 Kansas Rawlins 2-E-l Imperial 4-B-l Smith 2-E-2 Los Angeles (Lead) 3 Hamilton & Kearny Nemaha 3-E-l 2-F-4 Colorado Adams Montrose 2-D-4 3-D-l Marion 3-F-2 La Plata & Rio Grande 3-D-2 Kentucky Ohio 3-H-2 Otero 3-E-3 Hopkins 3-H-4 Greeley (Lead) 8 Louisiana Jefferson 4-G-3 Connecticut New London 2-K-2 Rapides 4-G-4 Baton Rouge (Lead) 17 Florida Bay 4-H-l Madison 4-1-3 Maine Penobscot l-K-2 Polk 5-1-1 Gray (Lead) 25 Hardee 5-1-2 Maryland Prince Georges 2-J-l Gainesville (Lead) 20 L Patuxent (Lead) 22 28 Pesticides Monitoring Journal TABLE 1. — Mercury and lead sampling site locations, 1970 — Continued Sampling Sampling Stati: City or Site State City or Site County Number '•= County Number '■= Michigan Chippewa 1-H-l Ohio (Cont'd.) Sandusky (Lead) 14 Grand Traverse l-H-2 Columbus (Lead) 15 Kent 2-H-l Inaham :-H^ Oklahoma Greer Canadian 3E-4 3-F-l Minnesota Swift l-F-2 Nowata 3-F-3 Pine IGI Okmulgee 3-F-4 Aitkin l-G-4 Tishomingo (Lead) 10 Twin Cities (Lead) 12 .lississippi Leake 4-G-l Oregon Yamhill Lane Klamath Baker l-A-3 1-A^ 2-A-» l-B-4 Harrison Jackson 4-G-2 4-H-2 .lissouri Stoddard 3-G-1 Harney 2-B-2 Bollinger 3-G-4 Corvallis (Lead) 2 viontana Meagher l-C-1 Pennsylvania Somerset 2-J-2 Missoula l-C-4 Cuzerne 2-J-3 Richland 1-D-l Yellowstone l-D-4 Souch Carolina Aiken 4-1-1 'lebraska Keith 2-E-3 Lincoln 2-E-4 South Dakota Potter l-E-1 Clay :-F-i Hughes 1-E^ Antelope 2-F-2 Brown Mitchell (Lead) l-F-3 U Nevada White Pine 2 B-3 Humboldt 2B-4 Tennessee Davidson 3-H-3 Nvc 1-B-2 Nashville (Lead) 18 Clark 3-B-3 Reno (Lead) 4 Texas Clay 4-F-3 •iew Mexico Bernalillo Santa Fe & Torrance 3-D-3 3-D-4 Morris 4-F^ Luna 4-D-1 Utah Weber 2-C-l Chaves 4-D-3 Sevier Millard 3-C-l Quay 3-E-2 Salt Lake City (Lead) 6 Carlsbad (Lead) 9 Vermont Addison I-K-1 Mew Jersey N. Brunswick (Lead) 23 Virginia Amherst 3-1-4 Mew York Oswego 2-J-4 Prince George 3-J-2 Rennselaer 2-K-l Caroline 3-J-3 Jamestown (Lead) 24 Morih Carolina Wilkes 3-1-1 Washington Pierce Yakima l-A-1 l-A-2 Union Macon Pender Raleigh (Lead) 3-1-2 3-1-3 3-J-l 21 Spokane Whitman Yakima (Lead) l-B-2 l-B-3 1 Vorth Dakol;i Ward l-E-3 Wisconsin Curtiss l-G-2 Cavelier I-F-1 Trempeleau l-G-3 Dickey l-F^ Wyoming Big Horn l-D-2 Dhio Washington 2-I-I Brook l-D-3 Erie 2-1-2 Goshen 2-D-I Jefferson 2-1-3 Washakie 2-D-2 Mercury sampling sites are described by the l-A-1). Lead samples were taken near the cities indi A'ere taken and arc identified by a three place site number (e.g.. nber identified the site locatii A nalyiical Procedures Residue analyses were done by the Wisconsin Alumni Research Foundation - under contract with the Bureau of Sport Fisheries and Wildlife. Birds were prepared hy skinning and removing the beak and wings at the first joint out from the bodv ; the removed parts were dis- carded. Each lO-bird "pool" was ground together in a Hobart food chopper, and a subsample taken for analysis - Mention of this commercial laboratory is for identification only ; does not constitute endorsement by the U. S. Department of the terior. Vol. 6, No. I, June 1972 by atomic absorption spectrophotometry. Results are reported on a whole bod\. wet-ueighi basis. A cold vapor atomic absorption technique was suggested b\' the contracting laboratory as being more rapid with greater selectivity and less interference. Digestion for this technique v\as a modification of one reported by the Joint Mercury Residue Panel [4). The methodology was demonstrated by the contractor to provide results com- parable to the WARF "boat" method for both bird and 29 fish tissue and was accepted for use. A 25 ml sulfuric- nitric acid mixture (4;1) was added to a 10-g aliquot of the sample, and the mixture was heated slowly for 30 to 45 minutes to reach full temperature; the sample was then refluxed for 1 hour. After the digest had cooled to room temperature, it was transferred to a 100-ml volumetric flask quantitatively with ice water: the con- tainer was stoppered, and the sample again was allowed to return to room temperature. Determination was made with a Perkin-Elmer atomic absorption spectrophotom- eter Model 30.^ fitted with a cold vapor device and a Perkin-Elmer Model .^04 recorder. Instrument conditions were Wavelength Slit Range Source Air 2537 A (Selling 254) 3 mm, 20 A UV Mercurx' hollow cathode lamp 3 liters per minute Recorder noise suppression — I. expansion — 3x The standard curve used for determination had almost a 20-fold range starting with 0.010 /.ig of mercury. The curve was plotted using peak height versus micrograms of mercury. An 0.5 gram equivalent aliquot was used to measure for mercury for an indicated sensitivity of 0.05 ppm. This was used since this is the level at which natural oc- curring and background residues could he expected. In terms of practical instrument sensitivity. 0.01 f_ig was the lower level of sensitivity for the analytical method. The procedures include methylmercury as part of the total mercury reported. Recovery studies were conducted on the analytical method using samples not reported in this paper. Re- coveries ranged from SeCr to 1069?^. Figures reported in this paper were not corrected for recovery. LEAD A 25-g portion of the sample homogenate was dried and charred on a hot plate, then transferred to a 500" C muffle furnace and ashed overnight. The ash was cooled, wet with nitric acid, then taken to dryness, and returned to the mulTle for 20 minutes. After the sample was again cooled, 2 ml of concentrated hydrochloric acid and about 15 ml of water were added. The mixture then was brought to a boil, cooled, and made to volume for analysis. Determination was made with a Model 303 Perkin-Elmer atomic absorption spectrophotometer in accordance with standard Perkin-Elmer procedures for lead (5). Instrument settings were: Wavelength 283.3 backgroimd at 280.0 negative Recorder noise suppression — 3, expansion — 3x 30 Recovery studies were not done for lead analysis. The lower level of sensitivity for lead was 0.1 ppm. Results and Discussion MHRCURY Residue levels of mercury in the 125 bird pools analyzed are shown in Table 2. Values are reported for individual sites grouped by 5-degree blocks, and block means are given. These preliminary findings for mercury residues in starlings appear somewhat encouraging in light of recent concern about relatively high residues in a variety of fish and game birds. With the exceptions of two high levels of 1.5 ppm and I.'' ppm found in north- western Oregon (l-A-3 and l-A-4, respectively) and one sample approaching 0.5 ppm in California (2-A-l), the residue levels for mercury in starlings appear to be uniformly low throughout the contiguous United States. Of the 125 samples analyzed. 102 showed levels equal to or less than 0.09 ppm on a whole body, wet-weight basis: 53 of these 102 samples were below the upper value of the World Health Organization's "practical residue limit" (range, 0.02-0.05 ppm) (S). The practical residue limit describes residues expected to be found in food from background and natural environmental con- tamination. Of the 23 samples in which mercury was found in excess of 0.09 ppm, only the 3 West Coast samples (l-A-3, l-A-4, 2-A-l) and 1 sample from Virginia (3-J-2) exceeded 0.2 ppm. The mercury levels reported in this paper could well reflect environmental conditions that are not associated with contaminated aquatic food webs or with birds feed- ing on mercury-treated seeds. The wide-ranging, omni- vorous, terrestrial ground-feeding habits of the starling support this hypothesis. On the other hand, the residues could be a result of a short physiological retention time or could possibly be directly influenced by the season during which sample collections were made (November and December ) . Data illustrating the half-life of mercury residues in starlings on a whole-body basis would be helpful in interpreting these monitoring findings. LEAD Lead residues were found in all 23 survey samples col- lected. Whole body, wet-weight residues ranged from a low of 0.4 ppm at Yakima. Wash., to a high of 13.3 ppm at Chicago. III. The mean level for the survey was 3.18 ppm with a standard error of 0.62 ppm. When the ex- ceptionally high reading of 13.3 ppm (almost twice as much as the next highest residue) is dropped, the mean becomes 2.70 ppm with a standard error of 0.45 ppm. Lead monitoring findings arc presented in Table 3. Little is known about environmental dispersal of lead or about its assimilation by wildlife other than that reported as a result of ingestion of shotgun pellets by Pesticides Monitoring Journal TABLE 2. — Mercury residues in slarlings, 1970 Sampling Mercury Sampling Mercury Sampling Mercury Sampling Mercury Site Residue ' Site Residue ' Site Residue ' Site Residue ' Number (PPM) Number (PPM) Number (ppm) Number (ppm) 1-A-l 0.05 3-D-l 0.05 4-G-l <0.05 3-I-I <0.05 2 0.06 2 <0.05 2 <0.05 2 0.05 3 1.50 3 <0.05 3 <0.05 3 <0.05 4 1.90 4 <0.05 4 0.10 4 0.08 Mean 0.878 Mean <0.05 Mean < 0.062 Mean < 0.058 SE 0.417 SE SE <0.0I1 SE < 0.007 2-A-l 0.05 4.D-1 0.08 l-H-1 0.05 4-1-1 <0.05 2 <0.05 2 — 2 0.06 2 <0.05 3 0.07 3 <0.05 Mean 0.055 3 <0.05 4 0.11 Mean < 0.065 SE 0.067 Mean <0.050 Mean <0.175 SE <0.010 SE SE < 0.085 1-E-l <0.05 2-H-l 0.05 2 0.07 3 0.19 4 0.05 Mean <0.090 SE <0.029 5-M <0.05 3-A-l <0.05 2 — 2 <0.05 2 0.07 3 0.05 Mean <0.050 3 <0.05 4 <0.05 SE <0.008 Mean <0.057 Mean < 0.050 SE <0.0I8 SE 2-J-l 0.10 2 0.10 I-B-1 0.05 2-E-l 0.10 3-H-l <0.05 3 0.10 2 0.07 2 0.07 2 <0.05 4 0.06 3 0.06 3 0.05 3 0.05 Mean 0.090 4 n.14 4 <0.05 4 0.10 SE 0.008 Mean 0.080 Mean <0.068 Mean 0.062 SE 0.023 SE <0.010 SE . ■ 7 birds. 4 0.18 wci-weighi basis- ' 8 birds. l-C-l - 0.06 Mean 0.083 - 2 birds. ■ 14 birds. 2 — SE 0,028 3 — 4 <0.05 3-F- 1 0.13 Mean < 0.060 <0.007 3 0.15 0.13 waterfowl and certain game birds. Available information 2-C-l ■ 0.09 4 0.09 0.125 indicates that contamination of vegetation may be di- 2 — SE o'oio rectly related to the proximity of lead pollution levels 3 <0.05 4 0.06 4-F-l in air {6). Mean < 0.067 _ SE < 0.009 3 4 0.08 < 0.05 Bagley and Locke ( 7 ) reported occurrence of lead l-C-l 0.08 Mean 0.065 residues in the liver and tibia of birds that were free of 2 — SE onin .1 ■■ 4 Mean <0.05 ' a row number, a column letter, and a site number; e.g., the site near Tacoma, Wash., is designated 1-A-l. Collections were made at 125 of the possible 1.^9 sampling locations (90%). Starlings again proved difficult to collect in some areas. Sampling sites in Texas presented the greatest collection problem, with no samples being taken at seven of the nine preselected locations. Since the area in question is one of high pesticide use. nev\ collection techniques will be developed or an alternate representative species will be selected prior to the 1972 collection. There is no specific information, other than general ob- servation, concerning starling population variation from block to block. The sampling design takes into account the fact that differences in number of birds do occur between and v\iihin the blocks. The study, however, is designed to measure trends of environmental residues rather than effects on starling populations. The sample from each site normally consisted of a "pool" of birds. Pools containing fewer than 10 birds are indicated by footnote in the appropriate tables. Birds collected for organochlorine residue determination were either trapped or shot. Each lO-bird pool was wrapped in aluminum foil, placed in polyethylene bags, and frozen immediately for later laboratory analyses. Sample Preparation and Analyllcal Metliods Residue analyses were done by the Wisconsin Alumni Research Foundation - under contract with the Bureau of Sport Fisheries and Wildlife. Birds were prepared by skinning and removing the beak and wings at the first Vol. 6, No. 1, June 1972 ■ Mention of this commercial laboratory is for identification only and does not constitute endorsement by the U. S. Department of the 33 FIGURE 1. — Starling monitoring sites— 1970 joint out from the body; the removed parts were dis- carded. Each 10-bird pool was ground together in a Hobart food chopper and a subsample taken for analysis. Every effort was made to use essentially the same pro- cedures for preparation and analyses of samples as in the baseline re, -t (2). Determination was made using two columns with a Barber-Coleman Pesticide Analyzer, Model 5360. Normal instrument conditions were: Column: Temperatures: Carrier gas: Flow rate: Glass, 4 ft X 4 mm, packed with 5% DC-200 on 80/100 Gas Chrom Q Injector Column Detector Nitrogen Such that p.p' 230° C 195° C 250° C •DDT had a retention time of 6 to 8 minutes Modifications of techniques were used for a greater de- gree of accuracy and discrimination in identifying the isomers (alpha, beta, delta, and gamma) of benzene hexachloride. For this determination, the column was packed with 3% OV-17 rather 5% DC-200, and ap- propriate instrument changes were made as follows: Column: Glass, 4 ft X 4 mm, packed with 3% OV-17 on 80/100 Gas Chrom Q Temperatures: Injector 230° C Column 180° C Detector 240° C Flow rate: Such that gamma BHC has a reten- tion time of 2 minutes Polychlorinated biphenyls (PCB's) were estimated b> using the peaks between DDD and DDT on the DC-20C column with Aroclor 1254 as a standard. On the basis of the findings of Risebrough. Reiche, and Olcott (3) regarding the lack of significant PCB interference with analytical findings for p,p'-DDE and because of a tight budgetary allowance for starling monitoring efforts, tha PCB question was not pursued. However, it is expected that a closer analytical scrutiny would reveal PCB'i other than the Aroclor 1254 estimates. The PCB esti mates are provided only to help place in context the readings for DDT and DDD and to demonstrate the common occurrence of PCB's in starling tissues. The residue data were not corrected for recovery. The standardized analytical procedure results in an 88% to 105% recovery rate for the chemicals reported in this paper. Recovery and confirmatory tests were done in- ternally by the commercial laboratory on a quality con- trol basis. Limits of detection ranged from 0.005 ppm to 0.01 ppm. 34 Pesticides Monitoring Journal TABLE 1. — Starling sampling site locations by State and county, 1970 I— Sampling Site Sampling Site State Number County State Number County Alabama 3-H-l Marion Montana l-C-1 Meagher 4-H-3 Talladega l-C-4 l-D-1 Missoula Richland Arizona 3-C-3 3-C^ Navajo Yavapi l-D-J Yellowstone 4-C-l Maricopa Nebraska 2-E-3 Keith 4-C-2 Graham 2-E^ 2-F-l Lincoln Clay Arkansas 3-G-2 3-G-3 Yell/Pope Lonoke/Pulaski Nevadii 2-F-2 2-B-3 Antelope White Pine California 2-A-l Colusa 2-B-4 Humboldt 2-A-2 Shasta 3-B-2 Nye 2-A-3 Modoc 3-B-3 Clark 3-A-l Ventura 3-A-2 Stanislaus New Mexico 3-D-3 Bernalillo 3-A-3 Monterey 3-D-l Santa Fe/Torrance 3-B-l Inyo 4-D-l Luna 3-B^ Kern 4-D-3 Chaves 4-B-l Imperial 3.E-2 Quay .'olorado :-D-4 Adams New York 2-J-4 Oswego 3-D-: Montrose 2-K-l Rennselacr 3-D-2 La Plata Rio Grande 3-E-3 Oicro North Carolin.i 3-1-1 3-1-2 Wilkes Union ronnccticut 2-K-2 New London 3-1-3 3-J-l Macon Pender -lorida 4-H-l Bay 4-1-3 Madison North Dakota l-E-3 Ward 5-1-1 Polk l-F-l Cavelier ■i-I^ Hardee l-F-4 Dickey jeorgia 4-H-» Pike Ohio 2-I-I Washington 4-1-2 Wayne 2-1-2 2-1-3 Erie Jefferson daho l-B-l Nczpcrce 2-B-l Owyhee Oklahoma 3-E-» Greer 2-C-3 Franklin 3-F-l Canadian 2-CA Minidoka 3-F-3 3-F^ Nowata Okmulgee illinois 2-G-l Stephencon 2-G-3 Sangamon Oregon l-A-3 Yamhill :-H-2 Cook l-A-4 2-A-4 Lane Klamath Indiana :-H-3 Henry l-B-4 2-B-: Baker Harney Iowa 2-F-3 Pottawattamie 2-G-2 Polk IVnnNVlvania 2-J-2 Somerset 2-G^ Butler 2-J-3 C ii/ernc Kansas 2-E-l Rawlins South Carolina 4-I-I Aiken 2-E-2 Smith South Dakota l-E-l Potter 3-E-l Hamilton Kearny l-E-4 Hughes 2-F^ Nemaha l-F-3 Brown 3-F-2 Marion Tennessee 3-H-3 Davidson Kentucky 3-H-2 Ohio 3-H-4 Hopkins Texas 4-F-3 4-F-4 tlay Morris Louisiana 4-G-3 Jefferson Utah 2-C-l Weber 4-G-4 Rapides 3-C-l Sevier Millard Maine l-K-2 Penobscot Vcrnioni 1-K-l Addison Maryland 2.J-I Prince Georges Virginia 3-1-4 3-J-2 Amherst Prince George Michigan I-H-1 i-H-2 Chippewa Grand Traverse 3.J-3 Caroline 2-H-l Kent Washington l-A-l Pierce 2-H^ Inahani l-A-2 l-B-2 Yakima Spokane Minnesota l-F-2 1-G-l Swift Pine l-B-3 Whitman I-G-4 Aitkin Wisconsin l-G-2 l-G-3 t uriiss Tremrclcau Mississippi 4-G-l Leake Wyoming l-D-2 Big Horn 4-G-2 Harrison l-U-3 Brook 4-H-2 Jackson 2D-I l-n-2 Cioshcn Washakie. Missouri 3-G-l 3-G^ Stoddard Bollinger Total sues =. 12? Vol. 6, No. 1 . June 1972 .?5 Results and Discussion Residue levels of organochlorine insecticides and PCB's for the November/ December 1970 collection are pre- sented in Table 7. The sampling design used in this study was chosen primarily because it permitted statis- tical comparison of the distribution of pesticide residues on a nationwide basis. The arbitrarily selected 5-degree blocks are the basic units for evaluating nationwide trends. Comparison of the distribution of average resi- dues by frequency of occurrence in different quantitative ranges for the 1967-68 and 1970 collections (Table 4) offers an additional tool for evaluating changes in residue levRls. DDT AND METABOLITES As in 1967-68. DDT and its metabolites were found in all samples taken. The 1970 block averages appear to reflect a general nationwide decline in levels, although this is only apparent and is not significant at the 95% confidence level (Table 2). TABLE 2. — Block averages of residues of DDT and its metabolites Baseline Data 1967-68 Fall 1970 Average Average Sampling Residue Standard Residue Standard Block Level (PPM) Error Level (PPM) Error lA L734 .350 .775 .260 2A .755 .167 .472 .093 3A 2.281 .318 1.779 .768 IB .809 1.320 .345 .064 2B 1.070 .331 .975 .400 ?B 1.767 .590 1.053 .519 43 3.450 1.490 2.192 IC .341 .120 .145 .002 2C 3.616 2.190 .373 .088 3C 1.988 .651 .470 .152 4C 12.966 4.511 7.903 4.930 ID .159 .038 .106 .017 2D .432 .104 .263 .078 3D 1.162 .237 .502 .069 "(D 12.574 8.155 3.130 1.160 IE .919 .433 .099 .010 2E .342 .065 .256 .051 3E 1.736 .706 1.460 1.114 IF .219 .044 .244 .098 2F .297 .050 .171 .032 3F .713 .144 .229 .065 4F .667 — .172 .007 IG .305 .064 .178 .023 2G .443 .080 .266 .023 3G 2.134 .870 1.822 1.008 4G 4.201 .996 2.449 .877 IH 1.012 .312 .231 .042 2H 1.089 .182 1.213 .402 3H 1.463 .553 .937 .446 4H 2.110 .423 2.135 .425 21 .576 .209 .455 .155 31 .673 .136 .409 .121 41 4.335 .812 2.619 .706 51 1.550 .299 .316 .117 2J .689 .102 .716 .321 3] .795 .211 .709 .136 IK .364 .053 .303 .077 2K .593 .081 .411 .068 Individual sites having DDT and metabolite residues greater than 3.0 ppm in baseline and/ or 1970 data are listed in Table 3. and frequency of occurrence of residues in different quantitative ranges is shown in Table 4. Sites containing the highest DDT and metabolite levels continue to be found in southern Arizona and New Mexico and in areas of the Southeast, including parts of Florida. Georgia. Alabama, Mississippi, Louisiana, and Arkansas. Because starlings were not available, we do not have 1970 data for two sites in Utah that had high residue levels in the baseline collections. Other States yielding relatively high residue levels (greater than 3.0 ppm) at one or more sites include Oklahoma. California, and South Carolina. As with DDT. dieldrin residue levels are apparently de- clining from the baseline findings, although again the decline is not significant at the 95% confidence level (Table 5). Two exceptionally high residue levels of 3.59 and 1.52 ppm were found, however, along the upper Mississippi River drainage area (Sites 2-G-3 and 2-G-4). States from which samples were obtained with relatively high residue levels (greater than 0.3 ppm) at one or more sites include Georgia. Illinois, Iowa, Kansas, Missouri, and Washington. Individual sites having diel- drin residue levels greater than 0.3 ppm in baseline and/or 1970 collections are listed in Table 6. and fre- quency of occurrence of residues in different quantita- tive ranges is shown in Table 4. BHC was found in all 125 samples collected in 1970; whereas, in the 1967-68 baseline study of three collec- tions (375 samples), it was found in only 45 samples. The lindane reported in 105 samples of the baseline study is thought to have resulted as a product of tech- nical BHC (Table 7). BHC figures presented for 1970 cannot be related di- rectly to the 1967-68 baseline figures, and it was decided not to re-analyze the 1967-68 baseline samples with the new techniques at this time because the levels were relatively low compared to established tolerances for edible food and feed. HEPTACHLOR EPOXIDE Heptachlor epoxide was found m all samples collected in 1970 (Table 7) and in 168 of 375 samples in the 1967-68 baseline study. Although the frequency of oc- currence of heptachlor epoxide was greater for the 1970 collection, there is no statistically significant differ- ence between the residue levels found in the 1970 sample and the baseline data. Any attempt at describing a trend in heptachlor epoxide residue levels in starlings should 36 Pesticides Monitoring Journal 1.0 and <2.0 25 5 >2.0 and <3.0 12 7 >3.0 and <4.U 3 5 >4.0 and <5.0 3 2 >5.0 and <10.0 5 2 >10.0 and <15.0 0 1 >15.0 and <20.0 1 - >20.0 and <25.0 1 - Total sites 126 125 <0.1 65 98 >0.1 and <0.2 40 12 >0.2 and <0.3 11 6 >0.3 and <0.4 2 2 >0.4 and <0.5 3 1 >0.5 and ^1.0 4 4 >1.0 and <1.5 I 1 >1.5 and <2.0 - - >2.0 and <2.5 — - >2.5 - 1 Total sites 126 125 TABLE 5.— Block averages of dieldrin residues Baseline Data 1967-68 Fall 1970 Average Average Sampling Residue Standard Residue Standard Block Level (PPM) Error Level (PPM) Error lA .339 .094 .129 .019 2A .066 .031 .020 .005 3A .074 .016 .041 .008 IB .339 .120 .237 .116 2B .073 .019 .023 .005 3B .128 .029 .030 .005 4B .167 .061 .026 — IC .062 .025 .005 2C .021 .030 .015 .007 3C .102 .029 .035 .012 4C .069 .018 .014 .007 ID .028 .010 .012 .005 2D .089 .028 .005 — 3D .107 .037 .021 .005 4D .041 .009 .088 .058 IE .093 .040 .009 .001 2E .143 .049 .095 .034 3E .095 .019 .124 .086 IF .169 .067 .052 .024 2F .123 .033 .093 .060 3F .079 .035 .038 .018 4F .034 — .020 .010 IG .094 .040 .065 .023 2G .338 .099 1.458 .665 3G .755 .060 .215 .095 4G .297 .119 .061 .017 !H .080 .037 .032 .012 2H .127 .043 .162 .068 3H .104 .031 .067 .016 4H .142 .035 .120 .047 21 .118 .048 .124 .052 31 .360 .233 .020 .005 4) .045 .005 .305 .183 51 .073 .023 .018 .007 2J .133 .060 .063 .020 3J .120 .078 .072 .036 IK .023 .009 .014 _ 2K .012 .001 .015 .001 TABLE 6. — Sites with residue levels of dieldrin greater than 0.3 ppm in baseline and/or 1970 collections Dieldrin Residues in ppm Sampling Site Number Baseline Data 1967-68 1970 l-A-3 0.528 0.160 1-A^ 0.492 0.140 l-B-3 0.587 0.600 l-B-4 0.418 0.018 3-E-l 0.102 0.420 2-G-l 0.280 0.590 2-G-3 0.657 3.590 2-G-4 0.032 1.520 3-G-l 0.403 0.230 3-G-3 0.317 0.067 3-G-4 0.207 0.520 4-G-2 0.970 0.067 2-H-2 0.208 0.330 3-1-1 1.385 0.018 4-1-2 0.027 0.750 3-J-l 0.333 0.160 Vol. 6, No. 1, June 1972 37 TABLE 7. — Pesticide residue levels in starlings, 1970 1 SAMPLlNtJ Site Number Wei- Weight (CRAMS) Residues in PPM (mg/g, wet-weight) 1 Lipid Weight (CRAMS) DDE DDD DDT DDT AND Metab- olites Esti- mated PCB's DiELDRIN Hepta- CHLOR Epoxide BHC 1-A-l l-A-2 l-A-3 1-A^ 19.98 20.02 19.99 20.02 0.115 0.370 0.814 0.869 0.430 0.320 0.520 1.620 0.029 0.016 0.033 0.013 0.022 0.021 0.045 0.029 0.481 0.357 0.598 1.662 0.31 0.15 0.38 0.23 0.150 0.066 0.160 0.140 0.053 0.009 0.016 0.012 0.009 0.390 0.015 O.IIO 2-A-l 2-A-2 2-A-3 2-A-4 20.00 20.03 19.98 20.00 0.789 0.742 1.210 1.281 0.670 0.180 0.550 0.380 0.013 0.009 0.008 0.006 0.023 0.022 0.014 0.013 0.706 0.211 0.572 0.399 0.26 0.25 0.17 0.14 0.022 0.016 0.034 0.006 0.013 0.009 0.019 0.088 0.013 0.009 0.013 0.021 3-A-l 3-A-2 3-A-3 20.03 20.00 19.99 0.813 0.803 0.830 3.590 0.710 0.770 0.017 0.023 0.031 0.053 0.090 0.053 3.660 0.823 0.854 0.65 0.96 0.39 0.021 0.057 0.045 0.034 0.016 0.019 0.005 0.015 0.015 l-Bl l-B-2 l-B-3 l-B-4 20.05 19.99 20.00 19.99 1.285 1.063 1.203 1.443 0.150 0.280 0.450 0.230 0.014 0.034 0.040 0.026 0.015 0.038 0.048 0.055 0.179 0.352 0.538 0.311 0.14 0.36 0.39 0.50 0.050 0.280 0.600 0.018 0.014 0.016 0.013 0.027 0.230 0.160 0.590 0.031 2-B-l 2-B-2 2-B-3 2-B-4 20.00 19.96 20.04 20.01 1.184 1.069 1.305 1.422 0.410 0.200 2.250 0.700 0.006 0.039 0.028 0.012 0.011 0.160 0.065 0.017 0.427 0.399 2.343 0.729 0.09 2.19 0.78 0.15 0.018 0.008 0.032 0.034 0.026 0.011 0.032 0.016 0.013 0.240 0.035 0.016 3-B-l 3-B-2 3-B-3 3-B-4 20,01 20.00 19.99 20.00 1.377 1.388 1.411 0.753 0.580 0.240 0.360 2.750 O.021 0.016 0.038 0.026 0.033 0.016 0.069 0.061 0.634 0.272 0.467 2.837 0.36 0.25 0.79 0.51 0.045 0.018 0.035 0.023 0.039 0.170 0.038 0.016 0.010 0.012 ■ 0.022 0.018 4-B-: 20.01 1.000 2.110 0.029 0.053 2.192 0.53 0.026 0.120 0.025 1-C-l ' l-C-4 ^ 20.00 20.01 2.454 n.737 0.110 n.064 0.015 0.028 0.024 0.049 0.149 0,141 0.17 0.66 0.005 0.005 0.010 0.009 0.031 0.015 2-C-l ■■■ 2-C-3 2-C-4 20.07 19.98 20.06 0.903 0.924 1.303 0.140 0.480 0.420 0.005 0.006 0.019 0.012 0.013 0.024 0,157 0,499 0,463 0.13 0.14 0.25 0.008 0.031 0.005 0.026 0.039 0.017 0.013 0.014 0.036 3-C-l 3-C-3 - 3-C-4 19.99 20.01 19.9S 1.479 0.969 0.777 0.750 0.350 0.150 0.021 0.022 0.009 0.044 0.047 0,017 0,815 0,419 0,176 0.27 0.36 0,15 0.039 0.008 0.057 0.022 0.010 0.012 0.013 0.007 0.008 4-C-l 4-C-2 20.06 20.10 0.924 0.638 14.800 0.870 0.036 0.022 0,038 0,040 14,874 0,932 0.32 0.31 0.005 0.022 0.007 0.015 0.034 0.008 1-D-l - l-D-2 l-D-3 l-D-4 20.00 19.97 20.03 19.99 0.978 0.860 2.397 1.045 0.078 0.050 0.094 0.064 0.005 0.014 0.011 0,025 0,005 0,025 0,017 0,034 0,088 0,089 0,122 0,123 0.05 0.29 0.17 0.30 0.005 0.029 0.007 0.008 0.006 0.015 0.080 0.010 0.016 0.005 0.017 0.014 2-D-l - 2-D-2 2-D-4 20.03 19.98 20.04 1.025 0.704 1.355 0.310 0.047 0.350 0.005 0.008 0.016 0,010 0,022 0,022 0,325 0.077 0.388 0.14 0.19 0.14 0.005 0.005 0.005 0.006 0.011 0.019 0.160 0.019 0.022 3-D-l 3-D-2 3-D-3 3-D-4 19.99 20.00 20.02 19.99 1.323 1.554 1.181 0.839 0.790 0.380 0.340 0.430 0.015 0.014 0,007 0,014 0,028 0,029 0,035 0.026 0.733 0.423 0.382 0.470 0.29 0.20 0.72 0.20 0.031 0.018 0.019 0,016 0.019 0.009 0.012 0.008 0.012 0.045 0.009 0.012 4-D-l 4-D-3 19.90 19.99 0.735 1.156 4.750 1.450 0,013 0,009 0.017 0.020 4.780 1.479 0.17 0.25 0,170 0,006 0.026 0.006 0.012 0.016 l-E-1 l-E-3 l-E-4 20.06 20.02 20.00 1.385 0.976 1.400 0.062 0.071 0.056 0,014 0,017 0,010 0.023 0.032 0,013 O.099 0.120 0,079 (1.26 0.37 0.1 1 0,005 0.008 0.013 0.006 0.009 0.024 0.013 0.011 0.014 2-E-l 2-E-2 2-E-3 2-E-4 20.02 20.01 20.00 19.99 1.069 0.943 1.561 1.518 0.130 0.082 0.320 0.200 0,028 0,030 0,043 0,017 0,044 0,034 0,055 0,039 0,202 0.146 0.418 0.256 0.41 0.29 0,47 0,38 0.21 0.04 1 O.044 0.086 0.015 0.009 0.016 0.120 0.017 0.010 0.014 0.023 3-E-l 3-E-2 3-E-3 3-E-4 20.00 19.93 19.99 20.09 1.176 0.739 1.018 0.794 (1.140 0.190 0.099 5.290 0,005 0,019 0,006 0,011 0,006 0,049 0,009 0,117 0.151 0.258 0.114 5.318 (1,09 0,36 0,17 0,12 0.420 0.026 0.014 0.034 0.017 0.012 O.OOS O.OIO 0.012 0.010 0.008 O.008 l-F-l l-F-2 l-F-3 l-F-4 19.99 20.00 20.01 20.01 1.639 1.639 1.799 1.521 0.015 0.110 0.520 0.081 0.016 0,044 0.021 0.017 0.019 0,063 0,028 0.041 0.050 0,217 0.569 0.139 0.14 0.58 0.19 0.26 0.02 i 0.048 0.130 0.007 0.015 O.I 00 0.019 0.009 0.018 0.017 0.015 0.016 38 Pe bTICIDES M ONITORING JOURNAl TABLE 7. — Pesticide residue levels in slarlings. 1970 — Continued Sampling Site Number Wet Weight (GRAMS) Lipid Weight (GRAMS) Residues in PPM (//g/g, wet-weight) DDE DDD DDT DDT AND Metab- olitis Esti- mated PCB's DiELDRIN Hepta- CHLOR Epoxide BHC 2-F-l :-F-2 2-F-3 2-F^ 19.98 19.98 20.00 20.04 1.571 1.351 2.269 0.910 0.130 0.180 0.180 0.047 0.009 0.006 0.025 0.009 0.016 0.028 0.034 0.019 0.155 0.214 0.239 0.075 0.13 0.25 0.33 0.14 0.015 0.049 0.300 0.009 0.013 0.056 0.093 0.007 0.011 0.020 0.048 0.016 .1-F-l 3-F-2 3-F-3 3-F^ 20.02 19.96 19.96 19.98 0.909 1.195 1.089 0.896 0.091 0.140 0.390 0.170 0.007 0.008 0.019 0.006 0.014 0.015 0.039 0.015 0.112 0.163 0.448 0.191 0.21 0.25 0.45 0.18 0.012 0.034 0.009 0.098 0.015 0.019 0.016 0.031 0.010 0.012 0.012 0.011 4-F-3 4-F-4 20.07 20.06 0.755 0.568 0.140 0.160 0.009 0.005 0.015 0.015 0.164 0.180 0.15 0.17 0.035 0.005 0.024 0.007 0.012 0.013 I-G-1 l-G-2 l-G-3 l-G-4 19.98 19.99 20.06 20.01 1.443 1.196 2.358 2.510 0.096 0.069 0.100 0.160 0.031 O.OIO 0.028 0.025 0.082 0.024 0.053 0.034 0.209 0.103 0.181 0.219 1.00 0.26 0.55 0.29 0.013 0.026 0.120 0.100 O.OII 0.016 0.045 0.028 0.013 0.013 0.016 0.020 2-G-l 2-G-2 2-G-3 2-G-4 19.98 20.02 20.04 20.01 1.763 1.909 1.636 1.870 0.250 0.150 0.200 0.210 0.019 0.019 0.029 0.014 0.038 0.028 0.080 0.028 0.307 0.197 0.309 0.252 0.29 0.29 0.87 0.22 0.59 0.13 3.59 1.52 0.340 0.028 0.970 0.110 0.024 0.120 0.030 0.034 3-G-l 3-G-2 3-G-3 3-G-4 20.02 20.00 19.98 19.97 2.002 0.827 0.916 2.384 0.630 0.680 5.240 0.450 0.032 0.019 0.034 0.040 0.047 0.031 0.039 0.045 0.709 0.730 5.313 0.535 0.48 0.38 0.28 0.43 0.230 0.043 0.067 0.520 0.084 0.100 0.013 0.120 0.021 0.014 0.017 0.041 4G-1 4-G-2 4-G-3 4-G-4 20.00 20.01 20.00 20.00 0.703 0.733 0.619 0.842 3.300 4.690 0.260 1.030 0.038 0.041 0.014 0.050 0.075 0.070 0.099 0.130 3.413 4.801 0.373 1.210 0.56 0.40 1.260 1.82 0.075 0.067 0.005 0.095 0.036 0.099 0.210 0.130 0.019 0.011 0.017 0.051 1-H-l l-H-2 20.06 19.98 2.594 0.897 0.150 0.120 0.068 0.015 0.073 0.036 0.291 0.171 0.82 0.46 0.016 0.048 0.034 0.021 0.026 0.039 2-H-l 2-H-2 2-H-3 2-H-4 20.00 20.00 19.97 19,96 2.319 1.703 1.348 1.935 0.410 2.410 0.360 0.830 0.099 0.050 (1.069 0.041 0.260 0.120 0.110 0.091 0.769 2.580 0.539 0.962 3.13 1.36 1.35 0.93 0.031 0.330 0.260 0.025 0.110 0.630 0.063 0.050 0.030 0.039 0.140 0.011 3-H-l 3-H-2 3-H-3 3-H-4 20.09 19.98 20.00 19.99 0.665 1.087 1.137 0.874 2.400 0.140 0.320 0.750 0.010 0.007 0.013 0.010 0.022 0.019 0.023 0.034 2.432 0.166 0.356 0.794 0.25 0.41 0.28 0.28 0.085 0.012 0.081 0.091 0.027 0.007 0.099 0.019 0.013 0.011 0.030 0.012 4-H-l 4-H-2 4-H-3 4-H^ 20.08 20.01 20.03 20.02 1.171 0.873 1.074 1.055 0.730 1.720 1.640 2.500 0.012 0.170 0.340 0.015 0.024 0.280 1.080 0.031 0.766 2.170 3.060 2.546 0.26 3.37 24.30 0.25 0.087 0.280 0.062 0.051 0.100 0.150 0.100 0.022 0.012 0.026 0.024 0.016 21-1 - 2-1-2 2-1-3 19.98 20.06 20.05 2.176 1.192 1.050 0.410 0.510 0.110 0.050 0.055 0.025 0.079 0.082 0.045 0.539 0.647 0.180 0.80 0.89 0.62 0.130 0.230 0.011 0.056 0.032 0.084 0.030 0.017 0.013 3-1-1 3-1-2 3-1-3 3-1^ 19.99 19.99 20.00 20.02 0.822 0.984 0.957 0.661 0.150 0.770 0.200 0.330 0.010 0.013 0.021 0.015 0.015 0.025 0.048 0.039 0.175 0.808 0.269 0.384 0.20 0.25 0.36 0.41 0.018 0.019 0.028 0.013 0.028 0.018 0.024 0.037 0.012 0.014 0.013 0.011 4-1-1 4-1-2 4-1-3 20.01 19.99 20.02 0.763 0.801 0.738 3.000 0.880 3.820 0.009 0.016 0.015 0.017 0.064 0.037 3.026 0.960 3.872 0.13 0.73 0.47 0.120 0.750 0.044 0.019 0.038 0.032 0.013 0.026 0.061 5-I-I 5-1-2 19.98 19.99 0.561 0.701 0.390 0.140 0.009 0.016 0.034 0.043 0.433 0.199 0.38 0.43 0.025 0.010 0.040 0.009 0.007 0.005 2-J-l 2-J-2 2-J-3 2-J-4 20.09 20.02 20.00 20.00 0.763 1.601 1.097 1.989 0.230 0.240 1.750 0.260 0.013 0.041 0.033 0.035 0.053 0.087 0.044 0.078 0.296 0.368 1.827 0.373 0.75 0.81 0.56 0.65 0.030 0.097 0.110 0.016 0.093 0.046 0.044 0.025 0.018 0.025 0.015 0.013 3-J-l 3-J-2 3-J-3 20.00 20.06 20.02 0.867 0.834 0.676 0.320 0.940 0.520 0.033 0.014 0.067 0.120 0.077 0.037 0.473 1.031 0.624 1.18 0.79 0.31 0.160 0.022 0.033 0.018 0.055 0.160 0.009 0.011 0.019 1-K-l I-K-2 20.00 20.01 1.095 1.202 0.110 0.320 0.031 0.032 0.053 0.060 0.194 0.412 0.75 0.69 0.013 0.014 0.010 0.022 0.011 0.016 2-K-l 2-K-2 20.04 19.99 0.920 0.654 0.450 0.290 0.028 0.009 0.028 0.016 0.506 0.315 0.33 0.25 0.017 0.013 0.021 0.024 0.017 0.012 1 2 birds. ■' 7 birds. ■■ 8 birds. ' 14 birds. Vol. 6, No. 1, June 1972 39 A cknowledgment Collections were made by field personnel of the Bureau of Sport Fisheries and Wildlife. Regional Pesticide Spe- cialists of the Division of Wildlife Services were re- sponsible for coordinating and reporting collections and assuring that samples were received by the contracting laboratory in proper condition. The Regional Pesticide Specialists are: James B. Elder Twm Cities, Mmn. Robert H. Hillen Albuquerque, N. Mex. David J. Lenhart Portland, Oreg. John C. Oberheu Atlanta, Ga. John W. Peterson Boston, Mass. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED il) Duslimm. E. H.. W. E. Martin. R. G. Heash. and W. L. Rcichel. 1971. Monitoring pesticides in wildlife Pestic Monit. J. 5(l):50-52. a) Martin. William E. 1969. Organochlorine insecticide residues in starlings. Pestic. Monit. J. 3(2):102-1 14. (3) Risebrough. R. W.. P. Reiclie, and H. S. Olcott. 1969. Current progress in the determination of the polychlo- rinated biphenyls. Bull. Environ. Contam. Toxicol. 4(4)- 40 Pesticides Monitoring Journal The Occurrence of Mirex in Starlings Collected in Seven Southeastern States — 1 970 ' John t . Oberheu ABSTRAC1 Sch-cU'il samples of slaiUiif;s collected for llie Nalioiuil Pesticides Moniloiinf; Progniin were analyzed for mirex. the cliemical used for eradication of the imported fire ant. Whole bodies (le.ss skin, beak. feet, and outer wing.^) of 10 birds from each sampling site were pooled for analysis. Residues present in 10 of the 12 sample pools ranged from 0.01 to 1.66 ppm. Introduction During the fall of 1970, the U. S. Department of Agriculture planned to treat 120 million acres in the southeastern United States with mirex to eradicate the imported fire ant. Very little information was availahle on the uptake of mirex in animal food chains, and there was widespread concern among conservationists about the environmental hazards of this chemical. During November and December 1970, samples of starlings (Sturmts vulgaris) were collected by the Bureau of Sport Fisheries and Wildlife from designated sam- pling sites throughout the country as a part of the na- tional pesticides monitoring network, described by Dustman et al. (2). Since the standard analysis of these monitoring samples does not include determination of mirex residues, arrangements were made for special analysis of samples collected in seven of the States which either had been or would be treated in the fire ant eradication program. This paper presents the results of these analyses. Data on organochlorine residues in the nationwide starling monitoring samples are reported separately by Martin and Nickerson (5): mercury and lead data are included in Martin (4). Sampling and Analytical Procedures Details on selection of sample sites, methods of collec- tion, and analytical procedures for the starling samples were described by Martin (.?.-/) and Martin and Nicker- son (5). Each sample consisted of a pool of 10 starlings collected by trapping or shooting. Specimens were wrapped in aluminum foil, placed in plastic bags, and frozen immediately. They were kept frozen until proc- essed for analysis by the Wisconsin Alumni Research Foundation. - The birds were skmned, and beaks, legs, and outer wings were clipped off. The bodies were ground thoroughly in a Hobart food chopper. A 20-g portion of the homog- enale \\as weighed into a 1.50-ml beaker and placed in a 40 C oven for 72-96 hours. After dry-weight calcu- lation, the samples were ground with 100 g of NaoS04 and placed in a 3.^-x 94-mm Whatman extraction thimble. Samples were extracted for 8 hours on a Soxhlet extractor using 70 ml of ethyl ether and 170 ml of petroleum ether. The solvent was concentrated to 10-15 ml on a steam bath and made to 50 ml with petroleum ether. Cleanup was accomplished by placing an aliquot of the sample on previously standardized Florisil (/). Typical elutions were 150 ml of 5T ethyl ether in petroleum ether, followed by 240 ml of 15% ethyl ether in petroleum ether. The resulting solutions were concen- trated on a steam hath ( 10-15 ml) and made to 25 ml with hexane. From the Bureau of Sport Fisheries and Wildlife. U. S. Dcpartn of the Interior, Atlanta. Ga. 30323. Vol. 6. No. 1. June 1972 - Mention of this commercial laboratory is for identificatic does not constitute endorsement by the U. S. Departn Interior. 1 only and ;nt of the 41 A \0-fi\ portion of the sample solution was injected into a Barber-Coleman, Model 5360, gas chromatograph, operating with the following instrument conditions: Column: Glass, 4' x 4 mm, packed with 5% DC-200 on 80/100 Gas Chrom Q Temperatures: Column 210° C Injector 230° C Detector 240° C Carrier gas: Nitrogen Flow rate: Mirex off column in 12-15 minutes Results Table 1 presents the residue levels of mirex in starlings from the 12 collection sites, a history of the nearest mirex treatments, and each site's rated potential for accumulating residues. All but two of the samples contained detectable levels of mirex. The highest levels occurred at Anniston, Ala., and Thomaston, Ga., both locations of high exposure potential. Although starlings are known to be migratory birds that can range widely for food, the residues oc- curring in most of the samples correspond generally with the exposure potential. The significance of these residue levels in birds is not presently known. The oc- currence in 10 out of 12 samples does, however, prove that mirex will readily appear in animal food chains despite the very low dosage (1.7 g per acre) at which it is applied (6). See Appendix for chemical name of mirex LITERATURE CITED (11 Barry. H. C. J. G. Hundley, and L. Y. Johnson. 1968. Pesticide analytical manual. Vol. 1, Sec. 211.15. Food and Drug Admin., U. S. Dep. Health, Educ, and Wel- fare. Washington, D. C. 20204. (2) Dustman. E. H.. W. E. Martin, R. G. Heath, and W. L. Reichel. 1971. Monitoring pesticides in wildlife. Pestic. Monit. J. 5(l):50-52. (3) Martin. William E. 1969. Organochlorine insecticide residues in starlings. Pestic. Monit. J. 3(2):102-114. (4) Martin. William E. 1972. Mercury and lead residues in starlings — 1970. Pestic. Monit. J. This issue. (5) Martin. W. £., and Paul R. Nickerson. 1972. Organo- chlorine residues in starlings — 1970. Pestic. Monit. J. This issue. (6) U. S. Department of Agriculture. Agricultural Research .Service. 1970. Status report of research on the imported fire ant — immediate and long-range potentials and goals. TABLE 1. — Levels of inire.x in starlings, history of mire.x treatment, and exposure potential for 1970 collection sites .Sample Sitf Location Mirex Residue.s (PPM) 1 Nearest Mirex Treatmen I Dates OF Treatmen 1 Exposure Potential Penderlee. N. C. ND 65 miles Spring and fall of 1966. 1968, and 1969 Low Monroe, N. C. ND 100 miles Spring and summer 1963, summer 1964, spring 1965 and fall 1967 Low Aiken, S.C. 0.08 Treated (5,000 acres) Fall of 1966 and 1967, spring 1970 Moderate to high Carthage, Miss. 0.08 15 miles (855,000 acres) Spring 1967 Low to moderate Gulf port. Miss. 0.42 Treated (75,000 acres) Summer 1969 Moderate to high Alexandria. La. 0.10 Treated (802,000 acres) Spring and fall 1965, spring 1966 Low Annislon, Ala. 1.61 Immediately adjacent (5,000 acres) .Spring 1970. Bait available for landovfner treatments High I'homaston, Ga. 1.66 3 miles ( 1,840,000 acres) Fall 1969 Moderate to high Jcssup, Ga. 0.62 Treated (200,000 acres) Spring and fall 1970 High Panama Cily.Fla, 0.31 Same county (800 - 2.240 .acres) Fall 1964 and 1965, spring 1966 and 1967 Low to moderate Madison, Ha. 0.01 75 miles ( 1.000 .acres) Annual treatment since 1965 Low Winter Haven. Fla. 0.34 Treated (368,000 acres) Spring and summer 1967. County treatments of 2,500-368.000 acres annually 1964-69 Moderate NOTE: ND = not detected. 1 Wet-weight basis. 42 Pesticides Monitoring Journal Organochlorine Pesticide Residues in Commercially Caught Fish in Canada — 1970 J. Reinke,' J. F. Uthe,' and D. Jamieson ■ ABSTRACT Organochlorine pcslicicic residues Here determined for com- mercial ly caught fish from a total of 78 locations in 68 central Canadian lakes and rivers. Only a few of these waters yielded fish with appreciable concentrations of DDT and its analogs f>/ ppm), and in only a few cases did the con- centrations exceed the maximum permissible level of 5 ppm. Of the other organochlorine pesticides commonly used, namely lindane, aldrin. heptachlor, heplachlor epoxide, eii- drin, dieldrin. and chlordanc. oidy dieldrin was found at significant levels in a number of samples, but these amounts were still below the nuiximum permissible level. Trace amounts of lindane were found in some samples. The pres- ence of polychlorinaled hiphenyls (PCB's) was noted in samples from the Great Lakes and the south end of Lake Winnipeg. All results were confirmed by multiple-column gas chromatography and thin layer chromatography . PCB's were separated from DDE on aluminum oxide C (type El plates run in a Iriethylamine-hexane solvent system. Introduction In recent years the fishing industry as a whole has suffered adversely from the effects of a wide variety of pollutants. The finding of extremely high concen- trations of DDT in coho salmon (Oncorhynchiis kisutch) from the Great Lakes (6) and northern anchovy {EngrauUs inorda.x) off Los Angeles (7) has led to certain species heing banned from the market and. undoubtedly, has resulted in public distrust of some fish products. Similiarly. the recent fishery disasters due to mercury, although eliminating contaminated products from the market, have caused adverse publicity resulting in reduced sales (3). To meet the need created by these incidents for a detailed survey of organochlorine pesti- cide residues in fish from commerciallv fished lakes and ' Fisheries Rescarcli Bo.ird of Canada. F 19, Manitoba. - Department of Fisfieries, Inspection Br; Vol. 6, No. I. June 1972 ,hwalcr Institute. Winmt ch. Winnipeg. Manitoba rivers in centra! Canada, a study was carried out in 1970 on fish collected from 78 locations in 68 Canadian waters (Fig. 1 ) and is reported here. All analyses were done in duplicate, with all pesticides being determined by quantitation of gas-liquid chromato- grams obtained from two different column packings: the second column packing was chosen to separate pesticides not widely separated by the first column. The identities of the pesticides were confirmed by thin layer chroma- tography. Materials and Methods S.AMPLING PROCEDURES Fish samples were collected from commercial fishermen by officers of the Inspection Service of the Department of Fisheries and Forestry. A sample consisted of 5 lb of headless dressed fish; if the fish were large, as few as three were pooled to make up a sample. The fish were frozen and shipped to Winnipeg where they were ground (Hobart, Model L800): a 2-lb portion of each sample was refrozen in a block and stored at —40° C until analyzed. ANALYTICAL PROCEDURES For sample extraction, the method of Mills ei al. (4) was used with slight modifications. Hexane, petroleum ether, and acetonitrile were purchased as reagents certi- fied for pesticide analysis. Acetone was redistilled prior to use. and diethyl ether was purified according to the method of Grussendorf er al. (2). A 25-g portion of fish was taken from the center of the frozen sample block and blended with 75 ml of acetonitrile for 2 minutes at high speed in a Waring blender (Model B). The homogenate was suction filtered through a sintered glass funnel directly into a 1 -liter separatory funnel and re-extracted twice with 25 ml of acetonitrile; then, 350 ml of distilled water, 7 ml of saturated aqueous NaCI. 43 FIGURE 1. — Map of sampling locations, Canada — 1970 imv^ NORTHWEST TERIUTORIES tr^' ^ ^^ /SASK\rCHEWASl CANADA and 57 ml of petroleum ether were added to the separa- tory funnel, shaken vigorously, and allowed to separate into layers. The aqueous layer was discarded, and the organic layer was washed twice with 100 ml of water and drained into a 100-ml graduated cylinder; the re- covered petroleum ether was then measured to determine the correction factor, transferred to a 250-ml round bottom flask, and reduced to approximately 1 ml on a rotary evaporator at 40° C. The sample was quantitatively transferred to the cleanup column by rinsing the round bottom flask with two 10-ml aliquots of 8% ether-hexane. The column was made up of 30 g of 2% HnO-deactivated Florisil (60/80 mesh. PR grade, Floridin Co.) with Vi inch of anhydrous NanS04 (reagent grade, Fisher Scientific) above and below the Florisil. The Florisil had been stored at 130" C prior to deactivation; after deactivation, it had been slowly tumbled for Vi hour, then left to equilibrate further for 24 hours. It was then stored in a glass- stoppered bottle and was stable for 1 week. The pesticides were eluted with 8% diethyl ether :hexane (8:92; v/v) to give a total eluate of 220 ml. This eluate was evaporated on a rotary evaporator to ap- proximately 1 ml and then made up to the required volume with hexane prior to gas chromatography. All pesticides reported were confirmed by thin layer chroma- tography. 44 Gas-Liquid Chromatography A Hewett-Packard Model 5750, fitted with a pulsed d.c. Ni"' electron capture detector, was used for gas chromatographic analysis. Operating parameters were as follows: Columns: Temperatures: Carrier gas: Purge gas: Glass, 6' x V4", o.d., packed with either 2% SE-30/3% QF-1 or 3% OV-225 on 80/100 mesh HMDS treated Chromosorb W. Injection port 230° C Column oven 200° C Detector 260° C Helium 10% methane in argon Standard solutions (1 /tg/ml) of lindane, aldrin, hepta- chlor, heptachlor epoxide, endrin, p./^'-DDE, p,p'-DDT, ^j.^'-DDD, o./j'-DDT, and dieldrin were prepared in hexane. Each standard gave a single peak on gas chroma- tography and a single spot on a thin layer plate. The chlordane standard was reported tc be 95% a-chlordane; gas chromatography showed two peaks only. Quantitation was based on the peak heights obtained on injection of known amounts of pesticides. Care was taken to ensure that all heights were within the linear range of the detector, and, rather than make extrapola- tions, the samples were diluted. The following calcula- Pesticides Monitoring Journal tions were used to determine parts per million of residues in fish samples; ng/5 /il ppm ot residue = ', x c.r. X — weight of samples n — number of milliliters in final volume 5 ^1 = volume injected peak height of sample peak height of standard ng in volume injected correction factor (c.f.) = ml petroleum ether recovered ml petroleum ether used Thin Layer Chromaiu^raphy Aluminum oxide G (E. Merck, Darmstadt) plates, 0.5 mm thick, were prepared according to the method of Moats (5). The plates were run in a hexane:triethyl- amine (Eastman Co.) solution (100:7, v/v). Retention factors for pesticides confirmed hy TLC are as follows: Compounds Methoxychlor Lindane /)./)'-DDD Dieldrin Chlordane cis trans Heptachlor epoxide BHC Endrin P.p'-DDT o,p'-DDT Heptachlor /7,A)'-DDE Aldrin PCB's (five spots) Retention Factors .119 .224 .268 .283 ..328 ..328 .335 .358 .388 .447 .597 .611 .642 .436, .530, .536. .657, .751 This particular solvent system was chosen because it separated the pesticides and at the same time separated the PCB spots in a manner which allowed for DDE identification and isolation. This method is sensitive to 1 .0 jxg for visible identification. If spots were not visible, the area was scraped and eluted with 1 : 1 hexane: acetone and injected to the gas chromatograph for confirmation. RECOVERY STUDIES During the course of the survey, recovery studies were performed every other month. The studies were carried out by spiking previously analyzed samples with known amounts of the desired pesticides. The difference between the spiked and the unspiked result was used to indicate Vol. 6, No. I, June 1972 the percent recovered. Similar studies were performed with blanks at various steps in the analyses. Recovery values shown below represent the average values of all eight recovery studies carried out: Heptachlor 72% /..p'-DDT 84% Aldrin 72% p.p'-DDD 90% Heptachlor epoxide 77% /J.p'-DDE 90% Lindane 80% o.^'-DDT 94% Endrin 81% Dieldrin 100% The standard deviation for all pesticides was ±6%. The results of recovery studies showed lower recovery values for the compounds with lower boiling points, i.e., lindane, heptachlor, aldrin, endrin, and heptachlor epox- ide. Also, recovery values for these compounds were lower than results of Brown ( / ) in his comparison of the Mills and Langlois cleanup procedures using fatty and non-fatty samples. Brown's recovery results (/), however, are lower for the remaining pesticides exam- ined except for DDD in fish oil in which he had a recover) of 111%: this was apparently due to both o.p'-DDT and /;.p'-DDD peaks eluting simultaneously under his GLC conditions. Because small amounts of only a few pesticides with low boiling points were found, their lower recovery values, in this instance, are not considered to be critical. The cause of the low recovery values for the com- pounds mentioned above could be the fact that the sample volume was reduced two times by rotary vacuum evaporator before it was ready for gas-chromatographic analyses. Results were expressed without correction for percent recovery. Results and Discussion Pesticides were found in fish from most of the 68 lakes and rivers sampled (Table 1 ). However, the only waters which showed significant amounts of DDT and its analogs ( > I ppm) were in the Provinces of Ontario and Alberta and are as follows: Province of Alberta Lake St. Paul Sturgeon River Cold River Bow River Province of Ontario The Great Lakes Huron Erie Ontario Michigan Superior Lake St. Clair Lake Nipigan Ottawa River Of the pesticides analyzed for, DDT and its analogs appeared most often with dieldrin appearing almost as 45 frequently. PCB's were quite prominent throughout the Great Lakes and appeared to a lesser degree in southern Lake Winnipeg in Manitoba and in the Bow River area of Alberta. It should be noted that, because of the in- terference of PCB's with DDT and its analogs, the DDT results of the survey in the areas where PCB's were found may, to some extent, be erroneous, but thin layer studies indicated that the reported values would be higher by 10'"^ at most. The fact that not all regions with DDT present in fish samples had PCB's present would indicate that PCB's are not being used to extend the kill life of organochlorine pesticides and that these compounds do not enter the environment as a breakdown product of pesticides. Trace amounts of other pesticides (especially lindane, heptachlor, and heptachlor epoxide) were found in the Great Lakes, some lakes in northern Manitoba and Saskatchewan, and in many lakes in the Northwest Territories. Results showed that pesticide concentrations differed for various species in the same lake and that the pesticide concentrations in the same species varied with body size and weight. See Appendix for chemical names of compounds discussed in thM paper. LITERATURE CITED (/) Brown. H. E. 196S. A comparison of the Mills and Langlois cleanup procedures for analysis of chlorinated hydrocarbon residues in fatty and non-fatty samples, Proc. 1st seminar on pestic. residue analyses (Eastern Canada) Nov. 18-19. p. 20-25. (2) Grussendorf. O. W.. A. J. McGinnis, and J. Solomon. 1970. Rapid sample preparation for gas-liquid chroma- tography of pesticide residues by ball-grinding extraction, freeze-out, and semimicro column cleanup. J. Assoc. Off. Anal. Chem. 53(5):1048-1054. (3) Kroekcr, Wally. 1971. Report on a speech by Dave F. Comey (Freshwater Fish Marketing Corporation) to the 13th Annual Meeting of the Manitoba Federation of Fishermen. Winnipeg Tribune. 1 Apr. p. 19. 14 1 Mills. Paul A.. J. H. Onlcy. and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residue in non- fatty foods. J. Assoc. Off. Anal. Chem. 46(2):186-I91. (5j .Moats, William A. 1969. Note on the use of vegetable oil as a source of peroxide in thin layer plates for an- alysis of chlorinated pesticides. J. Assoc. Off, Anal. Chem, 52(4):871-872. 16) Rcinert, Robert E. 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4):233-240. (7) Risehrouglt. R. W. 1969. Chlorinated hydrocarbons in marine ecosystems, p. 5 to 23. In Morton W. Miller and George G. Berg [ed.] Chemical fallout-current research on persistent pesticides. Charles C. Thomas, Springfield, TABLE 1. — Pesticide residue levels in fish, by provinces and waters. Canada — 1970 IT = (race = <0no5 ppm: — = not delected] IjKE OR River ' Latitude AND Longitude Fish Species Pesticide Residue Levels (PPM) DiELDRiN p.p'-DDE o.p'-DDT p.p'-DDD p.p'-DDT Total DDT 46 PROVINCE OF ONTARIO Lake Huron 44' 30' 82' 15' Coho salmon 2,20 0.70 0,80 1.30 5.00 do. — 8.90 1.20 1,50 3,90 15.50 do. — 6,70 0.70 1,00 2.60 11.00 (ManitouUn Is.) do. 0,16 1,80 0,20 0.50 0.80 3.30 (Georgian Bay) do. 0.40 11,10 0.90 1.40 3.00 16.40 Do. do. 0.20 5.60 0.90 1.40 2.00 10.60 Do. do. 0,20 1.00 0.30 0.30 0.70 2.30 (Southern) do. 0,07 0.49 0.12 0.17 0,51 1.20 Do. do. 0.08 0.55 0.17 0,16 0,56 1.44 Do. do. 0.08 0.43 0.18 0.13 0.41 1.15 Whitefish 0.15 0.20 0.11 0.08 0.38 0.83 do. 0.15 0.23 0,12 0,07 0.33 0.75 do. 0,12 0.26 0.13 0.08 0.44 0.91 (Northern) do. 0.21 0.36 0.20 0,15 0.86 1.57 Do. do. 0.25 0.47 0,20 0,12 0.58 1.37 Kokanec 0,20 0.50 0,10 0,10 0.60 1.30 (Northern) Yellow pickerel 0.01 0,19 0.04 0.55 0.18 0.47 (Georgian Bay) do. 0,15 1.68 0.28 0.46 1.87 4.29 (Northern) Sturgeon — 0.32 — 0.12 0.18 0.62 (Georgian Bay) Yellow perch 11.03 0.43 0.14 0.14 0.75 1.46 Do. Mullets 0.14 0.90 0.26 0.38 1.45 2.99 (Northern) Chub 0.31 0,72 0.46 0,31 1.59 3.08 (Georgian Bay) Rainbow trout 0.17 0,60 0,32 0.22 0.88 2.02 Lake Erie 42° 53' 78° 56' Mullets 0,04 0,18 0,01 0.18 0.13 0.50 do. 0,03 0.17 0,02 0.18 0,13 0.50 (Western) Perch 0,04 0.14 0,01 0.14 0.13 0.49 Do. do. 0,04 0.16 0,02 0.17 0,14 0.92 Catfish 0,11 0.49 0,13 0.73 0,33 1.68 Carp 0,08 0.51 0,02 0.37 0.06 0.96 Plsticidfs Monitoring Journai TABLE I. — Pesticide residue levels in fish, by provinces and waters. Canada- 1 970-Contitmed River ' Latitude AND Longitude Fish Species Pesticide Residue Levels (PPM) Lake or Dieldrin p,p'-DDE o.p'-DDT p,p'-DDD p,p'-DDT Total DDT PROVINCE OF ONTARIO— Continued Lake Erie (Cont'd) Alewife 0.56 0.17 _ 0.18 0.34 Sheepshead 0.06 0.27 0.03 0.35 0.27 0.92 Lake Ontario 43= 45- 78° 00' Pickerel 0.06 0.71 0.20 0.35 0.37 1.63 do. 0.07 0.53 0.21 0.33 0.41 1.48 do. 0.08 0.55 0.19 0.33 0.40 1.47 Rockbass 0.01 0.07 — 0.04 0.02 0.13 Lake herring 0.28 2.64 0.58 0.43 2.84 6.49 Crappies Pike Perch 0.02 0.17 0.28 0.12 0.12 0.45 0.15 0.67 _ 0.42 0.69 1.78 Whitefish 0.37 0.65 — 0.67 0.57 1.89 Lake Michigan 43° 45' 87° 00' Alewife 0.14 3.72 0.37 0.56 1.19 4.28 Chub 0.03 2.50 0.68 0.44 3.00 6.62 Lake Superior 48° 00' 88° 00' Smelt 0.16 T 0.16 Lake trout 0.06 0.68 0.11 0.16 0.36 1.32 St. Clair 47° 14' 84° 00' Coho 0.03 0.12 0.05 0.05 0.15 0.37 Pickerel 0.10 1. 11 0.12 0.58 1.09 2.90 Sturgeon River 46° 19' 79° 58' Mullet O.OI 0.14 0.05 0.20 0.52 0.91 Nipigon 49° 50' 88° 30' Northern pike _ 0.23 0.04 0.04 0.14 0.45 Pickerel — 0.20 0.04 0.03 0.09 0.36 Whitefish 0.05 0.80 0.15 0.05 0.47 1.47 Tullibec 0.06 0.80 0.28 0.43 0.92 2.45 Lake of the Woods 49° 00' 94° 50' Whitefish 0.01 0.12 0.01 0.05 0.02 0.20 do. 0.03 0.16 0.04 0.08 0.05 0.33 Ottawa River 45° 34' 74° 23' Crappies 0.01 0.11 0.02 0.02 0.05 0.20 Bullheads 0.03 0.08 — 0.95 0.67 0.24 do. 0.03 0.08 — 0.95 0.67 0.24 Sturgeon 0.52 0.82 0.51 0.89 1.14 3.36 St. Lawrence 45° 20' 73° 58' Yellow perch _ 0.01 _ 0.80 0.01 0.23 Bullheads 0.03 0.88 — 0.24 0.05 0.38 Lake St. Francis 45° 08' 74° 25' Yellow perch 0.03 O.OS - 0.04 0.06 0.15 Clay 50° 05' 93° 30' Pike 0.01 0.02 • 0.02 0.07 0.17 Whitefish 0.07 0.02 — 0.02 0.06 0.10 PROVINCE OF MANITOBA Winnipegosis 52° 30' 100° 00' Goldeye T 0.01 T T 0.01 (Dawson Bay) do. 0.01 0.02 0.02 0.01 — 0.05 (N) Mullet T 0.01 T T 0.01 (S) do. T 0.01 T T 0.01 (Duck Bay) do. T T T T T T (Dawson) do. T 0.01 — T 0.01 (N) Sauger T T T T T T (Duck Bay) do. T 0.01 T T T 0.01 (S) do. T T T T (S) Northern pike T T T T T T (N) do. T 0.01 T T T 0.01 (Duck Bay) do. 0.01 0.01 0,01 0.01 O.OI 0.04 (N) Pickerel T T T T T T (S) do. T 0.02 T T T 0.02 (Duck) do. T 0.02 T T T 0.02 (Dawson) do. T 0.01 — T — 0.01 God's 50° 40' 94° 15' Pike _ _ _ _ Walleye — — — — — — Reindeer 57° 20' 102° 00' Lake trout - - - - - - Family 51° 54' 95° 27' Walleye T T Pike — T — — — T Fishing 52° 08' 95° 24' Walleye - T - - - T Winnipeg 52° 00' 97° 00' Pike 0.01 0.15 0.01 0.09 0.05 0.30 (Southern) Sauger 0.02 0.11 0.03 0.09 0.02 0.25 (Northern) Northern pike 0.01 0.05 0.01 0.01 0.02 0.09 (Southern) do. 0.01 0.19 0.02 0.12 0.08 0.41 Vol. 6, No. 1, June 1972 47 TABLE 1— Pesticide residue levels in fish, by provinces and waters, Canada- 1 970-Continued River ' Latitude AND Longitude Fish Species Pesticide Residue Levels (PPM) Lake or DiELDRIN p,p'-DDE o.p'-DDT p.p'-DDD P,p'-DDT Total DDT PROVINCE OF MANITOBA— Continued Winnipeg (Cont'd) (Nonhern) Pickerel 0.01 0.04 0.01 0.01 0.01 0.07 (Southern) do. 0.01 0.16 0.02 0.04 0.31 0.53 (Northern) Whitefish 0.05 0.06 O.OI 0.02 0.02 0.11 do. 0.01 0.08 0.03 0.06 0.09 0.26 (Southern) Perch T 0.18 0.01 0.10 0.04 0.33 Do. Sheepshead 0.02 0.18 0.03 0.07 0.06 0.34 Tullibee 0.03 0.12 0.07 0.11 0.07 0.37 Manitoba 51° 00' 98° 45' Mullet T T T T T T Sauger T 0.03 — 0.01 T 0.04 do. T 0.03 T 0.01 T 0.04 (Northern) Northern pike T 0.02 T 0.02 T 0.04 (Western) do. — 0.02 T 0.01 T 0.03 (Southern) Pickerel — 0.02 0.01 — — 0.03 (Western) do. T 0.03 0.01 0.01 0.01 0.06 St. Martin 51° 37' 98° 29' Mullet T 0.02 T 0.01 T 0.03 Northern pike T 0.02 T T 0.01 0.03 Pickerel T 0.02 T T 0.01 0.03 " Perch T 0.02 T 0.01 T 0.03 Dauphin 51° 17' 99° 48' Mullet T 0.02 _ 0.01 T 0.03 do. T 0.02 — 0.01 — 0.03. Northern pike T 0.02 — 0.01 — 0.03 do. T 0.01 T 0.01 — 0.02 Pickerel T 0.02 T 0.01 — 0.03 do. T 0.02 0.01 0.01 T 0.04 Lockport 50° 05' 96° 56' Maria T 0.03 T 0.03 0.02 0.08 South Indian 57° 10' 98° 30' Pickerel T 0.01 T T T 0.01 Dogskin 51° 43' 95° 12' Pickerel T T - - T T Cedar 49° 55' 96° 27' Northern pike T 0.05 T 0.02 0.03 0.10 Clear 50° 41' 100° 00' Pickerel - 0.10 - 0.08 0.17 0.34 Summerberry River 53° 23' 100° 22' Pike T T - - - T PROVINCE OF SASKATCHEWAN Dillon 55° 45' 109° 30' Northern pike - - - - - - Buffalow Narrows 55° 51' 108° 29' Pickerel T T T - T T Pelican 50° 32' 106° 00' Whitefish T 0.01 0.01 0.01 - 0.03 Montreal 54° 20' 105° 40' Whitefish 0.01 0.01 0.02 0.01 - 0.04 Jackfish 51° 39' 101° 35' Whitefish 0.01 0.02 0.03 0.01 - 0.06 Last Mountain 51° 05' 105° 14' Whitefish 0.01 0.01 - T - 0.01 Primrose (Long Bay) 54° 55' 109° 45' Whitefish do. 0.01 T 0.25 0.05 0.05 0.01 0.06 0.04 0.19 0.05 0.55 0.15 Pinehouse 55° 32' 106° 35' Whitefish T 0.01 0.01 T - 0.02 Weyakwin 54° 30' 106° 00' Whitefish T 0.01 0.01 T - 0.02 Lac La Ronge 55° 04' 105° 19' Whitefish T 0.01 0.01 T - 0.02 lie La Cross 55° 40' 107° 45' Whitefish - 0.01 0.02 - - 0.03 Descharme 57° OS' 109° 13' Whitefish 0.01 T - 0.01 - 0.01 Wicken Camp 57° 29' 109° 38' Whitefish T T T T T T North Sask. River 53° 15' 105° 05' Burbot do. do. do. Goldeye do. T T T 0.08 0.20 0.10 0.10 0.02 0.22 0.09 0.29 0.06 0.01 O.OI 0.01 0.19 0.22 0.10 0.01 0.01 0.01 0.19 0.22 0.10 0.04 0.03 0.03 0.40 0.95 0.43 Athabasca 59° 15' 109° 15' Pickerel - T - - - T Utikumak 54° 50' 108° 14' Whitefish - 0.01 0.01 - - 0.01 48 Pesticides Monitoring Journal TABLE 1— Pesticide residue levels in fish, by provinces ind waters. Canada-1970-Contimied R River ' Latitude AND Longitude Fish Species Pesticide Residue Levels (PPM) Lake o Dieldrin P.p'-DDE o.p-DDT p,p'-DDD p,p'-DDT Total DDT PROVINCE OF ALBERTA Bellis 54° 09' 112° 09' Goldeye 0.01 0.12 0.02 0.08 0.06 0.28 do. 0.02 0.23 0.02 0.15 0.12 0.52 St. Paul 59° 59' 111° 17' Goldeye 0.02 0.60 _ 0.55 0.79 1.94 Burbot T 0.04 — 0.02 0.03 0.09 do. T 0.02 — 0.01 0.02 0.05 do. T 0.02 — 0.02 0.02 0.06 Walleye T 0.40 0.30 0.20 0.20 I.l Pike — 0.40 0.08 0.22 0.25 0.95 Pickerel 0.01 0.04 — 0.03 0.03 0.10 Sturgeon River 53° 46' 113° 10' Whitefish 0.03 0.08 0.08 0.08 0.23 0.47 Goldeye 0.06 0.37 0.48 0.28 1.08 2.21 Pickerel 0.01 0.04 — 0.03 0.05 0.12 Kinnaird 54° 47' 111° 31' Northern Pike T T 0.01 - - 0.01 Mymam 53° 40' 111° 14' Pickerel 0.01 0.06 _ 0.04 0.05 0.15 do. 0.01 0.05 — 0.04 0.05 0.14 Cold 52° 18' 112° 41' TuUibee 0.01 0.34 0.02 0.02 0.10 0.48 Whitefish 0.02 0.89 0.08 0.09 0.70 1.76 Lac La Biche 54° 46' 111° 58' Whitefish - 0.01 0.01 - - 0.02 Kackson Whitefish 0.01 T - 0.01 - 0.02 Bow River 49° 51' 111° 41' Trout eggs 0.92 0.57 _ 0.39 0.37 1.33 Rainbow Iroul 0.05 0.50 — — 0.32 0.87 do. 0.01 0.88 0.03 0.04 0.05 1.00 do. 0.05 0.35 0.29 0.26 0.43 1.33 Whitemud Creek 53° 27' 113° 33' Northern sucker 0.01 0.07 0.02 0.06 0.09 0.24 NORTHWEST TERRITORIES Great Slave 61° 23' 115° 38' Whitefish 0.01 0.01 T T T 0.01 Hjalmar 61° 33' 109° 25' Whitefish Lake trout 0.01 T 0.03 0.03 — — — 0.03 0.03 Nonacho 61° 42' 109° 40' Whitefish T T - - T T Rutledge 61° 33' 110° 47' Whitefish Lake trout do. Muktuk 0.01 T 0.07 0.01 0.02 T 0.16 0.01 0.05 T 0.10 T 0.10 0.02 0.02 T 0.41 Merkley 69° 45' 107° 40' Whitefish 0.01 T T T - T Gymer Whitefish 0.01 0.01 0.01 T T 0.02 Gordon 63° 10- 113° 12' Trout Whitefish 0.01 0.03 0.05 0.10 0.03 0.01 0.04 0.02 0.05 0.11 0.19 Mackay 63° 55' 110° 25' Whitefish 0.02 0.08 0.03 0.02 0.03 0.16 Cambridge Bay 68° 03' 105° 05' Arctic char do. Whale T T - z - T Baker 64° 00' 96° 00' Whitefish - - - - - - Kaminak 62° 10' 95° 00' Lake trout - - - - - - Jackson 62° 35' 114° 18' Whitefish T - - 0.01 - 0.01 ^ Specific location within waters, if known, given in parentheses. Vol. 6. No. I. June 1972 49 Residues of Organochlorine Pesticides,, Polychlorinated Biphenyls, and Mercury in Bald Eagle Eggs and Changes in Shell Thickness — 1969 and 1970 Stanley N. Wiemeyer,' Bernard M. Mulhern/ Frank J. Ligas,- Richard J. Hensel,'' John E. Mathisen/ Fred C. Robards,'' and Sergej Postupalsky" ABSTRACT Tweiily-lliicc bald eagle eggs collected in Alaska. Maine. Michigan, Minnesota, and Florida during 1969 and 1970 were analyzed for organochlorine pesticides, polychlorinated biphenyls, and mercury. All eggs contained residues of DDE, dieldrin. PCB's. and mercury. Average residue concentrations were lowest in eggs front Alaska. Significant eggshell thinning has occurred among eggs front niosi major areas sampled. Some eggs contained DDE residues of the same magnitude as those thai produced shell thinning in experimental species. Higli dieldrin residues in sinne eggs could he luiving an adverse effect on reproductive success. experimentally (23,35). Previous studies of field-col- lected bald eagles and their eggs have reported organo- chlorine or heavy metal residues (9,22.2S,33), causes of mortality (4.22), and mortality due to pesticide poisoning (4,22,29,33). This paper reports the results of analyses for organochlo- rine pesticides, polychlorinated biphenyls (PCB's), and mercury residues in bald eagle eggs collected in Alaska, Maine, Michigan. Minnesota, and Florida during 1969 and 1970. Eggshell characteristics and reproductive succe.ss are discussed in relation to these residues. Introduction Bald eagle {Haliaeetus leiicocephalus) populations and the reproductive success of this species have declined in many areas of the United States within the last 20 years (1.3.32). Several authors have related the decline of eagles and of other species of raptorial and fish-eating birds at the top of food chains to the adverse effects of organochlorine pesticides that are widespread in the environment (6,7, 11 ,26,27) . A reduction in eggshell thickness since the introduction and widespread use of organochlorine pesticides has been shown for a number of bird species (7,26,27): the adverse efi'ects of DDT and dieldrin in combination and of DDE on reproduc- tive success of a raptorial species have been shown Bureau of Sporl Fisheries ami Wildiifc. P.ntuxcni Wildlife Research Center, Laurel. Md. 20810. National Audobon Society. Corkscrew Swamp Saiicluary Immokalee F!a. 33934. Bureau of Sporl Fislicrics and Wildlife. Kodiak National Wildlife Refuge. Kodiak. Alaska 99615. Present address. Bureau of Sport Fish- eries and Wildlife. Alaska Area Office. 6917 .Seward Hit-liwav. An- chorage. Alaska 99502. Forest Service. Chippewa National Forest. Cass Lake. Minn. 566.11 Bureau of Sporl Fisheries and Wildiifc. P.O. Bo\ 12S7. .luncaii. Alaska 99801. Department of Wildlife Ecologv. Univcrsilv of Wisconsin, Madison. Wis. 53706. 50 SamjAing Procedures One egg was collected from each of 15 nests during the normal incubation period; 1 1 of the nests were located in Alaska, 3 in Maine, and I in Michigan. Eight addi- tional eggs collected after the normal incubation period included five eggs from four nests in Minnesota, two eggs from nests on the west coast of Florida, and one egg from a nest on Kodiak Island. Alaska. Following collection in the field, each egg was usually wrapped in aluminum foil, individually packed in a container, and shipped to the Patuxent Wildlife Research Center. The length and breadth of each egg was meas- ured in millimeters, and the volume of some eggs was measured by water displacement. The eggs were opened, and the age of embryos was estimated based on a 35-day incubation period. Egg contents were frozen prior to chemical analysis. Shells were air dried, and shell thick- ness was measured as previously described (9). Chemical Analysis Eggs were analyzed individually for residues of organo- chlorine pesticides, polychlorinated biphenyls (PCB's), and mercury. Each egg was mixed in an Omnimixer; a Pesticides Monitoring Journai 20-g aliquot was removed for pesticide and PCB an- alysis; and a 5-g aliquot was removed for mercury analysis. The 20-g aliquots were ground with anhydrous sodium sulfate and extracted for 7 hours with hexane in a Soxhlet apparatus. Extracts were cleaned up and then divided into halves; one half was used for pesticide analysis and the other saved for PCB analysis. For pesticide analysis, each cleaned extract was spotted on a thin layer plate, developed, and removed in four fractions as described by Mulhern et al. (22). All four fractions were analyzed separately by electron capture gas chromatography on a 3.8% UCW-98 on 80/100 Didtoport S column, and DDT residues in Fractions III or IV were confirmed on a 3% XE-60 column. The operating parameters for the UCW-98 and XE-60 columns are given in Table 1. Average recovery by this method was 85-96??^ with a detection limit of approx- imately 0.05 ppm. Residues were not corrected for recovery. In addition to zonal separation by thin layer chromatography (TLC) and analysis on two columns, residues in 209^ of the samples were confirmed by TLC (AgNO.j incorporated AloO^, plate — 5% benzene in hexane solvent). TABLE L — Chromatographic operating conditions using electron capture detection for pesticide analysis Columns Glass 'A" O.D. A B Column length 4 feet 6 feet Liquid phase .1.8% UCW-98 3% XE-60 Support Diatoport S Gas Chrom 0 Mesh size 80/100 60/80 Column flow rate 60 ml/min lOOnil'min Purge 40 ml/min - Gas 5% methane/argon nitrogen Temperature 200° C 170 C Retention time of dieldrin 8.6 minutes 16.3 minutes PCB analysis was by TLC as described by Mulhern et al. (21). Mercury analyses were for total mercury by a method developed by R.S. Christensen (personal cominunica- tion). The procedure involves acid digestion of the tissue and extraction of the mercury from the liquid digest with dithizone (20). Mercury determination was made on the dithizone extract by flame atomic absorp- tion spectrophotometry using the "sampling boat" tech- nique (S). The average recovery from tissue samples fortified with both inorganic and organic mercury compounds was 91%. The limit of detection was 0.05 ppm. The residue concentrations were calculated as micro- grams per milliliter on the basis of total egg volume. This is converted to a ppm basis assuming a specific gravity of 1.0 as described by Stickel el al. (33). Vol. 6, No. 1, June 1972 Measurements of length and breadth were used to estimate the volume of those eggs whose volumes were not determined by water displacement. The equation for this estimate was volume (ml) = 3.73 X length (cm) X breadth (cm) - 35.3 (L. F. Stickel, S. N. Wiemeyer, and L. J. Blus, manuscript in preparation) . Collection Date.'! and Embryonic Development of Samples Six eggs were collected from Kodiak Island between May 8 and 26, 1969; two were fresh with no signs of em- bryonic development while four contained 7- to 23-day- old embryos. An additional egg from Kodiak Island (Karluk Weir), collected on July 21, 1969, after it failed to hatch during the normal incubation period, was decomposed with no evidence of embryonic de- velopment; a small partion of this egg's contents may have been lost before it was opened. Five eggs from the Admiralty Island area, Alaska, col- lected between May 13 and 15, 1970, contained embryos estimated to be more than 15 days old. One (Tiedman Island) was decomposed and had lost a small portion of its contents before it was opened. Three eggs from nests in Maine were collected on April 14 and 15. 1969. One (Dyer Neck) was decomposed with no signs of embryonic development; however, the other two contained embryos 15 to 32 days old. The single egg from Baraga County, Michigan, collected on April 14. 1969, appeared fresh and exhibited no visible signs of embryonic development. Two eggs from Minnesota (Star Island, Rabideau Lake), collected on June 4 and 6, 1969, contained embryos 8 to 20 days old. Two additional eggs were collected from one nest in Minnesota (Six Mile Lake) on May 14. 1970; one contained a decomposed embryo 5 to 10 days old. and the addled contents of the other contained no evidence of embryonic development. An additional egg from Minnesota, collected on June 5. 1970. ex- hibited no indication of embryonic development in its addled contents. Two eggs collected in Lee County. Florida, on March 7 and May 2, 1969, were badly dehydrated and contained no signs of embryonic development. Results Results of the analyses for organochlorine pesticides, PCB's, and mercury are shown in Table 2. Average residue concentrations of organochlorines in bald eagle eggs from Alaska were the lowest found for any area in the United States to date. DDE residues in the eggs from the Admiralty Island area, excluding the one egg from South Midway Island, averaged only 0.95 ppm. 51 TABLE 2. — Organochlorine pesticides, polychlorinated biphenyls, and mercury in bald eagle eggs collected in Alaska, Maine, Michigan, Minnesota, and Florida in 1969 and 1970 [ND = not delected; T = <0.05 ppmj Nest Location Shell Thickness (MM)^ Egg Volume (ML) = Residije Concentration in ppm Heptachlor p.p'-DDE p.p'-DDD p.p'-DDT DiELDRiN Epoxide PCB's Mercury ALASKA— KODIAK 1969 Island Point 0.51 [134] 1.60 0.07 ND 0.09 0.02 1.9 0.2 Bird Island 0.52 1136] 4.93 0.23 ND 0.30 0.06 5.4 0.2 Spiridon Bay 0.52 [144] 1.43 0.07 ND 0.06 0.01 1.7 0.2 Grassey Point 0.53 [129] 1.89 0.21 ND 0.12 0.02 1.8 0.1 Uganik Island 0.60 [128] 1.28 0.06 ND 0.06 0.02 1.7 0.3 Eraser Lake 0.58 [126] 1.16 0.05 ND 0.02 0.01 1.6 0.1 Karluk Weir 0.59 [123] 1.15 0.14 ND 0.05 0.01 1.4 0.1 Average 0.55 1.92 0.12 ND 0.10 0.02 2.2 0.2 ALASKA, ADMIRALTY ISLAND AREA— 1970 Tiedman Island [0.60] 102 0.83 T ND T ND 0.85 0.1 Fools Inlet 0.60 103 1.81 T ND T ND 0.84 0.3 South Midway Island [0.55] 125 10.75 T ND 0.22 ND 2.3 0.2 Windfall Harbor 0.68 151 0.25 T ND 0.02 ND 0.43 0.2 Swan Island 0.60 133 0.91 T ND 0.03 T 0.88 0.2 Average = 0.61 2.91 T ND 0.06 T 1.1 0.2 MAINE- 1969 Franklin 0.49 142 11.86 0.55 0.24 0.22 0.02 4.9 0.3 Dyer Neck [0.47] 129 20.55 0.84 0.49 0.29 0.03 15.2 0.3 Boyden Pond 0.59 131 12.44 0.35 0.25 0.15 0.02 9.7 0.4 Average 0.52 14.95 0.58 0.33 0.22 0.02 9.9 0.3 MICmOAN— 1969 Van Zellen's Camp MINNESOTA— 1969 AND 1970 i Star Island 0.48 [130] 21.62 2.42 ND 2.29 0.17 12.4 0.3 Rabideau Lake 0.61 [120] 3.68 0.91 ND 0.63 0.11 8.0 0.3 Cass Lake 0.55 123 8.15 0.48 ND 0.62 T 6.2 0.3 Six Mile Lake (1) (2) 0.53 0.55 [124] [135] 2.37 7.27 0.07 0.42 ND ND 0.16 0.65 ND T 2.2 5.8 0.2 0.3 Average 0.55 9.57 1.02 ND 0.99 0.08 7.7 0.3 FLORIDA— 1969 Lee County — 1 Lee County — 3 0.61 0.52 [104] [98] 18.21 18.52 1.13 2.49 0.19 0.29 0.68 1.54 0.02 0.07 13.3 11.1 0.3 0.7 Average 0.57 18.37 1.81 0.24 1.11 0.05 12.2 0.5 1 Shell thicknesses in brackets may not be totally accurate due to disruption and/or loss of the shell membranes. These data have been excluded from Table 3 and from Discussion in the text. - Volumes in brackets computed as stated in text. ^ Trace considered to equal 0.025 ppm when computing averages. ' Parentheses designate different eggs from the same nest. Average computed on a nest basis. Residues of dieldrin averaged 0.06 ppm in all of the eggs from the Admiralty Island area, while DDD was present in only trace amounts. Residues in eggs from Kodiak Island were slightly higher, averaging 1.92 ppm DDE, 0.12 ppm DDD, and 0.10 ppm dieldrin. Residues in eggs from Maine collected in 1969 averaged 0.22 ppm dieldrin, 14.95 ppm DDE, 0.58 DDD, and 0.33 ppm DDT. Residues in Maine eggs collected in 1967 and 1968 averaged somewhat higher and contained 1.63 ppm dieldrin, 21.01 ppm DDE, 0.98 ppm DDD, and 0.50 ppm DDT (9). The concentration of organochlorine pesticides in the eggs from Chippewa National Forest, Minnesota, in 1969 and 1970 was generally similar to that found in eggs collected in Wisconsin in 1968 (9), with the ex- ception of the egg from Star Island collected in Min- nesota in 1969, which contained much higher residue concentrations. Excluding the Star Island egg, the residues in the eggs from Minnesota (on a nest basis) averaged 5.55 ppm DDE, 0.55 ppm DDD, and 0.55 ppm dieldrin. The single egg from the Michigan shore of Lake Superior contained an unusually high concentration of DDE and a moderate concentration of dieldrin. 52 Pesticides Monitoring Journal TABLE 3. — Bald eagle eggshell parameters for eggs collected in 1968 to 1970 and changes from pre-1946 norms Area Mean Eggshell Thickness ' (MM) Percent Change FROM Pre- 1946 Norms = Mean Shell Weight > (G) Percent Change FROM Pre- 1946 Norms - Mean Thickness Index 1" Percent Change FROM Pre- 1946 Norms = Alaska— Kodiak 0.5500 (7) — 10.4*» 12.460 (6) — '11.4«* 2.770 (6) —14.1*' Alaska — Admiralty 0.6267 (3) ■ 2.2 15.715 (2) — 3.345 (2) — Great Lake States 0.5486 (14) — 10.2«» 11.617 (11) —10.8* 2.777 (11) — 12.1" Florida 0.5183 (6) — 11.3' 9.650 (6) — 19.1*' 2.567 (6) — M7.2»« Maine 0.5425 (4) —1 1.0* 12.830 (2) — 2.750 (2) — NOTE: Sample size is given in parentheses. All parameters for all eggs could not be used because of the presence of the following conditions; loss and/or disruption of shell mem- branes, loss of portion of shell, residue of egg contents adhering to shell surfaces. The current samples of eggs may not be entirely random. ' Means arc calculated on a nest basis; data are, in part, from Krant/ ci al. IV). -Pre-1946 data from D. W. Anderson and J. J. Hickey (unpublished). "Ten times shell weight (gl divided by the product of the length and brcadlh (cm) as devised by Ratclifle (26). 'Sample variances unequal; method of determining significance level from Snedecor and Cochran <.U). •Significant change from pre-1946 norm /' <0.0I; T-tesl. *• Significant change from prc-1946 norm P <0.0()1; T-tcsl. DDE in the eggs from Lee County, Florida, averaged 18.37 ppm. which was considerably higher than the 10.72 ppm average in the eggs from Everglades National Park in 1968 (V). Dieldrin residues in eggs from l,ec C'ounty were 0.68 and 1 .54 ppm, about two and six times the highest level found in the Everglades eggs, which ranged from 0.1 1 to 0.28 ppm t9). Residues of PC'B's were lower than rcsidties of DDT plus its metabolites for most eggs in all areas excepi for the majority of eggs taken from Kodiak, Alaska. The highest concentration of PCB's occurred in the egg from Michigan, Average PCB concentrations in de- scending order were: Florida 12.2 ppm, Maine 9.9 ppm. Minnesota 7.7 ppm, Kodiak. Alaska 2.2 ppm. and Admiralty, Alaska 1.1 ppm. Mercury concentrations were uniformly low in the eggs sampled and averaged 0.2-0.3 ppm, with the exception that a higher concentration (0.7 ppm) occurred in one of the two eggs from Florida. Borg ci al. (2) found reduced hatchability of pheasant {Phasianiis c(>lchkii\) eggs that contained 1.3 to 2.0 ppm mercury. Eggshell thickness and weight of bald eagle eggs collected from 1968 to 1970 are compared in Table 3 with meas- urements of shells of eggs collected prior to the wide- spread use of organochlorine pesticides (D. W. Anderson and J. J. Hickey, iinpiihlishetl data). Thickness and weight were found to decline significantly (p<0.0l) in all areas where sufficient data were available, except for a nonsignificant (p>0.05) change in eggshell thickness for eggs from the Admiralty Island area. Hickey and Anderson (7) reported declines in shell weight of 18.0 and 19.8'~f for bald eagle eggs collected from two Florida counties since organochlorine pesticides were initially used. Vol. 6, No. 1. Juni-; 1972 Shells of eggs from individual nests in the recent sample from Kodiak, Alaska, were from 2 to I79f thinner than the prc-1946 norm. Shells from Admiralty, Alaska, were 29! thinner to I I ""< thicker than the earlier norm. The shells of some eggs from the Lake States were equal in thickness to the pre-1946 norm, and others varied from that to as much as 2IC/ thinner than the earlier norm. Eggshells from Florida were 25% thinner to 4% thicker than the prc-1946 norm, and those from Maine were 3 to 20''/ thinner than the earlier norm. Only those eggs that could be measured accurately (those used in Table 3) were incliuleil in the above data. Discussion Data on reproduction of bald eagles in the areas in which eggs were collected are included in Table 4. Lockie, RatclifTe, and Balharry (//), in a study of golden eagles (Aqiiila chrysaetos) in west Scotland, found that the proportion of eagles successfully rearing \oung doubled (from 3 K' to 69':r ) following the ban of dieldrin use in sheep dips, the average dieldrin resi- dues in eagle eggs dropped significantly (from 0.87 ppm to 0.38 ppm) during the same period. The low residues of DDE and other organochlorine pesticides, other than dieldrin, in the eggs of the Scottish eagles are not believed to have been a significant factor in repro- ductive success. Lockie and Ratcliffe (10) earlier cor- related reproductive failure with amounts of dieldrin exceeding 1.0 ppm in the eggs of these golden eagles. Potts (25) found a significant correlation between the residues of dieldrin in the eggs of shag (Phalacrocorax aristoielis) and reproductive failure; there was a sizeable increase in the percentage of clutches with no chicks surviving to the 1 0th day when there was more than 2.0 ppm dieldrin in the egg. 53 TABLE 4. — Reference data on reproduction of bald eagles in the areas in which eggs were collected Location Year Average Number OF Young per Active Nest/Year Percent of Active Nests in Which Young Were Raised Reference Karluk Lake, Kodiak National Wildlife Rcfupc. Alaska Kodiak National Wildlife Refuge. Alaska Admiralty Island, Alaska 1959, 1961, 1962 1963 1965 1.1 1.4 66 88 Hensel and Troyer (5) Trover and Hensel (34) Robards and King (30) Chippewa National Forest, Minnesota 1963-70 0.8 52 Mathisen (12-18) Mathisen and Stewart (19) Maine 1965 - 18 Sprunt and Ligas (32) Florida (west coast) 1965 - 45 Sprunt and Ligas (32) Michigan (shores of Great Lakes) 1967 - 6 Postupalsky (24) One-half of the bald eagle eggs from Maine that have been analyzed, as well as single eggs from Michigan. Minnesota, Wisconsin, and Florida have contained more than 1.0 ppm dieldrin — see also Krantz el ul. (9). If the results of Lockie el til. ill), regarding the adverse effects of dieldrin on golden eagle reproduction, are also applicable to reproductive success in bald eagles, then dieldrin could be a factor in bald eagle reproductive success in these areas. The DDE residues in a few of the eggs reported here, as well as in a number of eggs reported previously (9). especially many of those from Maine, were similar in magnitude to those that have produced shell thinning in experimental sparrow hawks (Faico sparveriiis) fed a low dietary level of DDE {35). Average declines in shell thickness, as expressed by shell weight or thickness index, greater than \l'"c have been accompanied by severe declines in populations and/or reproductive success in several species of raptorial birds (7,26.27): declines in shell thickness are commonly associated with an increased frequency of egg breakage (7.23.26.27). The decline in shell weight and thickness index of bald eagle eggs from Florida equalling that of some declining raptor populations, the presence of eagle eggshell fragments in two Kodiak. Alaska, nests at the time of the egg collection, and the moderate declines in shell thickness for most of the areas sampled induce considerable concern regarding the effects that shell thinning may be having on reproductive success and status of these bald eagle populations. ConciiLiion DDE residues in some eggs were of a magnitude that has produced shell thinning in experimental studies of other species. Significant shell thinning in most areas sampled causes concern for ultimate effects on repro- ductive success and populations. Dieldrin residues in the eggs from some areas could have an adverse effect on reproductive success. A cknowledginent The authors wish to acknowledge the assistance of several individuals who aided us in various portions of this study. R. S. Christensen of WARE Institute, Inc. (P.O. Box 2037. Madison, Wis.) kindly provided the method used in the mercury analyses. Thair G. Lamont performed the mercury analyses reported here. Daniel W. Anderson and Joseph J. Hickey graciously provided tmpublishcd eggshell data. Vernon D. Berns. Teryl G. Grubb. William C. Krantz. and Fred Lesser assisted in the egg collections. See Appendix for chen paper. npounds discussed in this LITERATURE CITED 111 Ahhnti. J. M. 1967. The Chesapeake hald eagles. Atl. Naturalist 22(n;20-2S. (2) Bars;. K.. H. Waiuilorp. K. Erne, and E. Hanko. 1969. Alkyl mercury poisoning in terrestrial Swedish wildlife. Viltrevy 6(4):.101-.'*79. (3) Brolev. C. L. 1958. The plight of the American bald eagle. Audubon Mag. 60(4) : 162-163. 171. (4) Coon, N. C, L. N. Locke, E. Cromartie, and W. L. Rcichcl. 1970. Causes of bald eagle mortality. 1960- 1965. J. Wildl. Dis. 6(l):72-76. (5) Hensel. R. J., and W. A. Troyer. 1964. Nesting studies studies of the hald eaale in Alaska. Condor 66(4):282- 286. (6) Hickey. J. .1 . Eiliior. 1969. Peregrine falcon populations: their biology and decline. Univ. Wis. Press. Madison. 596 pp. I7) Hickey. J. J., and D. W. Anderson. 1968. Chlorinated hydrocarbons and eggshell changes in raptorial and fish- eating birds. Science^ 162(3850): 271-273. (8) Kahn. H. L.. G. E. Peterson, and J. E. Scliallis. 1968. Atomic absorption microsampling with the "Sampling Boat" technique. At. Absorpt. Newsl. 7(2):35-39. (9i Kraiil:. IV. C. B. M. Mulhcrn. G. E. Bagley, A. Sprunt, IV. F. J. Lifias. and W. B. Rohcrt.mn. Jr. 1970. Organo- chlorine and heavy metal residues in bald eagle eggs. Pestic. Monit. J. 4(3):136-140. (10) Lockie, J. D., and D. A. Ratcliffe. J 964. Insecticides and Scottish golden eagles. Br. Birds 57(3):89-102. Pesticides Monitoring Journai (//) Lockic. J. D.. D. A. Ralcliffe. and R. Balharry. 1969. Breeding success and organo-chlorine residues in golden eagles in West Scotland. J. Appl. Ecol. 6(3):381-389. il2\ Mcilliiscn. J. 1963. The status of the bald eagle on the Chippewa National Forest. Flicker 35(4): 1 14-1 17. (/.I) 1964. Bald eaele nesting 1964. Loon 36(.3):1()4- 105. iNi 1965. Bald eagle status report. 1965 Chippewa National Forest. Loon'37(3):104-1()5. I //-I 1966. Bald eagle status report. 1966 Chippewa National Forest. Loon 38(4):134-136. U6l 1967. Bald eagle-osprey status report. 1967 Chippewa National Forest. Minnesota. Lmm 39(4): 121- 122. (17) I96S. Bald £ag!e-ospre\ status report. 1968 Loon 40(3):97-99. (18) 1969. Bald eagle-osprev status report. 1969. Loon 41(3):84-87. (19) Mdtliisoi, J., (jinl J. Sicwari. 1970. A band for an eagle. Loon 42(3):84-87. l20) Monk. H. E. 1961. Recommended methods of analysis of pesticide residues in food stulTs. Report by the Joint Mercury Residues Panel. Anal. 86:608-614. <2J) Miilhcin. B. M.. E. Ciomurlic. W. L. RcUhct. and A. .4. Bclislc. 1971. Semiquantitative determination of polychlorinated biphenyls in tissue samples by thin layer chromatography. J. Assoc. Off. Acric. Cheni. 54(3):548- 550. (22) Midhcrn. B. A/.. W. L. Rciclicl. L. ;V. Loikc. T. G. Lamont, A. Belisle, E. Cromanic. G. E. Baglcy, and R. M. Proiily. 1970. Organochlorine residues and autopsy data from bald eagles 1966-1968. Pestic. Monit. J. 4(31:141-144. (23) Poller. R. D., and S. N. Wienwyei: 1969. Dieldrin and DDT: effects on sparrow hawk eggshells and repri>- duction. Science 165(3889): 199-200. (24) Posnipal.\k\. S. 196S. Michigan bald eagle and osprey survey. Jack Pine Warbler 46(l):31-32. (25) Polls. G. R. I96S. Success of the shag on the Fame Islands. Northumberland, in relation to their content of dieldrin and [>.i>'-DDE. Nature 217(51351:1282-1284. (26) Ralcliffe. D. A. 1967. Decrease in eggshell weight in certain birds of prey. Nature 215(5097):208-210. (27) 1970. Changes attributable to pesticides in egg breakage frequency and eggshell thickness in some British'birds. J. Appl. Fcol. 7(0:67-115. i2S) Rciclnl. IV. L.. E. Cioniailic. T. G. Lamonl, B. M. Mallicin. and R. M. Pioiiiy. 1969. Pesticide residues in eagles. Pestic. Monit. J. 3(3):142-144. (29) Rciclicl. W. L.. T. G. Lamonl. E. Croinailic. and L. N. Locke. 1969. Residues in two bald eagles suspected of pesticide poisoning. Bull. Environ. Contam. Toxicol. 4(0:24-30. (30) Rohards. F. C. and J. G. King. 1967. Nesting and pro- ductivity of bald eagles: Southeast Alaska-1966. U.S. Dep. Inter. Bur. Sport Fish. Wild!.. Juneau. Alaska. 30 p. (31) Siiedecor. G. W.. and W. G. Cochran. 1967. Statistical Methods, si.xth edition. Iowa Stale Univ. Press, Ames. 593 p. (32) Spriiiil. .-t.. /r. aiul /-'. J. /./,i,'((.v. 1966. Audobon bald eagle studies-1960-1966. Proc. 62nd Annu. Conv. Nat. Audubon Soc. Sacramento, Calif. (33) Slickel. L. F.. /V. J. Cliiira. P. A. Slewari. C. M. Men:ie. R. M. Proiity, and W. L. Reichel. 1966. Bald eagle pesticide relations. Trans. 31st N. Am. Wildl. Natur. Resour. Conf.. p. 190-200. (34) Troycr. W. A., and R. J. Hcnsel. 1965. Nesting and pro- ductivity of bald eagles on the Kodiak National Wildlife Refuge. Alaska. Aul 82(41:636-638. (35) Wicmeyer, S. N., and R. D. Porter. 1970. DDE thins eggshells of captive American kestrels. Nature 227 (5259):737-738. Vol. 6, No. 1. June 1972 55 PESTICIDES IN WATER Organochlorine Pesticide Residues in Water, Sediment, Algae, and Fish, Hawaii— 1970-71 ' Arthur Bevenue, John W. Hylin, Yoshihiko Kawano, and Thomas W. Kelley ABSTRACT Rainwater, drinking water, and nonpolablc waters in Hawaii were sampled and found lo contain cidorinated insecticide residues in llic low parls-per-lrillion ransic. Dieldrin, p,p'- DDT, and lindane were lite pesticides most prevalent: penta- chlorophenol was present in samples from a sewui^'c fallout. The ratio of chlorinated pesticide residues in canal waters to residues in algae, sediment, and fish from the same canals was 1:4.000:9.000:32.000, respectively. According to pro- posed water quality standards, results of litis study indicated that pollution of Hawaii's water by organochlorine pesticides does not occur to any significant degree. Introduction The study reported here was conducted to determine the extent of organochlorine pesticide contamination of water, sediment, algae, and fish in the State of Hawaii, which consists of eight major islands; in order of de- scending size, they are Hawaii, Maui, Oahu, Kauai, Molokai, Lanai, Niihau, and Kahoolawe. These islands comprise an area of 6,425 square miles (/-.^). The Hawaiian Islands have an abundance of potable water due to moisture-laden trade winds which blow southerly from a string of high-pressure areas to the north of the Island chain. As the trade winds strike the mountains of the Islands, rise in altitude, and are cooled, the water vapor is converted to rain. The amount of rainfall is related to the heights of the mountains. For example, the islands of Niihau and Kauai are at ap- proximately equal latitudes; however. Niihau at an elevation of 1,281 feet has 26 inches of rainfall while Kauai at 5,170 feet has up to 482 inches. The unique formation of the Islands trap and store this rainwater; From the Deparlment of Aericuldiral BiochemMrv. Ilnivc^sirv ol Hawaii. Honolulu. Hawaii 96822. Published with the approval of the Director of the Hawaii Agricultural Experiment Station as Journal Series Paper No. 1378. 56 i.e., marine sediments and alluvial and talus sediments, deposited through the ages, have formed a relatively impermeable caprock around the Islands. At the highest elevations there may also be impermeable faults or dikes which impede the flow of rainwater — generally, however, rain falling at high elevations is rapidly absorbed into the porous volcanic basalt and percolates through the mountains to the water table where it accumulates to heights above sea level because of the caprock. Since fresh water is less dense than sea water, the fresh water in the water table literally floats on the sea water which has permeated the basalt. This relationship between the two waters was first discovered by Ghyben-Herzberg and is known as the Ghyben-Herzberg lense. Because the major part of the State's population resides on Oahu and also for convenience, this Island was sampled much more extensively than the other Islands of the State. Subterranean Oahu may he classed as a water bank. The Board of Water Supply of the City and CoLinty of Honolulu taps this zone of fresh water with skimming tunnels, shafts, and artesian wells {3). It has been conservatively estimated that Oahu's current sources of potable water are sufficient to meet anticipated needs until the year 2000; more optimistic reports predict that these sources will provide sufficient water to meet demands over the next 90 years. About 1.8 billion gallons of water, as rain, falls on Oahu each da\, 700 million gallons of which returns to the basin. At this time. Oahu uses about 4.^0 million gallons each day. Some areas of Oahu are only a few feet above sea level, and canals have been constructed to eliminate swamp- like areas and to receive surface runoff and storm-drain waters which eventually drain into the sea; much of this tirainage into the canals originates from cither in- dtistrial or residential areas. PfSTICIDLS MONIIORING JoUKNAI Hawaii produces about 75% of the world's pineapple crop and 25% of the United States' domestically grown sugar crop. Other agricultural activities include the commercial production of macadamia nuts, papaya, coflee, guava, passion fruit, avocados, bananas, taro. vegetable crops, beef cattle, dairy products, poultry, and swine. The sugar companies apply no insecticides to the land used for sugarcane production, but use primarily herbicides and rodenticides. The pineapple growers use insecticides, herbicides, and nematocides. Both use small amounts of plant growth regulators. Pasture lands are treated regularly with herbicides to control heavy brush foliage. In the other agricultural areas, the entire spectrum of pesticides is used. Termites are a constant problem in the islands, and commercial pest control operators use aldrin, dieldrin, chlordane, heptachlor, and pentachlorophenol in addition to the fumigants Vikane® (sulfuryl fluoride) and methyl bro- mide for their control. Numerous commercial formula- tions of insecticides, fungicides, and herbicides are sold locally for use in the average household. Waters obtained for this study included 10 samplings of rainwater, 45 drinking waters, and 46 nonpotable waters. Potable waters were sampled from 45 stations, including 28 wells, 4 shafts, 12 tunnels, and 3 springs on Oahu Island (Fig. 1). Nonpotable waters on Oahu were obtained from the Honolulu area on the leeward side and the Kaneohe-Kailua section on the windward side. Several swimming and surfing area were also sampled — Waialua Bay and Waimea Bay to the northwest and Kahana Bay in the northeastern area. In addition, two harbors, one industrial site, one sewage outfall, and two canals were sampled; sediment samples were also ob- tained from both canals (Fig. 2), and algae and fish specimens were obtained from one, the Ala Wai Canal. Nonpotable samples from the Island of Hawaii were from two populated areas (Hilo and Kona areas) and one unpopulated area of Punaluu (Black Sand Beach) (Fig. 3). Samplings from Kauai included five estuaries and one freshwater area (Fig. 3). The eight samples from Maui included water from a harbor, a pond, several streams, a golf trap at a resort, and a sump area which emptied excess drainage from a sugarcane field (Fig. 3). Materials and Methods WATER AND SEDIMENT New, 1-gal glass bottles with metal screw caps and teflon liners were used to collect all water samples. Prior to use, these bottles and separatory funnels used in the analytical procedure were rinsed thoroughly with a solution of concentrated sulfuric acid and sodium dichromate, followed by rinsing with water, redistilled acetone, and redistilled hexane. All other glassware used Vol. 6, No. 1, June 1972 in the analytical procedure was heat-treated for 16 hours at 200° C in an air-oven prior to use (4). One-gallon grab samples of potable and nonpotable waters were obtained from various areas of the State, including representative samples of the 50 outlet stations of the drinking water supply for the City and County of Honolulu on the Island of Oahu. Rain-water samples were collected from different areas on Oahu during the periv i from December 1970 through February 1971. FIGURE 1. — Sampling sites for drinking waters, Oahu, Hawaii— 1970-71 FIGURE 2. — Sampling sites for nonpotable waters, Oahu, Hawaii— 1970-71 57 FIGURE 3. — Sampling sites for noiipolable waters from the Islands of Hawaii, Kauai, and Maui — 1970-71 -^>.. ►" ^'^7/fyn^ TABLE 1. — pH and chloride ion concentration of water samples, Hawaii — 1970-71 Water SAMPtc pH (RANGi;) Chloride Ion Mg/Liter (RANGE) Rainwater 6.6 - 6.8 4-7 Potable Water Wells and Springs 7.U-S.4 LS - 200-(66) Shafts and Tunnels '6.8-9.4 1.1- 78-(28l Nonpotable Waters- Streams 7.2-7.8 .150- 17.150 Ponds 7,3 1.400- 5.680 Bays 7.4-8.1 2,450-19.525 Canals 7.1 -7.8 10.300 - 14,800 Lakes 7.9-8.1 12,070- 14,630 Harbors 6.7 -8.1 13,000- 19,460 Basin 7.9 18,970 Lagoon 8.2 19.180 'One sample of a total of 45 samples had a pH of 9.4 (sample obtained from a lime-treated station). - (Average) value. •Average value for sea water is usually given as 18,980 mg liter. A portion of each water sample was used to determine pH and chloride ion concentration (Table I). Total chloride was determined by titration of the acidified water with O.In or O.OIn silver nitrate solution and use of a Fisher Ag-AgCI, Model No. ^(^ titrimeter. Sufficient water was removed from each sample to leave 3.000 ml of water in the bottle. Redistilled hexane ( 100 ml) was added to each sample, and the bottle was rotated at high speed for I hour on a roller-type jar mill. After mixing, each sample was allowed to stand until the hexane and water phases separated. Fifty milliliters of the hexane layer was removed with a vol- umetric pipette, transferred to a 1 25-ml round-bottom flask, and concentrated to a small \olume using a rotar\ 58 flash evaporator. The concentrate was transferred to a calibrated centrifuge tube and the final volume adjusted to 0.5 ml with the aid of a stream of nitrogen. Suitable aliquots. usually 10 ;ul, were applied to the gas chroma- tograph. The sewage water sample was collected from an outfall discharge over a 24-hour day beginning at 7:00 a.m. December 14, 1970, and ending at 6:00 a.m. December 15. 1970. The sample was obtained at the sluice gate which was the last exposed point in the stream before flowing through the outfall sewer pipe. Samples were obtained hourly and then composited in proportion to hourly flow rates. The extraction procedure for the sewage water was modified in order to isolate any pentachlorophenol (PCP) in the water. Prior to the addition of hexane and the mixing step, the sample was adjusted to pH 1.3 with sodium hydroxide solution. The alkaline water was extracted three times with lOO-ml portions of retlistilled hexane in a separatory funnel: the hexane extracts were discarded. The sample was adjusted to pH 2 with concentrated sulfuric acid. 100 ml of redistilled hexane was added, the sample was mixed for 1 hour, and 50 ml of the hexane phase was con- centrated as previously described. The residtic was concentrated to near dryness in a centrifuge tube, and excess diazomethane solution was added to convert any PCP in the sample to its ether derivative. Nitrogen was passed over the sample to remove excess diazomethane. the residue was made to a definite volume with hexane. and suitable aliquots were applied to the gas chromatograph. A second sewage water sample, used for the analysis of chlorinated pesticides other than PCP. was cleaned up prior to analysis using the combined Florisil and silicic acid procedure of Armour and Burke (5). As noted by Armour and Burke, the Aroclors and aldrin are isolated in the first fraction of the silicic acid cleanup: the second fraction contains any remaining chlorinated pesticides except for dieldrin. which would be present in the I5'"'f Florisil fraction. In the present survey, all data were compared with 10 available types of Aroclors. If an\ pol\ chlorinated biphenyls were present in the examined samples, either they did not relate to the standard Aroclors used for comparison or were not de- tected: the latter was more often the case. Sediment samples were obtained from several canals on the Island of Oahu with a dredge sampler or a 1-gal paint can. The solids content of the sediments was de- termined by air-drying a portion of each sample for 24 hours, followed by drying in an air-oven for 16 hours at 110 C. The wet sediment samples (50-100 g) were mixed thoroughly with equal weights of anhydrous sodium sulfate which had been previously heated 16 hours at 400 C: 100 ml of redistilled hexane was added Pesticides Monitoring Journal to each sample, the mixtures were shaken on a wrist- action shaker for 1 hour, and then allowed to stand until the suspended material settled. A measured amount of the he.xane solution was removed and subjected to the Mills" Florisil cleanup procedure (6). The cleaned up extracts were concentrated, and aliquots of the con- centrate were applied to the gas chromatograph. CAS CHROMATOGRAPHY The following two gas chromatographs were used for analyzing the water and sediment samples: The first was a Varian-Aerograph Model 204. electron capture concentric tritium detector with '«" x 6' borosilicate glass column, with column temperature at 190 C. in- jector temperature at iTO" C. detector temperature at 200 C. carrier gas — nitrogen, and flow rate — 25 ml min. The second was an F&M Model 810. electron capture parallel plate tritium detector with a '4" x 4' borosilicate glass column, with column temperature at 190"C, injector and detector temperatures at 200" C. carrier gas — argon-methane (90:10). and flow rate — 75 mUmin. Leeds and Northrup Speedomax H re- corders. I m\ full scale with a chart speed of 0.5" niin were used. Four types of column packing v\ere used, nameh : (1) 3'~( SE-30 on Chromosorb W. AW. DMCS. 80/100 mesh; (2) Tr^'r QF-I and 2""^ Dr-200 on Chromosorb W. AW, DMCS. 80 100 mesh; (3) 4^r SE-30 and 6^f QF-l on Chromosorb W. HP. SO '100 mesh; and (4) \.5Q^r OV-17 and 1.95^; QF-l on Supclcoport. 100/200 mesh. The retention times of the pesticides on these columns, relative to aldrin. are given in Table 2. The limits of detectability of the pesticides ranged from about 0.05 ppt (lindane the most sensitive) to 0.5 ppt ( DDT the least sensitive): dieldrin was detected at about 0.2 ppt. This is an approximate range only, because detection limits \aried with the degree of purity of the water sample or the degree of success in cleaning up nonpotable water, sediment, and biota samples. The reported residue data are the amounts found by analysis: no attempt was made to correct the data based on re- cover} values obtained from fortified samples. Repeated attempts to obtain consistent and good recoveries of pesticides from samples spiked at the 1 and 2 ppt levels produced poor resLilts. Efforts on confirmatory analyses by thin layer chromatography (TLC) were confined to samples containing at least 10 ppt of a particular pesti- cide. Confirmation by the "p" value procedure was difli- cult. if not impossible, in the residue range studied. Neither TLC nor "p" \alues were practical when working with residues in the low ppt range. Confirma- tion procedures were therefore limited to at least two two different types of gas chromatograph columns, a practice commonly used by many laboratories especially in preliminary survey work and where the amount of a sample nia\ be limited. AIGAE AND FISH The residue data on the algae and fish specimens were provided by Cynthia Schultz of the Department of Oceanography of the University of Hawaii and were obtained from the Ala Wai Canal during the same time period of this investigation. The cleanup procedure for these specimens was a modification of the procedure of Kadoum (7). whereby the extracts, previously par- titioned with acetonitrile-hexane. were eluted through a micro-column of silica gel (Woehlm. Activity Grade No. 1. activated with 3'~f water) with a mixture of benzene- hexane (70:30). Analytical data were obtained with a MicroTek Model 220 gas chromatograph utilizing an electron capture detector. TABLE 2. — Rclcntion times of pesticides in vliroinatosriipliic cohiiiiiis relative to retention of lime of altlriii, Hawaii- 1970-71 Chromosorb W AW. DMCS 80/100 Mesh 3% QF-l 2% DC-200 Chromosorb W AW. DMCS 80/100 Mesh 4% SE-30 6% QF-l Chromosorb W HP 80/100 Mesh 1.50% OV-17 1.95% QF-l SUPELCOPORT 100/120 Mesh Lindane Heptachlor Aldrin Heptachlor epoxide p,p'-DDE Dieldrin p.p'-DDD p.p'-DDT Pentachlorophenol ethyl ether Pentachlorophenol methyl ether 0.43 0.77 1. 00 l.2f, 1.97 0.57 0.81 1.00 1.47 2.7') .1.36 0.54 0.81 1.00 1.43 1.95 3.44 0.57 0.64 0.81 1.00 1.62 2.43 2.60 3.89 4.69 0.55 0.46 Vol. 6, No. 1. June 1972 59 Results am' Discussion The residue data on rainwater samples from Oahu are given in Table 3. Hawaiian rainwater contained p.p'- DDT. dieldrin. and lindane in the low ppt range. The only comparative data that could be found in the literature were from 1965 (8.9): the residues in the present study were much lower than the levels noted previously in the cities of Cincinnati, Coshocton, and Ripley. Ohio. {8) but similar to the amounts observed in Central England (9). It is possible that with in- creased restricted usage of chlorinated pesticides in the United States in the past 2 years, new measurements of rainwater in Ohio might show considerably lower quantities of these pesticides than reported in the earlier study. TABLE 3. — Organochloiiiic pesticide residues in 10 rainwalci samples from Oiiliti, Hawaii, and in otiier studies TABLE 4, — Orf;aiiocldorine pesticide residues in 45 potable water samples from Oahu, Hawaii — February-May 1971 Hawaii 1970-71 Reported in Ohio 1965 (8) Reported in Central England 1965 (9) Compound Residues in PPT Range Average Range Average Range Average P,P'-DDT Dieldrin Lindane 1-13 3 1-27 5 1-19 5 70-340 187 6-50 25 2.4 3 3-16 9 12-52 29 ^ Delected, but no values reported. Residues in the drinking water samples were chlordane. DDT, dieldrin, and lindane and were in the low ppt range and about one-fifth or less the amounts noted in rainwater (Table 4). DDT was the predominant pesti- cide, appearing in 87% of the samples. Although extreme precautions were taken with the sampling procedures, pesticide contamination could have been present at the e.xternal source of sampling, because some of the sta- tions are surrounded by sugarcane and pineapple grow- ing areas or subdivision development projects. The residues for drinking water were insignificant com- pared to the allowable amounts (Table 4) proposed by the Federal Committee to the Secretary of the Interior on Water Quality Criteria (10). The Committee has defined "permissible criteria" as "those characteristics and concentrations of substances in raw surface waters which will allow the production of a safe, clear, potable, aesthetically pleasing, and acceptable public water sup- ply which meets the limits of drinking water standards after treatment." This Committee has also stated that it would be desirable to have no pesticides in drinking water supplies. Ettinger and Mount (//) have stated that the use of waters for fish propagation must be considered in any set of acceptable State water quality criteria and that it has a bearing on drinking water standards. They have proposed the maximum stream allowance for certain pesticides (Table 4) which are one-tenth or less the 60 Maxi- Maximum Percent mum Per- Reasonable Compound Range Average OF missible Stream Sampi.es Criteria (10) Allow- ances (11) Residues in PPT Chlord.nnc 0.5-5,0 1.0 9 3.000 250 P.p-UDT 0.6-2.2 1.0 87 42,000 500 Dieldrin 0.24). 7 0.3 15 17.000 250 Lind.nne 0.06-0.4 0.2 4 56.000 5,000 amounts permissible by the Public Health Service. These allowances are greater than the amounts found in the local drinking water supply in Oahu. It is of interest to note that in 1962 the standards were revised to specify that the carbon chloroform extract (which is a meas- urement of synthetic chemicals in the environment including chlorinated insecticides) should not exceed 200 ppb (12.13). As late as 1967. an effort was made to include specific pesticides under these standards; however, it was pointed out that this could not be done in a legal sense, because pesticides were not classed in the "communicable disease category" (14). Organochlorine pesticide residues in nonpotable waters were at the low ppt level, with p.p'-DDT representing the highest level (Table 5). In all areas sampled, dieldrin was consistently present and, in some instances, at a higher level than the other observed pesticides, A crude attempt was made to classify the sampled areas into rural and urban sections of the State. The data show that the only major difference in residues in the waters was for dieldrin. which averaged about seven times higher in the urban areas (Table 6). A detailed study was made of two canals and a stream, which were located primarily in the urban areas of Oahu, and a sewage outfall which received all sewage from the Honolulu area. One of the canals (Kapalama) and the stream passed through industrial areas. The water samples from the Kalihi stream were obtained near a wood treatment plant where, on the day of sampling, a heavy rain had drenched a large pile of pentachlorophenol-treated lumber. Drainage ditches from this lumber yard migrated to the sampled stream. The sample obtained from the ditch area nearest the lumber yard contained 1,143 ppt pentachlorophenol, whereas the sample obtained some distance from the yard and more a part of the stream contained 168 ppt pentachlorophenol, indicating a dispersion or diluent effect of the larger water area. Other pesticides. DDD, DDT, and dieldrin were also detected in the low ppt range, with dieldrin predominating in about 3-fold the quantities of DDT (Table 7). The sample from the sewage outfall contained 2.600 ppt pentachlorophenol. 198 ppt dieldrin, 107 ppt DDT, and 41 ppt lindane. Pi:sTiciDES Monitoring Journai TABLE 5.- -Average amount and range of organochlorine pesticide residues waters, Hawaii — August 1970-February 1971 in nonpotable No. OF Samples p,p'-DDE 1 p,p'-DDD 1 p,p'-DDT 1 DffiLDRiN Lindane Chlordane ' Residues in PPT Hawaii 4 - - 3.5 (3.2-3.8) 5.5 (1.9-8.3) — Kauai 6 — — 4.4 (3.4-7.1) 1.1 (0.4-2.1) 8 0.7 — 4.9 1.6 0.9 (0.5-0.8) (2.6-6.8) (0.5-5.1) (0.2-3.4) Oahu 4 0.5 O.I 1.4 1.5 0.7 (0.2-0.8) (0.1) (1.0-1.7) (1.2-1.7) (0.4-1.1) 5 0.3 7.8 14.0 2.0 0.1 0.1-0.5) (0.2-18.0) (0.2-64.0) (0.5-4.0) (0.1) 6 0.3 3.6 9.0 1.0 0.9 (0.1-0.6) (0.1-10.0) (0.4-41.0) (0.1-3.0) (0.3-2.0) Basin 1 — — 0.5 14.0 — Harbors 2 - — 0.5 (0.5) 3.5 (O.a-7.0) ~ Lagoon 1 _ — 0.5 11.0 — 9 0.1 2.4 4.0 13.0 0.9 6.9 (0.0-1.0) (1.3-3.9) (1.0-7.1) (0.4-18.6) (0.3-2.0) NOTE: — = ' Chlordane r not detected; figures in parenthesis = range. analysis was not included in the early part of the study. TABLE 6. — Pesticide residues in waters from 13 rural and 24 urban areas in Hawaii — 1970-71 Rural Urban Range Average Range Average Compound Residues IN PPT p.p'-DDE 0.1-0.5 0.3 0.2-0.8 0.5 p,p'-DDD O.l-IO.O 3.1 0.8-18.0 3.4 p.p'-DDT 0.2-41.0 6.1 0.8-64.0 6.3 Dieldrin 0.1-4.0 1.2 0.3-19.0 8.4 Lindane 0.1-1. 1 0.5 0.5-3.4 1.1 Total chlorinated pesticides 11.2 19.7 Extensive samplings of the waters of the two canals were made; these pesticide residue values are shown in Table 7. Again, the residues were in the low ppt range, with dieldrin predominating in quantity; however, the residues in the algae, fish, and sediments obtained from the same canals, were larger. Converting the total residues in the algae, sediment, and fish to parts per million places the values in the 0.1-1.0 ppm range, which is considerably lower than the 5.0 ppm DDT guideline value allowed in fish by Federal regulations. Converting dieldrin residue values found in the fish to parts per million gives values approximating the maxi- mum permissible amounts. The amounts of chlordane and dieldrin found in the waters and the sediments and the pentachlorophenol residues observed in the sewage suggests that these pesticides originated primarily in the urban areas where many households and honie builders use these compounds for the control of termites. Summarizing the data in Table 7, the total amount of chlorinated insecticide residues in the waters of the two canals was the same at about 0.03 ppb; the residues in sediments (dry-weight basis) were 600 ppb. The total Vol. 6, No. 1, June 1972 residues in the biota from the Ala Wai Canal on a fresh- weight basis were algae 130 ppb, small fish (guppies and mollies) 800 ppb, carnivore fish and detrital feeder fish each about 1.000 ppb. All three types of fish had similar amounts of total residue; however, the carnivore species contained a predominant amount of DDD, whereas the guppies, mollies, and detrital feeders con- tained predominant amounts of dieldrin. The ratio of residues in the canal waters to those in the biota from the canals, assigning the value of 1 to water, were: Water 1 Algae 4,300 Sediment (wet-weight basis) 9,000 Small fish 27,000 Carnivore fish 33,000 Detrital feeder fish 36,000 As noted by Gunther et al. (15) and others (16.17), published data on the solubility of pesticides in water are inconsistent and, at times, actually misleading and meaningless (Table 8). In waters containing salts, or- ganic substances, and colloidal material, the solubility of a given pesticide may vary greatly, no doubt due to absorption or binding of the pesticide to suspended soil particles, plankton, and other types of matter in the water. Pesticide residues found in natural water analyzed as received may vary considerably from residues found in the same water after it has been filtered through a glass fiber membrane. As stated by Walker (18), water con- taining suspended material appears to carry residues while water without this material may not contain measurable amounts of pesticides. 61 TABLE 7. — Pesticide data on nonpotable waters from selected areas, Oahu, Hawaii- August 1970-February 1971 Date Sampled p.p'-DDE p.p'-DDD p,p'-DDT DiELDRIN Lindane Chlordane PCP» Residues in PPT ALA WAI CANAL Water Station 1 Station 2 Station 3 8-12-70 2-18-71 8-12-70 2-26-71 8-12-70 2-18-71 1.0 2.0 1.3 3.0 1.3 3.0 2.6 1.0 1.6 3.0 1.6 2.0 1.6 5.0 9.6 17.0 18.6 16.0 0.4 1.0 2.0 1.3 2.0 0.3 (=) 9.4 ( = ) 13.0 r-) 4.8 Average 0.2 2.2 1.8 11.1 1.1 9.1 Sediment (drv-weight basis) Station 1 Station 2 Station 3 2-18-71 2-18-71 2-18-71 100,000 10,000 10,000 220,000 100,000 40,000 150,000 30,000 40,000 100,000 30,000 100 - 720,000 290,000 125,000 Average 40,000 120,000 73,333 43,366 - 378,000 Biota (fresti-weiglit basis) Algae Fish Guppy, IVIolly Carnivore (Elop.\ hawaiensis) ■"■ Planltton and detrital feeder (Chanos chanos) •'• June 197U through Feb. 1971 10,000 80,000 182.000 298,000 30,000 210.000 581,000 149,000 45,000 170.000 101,000 159,000 45,000 340,000 141,000 486,000 - - KAPALAMA CANAL Water Station I 2-9-71 2-16-71 3-1-71 Average . 3.9 3.9 7.1 4.7 6.4 16.4 10.2 18.0 1.0 0.5 (-1 3.0 4.4 2.6 6.1 •14.9 0.5 3.7 Sediment (dry-wciglit basisi Station 2 Station 3 2-19-71 2-19-71 20,000 90,000 50,000 170.000 370,000 140,000 z 255,000 125,000 Average 10,000 45,000 110,000 255,000 - 190,000 KALIHI STREAM Water (Industrial area) Station 1 Station 2 12-15-70 12-15-70 = 1.6 3.7 2.8 12.7 7.1 = ( = ) (=) 1.143 168 Average - 0.8 3.3 9.9 - 655 SAND ISLAND OUTFALL Sewage (24-hr. composite discharge) 12-14-70 — — 107 198 4! (=) 2,600 NOTE: — = not detected. 1 PCP = pentachlorophenol; analysis performed only on samples ind = Chlordane analysis was not included in the early part of the study. ^ Muscle tissue. Water standards or "water quality criteria" are defined differently by different specialists; in fact, at tfiis time, it is impossible to give an all-inclusive definition. For example, the publication of the Public Health Service on drinking water standards U3) states that "The Drinking Water Standards are regarded as a standard of quality which is generally attainable by good water quality control practices. Poor practice is an inherent health hazard. It has been the policy of the Committee to set limits which are not so low as to be impracticable nor so high as to encourage pollution of water. 62 "No attempt has been made to prescribe specific limits for every to.xic or undesirable contaminant which might enter a public water supply. While the Committee is fully cognizant of the need for continued attention to chemical contamination of water, the standards are limited to recognized need. Standards for innumerable substances would require an impossible burden of an- alytical examination." Another ill-defined area is toxicity data on fish. The publication "Water Quality Criteria" of the State of Pesticides Monitoring Journal California (19) states that "...the results by several investigators of the same pollutant may not compare closely. This wide discrepancy arises from variations in the species of fish or other organism used, its prior handling, the temperature, the season, the dissolved oj^ygen content, synergistic and antagonistic substances, the hardness and other mineral content of the water, and the time of exposure, . . . sometimes vague terms such as toxic concentration of lethal dose are used without further definition. . . . The effects of long-term exposures of fish populations to very low sublethal con- centrations are not clearly understood."" It has been noted (23) that water analyses have limited meaning when evaluating the effects of a pesticide on animal populations. Johnson (20) concluded that water data alone on pesticides are an inadequate criterion for determining the relative danger or safety to the fish population in a given area; but it has also been stated that the very low concentrations observed in water may be important because natural mechanisms can concen- trate residues many thousands of times. This is evident in the data obtained from the canal samples (Table 7). Results given below from a survey of the literature indicate no consistency in the relation between residues found in various parts of a gi\cn ecosxstem: Ruiio DJ Resiiliics in I arioiis Paris of Evosyslcm Water t.) fish- 1 :S. 501) Water to algae- 1 : 1. 000 Water to fish- 1:20,000 Water, sediment, and fish-1: 1,500:20,000 DDT. DDD, Sediment to fish-1 : 100 DDF DDT. DDD Water, sedimenl. and DDE algae, fish- 1 :20:40:8()0 accounted for the greatest percentage of pesticide residues Sliulx Conipoiiiu! Macek (2/)' DDT Holden ai) Dieldrin Wdodwell ('/ III. [2i]' DDT Johnson [20) DDE Hickey ci al. (24)' Hannon cl al. {25) ' source of pesticide contamination in fish (21.26). and, as stated by Eichelberger and Lichtenberg (27). there is no predictable safe level for pesticides in waters where food-chain buildup can occur. TABLE 8. — Reported water solubilities of some organo- chlorinc pesticides at room temperature, 25° C GUNTHER ROBECK Bevenue and Compound ct al. (15) el al. (16) Beckman (17) Residues in PPB Chlordane ' Insoluble P.p-DDD ' Insoluble ,..;.-DDT ' Insoluble 3.4 = 6 and 25 ■■■■ 16 and 40 Dicldrui - 150 and 195 250 ■ 140 and 180 Lindane - 600 and 6,800 7,300 ■■ 500 and 6.00(1 Pentachlorophcnol ' 14.000 lo 19.000 Sodium pentachloro- plienate 79,000 ( pH 5 ) 4.000,000 (pH 8) "Insoluble" = solubility up to at)OUt 1% or 10,000 ppm. Particle size 0.05 and 5.0 ii. Particle size 0.04 and 5.0 ji. At temperatures 20° to 30° C. Several investigators have suggested that bottom muds and sediments should be given more attention in any pesticide study of water (20.24.26) and that these data should be combined with other available ecological information to give a good pesticide-pollution index. In conclusion, it is emphasized that the present report is based on a preliminary survey of randomly selected samples. Future studies will include slick and strata sampling of the shoreline waters, seasonal sampling, an in-depth study of the sewage outfall, and, perhaps, con- centrated sampling of areas in the State suspected of potentially higher pesticide residues. However, based on ihese preliminary data, on the present usage pattern of the pesticides studied, and comparison with the proposed water quality standards, pollution of Hawaii's waters by organochlorinc pesticides does not occur to a significant degree. See Appendix for che paper. npounds discussed in this Lab experiment — exposed tish to 3 i^pi for 120 da Reports data on an East Coast estuar>. Reports data on an ecosystem of Lake Mictii^an Residue data on a lake in South Dakot.i. There is a general consensus that as man\ factors as possible should be examined in a given ecosystem. Pesticides are leached from soils by water, moved by erosion, and absorbed by mud-scavenging organisms (23): they are soluble in fats and oils; they tend to be concentrated in organic matter, algae, bacterial films, and slimes: and they can be suspended in colloidal forms (22). Most probably the food chain is the major Vol. 6, No. I, Junh 1972 MIHRATURK C ITED ih Jones. Thanuis C. (Editor). 1961. The Hawaii Book. J. G. Ferguson Publishing Co., Chicago, p. 14. l2) Department of Planning and Economic Development. Honolulu. Hawaii. 1971. The State of Hawaii Data Book. p. 43. (.1* .Stearns. Harold T. 1966. Geology of the State of Hawaii. Pacific Books. Palo Alto, Calif, p. 233-245. (4) Bevenue. A.. T. W. Kelley. and J. W. Hyiin. 1971. Problems in water analysis for pesticide residues. J. Chromatogr. 54:71-76. (5) Armour, J. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Assoc. Off. Anal. Chem. 53:761-768. 63 (6) Mills. P. A.. J. H. Unley. and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Anal. Chem. 46:186-191. (7) Kadoiim. A. M. 1967. A rapid method of sample cleanup for gas chromatographic analysis of insecticidal residues in plant, animal, soil, and surface and ground water extracts. Bull. Environ. Contam. Toxicol. 4:264-273. {8) Cohen. J. M.. and C. Pinkcilon. 1966. Widespread translocation of pesticides by air transport and rainout. Preprint Jan. 1966, DHEW, R. A. Taft Sanitary En- gineering Center, Cincinnati, Ohio 45226. (9) Wheallcy. G. A., and J. A. Hardnuin. 1965. Indications of the presence of organochlorine insecticides in rain- water in Central England. Nature 207:486-487. (10) Federal Water Polhilion Control Adminislralion. Wasli- ington, D. C. 1968. Report of the Committee on Water Quality Criteria, p. 20. (J J) Ellinger. M. B.. and D. I. Muunl. 1967. A wild fish should be safe to eat. Environ. Sci. Technol. 1:203-205. 1)2) Ellinger. M. B. I960. Proposed toxicity screening pro- cedure for use in protecting drinking-water quality. J. Am. Water Works Assoc. 52:689-694. 1 13) U. S. Deparlmeni of Heallli. Ediicalion. and Welfare, Public Health .Service. Reprinted 1969. (Revi.'ied 1962) Public Health Service Drinking Water Standards. 61 p (14) Anonymou.':. 1970. Drinking water: is it drinkable? Environ. Sci. Technol. 4:811-813. (15) Gunlher. F. A., W. E. Wesllake. and P. S. Jaglan. 1968 Reported solubilities of 738 pesticide chemicals in water Residue Rev. 20:1-148. (16) Robeck, G. G., K. A. Dostal, J. M. Cohen, and J. F Kreissl. 1965. Effectiveness of water treatment proc esses in pesticide removal. J. Am. Water Works Assoc 57:181-199. (J7) Bevenue. A., and H. Beckman. 1967. Pentachlorophenol: a discussion of its properties and its occurrence as a residue in human and animal tissues. Residue Rev. 19: 83-134. (18) Walker. K. C. 1970. The effects of horticultural prac- tices on man and his environment. Hortic. Sci. 5:239- 242. (19) The Resources Agency of California. Slate Water Qual- ity Control Board. Sacramento, Calif. 1963. Water Quality Criteria, 2d ed.. Publication No. 3-A. p. 113. l20) Johnson, D. W. 1968. Pesticides and fishes — a review of selected literature. Trans. Am. Fish. Soc. 97:398-424. (21) Macek. K. J., and S. Korn. 1970. Significance of the food chain in DDT accumulation by fish. J. Fish. Res. Board Can. 27:1496-1498. (22) Holden. A. V. 1965. Contamination of fresh water by persistent insecticides and their effects on fish. Ann. Appl. Biol. 55:332-335. (23) Woodwell. G. M., C. F. Wursler. Jr., and P. A. Issacson. 1967. DDT residues in an east coast estuary: a case of biological concentration of a persistent insecticide. Science 156:821-823. (24) Hickey, J. J., J. A. Keith, and F. B. Coon. 1966. An exploration of pesticides in a Lake Michigan ecosystem. J. Appl. Ecol. 3(Suppl):149-154. (25} Hannon. M. R., Y. A. Greiclui.s, R. L. Applegate, and A. C. Fox. 1970. Ecological distribution of pesticides in Lake Poinsett, South Dakota. Trans. Am. Fish. Soc. 99:496-500. (26) Huang, Jii-Chang. 1971. Organic pesticides in the aquatic environment. Water Sewage Works 1 18:139-144. (27) Eichelberger, J. W., and J. J. Lichtenberg. 1971. Per- sistence of pesticides in river water. Environ. Sci. Technol. 5:541-544. Pesticides Monitoring Journal PESTICIDES IN SOIL DDT Residues in Forest Floor and Soil After Aerial Spraying. Oregon — 1965-68 ' R, F. Tarrant, D. G. Moore. W. B. Bollen. and B, R. Leper ABSTRAC1 One month after aerial application oj DDT (12 ozacre) to in eastern Oregon forest, 3 oz/acrc of DDT residues (DDT. ts isomers and metabolites — ODD, DDE, p.p'-DDT, and o.p'-DDT) were detected in the forest fioor: 3 years later, 'he DDT content liad decreased by more than 50%. and had ■lot leached into the surface mineral soil. 4t the time of spray iiif;. water from two streams drainini; 'he sprayed area had a total DDT content oj about 0.3 pph. This low concentration decreased rapidly to levels below limits of analytical detection. No effect of the sprayiiii; was noted on .soil microbial populations, nitrification rale, or amount of nitrate nitrogen in the soil. Of the 12 o: of DDT applied per acre, about 26% reached the around surface initially: and over 36 months, about 6% more was brought to the ground in lilterfall. Thus, approx- imately one-third of the sprayed chemical reached the forest floor. The need for more efficient aerial methods of chemical application is evident. liUrodiiciion Only a few studies have been concerned with residues of DDT. its isomers and metabolites, in the forest en- vironment. Woodwell (4/) determined DDT residues in a forest in New Brunswick. Canada, which had been sprayed between 1952 and 1958 with a total of 4 lb/acre of DDT. He concluded that the maximum residue per- sistence time in forest soil would be 10 years and that o.A''-DDT was leached into the subsoil. Woodwell and Martin (42) reported that DDT residues in heavily sprayed forest soils in Maine and New Brunswick in- creased over a period of .^ years after final spraying. These authors hypothesized that DDT residues persist in the forest canopy and are carried to the soil by rain and litterfall. ' From the Pacific Norihwesi Forest and Range Experiment Statu U. S. Department of Asirictilture. Forest Service. Corvallis, On 97330. Vol. 6, No. I. Juni 1972 Yule (43) stated, however, that Woodwell's hypothesis of differential weathering and preferential retention of ().//-DDT by New Brunswick forest soils is untenable. He concluded from a study in the same locality that about I69f of the DDT originally applied still remained in surface soils after almost 20 years, but mainly in the form of the most toxic isomer. p.p'-DDT. He further demonstrated that the acidic, highly organic, forest surface soils held these DDT residues unavailable in toxic amounts to soil insects. DDT residues were also measured in a northern Penn- sylvania forest soil, 380 days after aerial spraying at a rate of 0.5 lb/acre (9). The only environmental change reported was a significant accumulation of DDT in the forest floor and surface soil. One year after spraying, no measurable increase in DDT residues was noted in fish, crayfish, or stream sediments. Beiyea {4) studied DDT residues in soils and a related food chain in northern Maine forests. He concluded that DDT would disappear from these soils in 10-12 years. In western Washington. DDT was applied to the surface of a gravelly soil beneath a stand of Douglas-fir [Pseudo- tsui;(i inenziesii (Mirb. ) Franco] at 0.5 and 5.0 lb/acre (29). Regardless of application rate, less than 1% of the DDT applied leached through the surface soil. In 1965. an opportunity to further study DDT residues in forests resulted from a spray project conducted by the U. S. Forest Service between June 10 and July 1 to control a serious outbreak of the Douglas-fir tussock moth (Heinerocainpa pseudoisufiata McD.) in eastern Oregon. Helicopters were used to spray 66,000 acres of forest with an insecticide formulation of 0.75 lb of technical grade DDT dissolved in 0.94 qt of hydro- carbon solvent and sufficient No. 2 fuel oil to make 1 gal of solution at 60° F; the application rate was 12 oz/acre. 65 A number of public agencies have already conducted surveillance and monitoring activities to determine residues in fish and wildlife, cattle, and forage, and to ascertain public health effects from the spray project (10.35). The present study reports observations of the persistence of the applied DDT in the forest floor and soil and some related effects for the first 3 years after the spray project. The area studied was along a 1-mile transect in the Malheur National Forest of eastern Oregon. Elevation of the area is 5,700 feet. The subhumid continental cli- mate includes dry, warm summers OlOO" F maximum temperature) and cold winters (—20" F minimum temperature). The daily range of temperatures in summer is often 40 to 50 degrees and the monthly range may exceed 60 degrees. Annual precipitation averages about 20 inches, one-third to one-half of which is snow. Most moisture available to plants is stored in the soil at the beginning of the growing season, and by midsummer soils become very dry: summer flow in small streams is intermittent. The soil of the study area, representative of perhaps several million acres of eastern Oregon forest land, is tentatively identified as a member of the Klicker series. This is a well-drained, moderately fine-textured, forested soil developed in residuum from basalt bedrock; small fragments of the basaltic parent material occur through- out the solum, and rock outcrops are common through- out the area. The A horizon, which may contain volcanic ash, ranges in texture from sill loam to silty clay loam, with the percent clay increasing gradually with soil depth. The soils are slightly acidic throughout the solum which ranges in depth from 15 to 35 inches. Permeability is moderate, and surface runoff is medium. Major tree species in the study area which partially determine the amount of litter and duff on the forest floor are ponderosa pine [Pinus pondcrosci (Laws).], White fir [Ahies concolor (Cord, c^ Glend..) lJndl.|. and Douglas-fir \Pseudatsiii;a nienziesii ( Mirb. ) Franco]- Saiiif>lini> Frocediiyes Five 1/10-acre plots were established along the transect nearest to equidistant points where maximum uniformity of stand composition and density could be found. Within each of the five plots, four sampling points were ran- domly selected. At each point, the forest floor over a 4-sq-ft area was carefully removed, and 1-qt samples of soil were collected at each of two depths, 0 to ?> inches and 3 to 6 inches, in step-like trenches. Extreme care was taken to avoid contaminating the lower sample with material from above, and all tools were cleaned frequently with acetone. Samples were placed in new 1-qi paper freezer containers, stored during the dav ui portable cooler chests, and frozen the same day they were collected. Samples of forest floor and soil were collected prior to the spray project, I month after the spraying, and at 1-year intervals. Litterfall, throughfall precipitation, and water samples from streams were col- lected every 6 months. Eight trays, each with a surface area of 10.9 sq ft, were randomly placed throughout each sample plot to collect litterfall, and four I -gal containers fitted with funnels having openings approximately I sq ft in size were randomly located in each sample plot to collect pre cipitation. Water samples from the east and west forks of Rattlesnake Creek within 50 feet of their confluence were taken in I -gal containers, submerged just deep enough to prevent undue disturbance of bottom sedi- ments. A luilyiical Procedures Soil samples were air-dried, ground, passed through a lO-mesh sieve, mixed, and subsampled. For samples intended for microbial analysis, the sieve was cleaned with 30"?^ ethanol and flamed between collections of each sample. Frozen litter and forest floor samples were chopped with dry ice. mixed, and subsampled. All sam- ples, including water, were stored at 0° F until extracted. EXTRACTION Soils: A 1 00-g subsample was extracted with 41:59 hexane: acetone (azeotropic) in a Soxhlet extractor for 16 hours (27). Litter and forest floor; A 25-g subsample was extracted with acetone in a Soxhlet extractor for 16 hours. Water: Volumes up to 4,000 ml were extracted with hexane in a continLious-cycling liquid-liquid extractoi for 1 6 hours. CLEANUP The soil and litter extracts were transferred to separa- tor}' funnels. Water was added to form a 2:1 v\ater- acetone sokition. The pesticides were partitioned intc hexane by shaking v\ith three lOO-ml aliquots of hex- ane (/7). The hexane extracts of soil, litter, and water were dried v\ith anhydrous sodium sulfate, evaporated to a sma vokime (5- to 10-ml), and transferred to a 15-g Florisil column (-10). The pesticides were eluted from the column with 100 ml of 1:3 dichloromethane;hexane Dichloromethane was removed by evaporation, and samples were transferred to volumelric flasks for an alysis. ANAI.Y.SIS The concentration of DDE. o.p'-DDJ. DDD, and p.p' DDT was quantified in a MicroTek 2000 MF gas chromatograph with a 1 30-mc tritium electron capture detector. This system gave good individual peak resolu- tion at the following retention times: DDE. 5.2 minutes: PESTiCiDES MoNrrORING JOURNAI »■ c; h ,/)-DDT, 6.8 minutes: DDD. 8.0 minutes: and /'./>'- )Dr. 9.5 minutes. Other operating parameters were: Column: Pyre\ glass. 180 cm \ 2 mm \.d.. packed with 5 '7 QF-1 (0.7 of length) and Sr'c DC-11 (0.3 of length) on 60/80 mesh Gas Chrom Q. precon- ditioned for 48 hours at 220 C. Temperature: Column 185^ C Detector 190- C Injector 205 ' C Carrier gas: Nitrogen at }0 ml min /linimum residue levels" for quantitative determinations vera 0.001 ppm for soil. 0.01 ppm for forest floor and Iter, and 0.01 pph for water. Average percent recovery nd range for DDT isomers and metabolites were as ollows: Forest Floor ■ORM Of Sou UND Liter Water DDT (PPM) (PPM) (PPB) )DE 99(92-103) 97(9.1-100) 99(98-100) .P-DDT 82(71-99) 99(96-100) 98(97-100) )DD 82(78-91) 85(80-94) 94(93-95) .P-DDT 97(92-100) 94(90-97) 99(98-100) JOTE: ( ) ONHRMATION t is most necessary to positively identify any apparent lODT determined hy gas-liquid chromatography (GLC). specially in samples of materials to which no known )DT application was made. A number of industrial lollutants are similar to DDT in structure and prop- •rties and can interfere with the detection or identifica- ion of DDT (19.22.2830.31): some naturally occur- ing plant or soil substances may also be potential ources of analytical error in determining the presence )f chlorinated hydrocarbon compounds (14.20). To tonfirm apparent DDT residues in this study, about lalf the samples were analyzed by GLC with a chloride- pecific. microcoulometric detection system (Infotronics nstrument Corp.). This step confirmed that substances vith the same retention time as the DDT standards letected by the electron capture detector did contain ;hlorine, but did not rule out the possible misinterpreta- ion of polychlorinated biphenyls (PCB's) as DDT somers and metabolites. Therefore, all samples analyzed f/hh the microcoulometric detector were hydrolyzed vvith alcoholic potassium hydroxide which would chem- cally alter DDT and DDD. but not PCB's (17). Hydrolyzed samples were then re-analyzed by both electron capture and microcoulometric detection sys- tems. DDD, o.p'-DDT. and p,p'-DDT peaks disappeared ifter hydrolysis, indicating that PCB's were not present in detectable qualities and that the quantitative measure- Tient of DDT isomers and metabolites by the electron :apture detection system was correct. Vol. 6. No. 1. Iuni 1972 The mass spectrophotometer provides the most positive means of identifying pesticides in biological samples; but in this study, only a few forest floor samples con- tained sufficient DDT to use this instrument. Two com- posite samples of forest floor from two different plots were extracted and purified for this particular analysis. The DDT isomers and metabolites were separated by chromatography of the final hexane extract on 500-^ silica gel H thin layer plates developed with 4:96 ben- zene: hexane. DDT standards were co-chromatographed on both edges of the 20- by 20-cm plates. After development, a 15-cm strip in the middle of the plate was covered, and the DDT standards were located by spra\ing the edge of the plate with 0.5""^ silver nitrate and exposing to UV light for 15 minutes. The o./Z-DDT. /»./''-DDT. and DDE were scraped from the appropriate section of the center of the plate, extracted from the silica gel with hexane, and analyzed by gas chroma- tography (electron capture detector). The pesticides separated by the thin layer method had the same re- tention times as the standards. Extracts containing the individual pesticides were in- troduced into a Model CH 7 (Varian Mat. Bmg. H.) mass spectrometer with a direct inlet probe. The mass spectra for o.p'-DDT. /)./)'-DDT, and DDE isolated from the forest floor samples agreed with spectra of appropriate standards and with published spectra (34). Sample spectra compared with published PCB spectra (3) indicated no PCB's present in the isolated pesticides. .All confirmation steps gave positive evidence that the substances isolated and measured were indeed DDT isomers and metabolites and that PCB's were not present ui detectable quantities. MKKOHIM WAIYSIS The number of bacteria in soil was estimated by plating sterile tap water dilutions of soil on sodium albuminate agar: mold counts were made on plates of peptone- glucose-acid agar (37). In each case, five plates were poured of each dilution: 1:50, 1:500, and 1:5,000 for molds: 1:5.000. 1:50,000. and 1:500,000 for bacteria. Mold colony counts were made on plates showing approximately 30 to 100 colonies after 3 days' incuba- tion: major genera were differentiated as mucors, Peni- rilliiiiu. and Aspcri>ilhix after 3 to 7 days. Total bacteria and Sireptomyces were counted on plates showing colonies in the range of 50 to 300 after 10 to 14 days' incubation; Sireptomyces were differentiated and their numbers expressed as a percentage of the total count. Incubation was 28 " C. Nitrite and nitrate were determined colorimetncally by the diazotization (2) and phenoldisulfonic acid ( 1 H) methods, respectively. For the nitrification study, 200 ppm N was added as ammonium sulfate to 100 g of soil (oven-dry basis) in 1-pt bottles. Moisture was adjusted 67 to 50% of water-holding capacity, and the bottles were capped with polyethylene film and incubated for 30 days at 28° C. Distilled water sufficient for a 1:5 dilution was then added, and the samples shaken for 15 minutes. After pH was measured, nitrite and nitrate in the supernatant were determined. Results and Discussion FOREST FLOOR SAMPLES A very small amount (0.13 ppm) of "apparent" total DDT residues (p.p'-DDE, p,p-DDD, o.p'- and p,p'- DDT) were found in prespray samples of the forest floor (Table 1); this was not confirmed as DDT, its isomers and metabolites by means other than GLC because of its insignificant contribution (<0.01 oz/ acre) to the totals found after spraying. One month after spraying, concentration of total DDT in the forest floor was slightly more than 7.5 ppm (Table 1 ), or 3.08 oz/acre (Fig. 1). Thus, an estimated 26% of the applied DDT (12 oz/acre) reached the forest floor shortly after spraying. DDT residues in the forest floor decreased steadily with time, and at the end of 3 years, more than half the DDT originally added had disap- peared. Volatilization, chemical or photochemical degradation, and bacterial decomposition are possible removal mechanisms (/2). TABLE I. — Concentration of DDT isomers and metabolites in the forest floor before and after aerial spraving, Oregon — 1965-68 FIGURE 1. — Total DDT in forest floor and mineral so during 36 months after aerial spraying, Oregon — 1965-68 Months Residues in PPM on a Dry-Weight Basis ' AFTER Spraying P.p'-DDE o.p'-DDT p.p'-DDD p.p-DDT Total DDT 0 .008 .025 .008 .089 ,!30 1 .190 1.294 .348 5.708 7.540 12 .214 .957 .352 3.914 5.437 24 .298 .584 .198 3.332 4.412 36 .096 .473 .114 2.641 3.324 ' Each value for DDE. DDD, o.p'- and p.p'-DDT represents the average of duplicate determinations on 20 replicate samples. The relationship between concentrations of all isomers and metabolites and months after spraying is negatively linear and significant at the 5% probability level. .SOIL SAMPLES DDT did not leach from the forest floor to underlying mineral soil. Apparent total DDT in prespray samples was 0.006 ppm (Table 2, or 0.05 oz/acre (Fig. 1) at the 0- to 3-inch depth; at the 3- to 6-inch depth, total DDT concentration was 0.002 ppm. or 0.02 oz/acre. One month after spraying, these levels had not changed, indicating that the forest floor effectively intercepted the spray solution. One year after spraying, the residue level of total DDT in soil at the 0- to 3-inch depth was 0.26 oz/acre: at the 3- to 6-inch depth, it was 0.05 oz/acre. This small difference in residues I month after spraying and I year later was attributed to the physical action of soil animals and, most probably, to minor, unavoid- able contamination during sampling. DDT has a solu- 68 □f..r.s. mi MiriiT^il S.iil 0 t,i J null di-p(li H MllRT.ll S.Ml A I.. (, IIKll dL'plll ^m I r~i bility in water of only about 1 ppb (7), and thus, doe not leach readily in soil (16,29,33). At the end of th second year, total DDT at the upper and lower so depth has decreased to 0.11 and 0.03 oz/acre, respec lively, and by the end of 3 years, was at prespray level: LITTERFALL SAMPLES DDT in litterfall totaled 0.73 oz/acre over the 3-yea sampling period, about 6% of the original applicatio (Fig. 2). DDT concentration decreased with time at greater rate than it did in the forest floor and so (Table 3), suggesting that photochemical decompositio and volatilization may be effective mechanisms of cherr ical degradation in tree canopies exposed to sunligh DDT concentration is also reduced in successive littei fall samples because of the constantly decreasin proportion of needles and twigs originally subjected t the spray. The contribution of DDT from litterfall t- the forest floor after spraying did not contribute strong] to total amount observed. Total loss of DDT from th forest floor over 3 years amounted to 2.46 oz/acre, mor than three times the amount brought down in litterfal over the same period. THROIIGHFALL PRECIPITATION SAMPLES Additions of DDT to the forest floor by throughfal precipitation were insignificant — 0.02 oz/acre for th' 3-year period following application (Fig. 2) Concentra tions varied with season (summer-fall vs. winter-spring and, in general, showed a gradual decrease with timi (Table 4). DDT concentrations in samples representini the dry summer and fall months were approximatel] three times greater than those for the wet winter-sprinj Pesticides Monitoring Journai TABLE 2. — Concentration of DDT isomers and metabolites in surface soil before and after aerial spraying, Oregon — 1965-68 Months AFTER SPRAYINO Residues in PPM on a Dry-Weight Basis ' Total p,p'-DDE o,p'-DDT p.p'-DDD p.p-DDT DDT 0- to 3-inch depth 0 .001 .002 _ .003 .006 I .001 .001 — .004 .006 12 .003 .005 — .021 .029 24 .001 .002 — .009 .012 36 - .001 - .005 .006 3- to 6-inch depth 0 — .001 — .001 .002 1 — .001 — .001 .002 12 — .002 — .004 .006 24 — .001 — .002 .003 36 - .001 — .001 .002 NOTE: — = not detected. ' Each value for DDE, DDD. o.p'- and p,p-DDT represents average of duplicate determinations on 20 replicate samples. FIGURE 2. — Total DDT brouglil to forest floor in litterfall and throughfall prccipilalioii during 36 months after aerial spraying, Oregon — 1965-68 season. Precipitation samples for the 13- to 18-month period after treatment contained higher DDT concen- trations than expected relative to the amount of rainfall for the period and the concentrations found at 6 and 30 months. However, the DDT levels, their seasonal variations, and the total range in concentrations found in this study are consistent with normal climatological variations and similar to those reported for other regions {1.36.39). Vol. 6, No. I, Juni; 1972 TABLE 3, — Concentration of DDT isomers and metabolites added to the forest floor in litterfall after aerial spraying, Oregon — 1965-68 Residues in PPM on a Dry-Weight Basis ' after Spraying P.P'-DDE o.p-DDT p.p'-DDD p.p'-DDT Total DDT 0-6 .66 1.57 .44 8.65 11.32 7-12 .19 1.65 .30 8.18 10.32 13-18 .13 1.06 .22 5.71 7.12 19-24 .15 1.07 .26 6.01 7.49 25-30 .09 62 .13 3.08 3.92 31-36 .07 .47 .10 2.44 3.08 Each value for DDE. DDD, o.p'- and p.p'-DDT represents the average of duplicate delerminalions on -20 replicate samples. The relationship between concentrations of DDT isomers and metabolites and months after spraying is negatively linear and significant at the 5*^^ probability level in all cases. TABLE 4. — Concentration of DDT added to the forest floor in throughfall precipitation after aerial spraying, Oregon— 1965-68 Months after Spraying Precipitation ' (MM) Total DDT Residue '-• (PPB) 0-6 162 .176 7-12 212 075 13-18 185 ,364 19-24 455 066 25-30 110 .103 31-36 241 .036 Rainfall level extrapolated from monthly climatological data for Burns. Oregon, using Mean Annual Precipitation Isohyetal Map. U. S. Weather Bureau River Forecast Center. Portland, July 1964 Total DDT residue includes p,p'-DDE, o.p-DDT, p,p'-DDD and p.p'-DDT. ODE residue accounted for an average 6.58":^ of total DDT residue and showed no statistically significant change with time. At the end of 3 years, DDT concentrations in through- fall precipitation had decreased appreciably, but still were 5 to 10 times greater than levels found in samples from an untreated forested area in western Oregon: however, the total amount of DDT brought down over this period in throughfall precipitation was negligible compared with that part of the intended application that initially reached the forest floor or was deposited in litterfall. Thus, throughfall precipitation was not a sig- nificant factor in determining the fate of applied DDT or in maintaining DDT concentrations in the forest floor. DDT IN STREAMWATER SAMPLES Streamwater was monitored in Rattlesnake Creek imme- diately above the confluence of the east and west forks, both of which flow from the sprayed area. The maximum total DDT concentration found over a period of SVi years after spraying was 0.277 ppb: this was in a sample taken a few hours after spraying (Table 5). This level was similar to those reported from North Carolina (15) and northeastern California {5) and less than those from northern Pennsylvania (9) and New Brunswick (44). Most samples, including those taken 3'/2 years after the spraying, contained concentrations of DDT near the lower limit of detection (0.01 ppb). 69 TABLE 5. — Total DDT content of streamwater flowing from sprayed area — before treatment and during 3 years after treatment, Oregon — 1965-68 Days from Time of Spraying Total DDT Residues IN PPB Date Rattlesnake Creek East Fork West Fork 1965 5/24 -JO 6/19 -4 — — 6/23 1 104 .277 7/14 21 .03 1 .022 8/26 64 .028 .015 11/17 147 .014 — 1966 6/7 349 — 7/19 391 OKI 1 1/9 505 1967 7/4 742 — — n/7 869 .032 .010 1968 7/16 1.131 Il/r2 1,251 .010 TABLE 6. — Soil microbial popidations, nitrate nitrogen con- lent, and nitrification rate before treatment and during 24 montlis after aerially spraying with DDT at 12 oz/acre. Oregon— 1965-68 NOTE: — = not detected. Blank = levels of DDT isomers and metabolites less than 0.01 ppb but greater than 0.002 ppb. Surveillance operations by the Bureau of Sport Fisheries and Wildlife {25) indicated that the DDT spraying had little effect on the waters and organisms of Malheur Lake, toward which Rattlesnake Creek flows. Levels of total DDT accumulation in the food chain of Rattle- snake Creek were very low in all components of the sampled community (S). MICROBIAL SOIL PROPERTIES AND NITROGEN RELATIONS The small amount of DDT in the top 6 inches of mineral soil had no significant effect on microbial pop- ulations, soil nitrification rate, or amount of nitrate nitrogen (Table 6). A number of findings similar to these are found in the literature: these reports, however, are based on laboratory studies in which DDT was added to soil at extremely high rates — 50-2.000 lb/ acre ( 13,21 ,24.26,32) . Effects of pesticide residues on mi- crobes in agricultural soils are usually negligible when the chemicals are used at recommended field rates (6. 1 1,23). Such field rates were usually much greater than those encountered in this study. Thus, it may be con- cluded that the small amount of total DDT residue in soil found after low-volume aerial spraying to control insects is not hazardous to soil microbes or their role in maintaining soil fertility. FATE OF AERIALLY APPLIED DDT Of a total aerial application of 12 oz of DDT per acre. 26% reached the forest floor initially, 6% was brought to the forest floor in litterfall over a 3-year period, and a fraction of 1 % of the total was washed from the tree canopy over 3 years (Table 7). Thus, about one-third of the total application reached the forest floor. 70 Soil Months after Aerial Spraying ' of Measurement INCHES) 0 1 12 24 Total bacteria — millions/g of soil 0-3 2.51 2.81 3.46 7.58 3-6 1.83 2.05 4.04 4.51 Streptomyces — percent of total bacteria 0-3 15.25 23.63 27.25 63.81 3-6 13.13 19.50 35.56 34.00 Total molds — thousands/y of soil 0-3 338.19 302.88 464.69 168.31 3-6 93.88 33.88 .323.31 35.06 Penicillia — percent of total molds 0-3 78.23 94.46 95.06 62.72 3-6 77.10 68,45 82.78 68.45 Nitrate nitrogen in soil — ppm 0-3 58.00 40.94 7.00 17.50 3-6 5.81 4.31 1.63 2.13 NitriHcation of added ammonium sulfate- - percent of total 0-3 9.59 -.56 -.50 -.17 added 3-6 .27 .04 -.26 -.13 Results of regression analysis indicated no significant relation be- tween soil DDT content and any of the variables measured at the iTc probability level. TABLE 7. — Total DDT deposited on the ground surface (forest floor) during 3 years after aerially spraying of DDT at 12 oz/acre, Oregon— 1965-68 ' Source of DDT AT Ground Surface Total DDT oz/acre Percent of Total Applied Initial deposit from spraying Total deposit during 3 years from: Litterfall Throughfall precipitation 3.08 .74 .02 25.66 6.17 .01 Total, all sources 3.84 31.84 Because this study did not include direct measurement of the amounts of DDT that reached the forest canopy, the extent of chemical loss from drift during spraying or by volatilization or degradation in the canopy after spraying cannot be assessed. In a study in Arizona, less than 50% of aerially sprayed insecticides were deposited on the agricultural target during summer months (38): in the same study, the distance from the spray aircraft to the target was inversely correlated with amount of on-target chemical application. Aircraft spraying forest lands must fly at far greater heights than those operating over level agricultural fields. Thus, the comparatively low amount of on-target application suggested by the present study is not surprising. This finding reaffirms that efficient methods of aerial spraying must be de- veloped in order to avoid great loss of chemical to nontarget areas. See Appendix for chemical names of compounds discussed m this paper. Pfsticides Monitoring Journal LITERATURE CITED II) Abbott. D. C, R. B. Harrison. J. O'G. Tattoii. and J. Thomson. 1965. Organochlorine pesticides in the atmos- pheric environment. Nature 208:1317-1318. (2) American Public Hcalili Association. 1955. Standard methods for examination of water, sewage, and indus- trial wastes. Ed. 10. 522 p. (3) BaglcY. G. E.. W. L. Reicliel. and E. Cromarlic. 1970. Identification of polychlorinated biphenyls in two bald eagles by combined gas-liquid chromatography — mass spectometry. J. Assoc. Off. Anal. 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Toxicol. 4:192-201. (32) Shaw. W. M.. and Brooks Robinson. 1960. Pesticide effects in soils on nitrification and plant growth. Soil ■Sci. 90:320-323. (33) Smith. Virgil K. 196S. Long-term movement of DDT applied to soil for termite control. Pestic. Monit. J. 2(1): 55-57. (34) Sphon. J. A., and J. N. Damico. 1970. The mass spectra of some chlorinated aromatic pesticidal compounds. Org. Mass Spectrom. 3:51-62. 135) Strickler. Gerald S.. and Paul J. Edgerton. 1970. Monitoring DDT residues on forage plants following a forest insect control program. Pestic. Monit. J. 4(3): 106-1 10. 71 (36) Tarrant, K. R.. and J. O'Ci. Talloii. 1968. Organochlo- in rainfall and runoff. J. Am. Water Works Assoc. 58; fine pesticides in rainwater in the British Isles. Nature 1075-1084. 219:725-727. (40) Wood. Bobby J. 1966. Elution of dieldrin and endrin (37) Waksmun. S. A., and E. B. Fred. 1922. A tentative out- from Florisil. J. Assoc. Off. Anal. Chem. 49:472-473. line of the plate method for determining the number of ''''' WoodwcU. George M. 1961. The persistence of DDT microorganisms in the soil. Soil Sci. 14:27-28. '" a forest soil. Forest Sci. 7:194-196. <3D, 11/ ^ 11/ li/ D ^ ) w D r> r- / /, II ^^ f42) Woodwetl. G. M.. and F. T. Martin. 1964. Persistence (38) Wore, G. W.. W. P. Cahill, P. D. Gerhurdl, and J. M. r r-vr^-r • i c u i i r . . j c- ■ 11/-,. ,ni,i n . ■ J , c. t\, r\ . .1 , c of DDT in soils of heavilv spraved forest Stands. Scicuce Witt. 1970. Pesticide drift. IV. On-target deposits from i4S-48i 4X^ aerial application of insecticides. J. Econ. Entomol. 63: , ,,, ^ ,' ... ."' ,„_,, „„-r . , . r .inn TQBT ' ' '''• ■ ^- '^7(A DDT residues in forest soils. Bull. 1982-1983. Environ. Contam. Toxicol. 5:139-143. (39) Weihel, S. R.. R. B. Weidner, J. M. Cohen, and A. O. (44) Yide. W. N., and A. D. Toinlin. 1970. DDT in forest Christian.son. 1966. Pesticides and other contaminants streams. Bull. Environ. Contam. Toxicol. 5:479-488. 72 PhSTiciDES Monitoring Journal GENERAL Decay of Parathion and Endosiilfan Residues on Field-Treated Tobacco, South Carolina — 1971 Julian E. Keil,' C. Boyd Loadholt.' Bob L. Brown. Samuel H. Sandifer,' and Wayne R. Sitterly ' ABSTRACT farathion and endosulfun were applied three limes at rates f 1.5 and .5 lb/acre, respectively, to field tobacco in South 'Carolina in an effort to determine the time required for these •esticides to degrade to "zero" residue levels. The maximum ■mes were estimated to he 7 days for parathion and 10 days or endosiilfan. During the study period, weather was charac- rized by high rainfall and lemperalures averaging 80° F. Introduction the recent increased use ot organophosphate pesticides ' uch as parathion as substitutes for the restricted chlori- lated hydrocarbons has revived concern about residues )f these compounds. Interest was further stimulated by he reported cluster of parathion poisonings among ^iorth Carolina tobacco workers in 1970 (J.I. Freeman, Personal eoniiiuinicalion) . < 'owarl el al. ( J ) m measurmg the hydrolysis rate of iiarathion reported thai S5'^r remained undegraded after I week. 15% after 2 weeks, and 17% was still unde- I graded at 6 weeks. Maier-Bode (3). however, reported j hat the question of how long parathion residues re- jnained in and on food plants has been answered. He I concluded that parathion as a spray or powder is ab- isorhed into plant tissues where metabolism occurs: any 'remaining surface residues are rapidly broken down by photolysis of the sun or evaporated into the atmosphere. Maier-Bode advised that German law requires a waiting Medical Un t»f South al University of South Caroliii.i. ' Department of Preventive Medicine. Carolina. Charleston, S. C. 29401. = Department of Biometry. The Medic Charleston. S. C. 29401. ■ South Carolina State Board ot Health, Sullivan's Island. S. C. 29482 ' Clemson University Experiment Station. St. Andrews Branch. Charles- ton. S. C. 29407. Vol.. 6. No. 1. Junk 1972 time of 14 days between parathion application and harvest to reduce residues to levels nonhazardous to human health. He also suggested that rain during this waiting period does not significantly affect the residue level. The U. S. Department of Agriculture has long suggested that workers entering tobacco fields within 5 days after application of parathion be protected against skin con- tact by use of protective clothing ( / ). The experiment reported here was designed to observe the decline with time of levels of parathion normally applied to field tobacco. The ultimate goal was to esti- mate and verify the safe interval suggested by USDA for entering fields after parathion treatment. Eindosulfan. a chlorinated hydrocarbon insecticide still registered for use on tobacco, was included as another treatment and also mixed with parathion to assay decay interaction of the two chemicals. Methods and Procedures Cokers 319 variety tobacco was planted on April 12. 1971. Plots consisting of three 12-foot rows were ran- domly selected for treatment with parathion. endosulfan. or parathion in combination with endosulfan or as appropriate controls. Each treatment or control plot was replicated four times in a completely randomized design for a total of 16 plots. Guard rows were used to reduce pesticide drift. Parathion and endosulfan were applied as sprays at rates of 1.5 and .5 lb active in- gredient (A.I.) per acre, respectively, on June 8. 21. and July 8. 1971. 73 Twelve foilage sample collections were made at times indicated in Table 1 and Fig. 1 and 2. Each time, 25-g, field-weighed samples were secured from the center alley of each plot from the foliage of two plants at locations approximately one-half the plant height. The samples were placed in acetone-washed, oven-dried, 1-pint containers. Rainfall data, shown in Fig. 1 and 2, were obtained as recorded at the Clemson University Truck Experiment Station, and temperature information was secured from the U. S. Weather Bureau. Since all plots were observed at 12 different times, the statistical analysis computed (Tables 2 and 3) was for a split plot in time where the whole plots were in a completely randomized design. Analytical Procedures To each 25-g sample of tobacco, 50 ml of nanograde hexane and 5 g of anhydrous sodium sulfate were added. The samples were shaken and allowed to stand for 3 hours. The hexane was then decanted into a Kuderna- Danish evaporator. This extraction was repeated twice more with 50 ml of hexane, and extracts were combined with the original. The extract was taken to near dryness on a steam bath using a three-bail Snyder column and rediluted to an exact volume. The extraction procedure used in this experiment was a modification of that of Reed and Priester (4). Sensitivity of the method al- lowed for detection of each compound at 0.0 1 ppm. A 5 /il of column injection was made from dilutions ranging from 1 ml to 50 ml of the residues redissolved in hexane. Determinations of residues were made using a MicroTek 220 gas chromatograph equipped with an electron capture (tritium) detector and a flame photo- metric detector. Carrier gas: Temperatures Instrument parameters were as follows: Column: Glass, 6' x 'A", packed with 1.5? OV-17/1.95% QF-1 onChromosoi W 100/120; DMCS, HP Repurified nitrogen at 60 ml/min Inlet 230° C Column 200° C Transfer 235° C Detectors: (A) Electron capture (tritium) Temperature 205° C (B) Flame photometric 1. Temperature 225° C 2. Mode — sulfur and phosphorus 3. Gas flows: Helium-200 ml/min; oxygen-20 ml/min Air-100 ml/min; nitrogen-60 mi/mi The 1.5% OV-l7/l.95% QF-1 column was efficient i resolving the parathion and endosulfan peaks and tht was used for both detectors. As the sensitivity of th electron capture detector is greater, it was used fc quantitation of the peaks on the basis of relative pea heights. The flame photometric detector was used fc confirmation of compounds detected. The two endosu fan isomers were quantitated independently but reporte as total endosulfan. Recoveries averaged 92.6% for parathion and 87.3' for endosLilfan. Results were not corrected for recover; Results and Discussion Fig. I presents parathion residue levels in relation t application time. Within the framework of this exper ment regarding temperature, moisture, and sunlight, th maximum time required for parathion to degrade t "zero" levels was estimated to be 7 days and the mir TABLE 1. — Parathion and endosulfan residues on field-trealed tobacco. South Carolina — 1971 Sampling Tim£ IN DAYS FROM LAST APPLICATION Mean Residual Level in ppm of Four Replicates per Treatment Application Parathion (1.5 A.I. LB/ACRE) Endosulfan (.5 a.i. lb/acre) Parathion (1.5 A.I. lb/acre)/ Endosulfan (.5 A.I. lb/acre) Control Parathion Endosulfan Parathion Endosulfan Parathion Endosulfan Parathion Endosulfan Junes 0 0 0 0 0 0 0 0 0 1 .619 161 .108 .905 1.049 1.489 .140 .091 10 .146 .195 ,144 ,459 .146 ,305 .091 .069 June 21 1 .436 .076 .009 .695 .736 1.189 ,041 .100 ,1 .091 .224 ,130 .234 .159 ,231 ,091 .221 ? .069 .106 ,071 .152 .070 ,174 .089 .072 « ,017 .056 ,012 .156 .014 .148 ,020 .067 l-l .004 .037 .003 .077 .007 ,106 0 .052 JulyX 1 1.123 .679 .380 1.751 1.304 1.741 ,584 .529 4 .632 ,418 ,169 .969 .694 .954 ,493 .389 « 0 .145 ,062 .311 0 .235 0 .147 18 0 .047 .002 .207 0 .174 0 .037 NOTE: LSDos = least significant difference at 95% probability level = .166 for parathion and .363 for endosulfan; residues were not corrected fo percent recovery (see methods). 74 Pesticides Monitoring Journai mini time 2 days. "Zero" levels are considered within le limits of actual zero, i.e., undetectable amounts, lus the calculated least difference considered statistically ignificant at the 5'"c level of significance. limilar information is provided for endosulfan in Fig. I and indicates reductions of residues to "zero" in 10, 2. nd 7 days, respectiveh, after three successive pesticide pplications. vlthough the e.\permiental design mcluded guard rows, here were still measurable amounts of drift of the in- ecticide between all plots. Table 1 lists the actual mounts of each insecticide detected in each of the four reatments. In most instances, the contaminant or drifted" chemical (e.g." endosulfan detected in the larathion treatment) was less than the LSD,,.-,. Thus, it ■i felt that experiment safeguards such as guard rows nd control plots were highly effective in reducing the ontamination between plots. ^he parathion-endosulfan treatment was included to letermine if any interaction existed between the two hcmicals. It was found that more parathion residue vas present when endosulfan was present; however, the ronverse was not true as can be seen from Tables I . '., and 3. -IGURE 1. — Avcraf;c parathion re •iidiics on lohaico Ictnci 1 ' i ' i ] • \ \- ■ ' 1 "•"•■• •■•■• -" ■■■• " -" '""•• < . . • -■ "■•"•• FIGURE 2. — Average residues of endosulfan on tobacco leaves ] o r T '\ ] 1 ' 1 ■• \: TABLE 2. — Analysis of variance for the variable parathion Source of Degrees of Sum of Mean Variation Freedom Squares Square F Treatment Parathion 1 1.8217 1.8217 100.765'* Total Endosulfan 1 .0282 .0282 1.559 Para x Endo 1 .1864 .1884 10.421 •• Error (a) i: .2169 .0181 Time 11 12.9523 1.1775 81.665'* Ti .X Para 11 4.0406 .3673 25.476" Ti X Endo 11 .2898 .0263 1.827* Ti X Para x Endo II .4412 .0401 2.782" Error (b) 132 1.9032 .0144 TABLE 3. — Analysis of variance for the variable endosulfan Source of Dercees of Sum of Mean Variation Freedom Squares Square F Treatment Parathion 1 .1201 .1201 1.034 Total Endosulfan 1 6.373 1 6.3731 54.873" Para x Endo 1 .0178 .0178 .154 Error (a) 12 1.3937 .1161 Time 11 21.1820 1 .9256 27.939** Ti x Para 1 1 .5584 .0508 .737 Ti X Endo II 8.0654 .7332 10.638'* Ti X Para x Endo 11 .6309 .0574 .832 Error (b) 132 9.0979 .0689 In excess of 12 inches ot r.iin tell during the period of the experiment, and it is felt that the unusual rainfall may have physically effected some residue reduction. Daily temperature means averaged SO. 9 F with a standard deviation of 2.3 and a range of 76 to S.'i F. This experiment should be repeated for confirmation purposes and to observe results under different environ- mental conditions including different moisture conditions to determine effects of weather on deeradation. Sec Appendix for chemical paper. of compounds discussed Vol. 6, No. 1, June; 1972 This sludv was supported b\ hnvironmcnlal Protection Ayency Co tracts. Numbers PH21-20I7 and 68-03-0045. Liri-RAruRh en tu f /) U. S. Department of Auriciilliirc. 1966. Agriculture Hand- book 313 p. 90. l2)CoH-arl. R. P.. F. L. Honiur. and E. A. Epps. Jr. 1971. Rate of hydrolysis of seven organophosphate pesticides. Bull. Environ. Contam. Toxicol. 6:231-234. ii) Maier-Bodc. H. I97U. Parathion residues. Dtsch. Med. Wochenschr. 95:2457. 14) Reed. J. K.. and L. E. Priester. 1969. DDT residues in tobacco and soybeans grown in soil treated with DDT. Pestic. Monit. J. 3(2):87-89. 75 APPENDIX Chemical Names of Compounds Discussed in This Issue ALBRIN BHC CHLORDANE DDE DDT (including its isomers and dehydrochlorination products) ENDOSULFAN (THIODAN®) ENDRIN HCB HEPTACHLOR HEPTACHLOR EPOXIDE LEAD LINDANE MERCURY MIREX PARATHION PCP POLYCHLORINATED BIPHENYLS (PCBs) IDE (DDD) (Including its isomers and dehydrochlori- nation products) Not less than 95% of l,2,3,4,!0,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-fMdo-fxo-5,8-dimethanonaphthalene 1,2,3,4, 5, 6-hexachlorocyclohexane, mixed isomers l,2,4,5,6,7,8,8-octachloro-3a,4.7,7a-tetrahydro-4,7-methanoindane l,l-dichloro-2,2-bis(p-chlorophenyl) ethylene l,l,l,-trichloro-2,2-bis(p-chIorophenyl iethane; technical DDT consists of a mixture of the p.p'-isomer and t o.p'-isomer (in a ratio of about 3 or 4 to 1 ) Not less than 85% of l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7.8a-octahydro-l.4-f»do-fjro-5,8-dimethanonapi thalene 6,7,8,9,10, lO-hexachloro- 1. 5. 5a,6.9,9a-hcxahydro-6.9-methano-2.4.3-benzodioxathiepin 3-oxidc l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4.4a,5,6,7.8,8a-octahydro-l,4-?Hdo-cHdo-5,8-dimethanonaphthalene hexachlorobenzcnc 1, 4.5,6,7,8, 8-heptachloro-3a,4.7,7a-tetrahydro-4,7-niethanomdene l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4.7-methanoindan Pb 1,2,3,4,5,6-hexachlorocyclohexanc, 99% or more gamma ist)mer Hg dodecach!orooctahydro-l.3,4-nietheno-l//-cyclobutalcrf]pentalenc 0, 0-diethyl 0-p-nitrophenyl phosphorothioate pentachlorophenol Mixtures of chlorinated biphenyl compounds iiaving various percentages of chlorination l,I-dichloro-2,2-bis(p-chlorophenyl iethane; technical TDE contains some o.p'-isomer also 76 Pesticides Monitoring Journai Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretive information which contribute to the understanding and evaluation of pesticides and their residues in relation to man and his environment. The publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries: medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. Accuracy, reliability, and limitations of the sam- pling and analytical methods employed must be clearly demonstrated through the use of appropriate procedures, such as recovery experiments at appropriate levels, confirmatory tests, internal standards, and inter-labora- tory checks. The procedure employed should he ref- erenced or outlined in brief form, and crucial points or modifications should be noted. Check or control samples should be employed where possible, and the sensitivity of the method should be given, particularly when very low levels of pesticides are being reported. Specific note should be made regarding correction of data for percent recoveries. Preparation of manuscripts should be in con- formance to the Style Manual for Biological Journals, American Institute of Biological Sciences, Washington, D. C. and/or the Style Manuai of the United States Government Print- ing Office. An abstract (not to exceed 200 words) should accompany each manuscript submitted. All material should be submitted in duplicate (original and one carbon) and sent by first-class mail in fiat form — not folded or rolled. Manuscripts should be typed on 8'/2 x 1 1 inch paper with generous margins on all sides, and each page should end with a completed para- graph. All copy, including tables and references, should be double spaced, and all pages should be num- bered. The first page of the manuscript must contain authors" full names listed under the title, with affiliations, and addresses footnoted helou. Charts, illustrations, and tables, properly titled. should be appended at the end of the article with Vol. 6. No. 1, June 1972 a notation in text to show where they should be inserted. Charts should be drawn so the numbers and texts will be legible when considerably reduced for publication. All drawings should be done in black ink on plain white paper. Photographs should be made on glossy paper. Details should be clear, but size is not important. The "number system" should be used for litera- ture citations in the text. List references alpha- betically, giving name of author/s/, year, full title of article, exact name of periodical, volume, and inclusive pages. The Journal also welcomes "brief" papers reporting monitoring data of a preliminary nature or studies of limited scope. A section entitled Briefs will be included, as necessary, to provide space for papers of this type to present timely and informative data. These papers must be limited in length to two Journal pages (850 words) and should conform to the format for regular papers accepted by the Journal. F'esticides ordinarily should be identified by common or generic names approved by national scientific so- cieties. The first reference to a particular pesticide should be followed by the chemical or scientific name in parentheses — assigned in accordance with Chemicai Abstracts nomenclature. Structural chemical formulas should be used when appropriate. Published data and information require prior approval by the Editorial Advisory Board: however, endorsement of published in- formation by any specific Federal agency is not intended or to be implied. Authors of accepted manuscripts will receive edited typescripts for approval before type is set. After publication, senior authors will be provided with 100 reprints. Manuscripts are received and reviewed with the under- standing that they previously have not been accepted for technical publication elsewhere. If a paper has been given or is intended for presentation at a meeting, or if a significant portion of its contents has been published or submitted for publication elsewhere, notation of such should be provided. Correspondence on editorial matters or circulation mat- ters relating to official subscriptions should be addressed to: Mrs. Sylvia P. ORear. Editorial Manager. Pesti- cides Monitoring Journal. Division of Pesticide Com- munity Studies, Office of Pesticides Programs. Environ- mental Protection Agency. 4770 Buford Highway. Bldg. 29. Chamblee, Ga. 30341. 77 The Pesticides Monitoring Journal is published quarterly under the auspices of the FEDERAL WORKING GROUP ON PEST MANAGEMENT (responsible to the Council on Environmental Quajity) and its MONITORING PANEL as a source of information on pesticide levels relative to man and his environment. The WORKING GROUP is comprised of representatives of the U. S. Departments of Agricul- ture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; and Transporta- tion; and the Environmental Protection Agency. The pesticide MONITORING PANEL consists of representatives of the Agricultural Research Service. Consumer and Marketing Service. Extension Senice. Forest Service, Department of Defense, Fish and Wildlife Service. Geological Survey. Food and Drug Administration. En- vironmental Protection Agency. National Marine Fisheries Service, National Science Founda- tion, and Tennessee Valley Authority. Publication of the Pesticides Monitoring Journal is carried out by the Division of Pesticide Community Studies of the Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies repre- sented on the pesticide MONITORING PANEL which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and interpretive articles. However, pertinent data in summarized form, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institu- tions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Manuscripts received for publication are reviewed by an Editorial .Advisor\ Board established by Ihc MONH'ORING PANEL. Authors are given the benefit of re\icw comments prior lo publication. Editorial Advisory Board members are: John R. Wessel, Food and Drug Administration. Chairman Paul F. Sand. Agricultural Research Service, Vice Chairman Anne R. Yobs. Environmental Protection Agency William F. Durham. Environmental Protection Agency Thomas W. Duke, Environmental Protection Agency William H. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Herman R. Feltz, Geological Survey Mention of trade names or commercial sources in the Pesticides Monitoring Journal is for identification only and does not represent endorsement by any Federal agency. Address correspondence to: Mrs. Sylvia P. O'Rear Editorial Manager PESTICIDES MONITORING JOURNAL Environmental Protection Agency 4770 Buford Highway, Bldg. 29 Chamblee. Georgia 30341 CONTENTS Volume 6 September 1972 Number 2 Page EDITORIAL These changing limes '" Herman Feltz PESTICIDES IN PEOPLE Total mercury in hair from 1.000 Idaho residents — 1971 80 W. W. Benson and Joe Gabica Comparative organochlorine pesticide residues in serum and biopsied lipoid tissue: a survey of 200 persons in Southern Idaho — 1970 o4 Joe Wyllie. Joe Gabica, and W. W. Benson RESIDUES IN FOOD AND FEED Arsenic residues in soil and potatoes from Wisconsin potato fields — 1970 89 D. R. Steevens, L. M. Walsh, and D. R. Keeney RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury concentrations in game birds. Stale of Washington — 1970 and 1971 9 I Frank E. Adley and Donald W. Brown Effects of estuarine dredging of toxaphene-contaminatcd sediments in Terry Creek, Brunswick, Ga. — 797/ _ 94 Charles J. Durant and Robert J. Reimold Organochlorine insecticide residues in water, sediment, and organisms. Aransas Bay, Texas — September 1969-June 1970 97 Roger R. Fay and Leo W. Newland Total mercury in largemouth bass (Micropterus salmoides) in Ross Barnett Reservoir, Mississippi — 1970 and 197L . 103 Luther A. Knight, Jr. and Jack Herring A survey of the selenium content of fish from 49 New York State waters . 107 Irene S. Pakkala, Walter H. Gutenmann, Donald J. Lisk, George E. Burdick, and Earl J. Harris Effects of insecticides on populations of rodents in Kansas — 1965-69 1 15 R. J. Robel, C. D. Stalling, M. E. Westfahl. and A. M. Kadoiim Mercury residues in fish from Saskatchewan waters with and without known sources of pollution — 7970 122 Arthur K. Sumner, Jadu G. Saha, and Young W. Lee PESTICIDES IN SOIL Pesticide residues in soil from eight cities — 1969 I 26 G. B. Wiersma, H. Tai, and P. F. Sand APPENDIX Chemical names of compounds discussed in this issue 1 30 EDITORIAL These Changing Times /OL. 6, No. 2, September 1972 The well-worn phrase that "time changes everything," or as some prefer to say, "everything changes with time," has been very much in evidence recently. First of all, you have probably noticed that there is a new "face" on this issue of the JOURNAL. The edi- torial staff has arranged to upgrade the quality of the cover to be more attractive and durable, yet retaining those characteristics by which the periodical is quickly recognized. Mr. Reo Duggan, Chairman of the Editorial Advisory Board of the PMJ since publication began in June 1967, has retired from service with the Food and Drug Administration. This issue of the PMJ is a fitting tribute to his untiring efforts which have brought about international recognition of the JOURNAL as one of stature in its field. Another Monitoring Panel member. Dr. Eugene Dust- man, has also retired. "Dusty" as we know him, was Director of the Patuxent Wildlife Research Center, USDI. Both Dr. Dustman and Mr. Duggan were charter members of the Panel dating back to about 1964 when it was known as the Subcommittee on Pesticide Moni- toring of the Federal Committee on Pest Control. These gentlemen have provided careful and expert guidance, and their absence is a challenge to us to uphold the respected manner in which they carried out their ob- ligations. In May, the Working Group approved the revised Charter of the Monitoring Panel, rewritten to be com- patible with the new charter for the Federal Working Group on Pest Management. Among the charges to the Panel, is to continue to have a task group serve as the interagency Editorial Advisory Board of the PMJ for publication of monitoring data. New members have been appointed. Mr. John Wessel, FDA, was chosen Chairman, and Dr. Paul Sand, USDA, Vice Chairman. The Panel pledges its full support to the Advisory Board and editorial staff. What else has time wrought? We'll no doubt see changes in monitoring programs in keeping with monetary and personnel constraints, and changes in methods for pest control or pest management — but that's another story for another time. Best wishes to our retirees and those who have assumed new responsibilities. Herman Feltz Chairman, Monitoring Panel 79 PESTICIDES IN PEOPLE Total Mercury in Hair From 1 ,000 Idaho Residents — 1971 ^ W. W. Benson and Joe Gabica ABSTRACT In a study of mercury in hair from 1 .000 people Ihroughoul Idaho, mercury was found in all samples. The mean con- centralion was 4. IS ppm, and mean levels for .samples from males and females were 2.45 and 5.90 ppm, respectively. Mercury levels ranged from a low of 0.12 ppm in a male to a high of 139.0 ppm in a female. No common source of mercury exposure was found, and there is no explanation at this time for the higher mercury levels in hair samples from women. Introduction During the fall of 1970, a study was conducted in Idaho to determine the presence of mercury in the environment, especially in pheasants. Because of the high mercury levels found in pheasants (/) and subse- quently in fish (2) and other environmental samples, the study reported here was initiated to determine mercury levels in Idaho residents. Interest in environmental mercury as a factor in human health has increased greatly during the past several years. Reports have been published based on accidental poisonings (3) and poisonings resulting from occupa- tional hazards (4). Most of these studies, however, have been carried out on human tissues and have not included hair samples. The current study was designed to survey mercury levels in hair samples from persons throughout Idaho to determine if levels were higher for residents of particular areas and to determine if the consumption of fish or other sources of exposure could be correlated with mercury levels in an individual. The study was also designed to provide baseline data for future studies. From the Idaho Community Study on Pesticides, Idaho Department of Health, Statehouse, Boise, Idaho 83707. 80 Hair was studied since it was known that mercu especially methyl mercury which is considered dangert to human health (5), could be detected in hair a because such samples could be readily obtained. Sampling Procedures In order to compare levels in residents for diffen ; areas, sampling was carried out on the basis of tl seven Idaho health districts which are apportioned I population and are approximately equal. Various ganizations and individuals in each district were p vided with return envelopes, printed to include nar address, age, sex, and occupation of participants well as their consumption of fish and frequency consumption. Initial requests met with an inadequ. response; consequently, return envelopes were provid to barbers and beauticians in each district who suppli the required hair samples. During analysis, if a sample tested above 15 ppm mercury, an additional hair sample was requested frc that individual and a blood sample was also collects Each of these persons was also asked to complete questionnaire listing known mercury products or acti" ties involving mercury products and was interviewed an effort to determine, if possible, other sources mercury exposure. Individuals with high levels mercury in their hair were specifically asked if thi used hair coloring and conditioning preparatior diuretics, skin bleaches, and ointments; however, i queries were made concerning dental fillings. All samples collected from men were short hair o tained close to the scalp usually from the sides and nee and, thus, represented mercury in the body at the tin of sampling. In contrast, the initial samples from womt were usually terminal hair ends and, depending on tl Pesticides Monitoring Journa ngth of hair, represented a body burden of mercury >perienced previously. For example, the terminal end oni hair 18 inches long, would represent that body jrden experienced 12 to 18 months previously. Conse- uently, any repeat samples from women were requested ) be hair from next to the scalp which would more .curately represent the present body burden. In all \cept one instance, the mercury levels were lower in ibsequent samples from women. In the one exception, le level increased from 39 to 62 ppm. The current udy presents only levels in initial hair samples; the ibsequent samples will be correlated with blood levels f mercury in a future report. Analytical Procedures ach man's hair sample, since it was received as fine lippings, was mixed and an aliquot taken for analysis: woman's hair sample, which was usually longer, had to e cut into fines and mixed before an aliquot was taken. 1 each case, a 1-g subsample was digested by either of vo methods: Method A employed nitric and sulfuric cid digestion using the A.O.A.C. method and equip- lent (6); Method B used nitric and sulfuric acid (in a itio of 10:1) digestion in an open 50-ml pyrex tube. laced in a boiling water bath for 2 hours. The two lethods were compared by determining the final mer- ury levels for samples digested by both methods: and lere was no significarlt difference (Table 1 ) TABLE 1. — Mercury levels determined after A.O.A.C. method and tube method of digestion Residues in ppm A.O.A.C. Tube (50-ml) 1.60 1.54 2.40 3.08 0.54 0.80 21.40 21.40 86.68 100.00 2.00 1.92 1.90 2.08 4.90 5.00 1.10 1.40 The digested hair samples were then diluted to volume with distilled water in a 100-ml vol' metric flask. The subsequent preparation procedure followed that out- lined in the Manual of Analytical Methods (7) with the following modifications: The 100-ml solution was quantitatively transferred to a 300-ml BOD bottle: 2 ml of 5*!^ potassium persulfate was added to each bottle and allowed to stand for 1 minute; 4 ml of 5'"c potassium permanganate was added to each bottle and allowed to stand for 1 minute; 2 ml of sodium chloride hydroxylamine sulfate was added to reduce the excess permanganate; and 5 ml of well-mixed stannous sulfate (or stannous chloride) suspension was added and the bottle immediately attached to the aeration assembly. Vol. 6, No. 2, September 1972 Prior to analyzing the hair samples, two types of equip- ment— the Coleman 50 mercury analyzer (C-50) and the Perkin-Elmer 303 atomic absorption spectrophotom- eter (P-E 303) — were compared by analyzing pheasant breast tissue. Results of analysis by each machine are given in Table 2. The C-50 provided accurate and rapid results when the mercury levels were above 0.05 ju.g, but for lower levels, the P-E 303 with a detection limit of 0.003 jug {8) was required. Hair samples were analyzed using the C-50; however, to insure that accuracy was being maintained, the work was frequently checked by the A.O.A.C. method using the P-E 303. If a hair sample contained residues over 15 ppm mer- cury, the remaining portion of hair taken from the individual was washed with a detergent having no measurable mercury, air-dried, and then reanalyzed. A TABLE 2. — Mercury residues in pheasant sample.K determined by two instruments Pheasant Mercury Residues in «c Number P-E 303 • C-50 = 1 .152 .06 2 .175 .10 3 .187 .18 4 .225 .18 5 .601 .81 6 .352 .37 7 .130 .10 8 .150 .10 9 .100 .10 10 .190 .10 II .120 .07 12 .135 .10 13 .098 .09 14 .225 .19 15 .225 .16 16 .086 .05 17 .088 .07 18 .742 .70 19 .913 .82 20 .591 .59 21 .404 .47 22 .233 .27 23 .231 .21 24 .154 .29 25 .203 .28 26 .264 .32 27 .600 .42 28 .124 .23 29 1.024 l.IO 30 1.300 1.22 31 .384 .42 32 .940 .81 33 .790 .77 34 .261 .14 35 .080 .07 36 .100 .07 37 .210 .15 38 .131 .10 39 .065 .07 40 .474 .53 41 .100 .10 42 .090 .07 43 .065 .06 44 .081 .05 45 .070 .07 46 .125 .22 47 .055 .14 M'OTE; Coefficient of Correlation: -f-.97; Regressional Line of Y on X: Y = .970. X = .001; and Standard Error of Estimate of Y on X is .067. Perkin-Elmer 303 atomic absorption spectrophotometer. Coleman 50 mercury analyzer. 81 I solvent extract of hair was not undertaken because of the solubility of many alkyl mercury compounds UO). Results of analyses of 12 random hair samples are given in Table 3 and indicate that there were no appreciable differences in mercury levels before and after hair washing. Any variance that did occur may have been due to the inability to make two homogeneous sub- samples from the same sample. Thus, the level of mer- cury was not considered attributable to external con- tamination, but was a part of the highly proteinized hair. After every 100 samples were analyzed, a test to de- termine recovery values was done by analyzing an homogenized hair sample twice, first as received and second containing a spike control with the amount of the spike being unknown to the analyst. The average recovery of spike controls was 99.7%, regardless of the digestion method used. In addition, each day a known standard was analyzed to calibrate both analytical in- struments. TABLE 3. — Mercury levels in 12 random samples of hair, analyzed as received and after washing Mercury Residues in ppm FIGURE 1. — Mercury residues in hair samples from IOC Idaho residents by age and sex of donors Hair as Received Washed Hair 13.86 25.60 17.40 16.40 107.00 132.00 22.40 17.60 38.00 26.40 36.00 24.00 39.00 31.00 15.20 10.00 18.40 22.00 13.60 12.00 21.20 23.00 16.40 19.60 Results and Discussion Mercury was found in all 1,000 hair samples, with the average concentration being 4.18 ppm. Mercury levels ranged from a low of 0.12 ppm in a male to a high of 139.0 ppm in a female. These levels in samples were sub- sequently evaluated according to the sex of the donor and by age groups for each sex (Fig. 1). The average level was higher for females (5.90 ppm) than males (2.45 ppm); similarly, according to the age group, fe- males had mercury levels 1.6- to 3.2-fold higher than those for males. One or more individuals in every age group, however, exceeded the normally expected level of mercury in human hair of 10 ppm (9); however, only 20 men (3.37%) had levels above 10 ppm compared with 61 women (14.99%). In two age groups (41 to 60 years and 60+ years), the maximum range approached the 150 ppm mercury level in hair considered danger- 82 ous (9). The highest level of mercury for males occurre for the age group 11-20 years; males within this af group are statistically the nation's largest food coi sumers ill). In comparing those individuals with high mercur levels, diet did not seem to play any great role in di termining these levels. Generally, individuals with hig levels ate little or no fish and, in most instances, n wild game. None of these subjects stated that they wei taking drugs containing mercury compounds, and n environmental exposure could be traced to individua with higher levels. Since few persons with high leve used hair coloring or conditioning preparations, th was also eliminated as a source of mercury exposun There did not appear to be any specific reason for th higher levels of mercury in females than males, an there was no available data to show evidence of enviror mental exposure differentially affecting males and U males {5.12-14). Sex differences in mercury levels might be influenced b hormonal mechanisms or the biochemical compositio of the sexes; however, further studies in this area ar needed. This rescnrch was supported under Contract No. 68-02-0552 by th Division of Pesticide Community Studies, Office of Pesticides Pre yrams. Environmental Protection Agency, through the Idaho Stat Department of Health. Pesticides Monitoring Journai LITERATURE CITED I) Benson, W. W.. Darrell W. Brock. Frank Shields III. Elmer R. Norberg, and James Clinc. 1971 . An analysis of mercury residues in Idaho pheasants. J. Idaho Acad. Sci. Spec. Res. Issue No. 2:17-26. ?) Gebhards. S., J. Cline. F. Shields, and L. Pearson. 1971. Mercury residue in Idaho fishes — 1970. J. Idaho Acad. Sci. Spec. Res. Issue No. 2:44-48. S) U. S. Deparlmeiil of Heallli. Education, and Welfare. Public Health Service. HSMHA, Center for Disease Control. 1971. Neurotropic disease surveillance, mer- cury poisoning. Rep. No. 1, March 15, 1971. 4) Hyland. John R . Jack Kevorkian, and Doiiald P. Cento. 1971. Total mercury levels in human tissues — a preliminary study. Lab, Med. 2(8):46-49. 5) Balo, L. C. and F. F. Dyer. 1965. Trace elcmenis in human hair. Nucleonics 23:72. 6) Horwitz. William (ed). 1970. Official methods of an- alysis of the Association of Official Analytical Chemists. Eleventh Edition. Assoc. Off. Anal. Chem. Washington, DC. 24.062 and 24.060. 7) Thompson. J. F. (ed). 1971. Analysis of pesticide resi- dues in human and environmental samples. Primate Research Laboratories, Environmental Protection Agency, Perrine, Fla., Section ]}. B:l-5, (S) Hatch. IV. Ronald, and Willard L. Olt. 196S. Determi- nation of sub-microgram quantities of mercury by atomic absorption spectrophotometry. Anal. Chem. 40(14):2085-2087. (9) Thomas Ely B. 1971. Alkyl mercury contamination of foods. J. Am. Med. Assoc. 215(2):287-288. [10) We.stoo, G. 1971. Determination of methylmercury compounds in foodstuffs: II. Determination of meth- ylmercury in fish. egg. meat, and li\er. .Acta f hem. Scand. 21:1790-1800. (//) Dii.mian. R. E., and F. J. McFarland. 1967. Assessments include raw food and feed commodities, market basket items prepared for consumption, meat samples taken at slaughter. Pestic. Monit. J. l(l):l-.5. [12) Rolhman. S. 1954. Physiology and biochemistry of the skin. Univ. Chicago Press, Chicago, 111. il3) Spector. W. S. 1956. Handbook of biological data. Saunders, Philadelphia, Pa. 267 p. 114) Scliroeder. Henry A., and Alexis P. Nason. 1969. Trace metails in human hair. J. Invest. Derm. 53(1): 71-77. OL. 6, No. 2, September 1972 83 Comparative Organochlorine Pesticide Residues in Serum and Biopsied Lipoid Tissue: A Survex of 200 Persons in Southern Idalio — 7970 ' Joe VVyllie. Joe Gabica. and W. \V. Benson ABSTR.^CT Paired samples of seriini and adipose tissue from patients undergoing abdominal surgery were studied in order to de- termine residue levels of organochlorine pesticides in the two tissues. Although the residue levels were found to vary with the type of pesticide and with sex and age of the donors, levels in Idaho residents did not differ greatly from persons elsewhere in terms of body burden. Attempts at establishing the degree of compartmental equilibria for p,p'-DDE and p,p'-DDT between the two tissues revealed that the distribution of these two residues was not directly proportional. Introduction Beginning with the report of Howell (/) in 1948 that DDT residues were present in human fat, the biological storage of persistent insecticides has been studied rather extensively. The literature on human storage was re- viewed by Robinson (70). The pesticide content of human adipose tissue using samples obtained primarily from autopsy {2-6) has been determined for \arious areas of the world. Fat samples taken from living per- sons, by biopsy or during routine surgery, have under- standably been examined less frequently (7-9). For obvious reasons, blood (and in many cases, serum) has become the tissue of choice for monitoring pesticide residues in humans. However, despite the abundance of available information concerning the respective occur- rence of pesticides in blood and fat, relatively little is known of their quantitative relationship to one another. To better understand this relationship, the Idaho Com- munity Study on Pesticides examined 202 paired serum and adipose tissue samples obtained voluntarily from From the Idaho Community Study on Pesticides, Idaho Department of Health, Statehouse, Boise, Idaho 83707. 84 hospitalized patients who lived in the highly agricultural region of southern Idaho. Sampling Procedures Both blood and adipose tissue samples were obtained from 141 female and 61 male Caucasian patients under- going abdominal surgery at Saint Luke's and Saint Alphonsus Hospitals, Boise, Idaho, and Merc\ Hospital, Nampa, Idaho. A 10-ml fasting whole blood sample was obtained from each volunteer during the hospital's routine blood collection for biochemistries and approxi- mately 5 g of panniculus fat was taken during the sub- sequent surgery. In an effort to maintain a maximum degree of validity, only adequately nourished patients were surveyed, A nalytical Procedures Whole blood was not extracted and analyzed. Because the Community Studies on Pesticides have evaluated serum analysis and use only serum samples in popu- lation studies, serum, rather than whole blood, was analyzed for serum-adipose tissue correlations. Following whole blood centrifugation, serum samples were extracted for organochlorine insecticides by a re- vised Dale-Cueto triple hexane extraction method [11.12). Two ml of serum was combined with 6 ml of nano- grade hexane containing a 20-ng internal standard of aldrin for subsequent recovery determinations and agitated for 3 minutes on a Vortex mixer. The mixture was then centrifuged for 10 minutes at 2.000 rpm and the hexane layer pipetted into a 50-ml concentrator tube. This procedure was repeated three times with unspiked Pesticides Monitoring Journal hexane, and the combined hexane fractions were then concentrated by means of a modified Snyder column on a steam bath to a final volume of 500 fj.]. Adipose tissues were extracted by a modified Mills (13) procedure, as follows: the 5-g sample was placed in a mortar and pestle containing 10 g of clean, sharp sand and I g of anhydrous sodium sulfate. This mixture was then ground vigorously into a uniform dry granular mass. One ml of nanograde hexane containing 1 /Mg of methoxychlor as an internal standard was added for subsequent calculation of percent recoveries. The re- sulting pulverized mixture was transferred to a 150-ml breaker by washing three times with 50-ml petroleum ether. This mixture was then filtered, evaporated to near dryness under nitrogen, cooled to room temperature in a desiccator, and reweighed for percent of fat content. Two grams of this fat weighed on an analytical balance was transferred to a 125-ml separatory funnel where par- titioning, extractions with hexane, and subsequent column fractionation were carried out following the procedures previously reported by Mills (/.?) and Mills. Onley, and Gaither (14). The concentrated hexane extracts of sera and fat were injected in 5-^\ aliquots into a MicroTck 220 gas chromatograph equipped with two different columns and tritium foil electron capture detectors. The operating analytical parameters were as follows: '4" X 6' glass columns, packed with \.5'"c OV-17 and I.95^c QF-I on 100 120 mesh Chromosorb W. DMCS. HP ( mesh Chrome )r A% SE-30 and 6rc sorb W. DMCS. HP QF-1 on 80 100 Temperatures: Column Injection char Detector 220° C nber 220° C 205° C Carrier gas: Flow rate: Nitrogen OV-17 QF-I- SE-30 QF-1- -70 ml/min 100 ml/min The two gas chromatographic columns used have a complete capability of separating for both quantitation and identification of the three isomers alpha-, beta-, and gamma- BHC and many other pesticides not before separable by a one-column determination. All quantitation of pesticide residues was based on relative peak heights. Each fifth fat sample extract and pooled sera were qualitatively analyzed by thin layer chromatography for confirmation of pesticides reported. Recovery for the aldrin spike in sera and the methoxy- chlor spike in adipose tissues was 60-90% and 75-95 Cc. respectively; results were corrected to 100%. Results and Discussion Seven organochlorine residues (p.p'-DDT. o.p-DDT. p.p-DDD, p.p'-DDE. dieldrin, fi-hHC. and heptachlor epoxide) were present in both fat and serum samples. Vol. 6, No. 2, September 1972 The means, ranges, and percent occurrence of these residues in samples are given in Table I. P.p'-DDE was the most prevalent and the most highly concentrated compound in both tissues followed by p.p'-DDT. Al- though dieldrin was the third most prevalent residue in sera, it was the sixth most frequently detected in adipose samples. This finding for dieldrin supports the conclu- sions of Morgan and Roan (.'>) that dieldrin might be more effectively stored in nonlipid tissues. The remain- ing four compounds occurred quite frequently in adi- pose tissue, but were detected much less often in serum. The current findings in sera differ slightly from a previ- ous study (16) of pesticide levels in sera from 1.000 persons from this region of Idaho in that mean serum p.p'-DDE concentrations are somewhat lower ( 15.5 ppb, this study versus 22.0 ppb) in the previous study and dieldrin in sera was detected much more frequently in this study (88%. this study versus 33% ). The present results for pesticide residues in fat generally agree quantitatively with those of recent investigations in other geographic areas, with the possible exceptions of Hawaii (2) which reported lower p.p'-DDE mean fat levels and Holland (17) where studies with adipose tissue revealed p.p'-DDE at mean concentrations of only 1.7 ppm. Overall, however, residues in persons in Idaho appear to be comparable to those found else- where. TABLE I. — Residue levels of organochlorine pesticides in serum and adipose tissue — Idaho. 1970 p.p'-DDE p.p-DDT Dieldrin g-BHC r.p-DDD Heptachlor epoxide o.p-DDT Residues in ppb Mean Range 2-70 0-14 0-10 0-15 0- 4 0- 2 Percent OCCUK- RENCE Adipose Tissue Residues in ppm Range 0.2-30 0.1-6.6 0-0.7 0-2.5 0-1.2 0-1.3 5-1.0 Percent Occur- rence 100 100 Concentrations of the four most commonly occurring pesticide residues in serum and adipose tissue (p.p'- DDE. p.p'-DDl. dieldrin, and /3-BHC), as a function of sex of the persons sampled, are shown in Table 2. In both serum and fat, males were found to have signifi- cantly higher average levels of p.p'-DDE. Males also had higher average levels of p.p-DDT than females in both serum and adipose tissue, but the difference was narrower in adipose tissue. Both sexes had comparable respective levels of dieldrin in both tissues. Mean /3- BHC levels in sera were considerably higher in males than females, but mean levels in fat were the same for both sexes. The detection of higher pesticide levels in men agrees with previous findings in Idaho (16) and other locations (6.18), but is at variance with the results 85 TABLE 2. — Residue levels of p,p'-DDE, p,p'-DDT, dieldrin, and ft-BHC in serum and adipose tissue by sex of persons sampled — Idaho, 1970 Males Females Compound (N = 61) (N = 141) Percent Percent ME4N Range Occurrence Mean Range Occurrence Serum P,P'-DDE 20.5 3-70 100 13.4 2-65 100 (Residues in pphl P.p'-DDT 4.9 0-14 99 3.7 0-14 98 Dieldrin 1.0 0-3 92 0.9 0-10 85 0-BHC 0.6 0-15 25 0.2 0-7 20 Adipose Tissue p,p'-DDE 8.5 0.2-23 100 6.6 0.3-30 100 (Residues in ppni) P.p'-DDT 2.1 0.1-7 100 1.8 0.2-7 100 Dieldrin 0.2 0-1 84 0.2 0-1 89 P-BHC 0.3 0-3 97 0.3 0-2 99 TABLE 3. -Residues levels of p,p'-DDE, p,p'-DDT, dieldrin, and ft-BHC in serum and adipose tissue hy age of persons sampled — Idaho, 1970 Compound Age 0-20 (N = 16) Age 21-40 (N = 47) Age 41-60 (N = 80) Age 61-90 (N = 59) Mean Percent Occurrence Mean Percent Occurrence Mean Percent Occurrence Mean Percent Occurrence Serum p.p'-DDE 7.57 100 14.27 100 16.11 100 17.87 100 (Residues in ppb) P.p'-DDT 2.55 100 4.46 98 3.92 98 4.52 98 Dieldrin .56 94 .88 83 1.06 89 .85 .86 3-BHC .09 13 M 21 .55 25 .36 20 Adipose Tissue P.p'-DDE 3.47 100 6.73 100 7.06 100 8.72 100 (Residues in ppin) P.p'-DDT 1.01 100 1.91 100 1.67 100 2.08 100 Dieldrin .14 100 .13 83 .17 88 .16 85 /3-BHC .15 '^_J .24 100 .36 98 .34 97 of Fiserova-Bergerova el al. (19). who found no (Jiffer- ences, as a function of sex, with respect to p.p'-DDT- derived materials in a group of 71 people in Florida. This tendency for males to store organochlorines at higher levels may be due in part to the relative complexity of female hormonal interrelationships which could con- ceivably result in increased microsomal enzyme activity and subsequent body burden reduction. The differing female pattern of fat deposition and the likelihood of males having greater environmental exposure to pesti- cides may also be contributing factors. Residue levels of p.p'-DDE, p,p'-DDT, dieldrin, and /3-BHC in serum and adipose tissue by age are shown in Table 3. Persons under 20 years of age had the lowest mean concentrations of all four pesticides in both sera and adipose; however, p.p'-DDE was the only residue that showed a consistent progression from the lowest level in people below 20 to its highest mean levels in persons ages 61 to 90 years. The tendency for p.p'-DDE levels to increase with age is what might be expected, and analysis of variance confirms this — p = .01 in serum and p < .01 in tissue. Mean levels of p,p'-DDT in- creased significally in both tissues between age groups 0-20 and 21-40 years; however, there was no significant difference among the age groups 21-40, 41-60, and 61- 90 years. This trend also carried a statistical significance in serum of p = .05 and in tissue, p — .05. 86 Both dieldrin and /3-BHC had similar patterns, i.e, there were no significant differences between the mean values found in the different age groups for either of these compounds. The means of positive findings are low for each compound in the total sampling, but the levels found varied widely. The statistical evaluation of this is negative. In Florida (/9) dieldrin levels in fat were reported to increase considerably in persons over 20 years of age; this could be due to differences in patterns of pesticide application and analytical techniques. The increase of p.p'-DDE in man with age may be expected in terms of in vivo organochlorine catabolism, according to the generally accepted scheme of Peterson and Robinson (20), DDT is dechlorinated in the body to DDD which then degrades to the excretable DDA or is excreted as DDT. DDE storage is not appreciably derived from ingestion of DDT, however, but by inges- tion of DDE previously broken down in the environ- ment from DDT (1 5.2 1). Failure of DDE to be effec- tively eliminated would then result in body burden levels that increase with age. DDT, in contrast, would be broken down and excreted much more readily, and thus, tissue levels would not be expected to increase so dramatically with time. The considerable difference between serum and adipose tissue in the relative frequencies of occurrence of p,p'- DDD, o,p-DDJ. /8-BHC, and heptachlor epoxide Pesticides Monitoring Journal [Table I) probably reflects the limitations of present analytical capabilities using serum samples of this size, rather than implying that these residues are sometimes present at high levels in fat but absent from serum. However, since p.p'-DDE and p.p'-DDT were detectable in both tissues in nearly all cases (Table 1). it would seem reasonable to correlate their respective tissue levels in an attempt to assay the degree of proportionalit\- between serum and adipose tissue residues. This was done by plotting the individual mean serum levels of £),p'-DDE and p.p'-DDT against their corresponding values for fat. From this information, Pearson correla- tion coefficients (r) were then derived. These point distribution studies are portrayed graphically in Fig. I through 4. It appears from these data that p.p'-DDE and p.p'-DDT levels in serum and adipose tissue from the persons sampled are not directly proportional, al- though females do seem to show a more positive cor- relation (Fig. 1 and 3) between levels in the two tissues than do males (Fig. 2 and 4). However, differences could be due to the occupationally and sc\uall\- related factors previoush' cited, as well as the smaller number of males sampled. Barquet ei al. {18) have postulated that serum and whole blood titres reflect both the DDE- and the total DDT-derived contents of adipose tissue; this assump- tion was based on two studies consisting of 59 and 65 persons each. This relationship has also been proposed by Radomski el al. (22) who examined 20 specimens of whole blood and adipose tissue obtained from autopsy sources and reported pesticide levels between the two tissues to be highly proportional. In contrast, we must tentatively conclude that lipid stored organochlorines are not always accurately predictable on the basis of serum levels. It thus appears that although serum residues may provide a convenient and useful estimate of acute exposure, their validity as an index of chroni- cally acquired adipose bod\ burden may be somewhat limited. To be sure, samples obtained from hospital -IGURE 1. — Dislribiilion of pp'-DDE residue levels in serum and adipose tissue from 141 females FIGURE 2. — Dislribuiion of p.p'-DDE residue levels serum and adipose tissue from 61 males FIGURE 3. — Distribution of p.p'-DDT residue levels in serum and adipose tissue from 141 females FIGURE 4. — Distribution of p.p'-DDT residue levels in serum and adipose tissue from 61 males Vol, 6, No. 2, September 1972 87 patients awaiting surgery are subject to some bias: for example, pathologically and chemotherapeutically in- duced biochemical changes could conceivably affect pesticide metabolism in such persons. However, the difficulties involved in obtaining adipose biopsies of sufficient size and number from the general population makes the use of hospital specimens a more practical choice at this time. See Appendix for chemical names of compounds discussed jn this paper. This research was supported under Contract No. 68-02-0552 by the Division of Pesticide Community Studies. Office of Pesticides Pro- grams. Environmental Protection Agency, through the Idaho State Department of Health. LITERATURE CITED (/) Howell. D. E. 1948. A case of DDT storage in human fat. Proc. Okla. Acad. Sci. 29:31. (2) Casarelt. L. J.. G. C. Fryer. W. L. Yauger. and H. W Klemmer. 1968. Organochlorine pesticide residues in human tissue — Hawaii. Arch. Environ. Health 17:306- 311. (3) Hoffman. W. S.. W. ]. Fishbein. and M. B. .Andehnan. 1964. Pesticide storage in human fat tissue. J. Am. Med. Assoc. 188(9):8I9. (4) Hoffman. W. S.. H. Adier. W . J. Fishbein. and F. C. Bayer. 1967. Relation of pesticide concentrations in fat to pathological changes in tissue. Arch. Environ. Health 15:758-765. (5) Morgan. D. P.. and C. D. Roan. 1970. Chlorinated hydrocarbon pesticide residue in human tissues. Arch. Environ. Health 20:452-457. (6) Zavon. M. R.. C. H. Hine. and E. D. Parker. 1965. Chlorinated hydrocarbon insecticides in human body fat in the United States. J. Am. Med. Assoc. 193(10): 181-183. (7) Dale. W. £., and C. E. Quinby. 1963. Chlorinated insecticides in the body fat of people in the United States. Science 142:595. (8) Lang. E. P.. F. M. Kunze, and C. S. Prickett. 195. Occurrence of DDT in human fat and milk. Am. Mec Assoc. Arch. Ind. Hyg. 3:245. (9) Shell Research, Lid. Great Britain, unpublished ob servations. (10) Robinson. J. 1969. The burden of chlorinated hydrc carbon pesticides in man Can. Med. Assoc. J. 100:18(1 191. (//) Dale. W. £., A. Curley. and C. Ciielo. 1966. Hexan extractible chlorinated insecticides in human blood. Lif Sci. 5:47-54. (12) Dale. W. £.. A. Curley. and W . J. Hayes. Jr. 1967 Determination of chlorinated insecticides in humai blood. Ind. Med. Surg. 36(4):275-280. (13) Mills. P. A. 1961. Collaborative study of certaii chlorinated organic pesticides in dairy products. ] Assoc. Off. Agric. Chem. 44:171. (14) Mills. P. A.. J. H. Onlcy. and R. A. Cailher. 1963 Rapid method for chlorinated pesticide residues ii nonfatty foods. J. Assoc. Off. Agric. Chem. 46:186-191 (15) Morgan. D. P.. and C. D. Roan. 1971. Absorptior storage and metabolic conversion of ingested DDT am DDT metabolites in man. Arch. Environ. Healtl 22:301-308. (16) Watson. M.. W . W. Ben.wn. and J. Gabica. 197C Serum organochlorine pesticide levels in people ii Southern Idaho. Pestic. Monit. J. 4(2):47-50. (17) DeVlieger. M.. J. Robinson, M. K. Baldwin. A. N Crabiree. and M. C. Van Dijk. 1968. The organo chlorine content of human tissues. Arch. Enviroir Health 17:759-767. (18) Barquet. A.. C. Morgade, J. Andrews, Jr., and R. A Graves. 1970. Changing profile of pesticide analysis ii human fat and blood. Ind. Med. 39:7. (19) Fiserova-Bergerova. V .. J. L. Radomski. J. E. Davie: and J. H. Davis. 1967. Levels of chlorinated hydro carbon pesticides in human tissues. Ind. Med. Surg 36:65-70. (20) Peterson. J. £., and W. H. Robinson. 1964. Metaboli products of p.p'-DDT in the rat. Toxicol. Appl. Phar macol. 6:321-327. (21) Roan. C. D., D. P. Morgan, and E. H. Paschal. 1971 Urinary excretion of DDA following ingestion of DD' and DDT metabolites in man. Arch. Environ. Healtl 22:309-315. (22) Radomski. J. L.. IV. B. Dicclimann. A. A. Rey. and T Mcrkin. 1971. Human pesticide blood levels as : measure of body burden and pesticide exposure Toxicol. Appl. Pharmacol. 20:175-185. 88 Pesticides Monitoring Journal RESIDUES IN FOOD AND FEED Arsenic Residues in Soil and Potatoes From Wisconsin Potato Fields — 1970 ' D. R. Steevens. 1,. M. Walsh, and D. k Kccncv ABSTRACT ^Olato fields in Wisconsin known to have Incn uvultd willi sodium arsenilc (NaAsOj were siiivcyeil in 1970 to tlclcrniinc 'esidue levels of arsenic (As) in potato tuber peelings and *iesh and in the soil. Total soil As residues ranged from 2.2 lo 25.7 ppni and were generally related to the amounts ■ipplied. Potato tuber peelings contained 0.2 to 2.6 ppm As. hut regardless of the amount of NaA.tO, applied, the tuhcr Wesh did not exceed 0.6 ppm As. It was concluded that As had not accumulated in these Wisconsin potato lu'lds to Votentially harmful levels. Introduction 'Accumulation of arsenic (As) in soil as a result of re- peated use of pesticides containing As in orchards, cot- iton, and tobacco fields has been found to adverseh laffect the quality and quantity of crops grown (1.4). IStudies to investigate the possible toxic effects and plant luptake of As applied to a Plainfield sand in Wisconsin |(i,6) showed that phytotoxic effects to vegetable crops |did not occur until 90 kg of As per hectare (ha) or more Ihad been applied. Residual phytotoxicity remained for [four cropping seasons after applicatio- of As at rates of 190 to 720 kg/ ha. Except for potato peelings, edible por- tions of vegetable crops were not contaminated with As. In view of this finding and the fact that sodium arsenite f had been used extensively in Wisconsin as a potato vine defoliant (applied at about 9 kg As ha) from 1950 to 196S. this study was undertaken to survey commercial potato fields in Wisconsin to ascertain if excessive levels of As had accumulated in the soil and potato tubers (flesh and peelings) due to use of sodium arsenite. 1 From the Department of Soil Science, Univ. of Wisconsin, Madison, Wis. 53706. Vol. 6, No. 2, September 1972 Materials and Methods In August 1970. soil and potato tuber samples were collected from a total of 18 potato fields in the three principal potato-growing areas of Wisconsin. At each site, a composite soil sample consisting of 10 randomly selected cores was taken from the plow layer. A com- posite potato tuber sample was also obtained at each site by taking tubers from five potato hills selected at random. The soil samples were air-dried (60 C) and ground (< SO mesh). Potato tuber samples were scrubbed using distilled water and a nylon fiber brush. Potato tuber peelings and flesh were analyzed separately; samples were air-dried (6()"C) and ground (20 Mesh). For total As analyses, plant tissue samples uere digested by using the HNO -HCIO. procedure of Blanchar el al. (- ). and soil samples were digested by the H SO. -HCIO. procedure of Small and McCants [5] with modification made by Jacobs et al. (.?). This procedure gave quantita- tive (>95'^) recovery of 10-100 ppm As added as AslO^ to soils. In addition, the amount of available soil As was determined by extracting with Bray P-l solution (0.025N HCI and 0.03n NH.F). an extractant com- monly used to determine available soil phosphorus (.'). Arsenic in the potato and soil digests and soil extracts was determined by the reduction-distillation method of Small and McCants (5) with modification made by Jacobs et al. {3). The sensitivity limit for this method was 0.1 ppm of As. Results and Discussion Results of analyses of soil and potato tubers are reported in Table I; arsenic residues reported represent the average of analyses of duplicate samples. 89 In general, total soil As levels were related positively with As application as reported by growers, although wide variations were noted (Table 1). Part of this disparity is probably due to the fact that the stated amount of As application was usually only an estimate. The level of naturally occurring As in soils is considered to be from 2 to 10 ppm (1.4). In this survey, As levels in the soil were <10 ppm at 7 sites and 10.0 to 25.7 ppm at 11 sites. The available Bray P-1 extractable As in soil was less than 5 ppm for all sites sampled. In comparison with the data obtained in experimental field plots {3,6), soil As levels were below any concentration deterimental to crops. The As concentration in potato peelings taken from the survey sites ranged from 0.2 to 2.3 ppm. while the greatest As level in the flesh was 0.6 ppm. The As tolerance limit for several vegetable crops has been established at 2.6 ppm (7); all potato samples obtained in this survey were well below this limit, especially con- sidering that the peelings constitute only a small portion of the total potato tuber. Sodium arsenite was removed from registration as a potato vine defoliant in 1969. The results of this survey indicate that past usage of NaAsO- has not resulted in levels of As in Wisconsin soils which would be ph\- totoxic or which would cause harmful levels of As to accumulate in potato tubers. This study was supported by the College of Agricultural and Life Sciences (Project No. 1027), University of Wisconsin, Madison. Wis. LITERATURE CITED (/) B/.s-/i<)/), R. F.. and D. Cliisholm. 1962. Arsenic accumu- lation in Annapolis valley orchard soils. Can. J. Soil Sci. 42:77-80. (2) Blanchar. R. W.. C, . Rchm. aiut A. C. CaUlwdl. I '^65. Sulfur in plant materials by digestion with nitric ;incl perchloric acid. Soil Sci. Soc. Am. Proc. 29:71-72. iS) .lacohs. L. W.. D. R. Kcciicy. unci L. M. Walsh. 1970. Arsenic residue toxicity to vegetable crops grown on Plainfield sand. Agron. I. 62:588-591. {4) Miles, J. R. W. 1968. Arsenic residues in agriculture soils of Southwestern Ontario. 3. Agric. Food Chem. 16:620-622. (.')) .Small, H. C. and C. B. McCants. 1961. Determination of arsenic in flue-cured tobacco and in soils. Soil Sci. Soc. Am. Proc. 25:346-348. (6) Stecvens, D. R., L. M. Walsh, and D. R. Kcency. Arsenic phytotoxicity on a Plainfield sand as affected by ferric-sulfate and aluminum sulfate. J. Environ. ' Qual. (Submitted for publication). (7) U. .S. Department of Agriculture. Pesticide Regiilalioti Division. 1968. Summary of registered agricultural pesti cide chemical uses. Loose Leaf. N.P. -Amount of arsenic applied as NaA.i02, total and e.xtractahle Bray P-l arsenic in soil samples, and arsenic concen- tration in potato tuber peelings and flesh from Wisconsin potato fields — 7970 Sampling Sites Total Arsenic Applied (kg/ha)' Total Arsenic (PPM)-' Bray P-1 Extractable Arsenic (PPM)- Peeling (PPM)- Flesh (PPM)- Sandy loams (Northwestern Wisconsin, Spooner area) Silt loams (North-central Wisconsin, Antigo area) Loamy sands (Central Wisconsin. Stevens Point area) 2.S.9 10.4 1 3.9 16.0 in.n 14.9 10.1 12..1 10.4 Plainfield sand [Data from a previous study in Wisconsin (6)] 720" 12.5 24.3 45.0 121.0 22.2 53.7 NOTE: T = trace = <.lppm. ^ Growers' estimate of total arsenic applied to sites 1-18. - Average of duplicate samples. 3 Phytotoxicity was noted in studies {3.6) after application of arsenic at rates of 90-720 kg/ha 90 Pesticiues Monitoring Journal RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury Concentrations in Game Birds. State of Washington — 7970 and 1971 Frank F. Acllcv anJ Oonnkl \V. Brown ABSTRACT In a survey to dclcnnine llie presence of iiurcury in llie liver of game birds, 246 specimens conlribiited by I- to 15-g aliquot of the dried sediment was mixed with a desiccant in a 1:.^ ratio by weight. The extraction and cleanup procedures were identical to those previously described for oyster samples. The oyster and sediment extracts were then quantified on Varian model 600 D gas chromatographs equipped with tritium electron capture detectors and glass columns (5' by Vs". o.d.) packed with 3% DC-200. Operating parameters were: oven temperature — 193° C; injector and detector temperatures — 210° C: and carrier gas — N: at 20 ml/min. For confirmation, extracts were injected on a mixed column of 5% QF-1 and 37c DC-200 (1:1 by weight) with the same operating parameters as above. Recovery rates of toxaphene in oysters and in sediments were above 85% and 909c. respectively. Toxaphene Vol. 6, No. 2, September 1972 concentrations below 0.25 ppm were considered in- significant for the purpose of this stud\. The data were not corrected for percent recovery. Results and Discussion The results of toxaphene analyses of oyster samples are presented in Fig. 2. The mean of the weekly concentra- tions in May was 3.30 ppm. Oysters collected on June 10, 1971, at about 10 a.m. on the day the dredging operation began, had a higher concentration than sub- sequent samples but contained 1.24 ppm less than the May average. The results of toxaphene analysis of the sediment core samples are summarized in Table 1. The concentrations in the first 10-cm increment (surface to 10-cm depth) of the three samples ranged from 35.5 to 1,858.3 ppm. The composite sample of surface sediment obtained after dredging (site B) contained 32.8 ppm toxaphene on a dry-weight basis. .Analyses of oysters and sediment (before and after dredging operations) revealed no significant increase of toxaphene residues resulting from the dredging and resultant spoil runoff. During the course of field observations, a few anchovies (which are also filter feeders) were observed in distress as a result of the dredging operation. The cause ap- peared to be related to the heavy suspeniled sediment FIGURE 2. — Coiicciitralion of toxaphene (in ppm. wet- wcighi basis) in llie American oyster (Crassostrea virginica) collected from near the intersection of Terry Creek with Back River, liriinswick, Ga. (as depicted in Fig. 1 ) APR M.W JUNE JULY AUG SEPT OCT 1971 95 -Toxaplienc conccnirations in three sediment cores, by lO-cm increments, collected from Terry Creek, Brunswick G a.— June 10, 1971 Residues in PPM and Content of Sediment Sampling Location Surf, to 10 CM 10-20 CM 20-30 CM 30-40 CM 40-50 CM 50-60 CM 60-70 CM 70-80 CM Site C ' 1.858.3 mud & some chips 1.340.5 mud & few chips 1,324.0 mud 1,367.2 mud 1,236.7 mud 433.6 mud 68.5 mud 83.2 mud' Site D- 111.85 mud & few chips 615.64 mud& many chips 16.04 mud 17.46 mud 5.42 mud 3.4 mud 2.88 mud ~ Site E = 35.5 mud 35.47 mud 21.9 mud 70.65 mud 79.8 mud 21.0 mud 18.5 mud 5.11 mud NOTE: — = no sample taken. • North shore of Terry Creek. 50 yd from junction with Dupree Creek and .2 mile from loxaphene plant outfall. - South shore of Terry Creek. .8 mile from the plant outfall and one half the distance from the outfall to Back River. ■' South shore of Terry Creek. 1.4 miles from the plant outfall and 50 yd west of Back River. load in the water which clogged the gill cavities of the fish, probably causing them to suffocate, rather than related to pesticide poisoning. Several weeks prior to the Terry Creek operation, menhaden and anchovies were observed in distress with clogged gill covers in the vicinity of another dredging operation in the Intra- coastal Waterway just north of Altamaha Sound. No lethal concentrations of pesticides were suspected in the Altamaha Sound area, since oysters collected there at monthly intervals for several years have contained no more than trace amounts of pesticides and no toxaphene. The anticipated sudden kill of fish and shellfish from toxaphene poisoning in Terry Creek did not occur, probably for a combination of reasons: (I) There was less runoflf of to.xaphene contaminated sediments than expected from the dredging operation. (2) The toxa- phene was bound to the clay particles and therefore not available to the biota. (3) The toxaphene in the lower sediments (below 10 cm) had undergone degradation and detoxification; chromatograms of sediments showed a marked difference with depth (illustrated by a buildup of peaks in the first portion of the chromatograms and diminishing peaks in the later portion) suggesting in situ dechlorination. (4) Lastly, the possibility exists that some fin fish were able to avoid the area in question. Any future dredging activities should be planned anc coordinated with further research. The relation ol suspended sediment load to toxaphene concentratior should be of primary concern. Additional research i: needed to document whether or not sediment toxaphene concentration increases in the direction from the mouth of Terry Creek toward the toxaphene plant outfal (Fig. 1). Detoxification studies in the form of static bioassays using toxaphene extracted from core sedi ments are currently in progress. See Appendix for cher of toxaphene. This work was funded in part by a grant from Hercules. Inc. t' (he University of Georgia. LITERATURK CITED (/) Butler. P. A. 1969. Monitoring pesticide pollution Bioscience 19( 10):889-891. (2) Wilson. A. J.. Jr. 1967. Pesticide analytical manual fo BCF contracting agencies, U. S. Bur. Commer. Fish. Gul Breeze. Fla. 1-11 p. 96 Pesticides Monitoring Journai Organochlorine Insecticide Residues in Water. Sediment, and Organisms. Aransas Bay. Texas — September 1969 -June 1970 Rdger R. Hay' and Leo W. Neuland- ABSTRACT All iincsligatioii was coiidiicUil lo (Uteiniiiic llic presence and (listribiilion of organochlorine insecticide residues in Aransas Bay and its contributing hays at Rock port. Tex. A total of SO water samples. 29 sediment samples, and 1 1 samples of 8 different types of organisms were collected and analyzed from September 1969 through June 1970. Organochlorine insecticide residues were detected in only J water samples and 3 sediment samples and. although resi- dues were detected in 8 of the II organism samples, these were all at low levels f<67 pph). The predominant residues found in the organisins were dieldrin, p.p'-DDD. and p.p'- DDE. The occurrence or concentration of residues coidd not be related to salinity or pH of the water or percent organic content of the sediments. Introduction The extensive use of organochlorine insecticides has led to an accumulation of these residues in the environment. In estuaries, the persistence of organochlorine residues creates a hazard to fish and other forms of marine life {3). Estuaries, in addition to supporting large shellfish populations, provide spawning and nursery grounds for many species of fish. Shellfish lar. ..e and young fish are extremely susceptible to chemical pollutants and other forms of environmental stress. The problem is compounded by the fact that some fish and shellfish are known to concentrate organochlorine residues in their tissues and, thus, pass these residues along the food chain. 1 Department of Biology, Texas Christian University, Ft. Worth. Tex. 76129. Present address: Department of Oceanography. Texas A&M University. College Station. Tex. 77843. - Department of Geologv, Texas Christian University, Ft. Worth, Tex. 76129. Vol. 6, No. 2, September 1972 Insecticides entering the estuary in water can be in- troduced into the food chain (1) when residues are absorbed by plankton or other organisms and (2) when residues are adsorbed to suspended particles which settle and become part of the bottom sediment where benthic fauna feed (5). Insecticides entering on silt and detritus also may become part of the sediment. The food chain at the same time pla\s an important role in removing insecticides from estuaries since fish and porpoise immobilize insecticide residues in their body tissues and. thus, these insecticides are removed from estuaries when fish migrate to sea. Similarly, fish-eating birds accumulate large amounts of insecticides and then distribute them along migratory pathways. The major portion of insecticides entering estuaries, however, are lost through dilution, chemical decay, and adsorption by bottom deposits {^). The effects on aquatic organisms of chronic exposure to organochlorine insecticides were first realized with the reproductive failure of lake trout in New York and high mortalities in hatchery-reared coho salmon related to /i./i-DDT residues in the eggs (2). Investi- gations have shown that, of the commonly used organo- chlorine insecticides, endrin has the highest acute toxi- city to fish. Fish subjected to chronic exposure of low- concentrations of endrin were found to be more suscep- tible than control fish to lethal concentrations of endrin during the first 24 hours of exposure: however, by 72 hours the two groups exhibited similar survival {10). Extensive experimentation has been conducted to de- termine the effects on oysters of chronic exposure to sublethal concentrations of p.p'-DUT and other or- ganochlorine insecticides. Under controlled laboratory conditions, oysters exposed to p.p'-HYyj at concentra- 97 tions of 1 to 2 parts per billion (ppb) at 30 C appeared to grow and behave in a manner similar to that of the control groups; analyses of the tissues, however, revealed concentrations of p.p'-DDT many times that of the environment (4). A concentration of 7 to 10 ppb p.p'- DDT in water inhibited 50% of the normal shell deposi- tion in oysters (.?). Physiological irritation was shown by spasmodic shell movements when the concentration of p.p'-DDT in the water was increased to 0.1 parts per million (ppm), and at a concentration of 1 ppm, the oysters usually remained closed (4). In the presence of continuous low level p.p'-DDT pollution, oysters con- centrated the insecticide in their tissues to more than 25 ppm within 1 week without showing any harmful effects; however, 50% of the small fish and shrimp fed this oyster meat died within 2 days (4). Dissection of oysters containing p.p'-DDT residues has shown that 67% of the p.p'-T>DT was stored in the intestinal tract, digestive gland, and gonads. The gonads were found to be a major site of /),/)'-DDT storage with residues in excess of 25 ppm reported in the gametes. An attempt was made to culture oyster larvae from such highly contaminated gametes in order to determine the effects of inherent p,p'-DDT on oyster development. Unfortunately, the experiment failed at an early stage due to technical difficulties in the laboratory (4). The Gulf Breeze Laboratory of the Environmental Pro- tection Agency (formerly under the Bureau of Com- mercial Fisheries, USDI) at Gulf Breeze, Fla., is en- gaged in a monitoring program for organochlorine insecticides. Oyster samples from coastal States are col- lected at 30-day intervals and analyzed for organo- chlorine insecticide residues. In 1967, oyster samples were obtained on a monthly basis from 12 stations in Texas. Of the 129 samples analyzed. 90% contained one or more organochlorine insecticide residues (6). A similar investigation of Galveston Bay following exten- sive mosquito control programs in the fall of 1964 (7) reported no indication of elevated insecticide levels in water and oyster samples. Insecticide levels were low in both water and oysters, usually less than 0.01 ppm if detected. The study reported here was conducted to determine the organochlorine residues in Aransas Bay, Tex., and its adjacent contributing bays, Copano, Mission, and St. Charles. (Fig. 1) from September 1969 through June 1970. The land area surrounding Aransas, Copano, and St. Charles Bays is primarily ranch land with secondary agricultural usage. The area is drained by the Aransas and Mission Rivers and the Copano, Cavasso, Salt, and Burgentine Creeks. Samples collected for analysis in- cluded water, sediment, and various types of organisms. Locations of sampling stations arc shown in Fig. 1. 98 FIGURE 1. — The area of investigation showing sampling stations, Aransas Bay, Texas — 1969-70 Collection of Samples Water samples were collected monthly from Septembeif 1969 through June 1970. Samples were taken at the sur- face in clean 2-qt glass jars with aluminum foil lined' lids and stored in darkness to prevent photochemical: alteration of insecticide residues. Sediment samples were collected in September and November 1969, and January, May, and June 1970 using a grab sampler; samples were then refrigerated to minimize loss of the insecticide due to biochemical degradation. Dates of collection of organism samples listed below depended on their availability; shrimp, oysters, and crabs were obtained in January and March 1970, and the fish samples were collected in July 1969. sea trout Cynoscion arenarius drum Pogonias cromis oysters Crassostrea virginicia blue crab CaUinectes sapidus silversidc minnows Mcnidia menidia vellowiail croaker Bairdella chrysura ribbon fish Trichiurus lepturns brown shrimp Penaeus aztecus Pesticides Monitoring Journal Each sample represented an average of at least 12 in- dividuals of a species. All organisms were collected with a trawl, except for oysters which were picked from the reef, and then frozen until analysis. A nalytical Procedures The procedure for quantitatively e.xtracting organo- chlorine insecticides from water, sediments, and or- ganisms is described below. The solvents, hexane and hexane: acetone (41:59) used in the extraction tech- niques, were repurified by glass distillation employing a 3-ball Snyder column. WATER One liter of water was separated from suspended material by centrifugation or settling: then 500 ml of the sample was extracted with 100 ml of hexane by shaking for 1 minute in a separatory funnel. After separation of the layers was complete, the water was drawn off: the remaining 500 ml of water added, and the sample ex- tracted by shaking for 1 minute. If emulsification was encountered between the hexane and water, anhydrous NaL'SOi was added to break the emulsion. The hexane phase was quantitatively transferred to a Kuderna- Danish concentrating apparatus equipped with a 3-ball Snyder column and concentrated in a water bath of 5 ml. The extract was transferred to a 10-ml volumetric flask and brought to volume. The hexane extract was analyzed directly by gas-liquid chromatography (CiLC without further cleanup. SEDIMENT On removal from refrigeration, the sediment samples were spread and allowed to dry at room temperature. The dry sediments were ground with a mortar and pestle to pass through a #30 mesh sieve, thus insuring uniform saturation of the sample with solvent. A 20- to 30-g subsample (dry weight) was weighed, placed in a Soxhlet extraction apparatus, and refluxed for 6 hours using hexane: acetone as the extracting solvent. Since acetone is unsuitable as a solvent in GLC employing an electron capture (EC) detector, the insecticides were partitioned into the hexane phase by the addition of water. The hexane phase was then transferred to a Kuderna-Danish evaporating appar.i.us with a Snyder column and concentrated to approximately 10 ml for cleanup by column chromatography. ORGANISMS Immediately after thawing, the individual organisms making up a sample were ground to a fine mixture in a blender. A portion of this homogenate was weighed, and three times the subsample's weight of anhydrous Na^SOi was added. The mixture was blended thoroughly to insure adequate distribution of the NaiSOi and adsorption of the water. The sample was extracted following the same procedure as described for sediments. Vol. 6, No. 2, September 1972 Following the extraction and partitioning of the in- secticides into the hexane phase, the sample was con- centrated in the Kuderna-Danish apparatus to approxi- mately 10 ml for cleanup by column chromatography. CLEANUP OF SAMPLE EXTRACTS The presence of relatively large amounts of interfering materials in sediments and biological samples requires that these samples be cleaned up prior to analysis by GLC. Column chromatograph\ was selected as a method of cleanup because of its large carrying capacity and its ability to pre-separate insecticide mixtures, thereby aiding in the analysis of subsequent gas chromatograms. Florisil (activated magnesium silicate) was employed as the adsorbent, and elutions were made with 51^ ether in hexane and 15'"f ether in hexane. The procedure followed was essentially that described in reference (9) with modifications I.S). GAS-LIQUID CHROMATOGRAPHY A Varian Aerograph model 204B equipped with a "H-foil EC detector was employed for the separation and identification of organochlorine insecticide residues. The use of all glass columns and on-column injection was required to a\oid sample degradation resulting from contact of the sample with metal surfaces. Gas chro- matographic conditions were as follows: Columns: I m long x 4 mm i.d. glass packed with 10% DC-200 or W'r QF-1 on 60/80 mesti Gas Chrom Q Temperaiures: Columns: 195° C (QF-1) 215° C (DC-200) Injector: 230° C Carrier gas: Sensitivity: N.. with a flow rate of 75 ml/min 1.2 X 10-" amps full scale Identification was based on retention times from the polar (QF-1) and non-polar {DC-200) columns. The use of two columns of differing polarity decreases the pos- sibility of erroneous identifications. An L&N Speedomax W recorder with a disc integrator was used to calculate peak areas. All of the samples were analyzed for the following organochlorine insecticides; y-BHC, heptachlor, hep- tachlor epoxide, aldrin, dieldrin, endrin, ^.^'-DDE, A'.p'-DDD, and /'.p'-DDT. Analysis was not performed for polychlorinated biphenyls, since the investigation was planned and executed prior to the availability of methods and standards for these compounds. RECOVERY Organochlorine insecticide standards of greater than 99'"f purity were obtained from the following sources: heptachlor, heptachlor epoxide, and endrin from Velsicol Corporation; aldrin and dieldrin from Shell Chemical Company; p./^'-DDD from Rohm and Haas; y-BHC from the U. S. Food and Drug Administration; p.p'- DDT from City Chemical Corporation; and ;).p'-DDE 99 from the Pesticide Repository, Perrine Primate Labora- tory, Environmental Protection Agency. Recovery rates were assumed to be in the range of 90-100% according to the methods used {1,8.9). Results and Discussion The results of the analysis for organochlorine residues are considered below, followed by an interpretation of these data. An attempt was made to relate the presence or concentration of insecticide residues to the physical and chemical characteristics of the area. Salinity and pH data of the water samples were obtained from the Texas Department of Parks and Wildlife at Rockport. and organic content of the sediments was determined by combustion of the sample at 500° C. A summary of these characteristics of the water and sediment from each sampling station is presented in Table 1 . TABLE L — Salinity and pH of water and organic matter content of sediments at the sampling stations. Aransas Bay, Texas — 1969-70 TABLE 2. — Organochlorine residues in water, Aransas Bay, Texas— 1969-70— Continued IT = Trace = <0.1 ppb; — = not detected] Water Sediments Sampling Percent Station Salinity Organic Content (PPT) pH (dry-weight basis) A-1 15.0 8.3 2.1 A-2 12.2 8.3 1.7 A-3 11. 1 8.3 14,3 A-4 16.1 8.3 5.4 A-5 20.5 7.9 5.0 C-1 6.6 8.1 5.7 C-2 1.1 8.2 4.7 C-3 8.9 8.(1 1.8 St. C^ 11.1 8.4 6.9 St. C-.'! 12.2 8.3 8.2 St. C-6 8.3 8.4 10.2 TABLE 2. — Organochlorine residues in water. Aransas Bay, Texas— 1969-70 IT = Trace = <0.1 ppb; — = = not detected] Residues Collection Sampling Detected in Date Location PPB (ng/g) 1969 Sept. A-l P.P'-DDT (T) endrin (4.4) A-2 A-3 A-4 A-5 — Oct. A-l P.P'-DDT (T) A-2 A-3 A-4 A-5 _ Nov. A-l A-2 _ A-3 A^ A-5 C-2 St. C-4 _ St. C-5 _ St. C-6 - Residues Collection Sampling Detected in Date Location PPB (ng/g) Dec. A-l A-2 - A-3 — A-4 — A-5 — C-1 heptachlor (T) C-2 — St. C-4 St. C-5 St. C-6 — 1970 Jan. A-l — A-2 — A-3 — A-4 — A-5 — C-1 — C-2 St. C-4 — St. C-5 — St. C-6 — Feb. A-l A-2 — A-3 — A-4 — A-3 — C-1 — C-2 — C-3 — St. C-4 St. C-5 — St. C-6 _ Mar. A-l — A-2 — A-3 — A-4 — A-5 — C-1 — C-2 — St. C-4 — St. C-5 — St. C-6 — Apr. A-l _ A-2 — A-3 — A-4 — A-5 — C-1 — C-2 — St. C-4 — St. c-5 — St. c-6 — May A-l _ A-2 — A-3 — A-4 — A-5 — c-1 — C-3 — June St. C-4 — St. C-5 — St. C-6 — 100 WATER The results from the analyses of water samples for organochlorine insecticides are shown in Table 2. Sensitivities were 0.05 ppb for all insecticides in water except DDT and its isomers; the sensitivity for DDT and its isomers was 0.1 ppm. Concentrations below 0.1 ppb could not be accurately quantified and were reported as trace (<0.1 ppb). Eighty water samples were an- alyzed, and 3 (3.8%) showed the presence of organo- Pesticides Monitoring Journal chlorine insecticide residues. Heptachior. endrin, ;ind p.p'-DDT were the only organochlorine residues de- tected in the water samples. No correlation could be made between the insecticide residues detected and the chemical properties of the area. These amounts represent only the insecticides dissolved in the water and do not include the suspended load of the water, i.e.. suspended plankton, detritus, and silt. Therefore, the data are reasonable considering the low solubility of organochlorine insecticides in water, the adsorptive properties of sediments, and the ability of organisms to concentrate insecticide residues in their tissues. SEDIMENT The results from the analyses of sediment samples for organochlorine insecticides are shown in Table 3. The limit of detection was 0.1 ppb. Organochlorine insec- ticides were detected in only ? (10.3'';) of the 29 samples analyzed. No correlation could be made between insecticide resi- dues detected in the sediment and the chemical prop- erties of the area. There was no relationship between insecticides reported in water samples and insecticides detected in the sediment: in each instance the residues detected in the water samples differed in type from the residues detected in the sediments. Heptachior. endrin, and p.p'-DDT were detected in the water, but only dieldrin and p.p'-DDD were found in the sediments. TABLE 3. -Organochlorine residues in sedinienl. Aninsas Bay, Texas— 1969-70 I — =: not detected] Residues Collection Sampling Detected in Date Location PPB (NG/G) 1969 Sept. A-1 dieldrin (0.7) A-2 ~~ A-3 dieldrin (0.5) A-4 A-5 — Nov. C-2 p,r-DDD (24.6) St.C^ — St. C-5 _ St. C-5 - 1970 Jan. A-1 — A-2 _ A-3 — A^ — A-5 _ CI — C-2 — St. C-4 St. C-5 St. C-6 May A-1 — A-2 — A-3 — A^ — A-5 _ C-1 C-3 June St. C-» St. C-5 St. C-6 — ORGANISMS The results from the analyses of organisms for organo- chlorine insecticides are shown in Table 4. The limit of detection was 0.1 ppb. Dieldrin, p,/7'-DDE, p.p'-DDD, and p.p'-DDT were the only insecticides present in any of the organisms. The concentrations ranged from a trace (<0.1 ppb) to 66.5 ppb. The predominant in- secticide residues detected in this investigation coin- cided with those found for this area by the Gulf Breeze l.aboratorv. and concentratons were similar. TABLE 4.- -Orgunoclilorinc residues in organisms, Aransas Bay, Texas— 1969-70 T — Trace = <0.1 ppb; — = not detected I Collection Date Type of Sample Sampling Location Residues Detected in ppb (ng/g) 1969 July 2nd year, (muscle) St. Chas. Bay dieldrin (3.4) P,P'-DDE (25.5) p.p-DDD (2.1) r.p-DDT (5.5) 2nd year, drum (whole) Si. Chas. Bay dieldrin (9.7) P.p-DDE (3.6) p.p-DDT (2.1) 1970 Jan. oysters A-1 P.p-DDE (5.9) P.P-DDD (T) Mar. blue crab (muscle) Aransas Bay P.P'-DDE (7.8) p.p-DDD (T) blue crab (viscera) Aransas Bay — blue crab (eggs) Aransas Bay - silverside minnows Aransas Bay P.P'-DDE (33.3) P.P'-DDD (30.0) dieldrin (13.3) yellowtail croaker Aransas Bay P.P-DDE (66.5) p.p-DDD (60.0) P.p-DDT (T) ribbon fish Aransas Bay P.p-DDE (33.6) P.P'-DDD (41.0) brown shrimp Aransas Bay — yellowtail croaker Aransas Bay P.p'-DDE (25.0) p.p-DDD (T) Vol. 6, No. 2, September 1972 Of particular interest is the lack of insecticide residues detected in shrimp and the low concentrations in the blue crabs and oysters. Butler (5) has postulated that the absence of insecticide residues in shrimp and other crustaceans is due to their high sensitivity to or- ganochlorine insecticides, antl that these animals arc killed when the concentration of insecticides reaches a threshold value; this threshold may be low and thus, death may occur before these organisms have had time to metabolize the insecticide. The low insecticide concentration in ihc oysters (p.p- DDE, '>.') ppb: p.p-DDD. <0.1 ppb) is accounted for by the uncontaminated water and sediment at Station A-1. Although oysters can concentrate insecticides in their tissues when placed in contaminated water, they also have the ability, unlike many other organisms, to "flush" insecticide residues from their tissues when placed in uncontaminated water (4). 101 Butler (6) interpreted the presence of a high percentage of p.p'-DDT as indicating direct exposure to the insecti- cide and the presence of metaboHtes alone or at dis- proportionately high levels, as indicating that the residues have been transmitted through the food chain. A high percentage of p.p'-DDT was reported in the tissues of the sea trout and drum taken in July 1969. The first water samples analyzed (September 1969 and October 1969) indicated a trace" of p.p'-DDT at Station A-1. No p.p'-DDT was found in any other water samples and only at one other time in any organism: this organism, the yellowtail croaker, (collected March 1970) had a trace of p.p'-DDT (<0.1 ppb) which constituted less than 0. 1*^ of the total residues detected in the sample. The small number of sediment and water samples in which organochlorine insecticides were present indicates that insecticide contamination of Aransas Bay is rela- tively low. and the presence of low organochlorine in- secticide concentrations in the organisms may he attrib- uted to transmission bv the food chain. A cknowledginent Appreciation is expressed to the Texas Parks and Wild- life Department. Rockport, Tex., for their help in the collection of the samples and especially to Mr. T. L. Heffernan. See Appendix for chemical names of paper. npounds discussed This research was supported by the Texas Christian University Re- search Foundation, Grant No. B6976. LITERATURE CITED (1) Barry. H. C J. G. Hundley, and L. Y. Johnson. 1963. (Revised Annually) Pesticide analytical manual. Vol. I. Food and Dnig Admin. U. S. Dep. Health. Educ and Welfare, Washington. D.C. 20204. (2) Burdick. G. £., E. J. Harris. H. J. Dean. T. M. Walker, Jack Skca. and David Colby. 1964. The accumulation of DDT in lake trout and the effect on reproduction. Trans. Am. Fish. Soc. 93(2): 127. (3) Biiller. Philip A. 1966. Fixation of DDT in estuaries. Trans. 3 1st North Am. Wildl. Nat. Resour. Conf. (4) Butler. Philip A. 1966. Pesticides in the marine en- vironment. J. Appl. Ecol. 3(Suppl.):253-259. Blackwell Scientific Publications, Oxford. (5) Builcr. Philip A. 1968. Pesticides in the estuary. Proc. Marsh Estuary Manage. Symp., La, State Univ.. Baton Rouge, La., July 19-20, 1967. (6) Butler. Philip A. 1969. The significance of DDT residues in estuarine fauna, p. 205-220. hi: Morton W. Miller and George G. Berg (eds.). Chemical fallout: current research on persistent pesticides. Charles C. Thomas, Springfield, 111. (7) Casper. Victor L. 1967. Galveston Bay pesticide study- water and oyster samples analyzed for pesticide residues following mosquito control program. Peslic. Monit. J. \0):n-\5. (S) Fay. R. R.. and L. IV. Newland. 1972. Elution of some organochlorine insecticide mixtures by florisil column chromatography. Tex. J. Sci. 24(2): 191 -196. (9) Federal Water Pollution Control Administration. 1969. FWPCA method for chlorinated hydrocarbon pesticides in water and wastewater. U. S. Dep. Interior, Cincinnati, Ohio. (/O) Lowe. Jack I. 1965. Some effects of endrin on estuarine fishes. Abstract 19th Ann. Conf. Southeastern Assoc. Game Fish Comm. 102 Pesticides Monitoring Journal p Total Mercury in Largemouth Bass (Micropterus salmoides) in Ross Barnett Reservoir, Mississippi — 7970 and 1971 Luther A. Knighl, Jr. and Jack Herring" ABSTRACT Total mercury in 7S largemoulh bass, Micropterus salmoides. from Ross Barnett Reservoir. Mississippi, was measured by atomic absorption spectrophotometry. The fish analyzed Here collected between November 1970 and October 1971 at intervals representing winter, spring, summer, and fall: specimens ranged in weight from 0.10 to .?./5 kg. Fish contained from 9.06 2.66 F 0.17 54.61 3.09 F 0.17 SEPTEMBER 30 AND OCTOBER 1, 1971 (FALL SAMPLES) 31.12 0.40 M <0.05 36.83 0.77 M <0.05 41.91 1.02 F 0.10 45.09 1.29 F 0.14 48.90 1.55 F 0.18 48.26 1.86 F 0.27 54.61 2.34 F 0.36 57.15 2.76 F 0.33 60.69 3.10 F 0.44 45.72 1.40 F 0.08 50.17 2.13 F 0.18 52.07 2.56 F 0.13 Total Number of Samples = 73 TABLE 2. — A verage concentrations of total mercury in Ross Barnelt Reservoir largemoiitli bass according In weight groups Average Mercltrv VVrrnHT Groue- Concentration Number oi (KG) IN PPM Fish 00.50 0.12 31 0.51-1.00 0.18 15 1.01-1.50 0.20 14 1.51-2.00 0.23 4 2.01-2.50 0.27 2 2.51-3.00 0.25 4 3.01-3.15 0.45 3 NOTE: In calculaling average concentrations, those less than 0.05 ppm were computed at 0.05 ppm. The ability of aquatic organisms to concentrate niercur\ above the level found in their environment is well known (/,9). However, the mechanism by which fish concentrate mercury is not fully understood. Rucker and Amend (12) found that mercury levels in muscle tissues from lake trout treated 1 hour per week for 12 weeks with 6.25% ethylmercury phosphate reached maximum concentrations of 4.4 ppm and returned to normal approximately 17 weeks following cessation of treatment. Studies have shown that fish absorb mercury compounds directly through their gills and through ingestion of a contaminated food {7,12). Vol. 6, No. 2, September 1972 Total Mercury (PPM) Number of Fish per Weight Group NOV. 18 & DEC. 30.1970 (WINTER SAMPLES) < 0.05-0.1 15 2 <0.1-Q.2 2 3 <0.2-0.3 4 < 0.3-0.4 <0.4-0.5 < 0.5-0.6 < 0.6-0.7 1 <0.7-0.8 MARCH 29, 1971 (SPRING SAMPLES) < 0.05-0.1 <0.1-0.2 - 0.2-0.3 1 < 0.3-0.4 1 < 0.4-0.5 <0.5-0.6 <0.6-0.7 < 0.7-0.8 ' JUNE .8 & JULY I 1971 (SUMMER SAMPLES) < 0.05-0.1 I <0.1-0.2 10 I 1 1 < 0.2-0.3 I < 0.3-0.4 < 0.4-0.5 <0.5-n.6 <0.6-0.7 < 0.7-0.8 SEPT 30 & OCT. 1. 1971 (FALL SAMPLES) u The authors thank W. H. Allaway and E. E. Cary for advice on the analysis of selenium and for supplying analytical reagents. The authors also thank W. D. Youngs of the Conservation Department, Cornell Uni- versity, for collecting the Cayuga lake trout of various ages. TABLE 1. — Percent recovery of selenium from fish TABLE 3. — Residues of total selenium in fish New York Stale waters in 1969 from Si;i.ENiuM Added Percem Species (PPM) Recovery Brown cattish 0.2 105.85 0.5 68.98 i.n 84.94 Lake {rout 0.5 100 1.0 97 Largemouih bass 0.2 75.60 0.5 86.88 1.0 85.69 Northern pike 0.2 80.90 n.^ 80.68 I.() 89.89 NOTE: Sensitivity level — 0.1 ppiii. TABLE 2. -Common and scientific names of fish analysed in this study Common Name Scientific Name Black crappic Ponwxi\ nivromaculatus Bowfin Amia calva Brook trout (Speckled trout) Salvelintis fontinalii Brown trout Salmo Inula Brown catfish (bullhead) and Ch.inncl catfish fclaturus xp. Burbot Lola tola Carp Cyprinus carpio Chain pickerel F.SOX niger Cisco Coregonux artcdii Coho salmon Oncorliynchus kisutch Freshwater drum Aplodinolus grunniens Gizzard shad Dorosoma cepedianum Goldfish Carassiits auratux Lake trout SahcUttus namavcush Lake whitefish Coregonus clupeaforniis Largemouth bass Micropterux xatmoides Muskellunge Esox masquinougy Northern pike Esox lucius Perch Perca sp. Rainbow trout Salmo gairdneri Rock bass A mhtopHles rupeslris Smallmouth bass MUropterus dolomieui Splake (Brook and Lake iroui cross) Striped bass Mnrnne saxatitis Sturgeon, Atlantic sturgeon, and Shortnose sturgeon Acipenser sp. Walleye pike Stizostedion xitreuni \itreum White bass (Silver bass) Roccus chrysops White sucker (Sucker) Caloslomus comntersoni Length (CM) WEIGH! (KG) Selenium Residue Level (PPM) BLUE MOUNTAIN LAKE— NO. 1 ■ Bullhead catfish 6R6527 F 28.4 .379 0.26 6R6528 M 28.9 .377 0.48 6R6529 F 27.9 .378 0.38 Riunhovi iroiil 6R6522 F .VVU .393 0.65 6R6521 M 3.V8 .173 0.57 Smallmouth bass 6R6526 M 30.5 .337 0.64 6R6524 M 28.2 .275 0.50 BUTTERFIELD LAKE— NO. 2- Bowfin 22BL-4 M 55.9 1.702 0.15 Bullhead catfish 24BL-4 1- 32.2 .669 o.in 23BL-4 F 33.0 .685 O.ll 25BL-4 !■■ 32.0 .680 O.IO Largemouth bass I9BL-4 F 34.8 .657 0.21 :iBL-J M .34.5 .626 0.18 ;0BL-4 F 33.0 .573 0.11 Northern pike 9BL-» _ _ 0.15 8BL^ — — — 0.15 IOBL-* — — — 0.21 7BL^ — — — 0.15 Rock h;is^ I4BL-4 M 22.9 .263 0.22 I^BL^ M 22.2 .277 0.15 Smallmouth bass IIBL-4 _ _ _ 0.22 i:bl-4 — — — 0.21 Sucker :rbl-4 M 38.6 .916 0.18 Wallcvc pike 26BL-4 M 55.9 1.753 0.17 29BL-4 M 47.3 1.071 0.20 27BL-4 M 48.7 1.268 0.19 CANADICE LAKE —NO. 3 - Bullhe.id catfish J6220 - 35.0 .574 0.12 1 akc troui J6293 M 47.8 1.246 0.42 J6295 M 76.8 4.855 0.44 Chain pickerel J6228 F 46.0 .699 0.32 J6222 F 40.7 .471 0.24 Rainbow iroui J6225 _ 29.2 .284 0.36 J6296 M 30.5 .370 0.31 J6297 M 32.5 .430 0.27 Rock bass .16212 M 21.8 .248 0.39 Smallmouth bass J62in M 36.1 .751 0.41 J621I M 28.4 .386 0.53 J 6291 M 29.2 .409 0.50 J6290 F 33.6 .603 0.48 J6292 F 29.2 .378 0.37 CANANDAIGUA LAKE— NO. 4- Brown trout J6288 M 56.7 2.595 0.39 Lake iroui J6287 M 55.2 1.821 0.36 J6286 M 52.6 1.545 0.41 J 6231 'M-Tmm. 44.4 .722 0.55 Lnrpcmnuth bass J6167 M 28.7 .370 0.18 Smallmouth bass J6162 F 28.7 .359 0.53 CONESUS LAKE— NO. 5 ■ Black crappie 1 J6102 1 — 1 - 1 - 0.20 CAROGA LAKE- -NO. 6" Smallmouth bass 1 6R6192 | F |40.9 L295 0.42 Vol. 6, No. 2, September 1972 109 TABLE 3. — Residues of loial selenium in fish from New York Stale waters in 1969 — Continued Length (CM) Weichi (KG) CAYUGA LAKE— NO. 8 ■ CHITTENANGO CREEK— NO. 10 = 3-CH-I 3-CH-2 3-CH-3 43.2 31.7 23.4 1.072 .447 COHOCTON RIVER— NO. 1 1 - 2CohRl 2CohR2 2CohR3 26.7 25.4 EIGHTH LAKE— NO. 12- Rainbow trout Selenium Residue Level (PPM) CATTARAUGUS CREEK— NO. 1- Coho salmon 2F120I M 41.6 .683 0.40 2F1202 M 40.2 .588 0.28 2F1203 M 37.9 .588 0.45 2F1204 F 54.4 1.77 0.26 2F1205 F 56.8 2.09 0.32 2F1206 F 61.0 2.19 0.24 2F1207 F 60.2 2.23 0.24 2F1208 F 63.0 3.04 0.27 2F1209 F 64.0 3.00 0.25 Largemouth bass 3-CL-2 3-CL-l M 15.25 31.7 .621 0,25 0,29 Chain pickerel CAY-1 CAY-2 CAY-3 - _ — 0.23 0.22 0.34 CHENANGO RIVER— NO. 9 Smallmouth bass 3-CHR-l F 22.2 .168 0.28 3-CHR-3 F 27.9 .343 0.24 3-CHR-2 ' — Imm. 24.8 .198 0.23 3-CHR-4 M 28.6 .295 0.27 3-ChR.Ch.-8 F 30.5 .436 0.21 3-CHR-5 M 34.9 .550 0.23 0.26 0.24 0.27 0.40 0.32 0,33 LAKE ERIE— NO. 13 = Burbot 2-LAER-6 - 58.4 1.980 0.33 Coho salmon 2-LE-Hg-7 F 41.3 .665 0.37 2-LE-Hg-6 F 44,5 .764 n.33 LE-CS 1-9-4-69 M 56.2 2.110 0.35 2-LE-Hg-8 M 48,3 1.147 0.45 (Sunset Bay) LE-CS-9 F 57.5 2.671 0.35 Do. LE-CS-8 F 55.0 2.392 0.34 Do. LE-CS-6 'M-Imm 35.0 .493 0.36 Do. LE-CS-7 F 56.8 2.520 0.31 Freshwater drum LE-FWD-1 M 45.0 1.005 0.81 2-LE-Hg-3 F 40.0 .733 0.45 2-LE-Hg-42 F 36.8 .670 0.42 2-LE-Hg-37 M 36.2 .650 0.35 2-LE-Hg-47 F 48.3 1.385 0.28 2-LE-Hg-38 M 37.5 .715 0.48 2-LE-Hg-45 M 34.3 .570 0.62 2-LE-Hg-43 M 35.6 .610 0.43 2-LE-Hg-41 F 37.5 .750 0.59 2-LE-Hg-46 M 36.2 .565 0.42 2-LE-Hg-40 F 32.4 .415 0.38 2-LE-Hg-44 M 36.8 .610 0.41 2-LE-Hg-39 — — 0.42 2-LE-Hg-48 M 48.9 1.395 0.24 2-LE-l — 43.2 .695 0.29 2-LE-3 F 30.7 .270 0.43 2-LE-Hg-2 F 36.2 .612 0.32 2-LE-2 F 50.8 1.750 0.37 2-LE-Hg-l M 38.1 .615 0.36 LE-FWD-2 M 29.2 .364 0.54 TABLE 3. — Residues of total selenium in fisli from New York State waters in 1969 — Continued Weight (KG) FERN LAKE— NO. 14 = LAKE ERIE- -NO. 13 =— Continued Gizzard .shad 2-LE-4 Composite of 31 fish 0.42 Lake trout 2-LEL-2 - - — 0.33 Rock bass 2-LE-Hg-3l M 27.3 .358 0.31 Silver bass 2-LE-Hg-51 F 37.5 .680 0.52 2-LE-Hg-68 F 36.2 .487 0.37 2-LE-Hg-7l F 35.6 .487 0.43 2-LE-Hg-53 F 36.2 .615 0.32 2-LE-He-70 M 34,9 .503 0.46 2-LE-Hg-52 F 36.2 .625 0.35 2-LE-Hg-72 F 40.0 .840 0.41 2-LE-Hg-69 M 34.9 .425 0.51 .Smallmouth bass LE-SMB-1 M 43.5 .932 0.40 2-LE-Hg-54 F 40.7 .860 0.30 2-LE-Hg — — — 0.31 2-LE-Hg-50 F 34.9 .645 0.29 2-LE-Hg-60 F 39.4 .649 0.57 2-LE-Hg-62 F 45.7 1.300 0.43 2-LE-Hg-58 M 33.0 .360 0.37 2-LE-Hg-56 F 35.6 .682 0.38 2-LE-Hg-59 F 37.5 .741 0.54 2-LE-Hg-57 M 40,0 .695 0.26 Sucker 2-LAER-5 _ 50.8 1.474 0.59 2-LE-Hg-l 3 F 51.5 1.530 0.47 2-LAER-4 M 30.5 .334 0.34 2-LE-Hg- 12 F 48.9 1.296 0.37 2-LE-Hg-65 F 44.5 1.150 0.51 2-LE-Hg-63 M 46.4 1.190 0.71 2-LAER-3 M 48.3 1.097 0.21 2-LE-Hg-l 1 IM 45.7 1.040 0.36 2-LE-Hg-64 F 46.4 1.260 0.44 2-LE-Hg-67 F 43.2 1.120 0.40 2-LE-Hg-66 F 49.5 1.150 0.33 Walleye pike 2-LE-Hg-23 F 69.3 4.210 0.30 2-LE-Hg-25 F 64.7 2.920 0.20 2-LE-Hg-32 F 63.5 3.375 0.25 2-LE-Hg-4 F 63.5 2.310 0.37 2-LE-Hg-33 M 73.7 5.070 0.40 2-LE-Hg-35 F 67.4 3.800 0.23 2-LE-Hg-36 F 62.3 3,380 0.33 2-LE-Hg-21 F 68.5 4.219 0.25 Yellow perch 2-LE-Hg-16 F 31.7 .515 0.31 2-LE-Hg-29 F 33.0 .609 0.37 2-LE-Hg-30 F 27.9 .485 0.27 2-LE-Hg-17 F 31.1 .516 0.35 2-LE-Hg-28 F 34.3 .697 0.28 2-LE-Hg-26 F 32.4 .612 0.27 2-LE-Hg-20 F 33.3 .605 0.32 2-LE-Hg-I9 F 36.2 .735 0.35 2-LE-Hg-18 F 34.9 .694 0.34 2-LE-Hg-27 F 30.5 .450 0.36 FORKED LAKE —NO. 15 = Brook trout 6R6641 - 43.7 .945 0.40 Lake trout 6R6642 M 53.3 .854 0,33 Smallmouth bass 6R664S F 37.1 .950 n.39 Speckled trout 6R6640 F 35.6 .645 0.57 FOURTH LAKE —NO. 16 = Lake trout 4-4L-12 F 55.9 1.872 0.39 4-4L-10 M 37.8 .497 0.37 4-4L-11 — — — 0.33 Sucker 4^L-23 M 29.2 .301 0.27 4-4L-22 F 30.2 .336 0.40 4^L-24 M 35.6 .554 0.72 110 Pesticides Monitoring Journal TABLE 3." — Residues of total selenium in fish from New York State waters in 1969 — Continued Length (CM) Weight (KG) GENESSEE RIVER— NO. 17 = Smallmouth bass J-6267 HUDSON RIVER— NO. 19-' LAKE GEORGE— NO. 22 ' 5R6676 6R6675 6R6452 20.3 31.2 28.7 .584 .352 Selenium Residue Level (PPM) HEMLOCK LAKE- -NO. 18 Bullhead catfish J6203 J6202 M 36.1 28.2 .739 .341 0.1 0.18 Chain pickerel J6198 J6199 J6197 M 31.7 45.7 50.8 .229 .754 1.245 0.44 0.56 0.38 Lake trout J6299 J6298 J6300 M F M 67.5 77.8 75.5 3.987 4.27n 4.580 0.42 0.39 0.47 Largeinouth bass J6229 J6201 M 26.2 28.4 .344 .468 0.19 0.42 Rainbow trout J6200 M 38.1 .688 0.45 Atlantic sturgeon J2067 »— Imm. 46.0 .410 0.69 J2065 ■'F-Imm. 62.0 1.285 0.84 J 2064 M 98.0 5.076 0.80 J 2066 3M-lmm. 64.0 1.075 0.26 J 2068 ^— Inim. 64.5 1.348 0.88 Goldfish 6R6667 0.18 6R6666 — — — 0.17 6R6665 — — — 0.14 Shorlnose sturgeon J2076 ' — Imm. 47.3 .636 0.37 Striped bass J2070 M 57.6 2.256 0.25 J 2071 M 53.4 2.042 0.37 J2072 F 41.1 .780 0.24 J2069 M 54.4 2.072 0.65 8HUDR2 M 40.6 .800 0.38 8HUDR3 M 43.7 .985 0.30 8HUDR1 M 40.2 .850 0.45 INDIAN LAKE— NO. 20-' Northern pike 6R6554 M 73.0 2.735 0.27 6R6142 M 64.3 1.433 0.35 Walleye pike 6R6553 M 70.6 2.562 0.27 6R6144 M 29.7 .380 0.33 Whitefish 6R6139 F 38.6 .595 0.43 6R6140 M 43.2 .789 0.32 6R6141 M 45.3 .641 0.71 6R6143 M 46.0 .873 0.24 LAKE CHAMPLAIN —NO. 2 -■ Channel catfish 5-LCCC-l M 53.4 1.630 0.14 5-LCCC-2 F 76.1 6.200 0.11 5-LCCC-3 — 61.0 2.630 0.12 6R6592 F 52.0 1.700 0.12 (South Bay) 6R6591 M 47.8 1.130 0.15 Do. 6R6593 M 60.5 2.760 0.14 Freshwater drum (South Bav) 6R6588 F 31.7 .306 0.24 Do. 6R6590 F 48.8 1.165 0.11 Do. 6R6589 M 36.8 .423 0.22 Walleye pike (South Bay) 6R6587 M 64.8 3.070 0.24 Do. 6R6585 F 40.2 .566 0.23 Do. 6R6586 M 54.9 1.455 0.26 0.38 0.35 0.47 TABLE 3. — Residues of total selenium in fish from New York Slate waters in 1969 — Continued Length (CM) Weight (KG) LAKE GEORGE— NO 22 = — Continued Brown bullhead 6R6680 6R6454 F F 32.8 32.8 .686 .508 0.28 0.29 Chain pickerel 6R6450 M 35.6 .258 0.30 Lake trout 6R6672 6R573 6R6674 6R6673 F M F 71.0 68.8 70.1 3.570 3.125 3.241 0.46 1.50 0.78 0.68 Larpemouth bass 6R6441 6R6453 6R6440 M F M 41.1 36.3 40.4 .973 .743 .789 0.51 0.40 0.57 Northern pike 6R6677 6R6671 6R6404 6R6407 6R6406 F F F F M 64.0 59.5 75.0 64.7 60.5 1.820 1.780 3.180 2.950 3.000 0.38 0.41 0.44 0.35 0.45 Rainbow trout 6R6681 6R6682 6R639 6R6425 M M F F 55.3 50.8 41.9 58.6 2.440 1.690 .692 2.410 0.55 0.53 0.52 0.63 Sinallmouth bass 6R6449 F 42.4 1.235 0.49 While sucker 6R6433 6R6434 6R6432 F M M 53.0 46.3 47.3 1.139 .872 .906 0.59 0.60 0.48 LAKE ONTARIO— NO. 23 Black crappie 2-LO-4 - - - 0.26 Carp .16067 - 27.4 .419 0.21 Coho salmon 69-LO-CSl F 57.7 2.555 0.34 20-LO^ M 58.5 2.640 0.30 21-LO^ F 48.3 .965 0.29 22-LO^ M 50.0 1.400 0.30 23-LO-4 F 55.9 2.180 0.39 73-30-69 F 51.3 2.060 0.39 (False Duck Is.) 73-29-69 F 55.8 2.040 0.38 (Outlet Beach) 73-49-69 F 63.0 3.110 0.43 (Amherst Bar) 73-18-69 M 60.1 3.190 0.47 (Pt. Petre) 73-27-69 F 56.1 2.090 0.31 (Perch Cove) 73-23-69 M 60.4 2.090 0.50 (Shelter Valley Mouth) 73-47-69 F 64.0 2.890 0.44 (Pennicon Reef) 73-16-69 F 56.8 2.460 0.37 Do. 73-13-69 M 50.3 1.740 0.29 73-13-69 M — — 0.25 (testes) Do. 73-17-69 M 64.8 3.780 0.38 (Wellington Beach) 73-51-69 M 60.5 2.120 0.46 Do. 73^4-69 M 64.8 3.010 0.40 Do. 73-53-69 M 59.9 2.100 0.68 Do. 73-52-69 F 66.0 3.290 0.44 Do. 73-48-69 F 64.8 3.010 0.47 Do. 73-50-69 M 54.0 1.620 0.49 Rock bass J6038 F 22.8 .268 0.31 J6097 F 24.1 .288 0.35- J 6098 M 25.5 .436 0.31 J6085 F 22.8 .301 0.31 Smallmouth bass J-6165 _ 0.28 9-LO-4 F 37.6 .826 0.43 16-LO-4 M 40.7 1.014 0.35 (Carleton Is.) 4CI-1 M 28.9 .320 0.37 Do. 4CI-2 M 27.4 .258 0.39 Do. 4CI-3 M 34.0 .573 0.38 Vol. 6, No. 2, September 1972 111 TABLE 3. — Residues of total selenium in fish from New York State waters in 1969 — Continued Length (CM) Weight (KG) Selenium Residue Level (PPM) LA KE ONTRARIO— NO. 23 = — Continued Smallmouth bass (Cont'd) (Ft. Peninsula) 4RA2637 F 37.4 .855 0.30 Do. 4RA2635 F 33.0 .558 0.37 Do. 4RA2632 — — — 0.32 Do. 4RA2638 F 33.6 .644 0.37 Do. 4RA2646 F 30.5 .533 0.38 Do. 4RA2644 M 38.1 .892 0.40 Do. 4RA2650 M 27.9 .320 0.49 Splake 17-LO-4 '— Iiiim. 34.8 .523 0.48 Sucker 15-LO-4 M 39.1 .657 0.24 14-LO-4 F 39.1 .703 0.20 White bass J6027 F 25.5 .272 0.24 J6030 — 24.9 .207 0.50 LAKE PLACID— NO. 24 = Brook trout LP-NE-2 F 30.5 .360 l.IO Lake trout (North End) 5-NELP-2 5-NELP-l M 41.5 31.7 .726 .299 0.77 0.80 Northern pike 3LP-5 lLP-5 2LP-5 M M M 76.6 57.4 64.0 3.870 1.408 1.642 0.40 0.34 0.34 Rainbow trout 5-LKP-l 5-LKP-3 5-LKP-2 F F F 25.4 40.9 42.1 .225 .715 .779 0.29 0.51 0.55 Smallmouth bass 5-LKP-4 5-LKP-5 M F 29.2 46.3 .336 1.420 0.76 0.45 White sucker 5-LP-WS-l 5-LP-WS-3 - 43.7 30.5 1.440 .417 0.37 0.65 Yellow perch 5-LP-5 F 31.7 .435 0.77 LAKE PLEASANT- -NO. 25 Brown bullhead 6R6118 6R61I9 M F 34.3 34.8 .681 .673 0.38 0.31 Bullhead catiish 6R6120 M 25.5 .309 0,24 Chain pickerel 6R6126 6R6127 6R6128 F F F 35.0 38.4 39.2 .255 .392 .405 0.40 0.29 0.25 Largemouth bass 6R6131 F 35.0 .622 0.24 Rainbow trout 6R6129 F 42.7 1.068 1.05 Rock bass 6R6124 6R6123 F F 26.4 25.4 .461 .325 0.98 0.78 Smallmouth bass 6R6125 6R6132 6R6130 F F 32.7 49.3 .484 1.775 0.84 0.40 0.74 Whitefish 6R6117 6R6116 M 53.8 61.0 2.153 2.035 0.62 0.82 Yellow perch 6R6135 6R6133 M M 30.0 27.4 .438 .335 0.86 0.92 LITTLE GREEN POND— NO. 26 = Rainbow trout 5-lgp-8 F 34.1 .392 0.67 5-lgp-7 M 32.0 .370 0.37 5-lgp-9 F 38.6 .608 0.44 Whitefish 5-lgp-l F 53.4 1.805 0.97 5-lgp-2 F 57.1 2.041 0.74 5-Igp-3 M 50.8 2.050 0.49 TABLE 3. — Residues of total selenium in fish from New York State waters in 1969 — Continued Length (CM) Weight (KG) LOON LAKE— NO. 29 = ONEIDA LAKE— NO. 30 = 3-OneL-l 3-OneL-2 59.6 48.3 !.060 1.030 ONONDAGA CREEK— NO. 31 = OS-P154-4-1 OS-P 154-4-2 OS-PI 54-4-3 32.2 29.5 24.1 .386 .314 PEPACTON RESERVOIR— NO. 33 = PISECO LAKE— NO. 34 ■ RAQUETTE LAKE— NO. 35 ^ Selenium Residue Level (PPM) LITTLE YORK LAKE— NO. 27 = Brown trout LY-3-1 M 34.3 .456 0.23 Bullhead catfish LY-3-3 F 31.7 .414 0.10 Largemouth bass LY-3-2 M 33.2 .720 0.15 LONG LAKE- -NO. 28 = Largemouth bass 6R6546 F 43.2 1.128 0.45 Northern pike 6R6541 6R6540 6R6542 F M M 53.8 71.4 61.0 1.167 2.305 1.335 0.40 0.54 0.55 Smallmouth bass 6R6545 6R6544 F F 40.9 35.6 .767 .672 0.54 0.51 Smallmouth bass 6R6414 - - '.201 0.15 Walleve pike 6R6409 F *.I90 0.22 6R6410 F — '187 0.19 6R6408 F — ■'.232 0.24 0.23 0.17 0.43 0.33 0.44 OTSEGO LAKE —NO. 32 = Cisco 7-OTSL-l 25.9 .161 0.30 7-OTSL-2 M 34.3 .365 0.33 7-OTSL-3 F 36.1 .488 0.36 Lake trout 7-OTSL-6 _ _ _ 0.34 7-OTSL-5 — — — 0.33 7-OTSL.4 - - — 0.33 Whitefish 7-OTSL-9 _ 0.33 7-OTSL-7 — — — 0.56 7-OTSL-8 - — — 0.42 Brown trout lPR-7 F 64.8 3.115 0.40 3PR-7 F 51.5 1.880 0.35 2PR-7 F 41.2 .953 0.37 Brown bullhead 6R6105 M 31.7 .425 0.14 Smallmouth bass 6R6104 F 35.3 .571 0.43 Whitefish 6R6I03 F 38.1 .431 0.52 6R6102 F 31.7 .295 0.48 6R6101 M 34.8 .328 0.43 Yellow perch 6R6111 M 29.2 .262 0.65 Lake trout 6R6523 - - - 0.97 Smallmouth bass 6R6207 6R6206 6R6208 F F F 28.9 27.6 27.4 .287 .287 .251 0.37 0.31 0.35 112 Pesticides Monitoring Journal TABLE 3." — Residues of total selenium in fish from New York State waters in 1969 — Continued Length (CM) Weight (KG) SARATOGA LAKE— NO. 39 = SKANEATELES LAKE— NO. 41 = Rainbow trout 3-SKL-l 3-SKL-3 1.235 .644 SPRING BROOK— NO. 42 - Coho salmon 5M381 4RA2991 4RA3601 54.4 56.8 61.5 1.710 2.160 2.680 Selenium Residue Level (PPM) RAQUETTE LAKE— NO. 35^^ — Continued Whitefish 6R6245 = — Imm. 33.0 .337 0.59 6R6244 F 34.8 .453 0.76 6R6625 F 31.7 .349 0.93 6R6243 F 35.6 .497 0.75 6R6627 M 34.0 .388 0.52 5R6626 M 35.3 .439 0.84 RUSHFORD LAKE— NO. 36 = Lake trout 2RL-1 1 F 1 75.2 1 4.195 0.23 SARANAC LAKE— NO. 37 ■- Smallmouth bass 5SL-5 1 F 1 33.2 1 .684 0.30 SALMON RIVER- NO. 38 = Coho salmon 69-SR-CS-6 M 61.5 1.910 0.29 69-SR-CS-* F 56.8 1.983 0.27 (Pulaski, N.Y.) 69-SR-CS-2 F 63.0 2.072 0.31 69-SR-CS-lO M 61.8 1.920 0.34 69-SR-CS-lO M — — 0.18 (testes) 69-SR-CS-7 M 60.5 2.046 0.31 69-SR-CS-8 M 57.3 1.984 0.44 SR-CS-1 F 48.8 1.036 0.27 69-SR-CS-5 F 53.9 1.661 0.31 69-SR-CS-n F 61.8 1.840 0.29 CSJ-SR-2 M 35.6 .620 0.31 CSJ-SR-1 M 40.7 .663 0.31 CSJ-SR-3 M 38.1 .544 0.30 69-SR-CS-9 F 61.8 1.735 0.35 SRCSJ-70-1 ■' — Imni. 33.0 .444 0.35 SRCSJ-70-2 do. 30.5 .280 0.34 SRCSJ-70-3 do. 34.9 .520 0.33 SRCSJ-70^ do. 32.4 .400 0.27 SRCSJ-70-5 do. 30.9 .326 n.34 SRCSJ-70-6 do. 30.9 .327 0.36 Walleye pike 1 6R6403 1 F - 1 .357 0.22 SCHROON LAKE— NO. 40 = Lake trout h 1- - 1 - 0.27 0.56 0.71 0.36 0.37 0.38 ST. LAWRENCE RIVER— NO. 43 = Brown bullhead 9SL-5 - - - 0.14 Muskellungc lOlSL-4 M 77.5 3.832 0.27 Smallmouth bass lSTL-4 M 29.5 .398 0.34 6STL-4 M 26.8 .263 0.41 2STL-4 M 26.9 .280 0.41 6SL-5 — — — 0.35 3STL-1 ^ — Imm. 23.9 .242 0.43 4STL.4 F 30.0 .339 0.34 5STL-t M 29.5 .344 0.39 Sturgeon G429 _ 102.5 6.830 0.33 G435 — 89.6 4.540 0.34 G430 — — 3.630 0.23 G432 — 97.3 5.690 0.33 G434 — 100.8 6.590 0.25 G431 — 103.5 8.200 0.29 G433 — 96.3 5.910 0.33 TABLE 3. — Residues of total selenium in fish from New York State waters in 1969 — Continued Length (CM) Weight (KG) Selenium Residue Level (PPM) ST. LAWRENCE RIVER- -NO. 43=— Continued Sturgeon l-SL-54 _ _ _ 0.38 (Cont'd) 3-SL-56 — — — 0.35 (Massena) 2-SL-56 — — — 0.46 Do. 4-SLS-6 M 95.5 7.210 0.31 Walleye pike I-STL-Hg.4 _ _ _ 0.31 (Massena) 4-MAS-l — — — 0.30 Do. 4-MAS-2 F 45.3 1.060 0.31 4-MAS-3 F 65.5 3.527 0.30 SUSQUEHANNA RIVER— NO. 44=' Walleye pike 3-SQR-l 3-Susq.R.-6 3-Susq.R.-7 M M 22.8 33.0 .125 .305 0.19 0.20 0.24 Yellow perch 3-Susq.R.-5 3-Susq.R.-4 3-Susq.R.-3 M M 27.9 24.8 .268 .166 0.18 0.21 0.19 TROUT LAKE— NO. 45 = Chain pickerel (West Shore) Do. 6R6456 6R6457 6R6458 F M F 62.0 46.3 49.5 1.570 .785 .918 0.20 0.27 0.24 Smallmouth bass 6R6459 F 43.7 1.197 0.30 UPPER SARANAC LAKE— NO. 46 = Larpemouth bass 5-US-2 5-US-l 34.8 31.2 .904 .432 WANETA LAKE— NO. 48 = I- I - I WEST CANADA LAKE— NO. 49 = 6R569 6R568 53.3 38.6 1.268 .426 0.34 0.32 UTOWANA LAKE— NO. 47 Smallmouth bass 6R6504 6R6505 F M 42.9 42.5 .949 1.030 0.53 0.60 Rainbow troul 6R6506 6R6508 M F 43.0 41.5 .844 .775 0.40 0.40 0.91 1.14 NOTE: — indicates data unknow-n. ' Specific location within waters, if known, given in parenthesi -■ Numbers refer to location of water in Fig. 1. • Imm. = immature. ' One fillel. TABLE 4. — Total selenium in Cayuga Lake trout by age of troul, 1970 Age (Years) Selenium (ppm) 1 0.53 2 0.52 3 0.40 4 0.29 5 0.40 6 0.52 7 0.49 8 0.61 9 0.44 12 0.52 NOTE: Sensitivity level = 0.1 ppm. VOL. 6, No. 2, September 1972 113 LITERATURE CITED (/) Allaway, W. H., and E. E. Cary. 1964. Determination of submicrogram amounts of selenium in biological ma- terials. Anal. Chem. 36(7):1359-1362. (2) Bache, C. A., C. McKoiie, and D. J. Lisk. 1971. Rapid determination of mercury in fish. J. Assoc. Off. Anal. Chem. 54(3);741-743. (3) Barnharl, R. A. 1958. Chemical factors affecting the survival of game fish in a Western Colorado reservoir. Colo. Coop. Fish. Res. Unit Quarterly Rep. 4:25. (4) Copeland, R. 1970. Selenium: the unknown pollutant. Limnos 3{4):7-9. (5) Goldschmidt, V. M. 1954. Geochemistry. (A. Muir. ed.) Oxford Univ. Press (Clarendon). Oxford, England. p. 532. (6) Kessler, T., A. G. Sharkey, Jr., and R. A. Eriedel. 1971. Spark source mass spectrometer investigation of coal particles and coal ash. Bur. Mines Tech. Prog. Rep. 42. U.S. Dep. of the Interior, Washington, D.C. p. 5. (7) Pakkala. I. S.. M. N. White. G. E. Biirdick. E. J. Harris, and D. J. Lisk. 1972. A survey of the lead content of fish from 49 New York State waters. Pestic. Monit. J. 5(4):348-355. (5) Parizek, J., and I. Ostadalovu. 1967. The protective effect of small amounts of selenite in sublimate in- toxication. Sep. Exper. 23:142-144, (9) Parizek, J., A. Babicky. I. Ostadalova. J. Kaloiiskova. and L. Pavlik. 1969. The effect of selenium compounds on the cross-placental passage of ""'Hg. Proc. Ninth Ann. Hanford Biol, Symp., Richland, Washington pp 137-143, (/O) Schroeder, H. A.. D. V. Frost, and J. J. Batassa. 197(1. Essential trace metals in man:selenium. J. Chronic. Dis. 23:227-243. (//) Sliah. K. R.. R. H. Filhy. and W. A. Haller. 1970. Determination of trace elements in petroleum by neutron activation analysis. J. Radioanal. Chem. 6:413- 422. (12) Sikov. M. R.. and D. D. Mahluni. eds. 1969. Radiation biology of the fetal and juvenile mammal. Proc. Ninth Ann. Hanford Biol. Symp., Richland, Washington, May 5-8. pp, 81-89, {13) Wells, N. 1966. Selenium content of some minerals and fertilizers, N.Z. J, Sci. 9(2):4(19-4I5, 114 Pesticides Monitoring Journal Effects of Insecticides on Populations of Rodents in Kansas — 1965-69 ^ R. J. Robel-. C. D. Stalling". M. E. Westfahl"'. and A. M. Kadoum ABSTRACT The general objeciive of ihis study was l<> ileleniiinc the effect of recomineiuled appticulions of commonly used insecticides on population dynamics of unconfined rodents in two sites in Ellis County, Kans. Six insecticides (diazinon. endrin. heptachlor. parathion. methyl parathion, and aldrini were applied to one field, while a second field served as a control. Insecticide applications began in .summer 1965 and continued throuijh .summer I96S. Live trapping of rodents svas condttcted on the treated field and the control field from 1965 through 1969. Specimens were collected each month for residue analysis. During 19 .separate 10-day trapping periods, 4.661 rodents were captured of which 162 were analyzed for the six in- secticides. Insecticidal residues were detected in 36 of these specimens. Dieldrin residues were detected in 33 specimens and heptachlor epoxide in 8 specimens (five of these speci- mens had residues of both dieldrin and heptaclilor epoxide). These residue levels were low with no dieldrin levels in specimens exceeding 0.50 ppin, and no lieplachlor epoxide levels exceeding 0.02 ppm. No residues of the other four insecticides were delected in any of the specimens. Species composition of the trapped rodents was similar for the two study cncas as were the population levels, with Peromyscus maniculatiis comprising about 14% of the rodent population on tlie two areas. Population fluctuation trends for the two areas were also similar. Average minimal longevity for P. maniculatus was 45.7 days on the treated area and 50.9 days on the control area. Monthly survival between June and September was about 45% on both areas. Recaptures of P. maniculatus the year following their initial marking were stiglitly greater on the untreated area than on the treated area. The sliglit differences in dynamics of the From the Division of Biology, Contribution No. 1049, and Depart- ment of Entomology. Contribution No. 1118. Kansas Agricultural Experiment Station. Kansas State University. Manhattan. Kans. Division of Biology. Kansas State University, Manhattan, Kans. 66502. Department of Entomology, Kansas State University. Manhattan, Kans. 66502. Vol. 6, No. 2, September 1972 rodent populations on the two areas could easily have been due to chance, minor differences between the two study areas, or differential emigration of specimens from the areas as well as direct or indirect effects of insecticidal applications. Introduction Although much research has been done on various aspects (persistence, toxicity, species susceptibility, biological accumulation, etc.) of insecticides, little effort has been expended to study the long-term effects of insecticides on populations of unconfined animals. This lack of research is even more apparent when one tries to ascertain the effects of recommended insecticidal applications on wildlife populations under natural condi- tions. Because of this lack of fundamental data, re- search on the effects of recommended insecticidal ap- plications on the population dynamics of unconfined small rodents was initiated in west central Kansas in 1965, as a subunit of a larger research project involving studies of fish populations, and insecticidal residues in soil, water, and vegetation. The results of the rodent population dynamics investigation arc reported in this paper, while the results of other aspects of the com- prehensive study were published separately in an earlier issue of the Pesticides Monitoring Journal (14). The St tidy Area This study was conducted on two sites in Ellis County, approximately 21 km (13 miles) southwest of Hays, Kans. Because the region was part of a newly created Cedar Bluffs Irrigation District and had not been in- tensively cultivated prior to 1965, insecticide use on the locale had been minimal. No insecticidal residues were detected in samples of water, soil, plants, or animals collected from the two study sites before the study be- gan in 1965. The history and development of the general region are described in detail by Knutson et al. (14). 115 Average annual rainfall for the area is 59 cm (23 in). of which 75% normally occurs in localized convective storms during the growing season (April through Sep- tember). The mean annual temperature is 12 C (54"F), with mean monthly extremes of 27°C (80°F) for July and — 2°C (29^F) for January. Silty clay loam is the most common soil type on the study sites. A more detailed discussion of climate and physical character- istics of the study area is presented in Leonard (16) and Knutson et al. {14). The two sites utilized during this study were a "treated area" which had insecticides applied to it at recommended levels and an "untreated area" which had no insecticides applied to it. The treated area was a 7.0-hectare (ha) (19.5 acre) field with three terraces. The untreated area consisted of a similar 8.4-ha (22.7 acre) field with one terrace and situated 1.6 km (1 mile) south of the treated area. Corn (Zea mays) and sorghum { Sorghum viilgare) were produced on both areas during the study period. The density and composition of vegetation on terraces and areas bordering both fields were similar and consisted mainly of small kochia (Kochia scoparia). dandelion (Taraxacum officinale), giant foxtail (Selaria faherii). yellow foxtail (Selaria lutescens), goldenrod (Solidago spp.), ragweed (Ambrosia spp.), and sandbur (Cen- chrus pauciflorus). Materials and Methods SAMPLING PROCEDURES Insecticidal applications on agricultural crops grown on the treated area were carefully monitored and were in accordance with recommended dosages and procedures of the Extension Entomologists of the Kansas Extension Service. Application rates varied from year to year and reflected the general insecticidal usage pattern of the region. A summary of the amounts of diazinon. endrin, heptachlor, parathion, methyl parathion. and aldrin ap- plied to the treated area is presented in Table 1. The dates of insecticidal applications appear in Table 2. A more detailed discussion of time and method of insec- ticidal application on the treated area appears in Knut- son et al. (14). No insecticides were intentionally ap- plied to the untreated area during the course of the study, however, some dieldrin-treated sorghum seeds may have been planted inadvertently on the untreated area during one or two of the years. TABLE L — Summary of insecticides applied to the treated area (pounds per acre) from 1965 to 1968 TABLE 2. — Dates of insecticide application to the treated area Methyl Year Diazinon Endrin Hepta- Para- Para- chlor thion thion Aldrin 1965 0.60 0.00 0.00 0.38 0.00 2.45 1966 2.29 0.30 0.67 1.40 0.38 1.20 1967 2.13 0.36 0.43 0.79 0.50 0.84 1968 3.46 0.28 0.41 1.01 0.53 0.30 Treatment ' Dates of Application 1965 1966 1967 1968 Soil Foliage May 10-1 1 .-Vug. 19 May 12 Aug. 3 May 15-16 Aug. 10 May 25 Aug. 5 parathi( heptachlor, parathion, and aldrin were used as soil treat- lile foliage was treated with diazinon, endrin, and methyl 116 Data on small rodent populations on the two areas were obtained by the capture-recapture method. Live traps similar to those of SchefTer (19) were placed at 18-m (60-ft) intervals on the terraces and along the edges of each study area: 215 live traps were used throughout the study, 151 on the treated area and 64 on the un- treated area. More traps were set on the treated area than on the untreated area because of extra terraces in the treated area. Initial trapping in August 1964 determined that rodents lived mainly in habitats along field edges and on the terraces of the two areas and moved laterally out into the fields foraging for food. At that time, 50 traps located within 60 feet of a terrace captured 21 ro- dents (42"^ success), while 50 traps located 120 feet or more from a terrace captured only 3 rodents (6% success). The soil under the crops was bare and weed- less, affording little cover in which rodents could reside. Thus, trapping intensity, i.e.. traps per 305 m (1,000 ft) of rodent habitat, was similar for both areas during the course of this study. Trapping was conducted on each area during 19 separate 10-day trapping periods, spring and summer 1965-1969. To reduce heat induced mortality of trapped animals, which could occur during daytime, all traps were baited and set at dusk, then emptied and/or sprung the following morning, and left unset until dusk. Traps were baited with a mixture of rolled oats and peanut butter (4). Bait from the previous day was re- moved before a new ball of the mixture, approximately 13 cm (0.5 in) in diameter, was placed in each trap. Additional bait was used during cold weather (//). Trapped animals were identified, marked, and released at the capture site. Toe clipping and ear notching com- binations (2) were used to mark captured animals. To facilitate analysis, all data were placed on computer input cards following a format similar to Brotzman and Giles (3). All data were analyzed on an IBM 360 50 computer. Population estimates were made using capture-recapture data and the procedures of Schnabel (20) and Schu- macher and Eschemeyer (27). Compensation was made for differences in available trapping areas on the two study sites by calculating population estimates for each 305-m (1,000 ft) unit of trapline. There were 8.7 such Pesticides Monitoring Journal units on the treated area and 3.8 units on the untreated area. An inde.v to annual mortality was determined b\ dividing the number of Jime and Jul>' recaptures of animals marked during the previous \ear b\ the total number of animals marked in the pre\ioLis year. During the last night of each trapping period of 1965 to 1968, five rodent specimens from each study area were collected for insecticidal residue analysis. ANALYTICAL PROCEDURES The specimens for insecticide anahsis v\ere quick frozen the morning they were captured. Prior to analysis for insecticidal residues, each specimen was allowed to thaw before being homogenized in a Warning high-peed blender. After homogenization. a 10-g sample of each specimen was analyzed separately for insecticidal resi- dues. The 10-g sample was placed in an Omnimixer with 50 ml of redistilled hexane and sufficient anhydrous sodium sulfate to take up the water. The mixture was then blended at high speed for 1-2 minutes, then decant- ed through No. 43 Whatman filter paper into a 100-ml suction flask. The residue was extracted with two addi- tional portions of hexane as described above, then filtered and combined in the suction flask. The container, filter paper, and contents were then washed with a final por- tion (10 ml) of hexane. The total hexane extract was transferred to a round-bottomed flask for concentration under vacuum at 35^-40°C to 2-3 ml of hexane. then transferred quantitatively to a 15 ml-centrifuge tube using 5 ml of hexane. An aliquot was used for cleanup and gas chromatographic analysis. All solvents were glass-distilled and purified for gas chromatographic analysis. Cleanup methods for extracts, recoveries of insecticides from fortified samples, and sensitivities by gas chroma- tographic analysis are reported by Kadoum U2.ljf). Insecticide residues were not corrected for recovery with the exception of methyl parathion. since recovery from fortifiew samples was essentially 100*"^. The insecticides were separated and detected by electron capture gas chromatography using a 6-ft glass column, packed with 3'~'r DC-ll on 60 ,S0 mesh silanized Has Chrom P (Applied Science Labs. State College. Pa.). Operating conditions were as follows: carrier gas — nitrogen at a flow rate of 36 ml'min; column temperature — 200°C; injection temperature — 240°C; detector cell — 220°C; volume of extract injected — 4 fj.\. The analytical pro- cedure was capable of detecting residues of as low as 0.01 ppm of diazinon. parathion. methyl parathion. malathion. endrin. aldrin. dieldrin, heptachlor. hepta- chlor epoxide. p.p'-DDE. <)./)'-DDT. and p.p'-DT>T. Results Nineteen 10-day trapping periods on the two study areas produced data from 40.850 trap-nights (number of trapping periods X number of nights per period X num- ber of traps set). 28.690 on the treated area and 12.160 on the untreated area. Totals of 3.306 and 1.355 individ- ual rodents were captured on the treated and untreated areas, respectively. Fifty-four percent were recaptured later, and 35.8'vf of the individuals were recaptured more than once. Data from 17 trapping periods during the summers of 1965-68 were used to estimate rodent populations on the two areas. June and Jul\ recaptures of mammals marked during the previous summer were used to estimate annual mortality and survival for 1965-68. Two additional 10-day trapping periods were conducted in June and July of 1969 to estimate annual mortality and survi\al for the 1968-69 period. P. maniculatus v\as the predominant species on both areas (Table 3). During the entire study, P. nuiniculaiiis made up 74.2^ of the captures on the treated area and 74.0'yr of those on the untreated area. Miis duischIiis was the next most abundant small mammal trapped, con- tributing 7.49f and 8.6% to the total captures on the treated and untreated areas, respectively. Sii>modoii hispidiis was the third most commonly trapped mammal constituting 7.51^ and 5.1*^^ of the total captures on the treated and untreated areas, respectively. Onychomys leiicogaster. Micratiis ochroi;asler. and Reithrodonloiuyi megalotis each contributed less than 5.0'~f to the number of mammals trapped on either of the two areas. Reithrodontomys inontamis. Perognathtis fiavus. P. flavesen'!. P. Siispidiis. Speiniophiliis iridecenilinealiis. TABLE 3. — Species composition of 3.306 and J, 355 mammals captured on the treated and untreated area, respectively, during this study Species Composition of Captures — (Percent) Species 1965 1966 1967 1968 1969 1965-69 TA UA TA UA TA UA TA UA TA UA TA UA Peromyscus maniculatus Mus musculus Onysliomys leucogaster Sigmodon liispidus Microtus octtrogasler Reittirodontomys megalotis Otlier species ' 64.1 16.6 3.3 3.5 4.7 1.5 6.1 68.4 14.8 0.0 4.8 8.9 2.1 0.9 64.8 9.1 1.0 11.4 10.8 0.5 2.4 63.6 10.4 8.2 10.8 3.3 1.3 2.3 83.0 3.0 0.7 9,0 0.0 3.8 0.3 85.5 7.2 1.2 0.9 0.0 1.5 3.5 78.9 4.3 5.8 7.2 0.9 0.9 1.9 73.7 6.1 5.3 6.6 1.8 0.9 5.6 82.3 3.3 4.0 3.1 2.0 4,7 0.7 81.5 0.4 13.5 0,4 0,7 2,2 1,4 74.2 7.4 2.7 7.5 3,7 2,1 2,3 74,0 8,6 4,6 5,1 3,2 1,5 2,9 NOTE: TA = Treated Area; UA = Untreated Area. ^ Other species included Reithrodontomys montanus. Perognaihus flav ordii. Vol. 6, No. 2, September 1972 p. hispidus. Spermophihis tridecemlineatus. and Dipodomys 117 and Dipodomys ordii, each constituted less than 1.0% of the mammals trapped on either of the two areas. Early in the analysis of data, attempts were made to estimate populations of each species of rodent on the area, but period-to-period and season-to-season variations were extremely large (Table 3). Therefore, population estimates of individual species were abandoned in favor of crude estimates of the composite rodent population and an estimate of the most abundant rodent species, P. maniculatus. The trappable populations estimated by the Schumacher-Eschemeyer method were slightly higher than those calculated by the Schnabel method. The differences in estimates by these two methods aver- aged 3.4% (range of 0.0% to 18.4%) for the entire study, and this difference was not significant for the entire study nor for any specific trapping period during the study. Insecticidal residues were detected in 36 of 162 speci- mens analyzed. Residues of dieldrin were detected in 33 specimens and heptachlor epoxide in 8 specimens (5 specimens contained residues of both dieldrin and heptachlor epoxide). No residues of the other four in- secticides were detected in any of the specimens. Residue concentrations were low ranging from 0.0 1 to 0.50 ppm of dieldrin and 0.01 to 0.02 ppm of heptachlor epoxide. Seven (7.1%) of 98 specimens from the treated area had detectable residues of heptachlor epoxide, while only 1 (1.6%) of 64 specimens from the untreated area showed heptachlor epoxide residues. Residues of dieldrin were detected in 26 (27.6%) of the 98 specimens from the treated area and in 7 (10.9%) of the 64 specimens analyzed from the untreated area (Table 4). Average dieldrin residue concentrations (0.07 ppm) were higher in specimens from the treated area than the average residue concentrations (0.04 ppm) in specimens from the untreated area. Of nine species of rodents analyzed for insecticidal residues, five contained detectable amounts of dieldrin (Table 5). Specimens of Miis iniiscidus, Spermophitus iridecemlineaius, and P. nmnicidatiis contained more dieldrin (average concentrations of 0.07 to 0.10 ppm) in their carcasses than the other specimens. Onychomys leucogasicr and Reithrodoiiiomys inei^alotis also con- tained dieldrin residues in their carcasses, but in lesser amounts (average concentrations of 0.03 ppm). With the exception of specimens of Reithrodontomys megalotis. average residue concentrations were greater in carcasses of species collected from the treated area than those from the untreated area. Heptachlor epoxide residues (0.01 to 0.02 ppm) were found in four specimens of P. inanicidatiix and in one each of Onychomys leiicog- asler. Sigmodon liispidiis. and Spennophihts trideceinli- neatiis from the treated area. One Onychomys leucog- asicr from the untreated area had residues (0.01 ppm) of heptachlor epoxide. Of the 36 specimens in which residues were detected. 20 (56.0%) were males and 16 (44%) were females. TABLE 4. — Summary of dieldrin residues (Ss^O.Ol ppm) in 162 collected during this study Treated Area U N TREATED AREA No. ANA- LYZED Dieldrin Residues Present No. Ana- lyzed Dieldrin Residues Present Year No. Positive Percent Positive Concentrations PPM) No. Positive Percent Positive Concentrations (PPM) Average Median Range Average Median Range 1965 1966 1967 1968 19 31 26 3 3 14 6 15.8 13.0 45.2 23.1 0.09 0.08 0.05 0.13 0.01 0.09 0.02 0.03 0.01-0.24 0.02-0.13 0.01-0.50 0.01-0.44 14 18 12 20 0 3 0.0 16.7 16.7 10.0 0.02 0.01 0.09 0.02 o.ni 0.09 0.01-0.03 0.01-0.01 0.04-0.15 Total 98 26 27.6 0.07 0.02 0.01-0.50 64 7 10.9 0.04 0.02 0.01-0.15 TABLE 5. Dieldrin residues (= ^0.01 ppm) ill nine rodent species analyzed during lit is study Treated Area Untreated Area Number Percent Concentration i N Those Number Percent CONCE NTRATION N Those Number Ana- lyzed Con- CON- Contaminated (ppm) Number Ana- lyzed Con- tami- nated Con- tami- nated Contaminated (PPM) Species nated nated Average Median Range Average Median Range Peromvscus maniculatus 31 12 38.7 0.08 O.OI 0.01-0,50 21 3 14.3 0.03 0.03 0.01-0.04 Mus muscutus 14 6 42.9 0.10 0.01 0.01-0.44 11 2 18.2 0.08 0.08 0.02-0.15 Onvchoinys leucogaster 9 3 33.3 0.03 0.02 0.02-0.05 7 1 14.3 0.01 — — Reithrodontomys megalotis 6 1 16.7 0.03 — — 5 1 20.0 0.03 — — Spermophilus tridecemlineatus 7 4 57.1 0.07 0.02 0.01-0.24 0 0 0 — — Sigmodon hispidus 15 0 0 — — — 6 0 0 — — — Microlus ochrogaster 9 0 0 — — — 8 0 0 — — — Perognathus flavesens 5 0 0 — — — 2 0 0 — — — Perognathus hispidus 2 0 0 - — — 4 0 0 — — — 118 Pesticides Monitoring Journal Fluctuations of the total rodent populations on the treated and untreated areas followed the same general trend during the study (Fig. 1). The longest time be- tween the date of first capture and date of last capture of a specific specimen was 34 months, a Sigmodon hispidiis male on the treated area. Two P. manicidatiis males survived at least 24 months on the treated area. Several individuals were known to have survived at least 14 months on the untreated area. For P. maniculaiiis. the average time between date of initial capture and date of last recapture varied from a high of 53.4 days on the untreated area to a low of 42.8 days on the treated area (Table 6). The average minimal longevity during 1965-68 for P. inanicidaiiis on the treated area was less than the average minimal longevity for P. maniculatus on the untreated area. FIGURE 1. — Estimated (Schumacher-Escliemeyer method) trappable population per 305 m ( 1 ,000 ft) of trapline on tlie treated and untreated areas. Vertical lines represent 95Tf confulence intervals about the mean. TABLE 6. — Average mirumal longevity (±S.D.) for Peromyscus maniculatus recaptured during this study 1965 1966 1967 1968 Mean (± S. E.) Treated Area (days) 48.1 ± 7.8 46.7 ±11.4 42.8 It 6.2 45.2 ± 5.8 45.7 2.3 Untreated Area (days) 49.8 ± 8.7 50.6 ± 14.2 53.4 ± 8.9 49.9 ± 9.1 50.9 ± 1.7 ' Indicates year in which the individuals were first captured. An inde,\ to summer mortality within each rodent population was determined by following a single group of marked individuals through a summer. Rodents marked during the June trapping period of each year on each area were considered separate groups and later recaptures of these rodents were used as evidence of survival. Life tables were constructed to obtain an index Vol. 6, No. 2, September 1972 to mortality (70). The index to monthly mortality was strikingly similar for both areas, averaging 54.5% and 54.9% on the treated and untreated areas, respectively (Table 7). The number of animals marked one year and recaptured during June or July the following year was small, averaging 3.4% and 5.9% for the treated and untreated areas, respectively (Table 8). TABLE 7. — Summer mortality of Peromyscus maniculatus on the two study areas determined from recaptures of P. maniculatus marked in the initial trap period of each year Number Marked in June Period August September Total TREATED AREA 1965 310 194 173 154 521 1966 389 204 176 155 535 1967 493 175 154 — 329 1968 376 188 164 142 494 Totals 1,568 761 667 451 1,879 Marked P. maniculatus Available 1,568 1,568 1.075 — Number Recaptured 761 667 451 1,879 Number Alive at Start 1,879 1.118 451 3,448 Percent Monthly Mortality 40.5 59.7 100.0 54.5 UNTREATED AREA 1965 107 60 54 47 161 1966 112 56 50 44 150 1967 128 57 50 — 107 1968 100 48 42 34 124 Totals 447 221 196 125 542 Marked P. maniculatus Available 447 447 319 — Number Recaptured 221 196 125 542 Number Alive at Start 542 321 125 988 Percent Monthly Mortality 40.8 61.1 100.0 54.9 TABLE 8. — Peromyscus maniculatus recaptured during June and July trapping periods the year following initial marking on the two areas Treated Area Untreated Area \EAR Marked Number Marked Recaptures Succeeding Year Number Marked Recaptures Succeeding Year 1965 1966 1967 1968 319 437 733 502 10 21 18 18 160 165 274 192 5 16 14 12 Total Percent Recapt 1,991 ured 67 3.4 791 47 5.9 Discussion This study was meant to be a comparison of two rodent populations; one exposed to insecticides and one not exposed to insecticides. However, the experimental de- sign did not permit replications or a study of two closed populations. As far as could be discerned from field observations, the only fundamental difference between 119 the two study areas which could have markedly in- fluenced rodent populations was the insecticide treat- ment. Since the populations were not closed, rodent immigration and emigration were unknowns in the study. Likewise since no large exclosures were used, natural predation on the two areas could not be controlled. It appears though that the rodent populations on the two areas were very similar in composition and dynamics. Without adequate replications, only major changes in the rodent populations could have been detected. Since no attempt was made in this study to accurately determine the total population of rodents on each of the two study areas, the many limitations of the basic capture- recapture method discussed by Manly (18). Cormack (5), Tanton (22). and Leslie {17) did not influence the results. The same methods of trapping and marking were used on both study areas, thus, although the population estimates could not be regarded as entirely unbiased, the estimates are comparable. The population parameters calculated from these capture-recapture data are like- wise comparable. The relative abundance of some mammals changed from year to year, but since these changes occurred on both areas, these changes could not be considered in- secticide induced. Year-to-year changes in population density and species composition are not uncommon in prairie regions of Kansas (6-9). The average longevities calculated from capture-re- capture data in this study are minimal values since they represent the time between first and last capture of the animal, not between birth and death. Unless there are differences in emigration rates of rodents from the two areas, these minimal longevity figures are comparable. Longevity of P. maniciilatiis on the treated area was slightly less than that of the population on the untreated area. Because the difference was slight and egress from the two populations not controlled, it is doubtful that the 5.2-day difference in longevity can be specifically attributable to insecticide applications on the treated area. An index to mortality of P. manicidatus during summer months as estimated from recaptures was almost iden- tical on the two areas. Again, unless there was differ- ential emigration and trap vulnerability on the two areas, these indices to mortality are comparable. Carry- over of marked P. maniculaiiis from one trapping sea- son to the next may have been a bit greater on the un- treated area, but this could not be confirmed since emi- gration was not controlled. The actual pathway of insecticidal contamination was not studied; however, the rodents probably acquired in- secticides through their food. Sigmodon. Microius, and Perognathus feed primarily on plant material and seeds and had no insecticide residues in their carcasses while 120 rodents ( Peromysciis. Mas. Onychomys, Reithrodonto- mys. and Spermopluliis) which had a diet that included insects in addition to seeds and plant material had insecticide residues in their carcasses. Contaminated in- sects (dead, dying, or those containing low levels of insecticides) could have been a source of contamination for insect eating rodents in our study as was found for insect eating rodents in Missouri (/.'>). Probably the most significant findings of this study were the low incidence and levels of contamination observed in the rodent population on the treated area. Only one species, Spermopluliis tridecendineatus. ex- hibited an incidence of contamination exceeding 50%. P. nianicidaius, the most abundant species on the area, had an incidence of contamination of only 38.7% on the treated area. Levels of contamination never exceeded 0.50 ppm of dieldrin for any specimen analyzed. Al- though levels of dieldrin contamination were higher in rodents from the treated area early in the study, levels of contamination increased on the imtreated area during the last year of our study. Collection of contaminated specimens on the untreated area was a result of im- migration onto that area by rodents from surrounding areas: similar movements probably were occurring on the treated area. It appears therefore that unless closed populations of rodents can be assured, their population dynamics are probably a poor indicator of insecticide contamination. It is doubtful that monitoring of rodent populations can detect anything but changes of ex- tremely large magnitude under unconfined conditions. A cknowledgment For making arrangements for this study, the authors extend sincere thanks to H. C. Knutson of the KSU De- partment of Entomology and to T. L. Harvey of the Hays Branch of the Kansas Agricultural Experiment Station. A. D. Dayton's advice on statistical treatment of the data is appreciated. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (/) Bernard. R. F. 1963. Studies on the eflfects of DDF on birds. Mus. Publ., Mich. State Univ.. Biol. Ser. 2:155- 192. (2) Blair. W. F. 1941. Techniques for the study of mammal populations. .T. Mamm. 22:148-157. (.?) Brotvnan. R. L., and R. J. Giles. Jr. 1966. Electronic data processing of capture-recapture and related eco- logical data. J. Wildl. Manage. 30:286-292. (4) Biickner. C. H. 1957. Population studies on small mammals of southeastern Manitoba. .1. Mamm. 38(1): 87-97. Pesticides Monitoring Journal (5) Connack, R. M. 1968. The statistics of capture-re- capture methods. Annu. Rev. Oceanogr. Mar. Biol. 6; 455-506. (6) Frydemiall. M. ]. 1969. Rodent populations on four habitats in central Kansas. Trans. Kans. Acad. Sci. 72: 213-222. (7) Gier. H. T.. and G. T. R. Bradshaw. 1957. Five-year report on the Kansas small mammal census. Trans. Kans. Acad. Sci. 60:259-272. (5) Haines. J. M.. and H. T. Gier. 1951. Distribution of microtine rodents in Kansas. Trans. Kans. Acad. Sci. 54:58-63 (9) Hays. H. A. 1958. The effect of microclimate on the distribution of small mammals in a tall-grass prairie plot. Trans. Kans. Acad. Sci. 61:40-63. (10) Hic/ pollution (Group I sites) and 4 with essentially onl\ natural sources of mercury (Group II sites). .Sampling Site.'i and Procedures The fish collection sites are shown in Fig. 1. Group 1 sites were located on the Saskatchewan River system and included Lloydminster (Site I) on the North Saskatchewan River at the Alberta-Saskatchewan border; Borden (Site 2); Squaw Rapids Dam (Site 3); Tobin Lake (Site 4); Clarkboro Ferry (Site 5); and Leader Ferry (Site 6). The city of Saskatoon (designated Site II) is a principal source of pollution, since a chlor-alkali plant there discharges effluents containing mercury into the river system: all sampling sites downstream from Saskatoon would be contaminated by this plant as well as by municipal wastes from Saskatoon and several other cities upstream. Sampling sites upstream from Saskatoon and on the South Saskatchewan River would be contaminated only by cities at appreciable distance upstream, such as Calgary in Alberta; Edmon- ton, also in Alberta, may contribute to pollution of the North Saskatchewan River. The Group II sampling sites. McLennan Lake (Site 7). Candle Lake (Site 8). Murray Lake (Site 9), and Last Mountain Lake (Site 10). did not receive industrial or municipal wastes. McLennan Lake in Northern Sas- katchewan is remote from human activities, while Vol. 6, No. 2, September 1972 FIGURE 1. — Map of Sa.^knlclicwan .'showing the collection sites— 1970 agricultural land forms a substantial part of the pre- cipitation area of Candle Lake, and Murray and Last Mountain Lakes are within agricultural areas. It has been pointed out that agricultural uses of mercury do not contribute to pollution of water or fish (12). Al- though water or bottom mud from the lakes were not analyzed, these Group II sites were considered ap- parently unpolluted by man. During the summer of 1970. a total of 125 fish were netted at the 10 sampling locations and brought to the laboratory as rapidly as possible. Muscle tissue samples were taken from the longitudinal dorsal muscles on the anterior section of each fish and frozen in plastic bags at —18" C until analyzed. A nalytical Procedure.'! The total mercury content of each muscle tissue sample was determined by atomic absorption spectrometry ac- cording to the method of Saha et al. (1.^). A 4- to 5-g sample of fish tissue was digested under reflux with con- centrated nitric acid and perchloric acid to destroy or- ganic matter. The acidity of the digest was adjusted to approximately In, and hydroxylamine hydrochloride was added to destroy excess oxidants. The solution was then extracted twice with chloroform to remove any 123 organic matter. Mercuric ions were then extracted with a chloroform solution of dithizone and determined by atomic absorption spectrometry. About 93 to 98% of the mercury added to muscle tissue as HgCL could be recovered by this method, and the minimum detectable amount was 0.005 ppm Hg. All fish specimens were analyzed in duplicate, and the mercury levels were not corrected for recovery. Results and Discussion The average mercury concentration with standard devia- tion, range, and median values for fish species from each sampling site are given in Table I. The mercury concentrations in fish from Group I sites ranged from 0.18 to 8.88 ppm and generally averaged above the 0.5 ppm Canadian actionable level. The goldeye fish from Lloydminster (Site 1) averaged 0.74 ppm of mercury; and long-nose suckers from Borden (Site 2). a point downstream from Lloydminster, had a rather high average level for the species (0.57 ppm) since this species is known to accumulate less mercury than other species, for example, pike. The waters at those two sites on the North Saskatchewan River were probably contaminated by industrial and municipal wastes from cities along the river bank. Squaw Rapids Dam (Site 3) and Tobin Lake (Site 4) were only 30 miles apart and both received contaminated waste from the chlor-alkali plant in Saskatoon (about 300 miles up- stream) and other industrial and municipal wastes from many cities along the river system. The average mercury content of pike varied considerably for these two sites (Site 3 — 1.94 ppm and Site 4 — 0.86 ppm) although the lower ranges were similar (Site 3 — 0.49 ppm and Site 4 — 0.63 ppm). These results are not unusual, since other studies have reported widely differing amounts of mer- cury in the same species from the same location (9,17). The highest average mercury concentrations were in goldeye (2.05 ppm) and pike (4.80 ppm) from Clark- boro Ferry (Site 5); these levels reflect the effects of direct discharge of individual wastes containing mercury into water, since the sampling site is only a few miles downstream from the chlor-alkali plant in Saskatoon (Site 11). It has been estimated that about 0.25 to 0.5 lb mercury can be lost to the environment for every ton of chlorine produced, and plants producing 100 tons or more of chlorine per day are rather common (3,4). A plant of this size can then discharge 9 to 18 thousand lb of mercury per annum into the environment, mainly in water. Fish (Sanger) from Leader Ferry (Site 6), a site upstream from the chlor-alkali plant in Saskatoon and contami- nated with municipal or other types of industrial wastes averaged only 0.67 ppm mercury. The mercury concentrations in fish from Group II sites ranged from 0.1 I to 1.13 ppm. Mean levels of mercury were low in walleye from Candle Lake and pike from McLennan Lake, averaging 0.18 ppm and 0.24 ppm of mercury, respectively. The walleye from Last Mountain Lake, however, averaged 0.45 ppm, a concentration barely within the 0.5 ppm Canadian actionable level. Of particular interest was the mercury content of perch from Murray Lake (0.71 ppm), a level about three times higher than in perch from Tobin Lake (0.24 ppm), a site with known industrial and municipal mercurial con- tamination. These results indicate that mercury levels in fish in excess of 0.5 ppm do not necessarily result TABLE 1. — Mercury residues in fish front some Saskatchewan waters with and without known sources of pollution — 7970 GROUP I (INDUSTRIAL AND/OR MUNICIPAL POLLUTION) 1. Lloydminster 1 Goldeye 10 0.74 ± 0.25 0.52-1.2 0.63 2. Borden ' Longnose sucker 15 0.57 ± 0.19 0.25-0.90 0.57 3. Squaw Rapids Dam - Pike 10 1.94 ■± 2.50 0.49-8.88 1.06 4. Tobin Lake = Pike 10 0.86 ± 0.24 0.63-1.2 0.91 Sauger 6 0.98 ± 0.26 0.79-1.50 0.89 Goldeye 16 0.42 ± 0.08 0.30-0.55 0.41 Perch 12 0.24 ± 0.07 0.18-0.42 0.21 5. Clarkboro Ferry ^■ Goldeye 5 2.05 ± 1.37 0.96-4.25 1.30 Pike 3 4.80 ± 2.25 2.60-6.11 6.09 6. Leader Ferry > Sauger 4 0.67 It 0.20 0.42-0.84 0.71 GROUP II (NO KNOWN SOURCES OF POLLUTION) 7. McLennan Lake 8. Candle Lake 9. Murray Lake 10. Last Mountain Lake Pike Walleye Perch Walleye 4 9 II 10 0.24 ± 0.07 0.18 ± 0.04 0.71 ± 0.20 0.45 ±0.13 0.16-0.32 0.11-0.24 0.42-1.13 0.23-0.68 0.23 0.19 0.70 0.41 Total 125 Polluted with industrial and municipal wastes from cities, but no chlor-alkali plant. Polluted with industrial and municipal wastes and by effluents from a chlor-alkali plant at considerable dista Polluted with industrial and municipal wastes and direct discharge of effluents from a chlor-alkali plant. 124 Pesticides Monitoring Journal from man's use of mercury, since the only sources of mercury for Group II sites are agricultural or natural levels in bedrock. High levels of mercury in fish from other apparently uncontaminated water have been re- ported earlier; Wobeser et al. (17) reported 0.8 ppm Hg in a lake trout from a Northern Canadian lake, and Johnels et al. (9) reported 0.75 to 1.1 ppm Hg in pike from several apparently uncontaminated waters in Sweden. Mercury content of bedrock was suggested as a possible source for such high levels (9). The bedrock in Saskatchewan is primarily sedimentary which, in general, has a higher mercury content than igneous rocks (6). The results obtained in this study show that high levels of mercury (greater than I ppm) can be expected in fish from waters contaminated directly by industrial eftlu- ents containing mercury such as those from the chlor- alkali industry. The mercury content of fish can exceed 0.5 ppm if the source waters are contaminated with in- dustrial and municipal wastes from urban centers even though they may have no chlor-alkali plant contamina- tion. Lastly, the mercury content of fish from some ap- parently uncontaminated waters may exceed the 0.5 ppm Canadian actionable level; such high levels are probably of natural origin and related to the mercury content of the bedrocks. Acknowledgment The authors wish to thank F. M. Alton and L. M. Royer of the Saskatchewan Department of Natural Re- sources who collected most of the fish specimens and to thank Shirley Remmen for technical assistance. A re- search grant from the Saskatchewan Research Council to support this work is also greatly appreciated. LITERATURE CITED (/) Abelson. H. 1970. Methylmercury. Science 169:3942. (2) Anderson. A. 1967. Mercury in the soil. Grundforbat- tring 20:95-105. {3) .Anonymous. 1970. Mercury in the environment. En- viron.'Sci. Technol. 4:890-892. {4) Bligh. E. G. 1970. Mercury and the contamination of freshwater fish. Fish. Res. Board Can. Manuscr. Rep. Ser. No. 1088. Winnipeg. Manitoba. i5) Bligli. E. G. 1971. Mercury levels in Canadian fish. Presented to the R. Soc. Can. Int. Symp. Mercury in Man's Environ., Ottawa Feb. 15-16, 1971. (6) Day. F. H. 1963. The chemical elements in nature. George G. Harrap & Co. Ltd.. London: p. 372. (7) Goldwatcr. L. J. 1971. Mercury in the environment. Sci. Am. 224:1 5-2 L (.S) Giirha. J. B. 1970. Mercury situation in Alberta. Proc. 1 8th Annu. Meet. Conf., Can. Agric. Chem. Assoc, Jasper, Alberta, p. 53-73. (9) Johnels. A. G.. T. Westernuiik. W. Beiq. P. I. Pf/xw/i. and B. Sjoslrand. 1967. Pike (Eso.x lucius L.) and some other aquatic organisms in Sweden as indicators of mercury contamination in the environment. Oikos 18: 323-333. [10) Kurland. L. 1960. The outbreak of a neurological dis- order in Minamata, Japan, and its relationship to the ingestion of seafood contaminated by mercuric com- pounds. World Neurol. 1:370-395. I//) Paviingion. J. R. 1962. A history of chemistry. Vol. 3 McMillan & Co., London, p. 77, 640. (/2) Saha. J. G. 1972. Significance of mercury in the en- vironment. Residue Rev. 42:103-163. {13) Saha. J. G.. Y. IV. Lee. R. D. Tinline. S. H. F. Chinn. and H. M. Auslenson. 1970. Mercury residues in cereal grains from seeds or soil treated with organo- mercury compounds. Can. J. Plant .Sci. 50:597-599. (14) .Saiikov, A. .4. 1946. Geokhimiyartuti (Geochemistry of mercury). Tr. Inst. Geol. Nauk. Akad. Nauk SSSR. 78, Min-Geokhim. Ser. No. 17. {15) .Slock, A., and F. Cuctiel. 1934. Die Verbreitung des Quecksilbers. Naturwiss. 22:390-393. (/6) West. J. M. 1969. Mercurv in minerals year book 1968. Vol. I-II. U.S. Gov. Printing Office, p. 693-701. (/7) Woheser. G.. i\. O. Mcl.sen. R. H. Dnnlop. and F. M. Anon. 1970. Mercury- concentrations in tissue of fish from the Saskatchewan River. J. Fish. Res. Board Can. 27:830-835. Vol. 6, No. 2, September 1972 125 PESTICIDES IN SOIL Pesticide Residues in Soil From Eight Cities — 1969 G. B. Wiersma'. H. Tar. and P. F. Sand ABSTRACT Soil samples from eight cities were analyzed for pesticide residues. Besides DDT and its metabolites (DDTR), other pesticides detected were dieldrin. chlordanc. heptachlor, heptachlor epoxide, toxaphene, and endrin. No organophos- phatc residues were delected. Levels of DDTR varied signifi- cantly among the eight cities, with the highest average residue level in Miami, Fla. (5.98 ppm) and the lowest in Houston, Tex. (0.35 ppm). When residue levels in lawn or garden areas were compared to those in unkept areas within the cities, DDTR residues were significantly greater for lawn areas. Introduction Much information has been developed on pesticide resi- dues in soils: however, little is available on residue levels in soil from urban areas. Fahey. Butcher, and Murphy (/) sampled urban soil in Battle Creek. Mich., for chlorinated hydrocarbons and found residues of DDT ranging from 0.07 to 79.92 ppm. Purves (2) studied the difference between residues of trace elements found in urban garden plots and those in rural areas and found residues of boron, lead, and zinc to be greater in urban garden plots than rural plots. The present report covers a preliminary survey of pesti- cide residues in soil initiated in response to the need for more intensive studies of pesticide residues in urban areas of the United States. * Pesticides Regulation Division. Office of Pesticides Programs, En- vironmental Protection Agency. Washington. D.C. 20460. - Pesticides Regulation Division. Office of Pesticides Programs. En- vironmental Protection Agency, Gulfport. Miss. 39501. Plant Protection Division. Agricultural Research Service. U. S. De- partment of Agriculture, Hyattsville, Md. 20782. 126 Satnpling Procedures Eight U.S. cities at different geographical locations throughout the country were selected for soil sampling during the summer and fall of 1969. Fifty sampling sites were randomly chosen within each city. Each site was a 50- by 50-ft plot, modified at times to meet local conditions, but always containing 2,500 square feet. Within each site, 9 soil cores (2 inches in diameter by 3 inches deep) were collected on a 3- by 3-grid. These cores were sifted through a 'j-inch mesh, composited, and shipped to the Pesticide Monitoring Laboratory in Gulfport, Miss. A nalytical Procedures A subsample of soil, weighing 300 g wet weight, was placed in a 2-qt jar with 600 ml of 3 : 1 hexane-isopro- panol solvent. The jars were sealed and rotated for 4 hours. After rotation, the soil was allowed to settle, and 200 ml of the extract solution was filtered into a 500-ml separatory funnel. The isopropanol was removed by two washings with distilled water. The hexane was then filtered through a funnel containing glass wool and an- hydrous sodium sulfate (NaLSO.). No further cleanup v\as normally required before analysis. Gas chromatography was employed for the analysis of organochlorine pesticides using the electron affinity de- tector and for organophosphorus pesticides using the flame photometric detector. The essential experimental conditions were as follows: Gas Chromalographs: 1. Hewlett-Packard Model 402 and Model 810 — tritium foil elec- tron affinity detector (pulsed-cell potential); carrier gas — 5% methane in argon and flow rate — about 80 ml 'min. 1. MicroTek Model 220 — tritium foil electron affinity detector (DC-cell potential); flame photometric detector, phosphorus fllter, hydrogen-oxygen flame (hydrogen flow rate — 150-200 ml min. oxygen flow rate — 30-35 ml 'min); carrier gas — puri- fied nitrogen and flow rate — about 100 ml/min Pesticides Monitoring Journal Columns: Glass, 183 cm long by 6 mm, o.d. and 4 mm, id. with the following packings: 3% or IQi^r DC-200 on 100120 mesh Gas Chrom Q 9'-c QF-1 on 100 120 mesh Gas Chrom Q 59c XE-60 on 100, 120 mesh Chromosorb W Temperatures: Detector 200' C Injection port 250° C Column DC-200 180° C Columns QF-1 and XE-60 160° C Peak height was used to measure the amount of pesticide residues. A dual-column system employing polar and nonpolar columns was utilized to identify and confirm pesticides. Further confirmation, when necessary, was made by thin layer chromatography or partition values. Average reco\ery values for most of the organochlorine pesticides ranged from 909c to 100%. and with the exception of chlordane and toxaphene, the detection limits were 0.01 to 0.02 ppm. Chlordane was calculated using gamma-chlordane as a standard (gamma-chlordane constitutes an average of 10*7 of technical chlordane), with a detection limit of 0.04 ppm. Toxaphene was measured hy comparing the summation of peak heights of several peaks (usually four selected peaks from its multiple-peak gas chromatogram) with the correspond- ing peaks of a known standard, and the detection limit was 0.05 ppm. All residues reported were corrected for recovery. The present analytical methodology should detect com- mon organophosphate pesticides such as DEF". diazin- on, EPN. ethion. azinphosmethyl. malathion. parathion. phorate, and carbophenothion. The recover) \alues ranged from 80*7 to 100'7, with detection limits rang- ing from 0.01 ppm for phorate to 0.1 ppm for azinphos- methyl and EPN. It should be noted, however, that the present extraction technique would not recover many of the possibly oxidized metabolic products. Arsenic was determined by atomic absorption spectro- photometry. The soil sample was first extracted with 9.6n' hydrochloric acid and then reduced to the As^-' state with stannous chloride. As^-' was partitioned from the acid to benzene, then further partitioned from benzene into water for the absorption measurement. A Perkin-Elmer Model .'^03 instrument was used, and absorbence was measured with an arsenic cathode lamp at 1970 A with argon as an aspirant to an air-hydrogen flame. This method was rapid and precise, but indicated an average recovery rate of 56"^^ for soil samples. The arsenic levels reported in this study were corrected for the recovery value: the detection limit after correction, was 0.2 ppm. Results and Discussion Table 1 shows the average residues detected for all cities. Miami had the highest combined residues of DDTR (DDT and related degradation products). It also Vol. 6. No. 2. September 1972 had the highest dieldrin and chlordane residues. The dieldrin residues were particularly outstanding, because the average residue in Miami was over 10 times greater than the next highest average dieldrin residue, which was detected in Bakersfield. The highest arsenic residues were found in Salt Lake City and the lowest, in Houston. No organophosphate residues were detected. The range of residues and the percent of sites with detectable residues are also given in Table 1. Although Bakersfield. Calif., had an average residue of 0.36 ppm for DDTR. the range was narrow (0.02 - 3.08 ppm) and 94"^ of the sites had detectable residues. This indicates an equal distribution of DDTR residues over the entire city. In contrast, Waterbur>'. Conn., has an average DDTR residue of 0.98 ppm and a wide range (0.01 - 10.35 ppm), with only 56'^c of the sites having detectable residues, indicating an unequal distribution over the city. With the exception of Houston and Manhattan, cities in this study were located in States where croplands had previously been sampled as part of the National Soils Monitoring Program. Residues of arsenic. DDTR. dieldrin. and chlordane. four commonly occurring pesticides, are compared in Table 2. In most cases, the average residues detected in the cities tended to be greater than the corresponding cropland residues: how- ever, because no tests of significance can be made on the data at this time, caution should he exercised in inter- preting the results in Table 2. Pesticide residue data can usually be described by a log normal distribution. Frequently, however, the data contain a large number of zero values, resulting either from the absence of pesticides or their presence at levels below the analytical sensitivity. To include these zero values when taking logarithms, a value must be substituted for the zero figure. After repeated tests for significant kurtosis and or skewness. the log (X — .01) transformation most closely approximated the normal distribution. Using this transformation, logarithmic means were determined for DDTR and arsenic residues. The 951^ confidence interval about each of these means was determined. The antilogs of these figures were taken to give estimates of the geometric mean and its 95^ confidence interval in the untransformed dimension. The results are given in Table 3. All figures are in parts per million. For DDTR. the geometric mean for soil from Miami. Fla.. (1.60 ppm) far exceeded means from the other cities: the confidence interval ranged from 0.91 to 2.82 ppm. Camden. N. J., had the second highest mean (0.37 ppm) with an upper limit of 0.62 ppm. Houston. Tex., had the lowest mean (0.02 ppm). and its upper limit (0.04 ppm) was the same as the lower limits for Manhattan. Kan., and Waterbury. Conn., which had virtually identical means and confidence intervals. 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J« < CL SOS < CL ffl 6 X 1 i s « 1 — E ^ — II Q Z i> n c j- > •o H O B. o a 128 Pesticides Monitoring Journal confidence intervals show some distinct variation in levels between the cities, but. in general, there is con- siderable overlap. The geometric means of the arsenic values tended to separate the cities into two general classes — those with residues greater than 5 ppm and those with residues less than 2 ppm. Houston and Miami had geometric means of<2 ppm, and the other cities had residues >5 ppm. These variations in elemental arsenic are proba- bly attributable to differences in geological conditions or possibly contamination from industrial or combustion sources rather than to differences in use of various arsenical pesticides. The residue levels of DDT and some of the other pesti- cides were too high to have resulted from general en- vironmental contamination, suggesting that they ma> have resulted from application of pesticides by cit\ governments, home owners, or other urban activities. In an effort to determine the sources of contamination from DDTR and arsenic in the cities, the soil residue data for each compound were pooled and divided into "lawn" and "unkept" areas. These areas are defined as follows; TABLE 2. — Comparison of residue levels of compounds present in both urban and cropland soils in six States close proximity to a house, unicipal parks or other town-c factory, wned or ■ Lawn Areas 1. Mowed grass structure. 2. Mowed grass i land. .^. Garden or cultivated areas. 4. A yard that is in obvious proximity to a home. Unkept Areas 1. Vacant lots where grass is apparently uncared for. 2. Small wooded lots, brush, or overgrown fields. 3. Areas such as power lines, gas lines, etc. 4. Bare exposed soil around construction sites, eroded areas. Residues in PPM Location Arsenic DDTR DiELDRIN Chlordane California Bakersfield 7.1 0.36 0.07 0.78 Cropland 5.2 1.43 0.02 0.01 New Jersey Camden 11.2 1.36 <0.01 0.36 Cropland ' 6.8 0.14 0.02 <0.01 Florida Miami 2.3 5.98 0.72 1.59 Cropland 0.8 0.85 0.08 0.36 Wisconsin Milwaukee 14.4 1.07 0.04 0.45 Cropland 3.8 0.02 0.01 0.01 Utah Salt Lake City 15.7 0.49 0.03 0.41 Cropland - 4.8 0.20 0.01 0.02 Connecticut Waierbury 8.5 0.98 0.01 0.96 Cropland '■'■ 10.0 0.59 0.01 0.01 Average of results for New Jersey, Delaware, and Maryland. Average of results for Arizona. New Mexico, Nevada, and Utah. Average of results for Maine. New Hampshire, Vermont, Massachu- setts. Rhode Island, and Connecticut, TABLE 3. — Geometric means and 95% confidence intervals for DDTR and arsenic residues in soil from six cities — 7969 DDTR Arsenic Cnv Upper G.M. Lower Upper CM. Lower (PPM) (PPM) (PPM) (PPM) (PPM) (PPM) Bakersfield, Calif. 0.27 0.20 0.13 6.7 5.5 4.5 Camden. N.J. 0.62 0.37 0.21 10.0 7.6 5.8 Houston. Tex. 0.04 0.02 0.01 1.5 1.1 0.7 Manhattan. Kans. 0.18 0.09 0.04 8.2 6.2 4.7 Miami. Fla. 2.82 1.60 0.91 1.1 0.6 0.3 Milwaukee. Wis. 0.50 0.31 0.19 13.1 8.4 5.4 Salt Lake City. Utah 0.21 0.12 0.06 12.6 9.6 7.4 Watcrbury, Conn. 0.18 0.08 0.04 7.8 6,1 4.8 A "t" test, for unequal numbers of observations, was used to test for significance. When arsenic residues were tested, no significant difference could be detected in residues between lawn and unkept areas. This supports the hypothesis that arsenic residues resulted either from background levels or from general pollution sources such as coal or petroleum combustion. However, a significant ditference (t = 4.15) was detected for DDTR residues, with the higher residues found in the lawn areas. This indicates that DDTR residues in the city areas probably occurred as a direct result of pesticides used within the city. In conclusion, the cities sampled in this study generally had heavy loads of chlorinated hydrocarbon pesticide residues in soil. These tended to be greater than crop- land residues from the same State, although tests of significance could not be made on these data. There was some distinct variation in residue levels between cities. Finally, within the cities, DDTR residues in lawn areas were significantly greater than those in unkept areas. Vol. 6, No. 2, September 1972 See Appendix for chemical names of paper. ompounds discussed LITERATURE CITED (/) Fahey. J. E.. J. W. Bucher, and R. T. Murphy. 1965. Chlorinated hydrocarbon insecticide residues in soils of urban areas. Battle Creek, Michigan, J. F.con. Entomol. .'58(3);1026-1027. (2) Purves, D. 1968. Trace element contamination of soils in urban areas. International Society of Soil Scientists, Trans. 9th Congress 2:351-355. (i) Wiersma. G. B.. P. F. Sand, and E. L. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(l):63-66. 129 I APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN ARSENIC AZINPHOSMETHYL BHC CARBOPHENOTHION (TRITHION®) CHLORDANE 7-CHLORDANE DDE DDT (including its isomers and dehydrochlorination products) DEF® DIAZINON DIELDRIN HNDRIN FPN ETHION HEPTACHLOR HEPTACHLOR EPOXIDE MALATHION MERCURY METHYL PARATHION PARATHION PHORATE SELENIUM TDE (DDD) (including its isomers and dehydrocalorina- tion products) TOXAPHENE Not less than 95% of 1,2,3,4, 10.10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-f"do-c.vo-5,8-dii As;03 0,0-dimethyl S-(4-oxo-l,2,3-benzotriazin-3[4W]-ylmethyl phosphorodithioate 1,2,3,4,5,6-hexachlorocyclohexane, mixed isomers .?-[(p-chlorophenylthio)methyl] 0,0-diethy! phosphorodithioate l,2,4,5,6,7,8,8-octachloro-3a,4,7.7a-tetrahydro-4,7-methanoindane gamma isomer of the p,p'-isomer and the 1 ,l-dichloro-2,2-bis ( p-chlorophenyl ) ethylene l.l,l-trichloro-2,2-bis(p-chlorophenyl)ethane; technical DDT consists of a o,p'-isomer (in a ratio of about 3 or 4 to I ) 5,5,5-tributyl phosphorotrithioate 0,0-diethyl 0-(2-isopropyl-4-methyl-6-pyrimidyl ) phosphorothioalc Not less than 85% of 1,2,3,4,10, 10-hexachloro-6.7-epoxy-l.4,4a,5,6,7,8a-octahydro-1.4-fndo-exo-5,8-dimethano= naphthalene l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8.8a-octahydro-l,4-e)!do-f/irfo-5,8-dimethanonaphthalene (7-ethyl (?-(p-nitrophenyl) phenylphosphonothioatc O.O.O'.O'-tetraethyl 5,5'-methylenebisphorodithioatc l,4,5,6,7,8,8-heptachIoro-3a,4,7,7a-tetrahydro-4,7-methanoindenc l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan diethyl niercaptosuccinate, S-ester with 0,0-diinethyl phosphorodithioate Hg 0,0-dimethyl 0-p-nitrophenyl phosphorothioate 0, 0-diethyI 0-p-nitrophenyl phosphorothioate 0,0-diethyI ^-(ethylthio) methyl phosphorodithioate Se t,l-dichloro-2,2-bis(p-chlorophenyl )ethane; technical TDE contains some o.p'-isomer also chlorinated camphene containing 67% to 69%. chiorm 130 Pesticides Monitoring Journal Information for Contributors The Pesticides Monitoring Journal welcomes from ji all sources qualified data and interpretive information I which contribute to the understanding and evaluation of J pesticides and their residues in relation to man and his environment. The publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries; medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. Accuracy, reliability, and limitations of the sam- pling and analytical methods employed must be clearly demonstrated through the use of appropriate procedures, such as recovery experiments at appropriate levels, confirmatory tests, internal standards, and inter-labora- tory checks. The procedure employed should be ref- erenced or outlined in brief form, and crucial points or modifications should be noted. Check or control samples should be employed where possible, and the sensitivity of the method should be given, particularly when very low levels of pesticides are being reported. Specific note should be made regarding correction of data for percent recoveries. Preparation of manuscripts should be in con- formance to the Style Manual for Biological Journals, American Institute of Biological Sciences, Washington, D. C. and/or the Style Manual of the United States Government Print- ing Office. — An abstract (not to exceed 200 words) should accompany each manuscript submitted. All material should be submitted in duplicate (original and one carbon) and sent by first-class mail in flat form — not folded or rolled. Manuscripts should be typed on 8V2 x 1 1 inch paper with generous margins on all sides, and each page should end with a completed para- graph. - All copy, including tables and references, should be double spaced, and all pages should be num- bered. The first page of the manuscript must contain authors' full names listed under the title, with affiliations, and addresses footnoted below. Charts, illustrations, and tables, properly titled, should be appended at the end of the article with Vol. 6, No. 2, September 1972 a notation in text to show where they should be inserted. Charts should be drawn so the numbers and texts will be legible when considerably reduced for publication. All drawings should be done in black ink on plain white paper. Photographs should be made on glossy paper. Details should be clear, but size is not important. The "number system" should be used for litera- ture citations in the text. List references alpha- betically, giving name of author/s/, year, full title of article, exact name of periodical, volume, and inclusive pages. The Journal also welcomes "brief" papers reporting monitoring data of a preliminary nature or studies of limited scope. A section entitled Briefs will be included, as necessary, to provide space for papers of this type to present timely and informative data. These papers must be limited in length to two Journal pages (850 words) and should conform to the format for regular papers accepted by the Journal. Pesticides ordinarily should be identified by common or generic names approved by national scientific so- cieties. The first reference to a particular pesticide should be followed by the chemical or scientific name in parentheses — assigned in accordance with Chemical Abstracts nomenclature. Structural chemical formulas should be used when appropriate. Published data and information require prior approval by the Editorial Advisory Board; however, endorsement of published in- formation by any specific Federal agency is not intended or to be implied. Authors of accepted manuscripts will receive edited typescripts for approval before type is set. After publication, senior authors will be provided with 100 reprints. Manuscripts are received and reviewed with the under- standing that they previously have not been accepted for technical publication elsewhere. If a paper has been given or is intended for presentation at a meeting, or if a significant portion of its contents has been published or submitted for publication elsewhere, notation of such should be provided. Correspondence on editorial matters or circulation mat- ters relating to official subscriptions should be addressed to; Mrs. Sylvia P. O'Rear. Editorial Manager, Pesti- cides Monitoring Journal, Division of Pesticide Com- munity Studies.Office of Pesticides Programs, Environ- mental Protection Agency, 4770 Buford Highway, Bldg. 29, Chamblee, Ga. 30341. 131 BRIEFS \ Residues of Chlorinated Hydrocarbon Pesticides in the Northern Quahog (Hard-Shell Clam), Mercenaria mercenaria — 1968 and 1969 Ronald M. Check' and Manuel T. Canario, Jr.- ABSTRACT Samples of the northern quaghog Ihard-sliell clam), Mer- cenaria mercenaria, nere coltecled monthly, when possible, from September 1968 to September 1969 at five locations in Narragansett Bay, Rhode Island, and one location in nearby Mount Hope Bay. All 56 composite samples contained diel- drin at an average level of 0.040 ppm: p,p'-DDD was pres- ent in 3 samples at an average level of 0.026 ppm. Quahogs from upper reaches of Narragansett Bay contained higher levels of residues than samples from lower Bay areas. Introduction Preliminary examinations of the northern quahog (hard- shell clam), Mercenaria mercenaria. revealed the pres- ence of chlorinated hydrocarbon pesticides in samples from Narragansett Bay. Rhode Island. As a result, a one-year survey was conducted with sampling at monthly intervals, when possible, from September 1968-Septem- ber 1969, to determine the amounts of various chlor- inated pesticides present in this species. Sampling and Analytical Procedures In September 1968, sampling stations were established at five sites in upper Narragansett Bay and one station in the southeastern corner of nearby Mount Hope Bay (Fig. 1). Shellfish samples were obtained by dredging. In the laboratory, clams were shucked and drained; a 300-g composite sample of meat, generally represent- ing 14-18 clams from each location, was blended in a Waring Blendor until homogenized. Blended samples were frozen until analyzed. NARRAGANSET AND VIC INI T Y Division of Laboratories Providence, R.I. 02903. ' Division of Food Protection and Sanitation ment of Health, Providence, R.I. 02903. Rhode Island Department of Health, Rhode Island Depart- FIGURE 1. — Locations of shellfish sampling sites in Narra- gansett Bay and Mount Hope Bay, R. I.. September 1968-September 1969 Vol. 6, No, 3, December 1972 229 The frozen 300-g samples were thawed, and 50-g sub- samples were slurried with 100 ml of acetonitrile and allowed to stand overnight. A 25-g aliquot was filtered from the slurry and partitioned into petroleum ether according to the procedure outlined in the Pesticide Analytical Manual (1). A 5-g aliquot was evaporated at room temperature to 2-3 ml and subjected to chemical cleanup by the sweep co-distillation method of Storherr et al. (2). The Florisil column step was included in the cleanup method. Puri- fied sample extracts were concentrated to the equi- valent of 1 g of sample per ml and analyzed by gas chromatography. The chromatograph was equipped with a Ni^3 electron capture detector and two 6-ft glass columns, '/i inch in diameter. One column contained 10% DC-200 and the other. 5% QF-1. These liquid phases were coated on Gas Chrom Q solid support. Nitrogen was used as the carrier gas. Injections onto the two columns provided tentative peak identification. All pesticide residues found were confirmed by thin layer chromatography using precoated aluminum oxide G plates. Standard solutions of the suspected pesticides were spotted beside samples and developed in n-heptane which had been redistilled over molten metallic sodium. Sample areas only were covered with aluminum foil, sprayed with Kovac's chromagenic reagent (i), and the plates were exposed to UV light. The foil was removed, and zones corresponding to standards were scraped from the plate and extracted from the aluminum oxide with 2 ml of 10% ethyl ether in petroleum ether. The 2-ml extracts were concentrated to 0.2 ml and reinjected through the two gas chromatographic columns for pesti- cide confirmation. Further tests using chemical derivatization and parti- tion coefficients were employed on initial samples to confirm the presence of dieldrin. The lower limits of detection for pesticides reported were 0.01 ppm for diel- drin and 0.02 ppm for p,p'-DDD, p.p'-DDE, and p,p'- DDT. Occasional samples were fortified with known amounts of dieldrin, o.p'-DDE, p.p'-DDE. p.p'-DDD, and p.p'- DDT and subjected to the methodology described. Re- coveries averaged 85%, 80%, 71%, 71%, and 73%, respectively. Ranges of recovery were 65% -100% for dieldrin and 50% -87% for p.p'-DDT. The recovery for p,p'-DDT and p.p'-DDE, while lower than that for dieldrin, was sufficient to show the presence of these compounds above the 0.02 ppm detection level used in this study. Several methods of analysis were evaluated initially including the traditional Florisil column cleanup procedure, but interfering peaks prevented positive iden- tification and accurate quantitation of DDE and DDT if these compounds were present. Many of these peaks may have been residues of various polychlorinated biphenyls, and it was necessary to eliminate them before an accurate pesticide profile could be obtained. The co- distillation method provided a means of separating unknown peaks from pesticides present in the samples. Future monitoring programs in conjunction with cur- rently available methodology should yield more informa- tion about possible PCB residues. Results and Discussion Analyses for chlorinated pesticides in quahogs taken from the sampling stations indicated in Fig. 1, revealed the presence of dieldrin in all 56 samples and p.p'-DDD in 3 samples (Table 1). The absence of DDE and DDT in amounts greater than 0.02 ppm was unexpected in the samples analyzed. The average levels of pesticides found during the year were 0.040 ppm for dieldrin and 0.026 ppm for p.p'-DDT>. In general, residues of diel- drin and DDD were higher in those samples from upper reaches of the Narragansett Bay than from the lower Bay areas. TABLE 1. — Dieldrin and p,p'-DDD residues detected in northern quahogs, Narragansett and Mount Hope Bays — September 1968-September 1969 Month OF Dieldrin and p.p'-DDD* Weight Basis. Residues in PPM, Drained Meat Wet- Sam- pling Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 1968 Sept. .060 .050 .010 .006 .021 .027 Oct. .090 .056 .043 .063 .055 .048 1969 Feb. .070 .082 .043 .036 .037 .029 Mar. 086 .066 .045 .062 .015 .026 Apr. .060 .063 .060 .049 .031 .024 May .066 .050 .042 June .047 .047 .049 .039 .013 July .044 .039 •.028 .053 •.030 .039 ♦.020 .029 .016 Aug. .030 .023 .028 .014 .013 .007 Sept .030 .026 .029 .026 .025 .023 NOTE: Blank = sample not analyzed. * P.p'-DDD residues were detected only in the July samples from Sta- tions 2, 3. and 4. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Barry H. C. J. G. Hundley, and L. Y. Johnson. 1965. Pesticide analytical manual. Vol. I, Food Drug Adm., U.S. Dep. Health, Educ, Welfare, Washington, D.C. 20204. (2) Storherr. R. W., E. J. Murray, I. Klein, and L. A. Rosen- berg. 1966. Sweep co-distillation cleanup of fortified edible oils for determination of organophosphate and chlorinated hydrocarbon pesticides. Div. Food Chem., Food Drug Adm., Washington, D.C. 20204. (3) Kovacs. M. F., Jr. 1966. Rapid detection of chlorinated pesticide residues by an improved TLC technique: 3V4 x 4" micro slides. J. Assoc. Off. Anal. Chem. 49(2):365-370. 230 Pesticides Monitoring Journal APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN ARSENIC ATRAZINE BHC CARBOPHENOTHION (TRITHION®) CHLORDANE 2,4-D DCPA (DACTHALS) DDE DDT (including its isomers and dehydrochlorination products) Not less than 95% of 1,2,3.4. 10,10-hexachloro-1.4,4a,5.8,8a-hexahydro-1.4-fndo-«o-5.8-dimethanonaphthalene AsiOs 2-chloro-4-ethyIamino-6-isopropylamino-5-triazine 1,2,3.4,5,6-hexachlorocyclohexane. mixed isomers 5-[(p-chlorophenylthio)mcthyI] 0.0-diethyl phosphorodithioate l,2,4,5,6,7,8,8-octach]oro-3a,4,7.7a-tetrahydro-4,7-melhanoindane 2,4-dichlorophenoxyacetic acid dimethyl ester of tetrachlorolerephlhalic acid l,l-dichloro-2,2-bis(p-chlorophenyl) ethylene l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane; technical DDT consists of a mixture of the p,p'-isomer and o,p'-isomer {in a ratio of about 3 or 4 to 1) DIAZINON DCBP DICOFOL (KELTHANE*) DIELDRIN DURSBAN® ENDOSULFAN (THIODAN®) ENDRIN ETHION HEPTACHLOR HEPTACHLOR EPOXIDE HCB ISODRIN LINDANE MALATHION MERCURY METHOXYCHLOR METHYL MERCURY PARATHION PCNB POLYCHLORINATED BIPHENYLS (PCB's) TDE (DDD) (including its isomers and dehydrochlorina- tion products) TOXAPHENE TRIFLURALIN 0,0-dielhyl 0-(2-isopropyl-4-methyI-6-pyrimidyl) phosphorothioate 4,4'-dichIorobenzophenone 4,4'-dichloro-fl-(trichloromelhyl)benzhydro! Not less than 85% of 1.2,3.4. 10. 10-hexachloro-6.7-epoxy-l,4,4a,5.6.7.8a-ociahydro-l,4-fndo-rxo-5,8-dimelhano= naphthalene 0.0-diethyl 0-(3.5,6-trichloro-2-pyridyl) phosphorothioate 6,7,8,9, 10, 10-hexachloro-l. 5, 5a,6.9,9a-hexahydro-6.9-methano-2,4,3-benzodioxathiepin 3-oxidc 1, 2,3,4, 10,10-hexachloro-6.7-e poxy- 1. 4.4a, 5.6.7.8.8a-octahydro-1.4-fndo-fnrfo-5,8-dimethanonaphthalene 0,0,0',0'-tetraethyl S,5'-methyIenebisphorodilhioale l,4,5,6,7,8.8-heptachloro-3a,4,7,7a-tetrahydro-4.7.methanoindene l,4,5,6,7,8.8-heplachloro-2,3-epoxy-3a.4.7.7a-tetrahydro-4.7-mcIhanoindan hexachlorobenzene 1.2,3 ,4,10, 10-hexachloro-l, 4,4a,5,8,8a-hexahydro-l,4-endo, fn Year Residues in PPM' Compound Carcass Brain Median Range N = Median Range N: P.P'-DDE 1969 6.9 0.16-30 28 0.68 T-62 28 1970 18 1.5-78 11 26 0.22-385 11 p,p'-DDD 1969 1.0 0.06-0.27 27 0.20 T-2.7 18 1970 1.5 0.28-11 11 1.5 0.05-7.2 11 P,P'-DDT 1969 0.22 0.07-0.75 12 0.06 0.06 1 1970 0.10 0.09-1.1 6 0.34 0.23-0.69 4 Dieldrin 1969 0.41 T-6.5 28 0.27 T-8.0 18 1970 0.74 <0.10-18 11 2.0 0.23-11 10 Heptachlor epoxide 1969 0.06 T-0.35 22 0.04 0.003-0.06 6 1970 O.IO T-0.41 9 0.36 0.06-1.0 7 Dichlorobenzophenone 1969 0.42 0.08-0.77 7 0.31 0.07-0.81 4 1970 T T 1 0.30 T-1.1 4 PCB Compounds 1969 10 T-150 28 2.5 T-65 28 1970 20 4-200 11 46 T-230 11 Mercury 1969 1.5 0.52-43 28 1970 2.5 0.47-9.4 11 NOTE: A total of 28 birds were collected in 1969 and 11 birds ' Calculated on a wet-weight basis. ' Numlwr of specimens that contained residues; the median is b ed on this number TABLE 5.— Association between PCB and DDE residues in bald eagles, 1969 and 1970 Carcass Brain PCB/DDE Ni Correlation Coefficient PCB/DDE Ni Correlation Median Range Median Range Coefficient 1969 1970 1.5 1.3 0.4-10 0.5-3.3 26 11 0.287 0.451 3.1 2.2 0.9-11 0.6-7.5 18 10 = 0.908 = 0.752 Number of specimens that contained more than trace amounts of both PCB compounds and DDE. P = <0.01. P = <0.05. 136 Pesticides Monitoring Journal high levels of dieldrin in the brains of the two eagles that drowned may have caused the birds to fall into the water and drown. The dieldrin levels ranged from 4.6 to 1 1 ppm, wet-weight basis. Experimental and field data have shown that the lowest lethal brain residue for dieldrin is about 4 or 5 ppm (5). The seventh eagle, an adult female from Michigan, contained 385 ppm of DDE and 6 ppm DDD in the brain, together with 235 ppm of PCB's. The level of DDE alone is well within the lethal range (6), but the high level of PCB's suggests that these compounds may have also contributed to death. In this study and previous studies (2, 4) since 1964, with the exception of one eagle of unknown sex. all bald eagles found to be possibly poisoned by dieldrin or DDT metabolites have been females. Of the 153 eagles analyzed during 1964-1970, 15 (9.8%) possibly died of dieldrin poisoning. AUTOPSY DATA The autopsy results for the 39 bald eagles are sum- marized in Table 8. Illegal shooting remained the most frequent single cause of death among the bald eagles examined in this laboratory with 46% of the birds col- lected during 1969-1970 having been shot. The four eagles dying from impact injuries, most fre- quently as the result of hitting a power line or tower, included one eagle from Virginia which had been struck by a private jet aircraft. Three eagles were extremely emaciated; two of these were later found to have possible lethal levels of dieldrin in the brain (Table 7), and the third, a bird from Wis- consin, had multiple injuries from porcupine quills. Two quills were still embedded in the back of the eagle's oral cavity, suggesting that this eagle died from the effects of starvation and secondary bacterial infection (see below). TABLE 7. — Data on six suspected cases of possible dieldrin poisoning and one suspected case of DDE poisoning, 1969 and 1970 Residue IN Brain (PPM) TABLE 6.- — Mercury found in 29 bald eagle carcasses, 1969 and 1970 Total PPM Hg I Methyl Mercury Equivalent ppmHg % OF Total Hg Found as Methyl Mercury 1.01 0.68 67.3 1.02 0.96 94.1 1.12 I.OI 90.2 1.13 1.09 96.5 1.17 0.98 83.8 1.26 0.76 60.3 1.31 0.90 68.7 1.42 0.92 64.8 1.49 1.28 85.9 1.53 1.41 92.2 1.53 0.38 24.8 1.70 0.80 47.0 1.72 1.36 79.1 1.77 1.75 98.9 2.07 1.74 84.0 2.18 1.45 66.5 2.20 1.88 85.4 2.50 1.99 79.6 2.74 2.44 89.0 2.96 0.48 16.2 3.01 2.85 94.7 3.58 1.56 43.6 4.42 2.05 46.4 5.65 4.68 82.8 5.83 3.98 68.3 8.32 6.71 80.6 9.40 2.72 28.9 11.00 7.60 69.1 43.00 44.56 103.6 MEDIAN 2.07 1.45 79.6 Missouri 1969 Ad F = 4.6 Drowning, emaciation Wisconsin 1969 Ad F -6.5 Open ' Illinois 1970 Im F 4.6 Open Michigan 1970 Ad F = 4.8 Drowning Minnesota 1970 Im F -•5.9 Emaciated; shotgun pellets around tail Maryland 1970 Ad F 11 Open 385/235 Parasitic enteritis Ad = adult, Im = immature. Dieldrin analyzed and confirmed by gas chromatography-mass spec- trometry. Open = no diagnosis could be made on the basis of autopsy findings. TABLE 8. — Probable causes of bald eagle mortality, 1969 and 1970 Of the 39 samples collected, 10 contained <1.0 ppm total and, thus, were not analyzed for methyl mercury. Cause of Death Number of Eagles Shot 18 Dieldrin i 6 DDE' 1 Impact 4 Electrocution 2 Emaciation 1 Nephrosis 1 Streptococcal infection 1 Avian cholera 1 Trapping injuries 1 Open 3 Total 39 See Table 7 for details. Vol. 6, No. 3, December 1972 137 One eagle from Michigan had an old trapping injury which had become secondarily infected and resulted in a fibrinous pericarditis. A pure culture of a gram-positive rod, subsequently identified as a Lactobacillus, was isolated from the pericardium. This isolate of Lactobacil- lus was noninfectious to laboratory mice and domestic pigeons and probably should be regarded as a post- mortem contaminant. Although Pseudomonas aeruginosa was isolated from the kidney and from an old infected bullet leg wound of an eagle from Wisconsin, the cause of death was a more recent gunshot wound which produced massive hemorrhage into the pericardial sac. Pasteurella multocida. the causative organism of avian chlorea, was isolated from three eagles. The first isola- tion was from an adult male from Ohio and apparently represents a frank case of avian chlorea. The second isolation of P. multocida was from the heart of the emaciated eagle which had been injured by porcupine quills; the third isolation was from the liver of an eagle shot in Florida. Several parasitic conditions were observed in these 39 eagles. Schizonts of Leucocytozoon were found in the hearts of an eagle from Maryland and one from Illinois; both eagles had possible lethal levels of dieldrin in the brain (Table 7). Another eagle from Michigan, subse- quently found to have high levels of DDE and PCB's in the brain, had a severe enteritis caused by a large number of as yet unidentified flukes; although the enteritis was severe, it was not regarded as the cause of the eagle's death. Conclusion Since the bald eagle is located at the top of food chains and is the final recipient of environmental pollutants, the presence of PCB's, DDE. dieldrin. and mercury in all 39 samples from 13 States, demonstrates continued widespread environmental contamination by these com- pounds. A cknowledgment Appreciation is extended to J. O. Knisley and P. Jones who assisted in the autopsies and dissections of eagles, to L. T. Young who prepared sections for histological examination, and to the cooperators from many States and organizations who submitted eagles for analysis. Special acknowledgment is due to Dr. R. Shillinger and his staff (Animal Health Laboratories, Maryland Depart- ment of Agriculture, College Park, Md.) for the identi- fication of the bacterial isolates and to the National Animal Disease Laboratory. USDA, Ames, Iowa, for identification of the Lactobacillus isolate. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Mulheni. B. M. 1968. An improved method for the separation and removal of organochlorine insecticides from thin layer plates. J. Chromatogr. 34:556-558. <2i Mulheni. B. M.. W. L. Reichel, L. N. Locke, T. G. La- ment. A. Belisle. E. Cromartie, G. E. Bagley. and R. M. Prouty. 1970. Organochlorine residues and autopsy data from bald eagles 1966-68. Pestic. Monit. J. 4(3):141-144. (3) Mulhern. B. M., E. Cromartie, W. L. Reichel. and A. A. Belisle. 1971. Semiquantitative determination of poly- chlorinated biphenyls in tissue samples by thin layer chromatography. J. Assoc. Off. Anal. Chem. 54(3): 548-550. (4) Reichel. W. L.. E. Cromartie, T. G. Lamont, B. M. Mul- hern, and R. M. Prouty. 1969. Pesticide residues in eagles. Pestic. Monit. J. 3(3): 142-144. 15) Stickel, W. H., L. F. Stickel, and J. W. Spann. 1969. Tissue residues of dieldrin in relation to mortality in birds and mammals, p. 174-204. In M. W. Miller and G. C. Berg [ed.] Chemical Fallout, Current Research on Persistent Pesticides. Chas. C. Thomas, Springfield, 111. 16) Stickel. W. H.. L. F. Stickel, and F. B. Coon. 1970. DDE and ODD residues correlated with mortality of experi- mental birds, p. 287-294. In W. B. Deichmann [ed.] Pesticides Symposia. Halos and Assoc, Miami, Fla. 138 Pesticides Monitoring Journal DDT, DDE, and Polychlorinated Biphenyls in Biota From the Gulf of Mexico and Caribbean Sea — 7977 C. S. Giam', A. R. Hanks% R. L. Richardson'. W. M. Sacket^, and M. K. Wong' ABSTRACT Residue levels of DDT, DDE, and PCB's were determined in various species of fish, shrimp, crabs, and other biota from the Gulf of Mexico and Carribean Sea. Samples were col- lected from the Gulf during two Gulf-wide cruises in May and October 1971 and from part of the Carribean Sea during the October cruise. DDT, DDE, and PCB's were found widely distributed in all biota: however, samples from coastal areas generally had higher levels than samples from the open waters. Introduction The occurrence of DDT and its metabolites and poly- chlorinated biphenyls (PCB's) in fish and wildlife is of current interest; however, data concerning the levels of these compounds in organisms from the open ocean are scarce (7-5). During 1971 and 1972 about 50 scientists are participat- ing in an intensive study program sponsored by the In- ternational Decade for Ocean Exploration (National Science Foundation) to identify problems related to oceanic environmental quality. This paper reports some of the results of this study, i.e., the concentrations of DDT, DDE, and PCB's in fish and other marine organ- isms collected in the Gulf of Mexico and the Caribbean Sea in May and October 1971. These "baseline con- centrations" should be useful as comparison data to investigators working in estuaries around the Gulf of Mexico. Fig. 1 shows the locations where samples were collected. Department of Chemistry. Texas A&M University. College Station. Tex. 77843. ■ Department of Agricultural Analytical Services, Texas A&M Univer- sity, College Station. Tex. 77843. Department of Oceanography, Texas A&M University, College Sta- tion, Tex. 77843. ' Department of Chemistry. Texas A&M University. College Station, Tex. 77843. On leave of absence from Nanyang University, Republic of Singapore. The Gulf of Mexico receives runoff from approximately two-thirds of the United States and one-half of Mexico. This large amount of runoff with its high load of pol- lutants is swept generally westward and trapped in the western Gulf where waters remain possibly as long as 100 years. The primary flushing mechanism is exchange in the eastern Gulf with the loop current which passes quickly through the Yucatan Strait and out through the Straits of Florida. Because of the characteristics of this unique system, a buildup in concentration of man- made toxic materials is possible in the western Gulf, and baseline concentrations reported here together with future analyses should provide an early indication of this. Sampling and Analytical Procedures Samples were collected by the scientific party aboard cruises 71-A-5 (in May 1971) and 71 -A- 12 (in October 1971) of the R/V Alaminos. the oceanography vessel of Texas A&M University. Most samples were obtained using nets, but a few tuna and shark were caught by hook and line. Smaller samples were transferred im- mediately to glass mason jars with caps lined with aluminum foil and frozen until analysis. The jars and foil had been pre-washed with absolute ethanol which was free of any chlorinated hydrocarbons. Appropriate organs and muscle samples were taken from the larger fish, placed in mason jars, and frozen until analysis. Small fish, shrimp, crabs, and other crustaceans were analyzed whole as composites of two or more fish or six crustaceans. Generally 50- to 100-g subsamples were taken from each composite for analysis. Subsamples of muscle tissue and organs analyzed generally weighed 50- to 100-g. The extraction and cleanup procedure used was that described in the "Pesticide Analytical Manual" Vol. 6, No. 3, December 1972 139 FIGURE 1. — Sampling stations in the Gulf of Mexico anil Caribbean Sect — May and October 1971 of the J. S. Food and Drug Administration (6). The final residue extracts were adjusted to a suitable volume (between 2 and 10 ml) for gas chromatographic analysis. No attempt was made to concentrate the eluate to less than 2 ml, and not more than 10 jixl of extract was in- jected into the chromatographic column. A Tracor gas chromatograph (Model MT 220) equipped with a "'^Ni electron capture detector and U-shaped glass columns, 6 ft x '4 inch, o.d., and packed with 5% DC- 200 on 80/100 mesh HP Chromosorb W was used. Columns packed with 5% OV-1 on 80/100 mesh HP Chromosorb W and a 6% mixture of OV-17 and QF-1 (in the ratio of 7:9) on 80/100 mesh HP Chromosorb W were also employed for further characterization. Nitrogen was used as the carrier gas at a flow rate of 60 cc/min. The injector, oven, and detector temperatures were 225° C, 200° C, and 275° C, respectively. Identification of PCB's as commercial Aroclor® formula- tions was based on good matching of the sample peaks with those of standard Aroclor® mixtures. Quantification was carried out when at least 50% of the peaks from a sample chromatogram matched peaks of the Arco- clor® formulation; three different columns were used for matching the arrays of Aroclor®. In instances where the concentrations of PCB's were so high that they inter- fered with the quantification of DDT and DDE, separa- tions of the PCB's from DDT and its metabolites were performed using a silica gel column (7). The presence of DDT and PCB's was further confirmed by the dis- appearance of the p.p'-DDT peak (and a corresponding increase in the p.p'-DDE peak) in the chromatograms of sample extract after alkaline alcoholysis treatment (8). The PCB peaks were not aff'ected. Percent recovery studies were performed using spiked liver and muscle samples. Recovery was 85% or better for all compounds identified in this study. (The group performing these analyses took part in a national and international cooperative analysis of chlorinated hydro- carbon insecticides and PCB's in marine samples, and their results were in excellent agreement with results from other laboratories.) The sensitivity of detection. 140 Pesticides Monitoring Journal depending on the weight of the sample, ranged from 0.1 to 0.3 jUg/kg wet weight for DDT and DDE and 1 to 3 /xg/kg for PCB's. Results were not corrected for per- cent recovery. Results and Discussion Results of analysis of samples from the Gulf of Mexico and the Caribbean Sea are given in Tables 1 and 2. DDT, DDE, and the PCB's were detected in nearly all the samples analyzed, indicating that these compounds were widely distributed in the Gulf and Caribbean Sea; however, the levels were generally low, as may be ex- pected in open ocean biota (5, 9). P. p'-DDD was not detected, and the analytical procedures excluded other organochlorine insecticides. The levels of residues in marine organisms varied ap- preciably, but because the number of samples analyzed from each location was small, no firm conclusions can be made at this time. Certain general trends were evi- dent, however, from the results of these analyses: (1) The samples from coastal areas, regardless of species, generally had higher levels of DDT, DDE and PCB's than samples from open waters. For example, samples obtained in May 1971 from Stations 27 and 28 — two sites near the Mississippi Delta, a highly polluted area — showed relatively higher concentrations. (2) The ratios of DDE to DDT varied widely between samples. A few samples from the coastal areas, i.e., shrimp collected at Stations 4, 6, 10, and 28 and other crustaceans from Station 27, showed rather high levels of DDT but rela- tively low levels of DDE (Table 1). Residue data from these specific samples may be fortuitous or may indicate that most of the DDT had not yet been metabolized. (3) In the livers obtained from larger fish (Table 2), con- centrations of DDE were generally higher than DDT, possibly indicating the capability of this organ to metabolize and degrade DDT. (4) In individual fish (Table 2). the liver generally had the highest levels of DDT, DDE, and PCB's and muscle tissue the lowest: appreciable concentrations were also detected in the gonads and the digestive tract. A cknowledgments We gratefully acknowledge the National Science Foundation (International Decade of Ocean Exploration program) for financial support of this work. Mr. W. Dill for identification of organisms analyzed in this study, and Mr. Jerry Burke of the Food and Drug Administra- tion and Dr. George Harvey of the Woods Hole Ocean- ographic Institute for intercalibration samples. See Appendix for chemical names of compounds discussed in this paper. TABLE 1. — DDT, DDE, and PCB residues in biota from tlie Gulf of Mexico and Caribbean Sea — May and October 1971 Month Sampling Station (See Fig. 1) Location Sample ' Residues IN (IG/KG. wet/weight BASIS Collection (1971) p.p'-DDT p.p'-DDE Total DDT PCB'S = May 1 Lat. 28°«.r Long. 95°08.4' Flounder ISyacium ounterii 84 10 94 32 Squid 65 4.6 70 «> 4 Lat. 27°47.1' Long. 96°49.6' Crabs (CalUnectes sp.) 1.8 7.4 9 •17 Fish (Unidentified) 141 18 159 •53 Flounder i Syacium papillosumi ;i 14 35 36 Sea pansy (Order Pennatulacea) 128 161 289 •850 Shrimp (Family Penaeidae) 26 7.0 33 13) \ 5 Lat. 26°02.8' Long. 96°48.5- Fish (Paraques acuminatus} Flounder (Syacium papillosum) 20 6.6 27 27 59 6 Lat. 24°23.4' Long. 97'23.9' Flounder (Syacium ounleri) 3.6 3.3 7 34 Shrimp (Family Penaeidae) 1.14 18 152 (3) Vol. 6, No. 3, December 1972 141 TABLE 1. — DDT, DDE. and PCS residues in biota from the Gulf of Mexico and Caribbean Sea- May and October 1971 — Continued Month Sampling Station (See Fio. 1) Location Sample ' Residues in ius/kg, wet/weight BASIS Collection (1971) P,p'-DDT p,p'-DDE Total DDT PCB's 2 May 9-9X Lat. 20°53.5' Long. 94°59.0' Flying fish (Family Exocoetidae) 7.2 4.5 12 20 10 Lat. 19°28.0' Long. 95°51.0' Colonial tunicate 188 8.7 197 ' 139 Shrimp (Family Penaeidae) 154 II 165 (31 11 Lat. 19°02.0' Long. 95°35.9' Fish (Perisledion oracile) 16 16 32 '54 Fish (Serranus atrobranchus) 33 8 41 (31 Fish (Saurida brasiliensus) 111 7 118 68 Fish (Halicutichthys aculeatus) 78 4.8 83 '64 Fish (Trichoosetta vontralis) 8.5 5.2 14 (3, 19 Lat. 20°44.0' Long. 92°50.0' Squirrel fish (Holocentrus sp.} 86 5.6 92 * 150 27 Lat. 28°40.9' Long. 89-10.0' Crustacean (Aristacus antiltensia) 86 16 102 151 Crustacean (Nephropsis aculeate) 151 6.0 157 22 Fish (Benthodesmus allanlicus) 91 4.3 95 36 Fish (Unidentified) 33 7.3 40 56 Holothuroids '■••■ (5, *8 28 Lat. 28°21.7' Long. 90°14.0' Bat fish 12 65 77 527 Croakers (Micropogon undulatus) II II 50 Shrimp (Parapenaeus longirostris) 304 34 338 167 October 10 Lat. 20°05.4' Long. 85°07.7' Flying fish (Family Exocoetidae) 5.1 4.6 10 26 12-3X Lat. 18°54.1' Long. 83°44.4' Flying fish (Family Exocoetidae) 46 19 65 (3) 15 Lat. 25°49' Long. 83°43' Fish (Synodus iniermedius) 4.5 10 15 14 16 Lat. 27°34' Long. 83°10' Flying fish (Family Exocoetidae) 18 12 30 65 17 Lat. 29°19.5' Long. 85°28.0' Rock shrimp 1.0 2.1 3 (3, 18 Lat. 30°00.5' Long. 87°17.5' Rock shrimp 5.2 2.7 8 6 Squid 4.6 4.3 9 40 Represents 50- to 100-g subsamples from a composite of two or more whole fish or six whole crustaceans/other invertebrates. Calculated as Aroclor 1260® unless otherwise indicated. Not estimated because of insufficient number of peaks on the chromatogram to characterize PCS formulations. Calculated as Aroclor 1254®. Not analyzed due to negligible concentrations of DDT and interference by PCB peaks. 142 Pesticides Monitoring Journal TABLE 2. — DDT, DDE, and PCB residues in organs and muscle tissue of fish from the Gulf of Mexico and Caribbean Sea- May and October 1971 Month Sampling Station (See Fig. 1) Location Fish Collected Tissue OR Organ Sampled i Residues in /iO/Ko, wet-weight basis Collection (1971) p,p'-DDT p,p'-DDE Total DDT PCB's = May 5 Lat. Long. 26°02.8' 96°48.5' Shark (Carcharinus falciformis) liver 200 499 699 1300 9 Lat. Long. 23°45.8' 92°37.4' White tip shark (Pterolamniops longimanus) gut gonads muscle liver 53 188 15 406 62 60 15 1100 115 248 30 1506 58 74 32 536 12 Lat. Long 18°27.5' 94°24.0' King mackerel tScomberomous cavalla) gut gonads muscle liver 15 3.0 17 72 14 15 7.4 51 29 18 24 123 90 56 34 83 Tuna (Eulhynnus alleleralus) gut muscle liver 14 44 45 13 31 39 27 75 84 76 58 59 19 Lat. Long. 20°44.0' 92°50.0' Parrot fish (Holichoeres radialus) liver 36 '■" 36 *284 Red snapper (Luljanus aya) liver gonads 3.9 34 9.5 6.1 13 40 18 16 Trigger fish tCanthidermis sufflamenj liver 83 52 135 15) Yellow tailed snapper (Ocyurus chrysurusj liver gonads gut 10 37 56 19 7.4 3.7 29 44 60 43 22 9 October 2 Lat. Long. 27°54.5' 93°36.0- Jack iThiinnm allanlicusi muscle 36 13 49 43 4 Lat. Long. 23°33.4' 89''54.5' Trigger fish (Canthidermis sufflamen} muscle 2.7 1.9 5 <1 8 Lat. Long. 22°16.4' g7°27.3' Tuna (Euthynnus alleleralus) muscle gonads liver 8.2 4.4 40 36 8.4 111 44 13 151 36 35 153 12 Lat. Long. 18°54.1' 83°44.4' Barracuda (Sohyraana barracuda) muscle liver 4.0 16 4.2 26 8 42 9 57 Fish (Haemulon phimieri) muscle 2.5 1.2 4 <1 Shark (Carcharhinus springeri) muscle liver 44 1.2 116 1 160 8 310 Trigger fish (Balisles vetula) muscle 1.4 0.6 2 <1 Trigger fish (Canthidermis sufflamen) muscle 1.7 0.9 3 <1 ^ Represents 50 to 100 g of organ or muscle samples. 2 Calculated as Aroclor 1260'S unless otherwise indicated. ^ Not analyzed due to negligible concentrations and interference by PCB peaks. * Calculated as Aroclor 1254'|i. '' Not estimated because of insufficient number of peaks on the chromatogram to characterize PCB formulations. LITERATURE CFTED (1) National Academy of Sciences. 1971. Chlorinated hydro- carbons in the marine environment. 42 p. (2) Butler, P. A. 1969. Monitoring pesticide pollution. Bio- science 19(10):889-891. (3) Wolman, A. A., and A. J. Wilson, Jr. 1970. Occurrence of pesticides in whales. Pestic. Monit. J. 4tl):8-10. (4} Duke, T. W., and A. J. Wilson, Jr. 1971. Chlorinated hydrocarbons in livers of fishes from the northeastern Pacific Ocean. Pestic. Monit. J. 5(2):228-232. (5) Grice, G. D., G. R. Harvey, V. T. Bowen, and R. H. Backus. 1972. The collection and preservation of open ocean marine organisms for pollutant analysis. Bull. Environ. Contam. Toxicol. 7(2/3):125-132. (6) U. S. Department of Health, Education, and Welfare, Food and Drug Administration. 1968. Pestic. Anal. Man. Vol. 1, Sect. 212.13. (7) Snyder, D., and R. Reinert. 1971. Rapid separation of polychlorinated biphenyls from DDT and its analogues on silica gel. Bull. Environ. Contam. Toxicol. 6(5): 385-390. (8) U. S. Department of Health, Education, and Welfare. Food and Drug Administration. 1968. Pestic. Anal. Man. Vol. l.Sect. 211.16d. (9) Earnest, R. D., and P. E. Benville, Jr. 1971. Correlation of DDT and lipid levels for certain San Francisco Bay fish. Pestic. Monit. J. 5{3):235-241. Vol. 6, No. 3, December 1972 143 Mercury Residues in Fish, 1969-1970 — National Pesticide Monitoring Program ' Croswell Henderson, Anthony Inglis", and Wendell L. Johnson ABSTRACT As part of the fish monitoring program conducted by the Bureau of Sport Fisheries and Wildlife since 1967, composite fish samples collected during the fall of 1969 and 1970 were analyzed for mercury. Three composite samples, each of a different species and consisting of 3-5 adidt fish, were col- lected at each of 50 monitoring stations in 1969; similarly, three composite samples and in most cases a replicate sample of one of the species were collected at each of 100 stations in 1970. Stations were located on major rivers and lakes throughout the United States. Total mercury residues equal to or exceeding the sensitivity level of 0.05 ppm were found in 129 of the 145 samples in 1969 and 373 of the 393 sam- ples in 1970. Values ranged from -^.0.05 to 1.25 ppm in 1969 samples and from -CO.05 to 1.80 ppm in 1970 samples. Analyses by two different laboratories of 40 selected samples from the 1970 collection gave comparable results. Analyses of 24 selected 1970 samples indicated that 90% or more of the mercury in fish was in the form of methyl mercury. From the Division of Fishery Services, Bureau of Sport Fisheries and Wildlife, U.S. Department of the Interior, Washington, D.C. 20240. Present address: Federal Working Group on Pest Management, Parklawn Building, Rockville, Md. 20852. Introduction A nationwide monitoring program to determine pesticide residue levels in fish has been conducted by the Bureau of Sport Fisheries and Wildlife each year since 1967. Composite fish samples collected from 50 stations dur- ing the first 2 years of the program (1967. 1968) were analyzed for whole body residues of 1 1 organochlorine insecticides; these results were reported in a previous issue of this Journal (3). In 1969, fish were collected from the same 50 stations, and analyses were expanded to also include lipids, polychlorinated biphenyls (PCB's), and mercury; results for lipids, organochlorine insecti- cides and PCB's were reported by Henderson, Inglis, and Johnson (4). In 1970, the number of sampling stations was increased to 100 and analyses again included organochlorine insecticides, PCB's, lipids, and mercury. This report presents the data on mercury residues in fish collected from 50 stations during 1969 and from 100 stations during 1970. Common names of fishes as designated by the American Fisheries Society (/) are used throughout this report. 144 Pesticides Monitoring Journal FIGURE 1. — Locations of fish sampling slalions, National Pesticide Monitoring Program — 1969 and 1970 Methods FISH COLLECTIONS The locations of sampling stations are shown in Fig. 1 and listed in Table 1. Fish were collected at Stations 1-50 in both 1969 and 1970, but at Stations 51-100 in 1970 only. As in previous collections, three composite samples, each of a different species and consisting of 3-5 adult fish of uniform size for each species, were collected at each station. In 1970, a replicate composite sample of one of the three species was also collected in order to determine possible variation in residue levels in similar samples from the same station. A special effort has been made to collect the same species each year. Fish collections were made by biologists from Fishery Services and other Divisions of the Bureau of Sport Fisheries and Wildlife with considerable assistance from State conservation agencies. Fish were collected by various means including seines, gill nets, traps, hook and line, electrofishing, etc. The use of fish toxicants was not permitted. Collections were made once each year, usually in September, October, or November. Each composite sample was wrapped in aluminum foil, frozen, packed in dry ice, and shipped to a laboratory for whole body residue analyses. Accompanying the shipment was a legend showing location, date collected, name of collector, collection method, species of fish, and the length, weight, and estimated age of each fish in each composite sample. LABORATORY ANALYSES A commercial laboratory (designated Laboratory C) conducted total mercury analyses on all of the 1969 and 1970 samples. The same laboratory conducted methyl mercury analyses on 24 selected samples from the 1970 Vol. 6, No. 3, December 1972 145 fish collection. Subsamples of 40 selected homogenates from the 1970 collection were sent to another labora- tory (designated Laboratory H) for total mercury analyses in order to cross-check or further confirm the results from Laboratory C. Analytical methods as fur- nished by participating laboratories are as follows: Laboratory C — Analyses for Total Mercury Each composite sample was thawed, cut into small pieces, and ground in a Hobart food chopper until ho- mogenized. An aliquot sample was removed for mercury analysis. The method used is described in a report by the Joint Mercury Residues Panel (7), modified by atomic absorption spectrometry with the boat tech- nique for 1969 samples and the cold vapor technique for 1970 samples. The procedures for digestion and analysis by the cold vapor technique were as follows: A 10-g portion of the fish homogenate was transferred to a 1 -liter round-bottom flask using little or no water; several glass beads were added. The flask was placed in a mantle and condensers and tap funnel inserted; 25 ml of a sulfuric-nitric acid mixture (4:1) was carefully introduced through the tap funnel (over approximately 10 minutes). The sample was heated slowly, so that the reaction would not become violent, for approximately Vi to % of an hour increasing the heat until full heat was reached. When necessary, small amounts of nitric acid were added to prevent carbonization. After reflux- ing for one hour, the sample was cooled to room tem- perature. When the digest was cool, the condenser and tap funnel were disconnected and the digest was trans- frered quantitatively with ice water to a 100-ml volu- metric flask. The flask was stoppered and allowed to come to room temperature. The digest was made to volume, mixed, and analyzed on an atomic absorption spec- trophotometer. For atomic absorption analysis, 50 ml of a reducing solution was transferred into a 300-ml Erlenmeyer flask. The reducing solution was made up with 5.0 g of NaCl, 10 g of hydroxylamine hydrochloride, 20 g of stannous chloride in 20% H2SO4, and diluted to 1 liter with 20% H2SO4. Additional 20% sulfuric acid was added to make a total volume of 75 ml with the amount of sample to be added. The sample was added with a pipet by draining down the side of the flask, the flask stoppered rapidly, and then stirred vigorously with a magnetic stirrer (teflon bar) for exactly 30 seconds. The stirrer was shut off and the teflon bar allowed to stop; then the air pump was turned on to force mercury through the cell. To clean out the cell, the air flow was reversed between each sample analysis. To establish a standard curve, an approximately 20- fold range of standards was used starting with 0.010 jxg of mercury. The standard curve was plotted using peak height versus micrograms of mercury. Analyses were performed on a Perkin-Elmer atomic absorption spectrometer, model 303, and a Perkin- Elmer recorder, model 304, with the following condi- tions: Wavelength— 2537 Angstroms (254 Setting— 303). Slit— 3 mm. 20 Angstroms (5 Setting— 303) Range — UV Source — Mercury hollow cathode lamp Air — 3 liters per minute Recorder noise suppression — 1, expansion — 3X The same digestion procedure as above was used for the boat method. Mercury was extracted from the acid solu- tion into a dithizone-chloroform solution with two 5-ml extractions. Extractions were placed into a small tan- talum boat and chloroform vaporized off. The boat was then placed directly into the flame, and the mercury vaporized. Fourteen samples analyzed by both the boat and cold vapor techniques gave comparable results. However, the cold vapor technique was found to be more rapid and to have greater sensitivity with less interference. Recovery experiments showed an average recovery rate of 97%. The results were not corrected for recovery; sensitivity was reported as 0.05 ppm. Laboratory C — Analyses for Methyl Mercury Methyl mercury was determined by the procedure de- veloped by Kamps and McMahon (S). Laboratory H — A nalyses for Total Mercury The digestion method used was patterned after that reported by the Analytical Methods Committee (2); the flameless atomic absorption method was quite similar to that reported by others (6). A description of the methods follows: For digestion, up to 10 g (wet weight) of sample was placed in a 250-ml flat-bottom flask with 3 boiling beads. This was placed under a condenser, and 10 ml of HNO.i added through the condenser. When necessary, the sample was warmed slightly to start the reaction, but heating was discontinued when foaming started. When the initial reaction was finished, the sample had been dissolved. The flasks were allowed to cool slightly, and then 10 ml of 1:1 H,.S04:HN0;i was added. The sample was heated slowly, without boiling, until refluxed, then refluxed for 3 hours. The flask was cooled until just warm to touch, and 10 ml of 30% H^Oo added in 1-ml increments, waiting between additions for foaming 146 Pesticides Monitoring Journal 1 I. 1969. Sta. 1 —50 1^70. Sta. 1 —50 1970. Sta. 1 — 100 ™ "^ Median — 0.15 mg kg ^^^ FDA action level — 0.50 ppm (applies to edible portions only) 16 Number of samples CO. 05 0.05 - 0.15 0.16 - 0.25 0.26 - 0.50 0.51 - 1.00 Mercurv residues — me ks. wet weiaht, whole fish FIGURE 2. — Mercury residues in fisli hy frequency of occurrence — 1969 anil 1970 to Stop. If no foaming occurred on the first addition, the sample was heated slightly until foaming began. After all 10 ml had been added, the sample was brought to a boil, and boiled for 1 hour (by then most of the brown NOo fumes had gone). The sample was chilled in ice water, and the condensers washed down with 50 ml of redistilled water; the sample was removed from the condensers after the fat solidified. At this point, the sample was analyzed or covered and left in the refrig- erator overnight. For atomic absorption analysis, the cold digestion sample was filtered through glass wool into a 100-ml graduated cylinder, and the flask and filter were washed with enough redistilled water to make the volume up to 100 ml. A I -ml or some other suitable aliquot was removed and added to a gas bubbling flask containing sufficient In H2SO4 to make a total volume of 20 ml. Two milliliters of the reductant solution (100 ml of H.SO4, 5 g of NaCl, 5.3 g of NHoOHiHCl, and 20 g of SnCU:2HoO, made to I liter) was added, the flask closed, the chart recorder started, the gas flow turned on, and the maxi- mum pen deflection on chart noted. Then, the gas flow was turned off and a suitable quantity of standard (from 0.1 ppm Hg in In H^SO,) added. The gas was turned on and measured as before, and the nanograms of Hg were plotted against the peak area on linear graph paper. Analyses were performed on a Jarrell-Ash Model 82 atomic absorption spectrometer equipped with a 25-cm quartz cell. Results and Discussion FISH COLLECTIONS A total of 145 composite samples were collected from the 50 sampling stations in 1969 and 393 samples from the 100 stations in 1970. Fifty-five species of fish were represented in the collections. Some species such as carp, channel catfish, and largemouth bass were col- lected at many different stations. For example, samples of carp were obtained from 56, channel catfish from Vol. 6, No. 3, December 1972 147 34, and largemouth bass from 33 of the 100 stations in 1970. Many of the species, however, were collected at only 1 or 2 of the 100 stations. Generally, collectors were successful in obtaining the same species at a sta- tion in both 1969 and 1970 collections. RESIDUE LEVELS IN FISH Total mercury residue levels for each composite sample and average values at each station for both 1969 and 1970 collections are shown in Table 1. All values are reported as ppm (mg/kg), wet-weight, whole fish. Also shown in Table 1 are station locations and species of fish: the number and the average length and weight of fish in the composite samples collected in both years are included. The analyses for mercury in 1969 samples were conducted on subsamples of fish homogenates that had been prepared primarily for organochlorine insecticide analyses. In order to make the 1969 and 1970 data more com- parable, the 1970 average residue values were computed as follows: the replicate samples of the same species were averaged and this average used with the values for the other species to compute the final average. Values less than the sensitivity level of 0.05 ppm were considered to be zero in computing averages. Mercury residues equal to or exceeding the sensitivity limit were found in 129 of the 145 samples in 1969 and 373 of the 393 samples in 1970. Values ranged from <0.05 to 1.25 ppm mercury in 1969 samples and from <0.05 to 1.80 ppm Hg in 1970 samples. While high residue levels were found in fish from some waters in most drainage basins, these high levels ap- peared to occur more frequently in samples from Atlantic Coastal streams and the Columbia River sys- tem (Fig. 1). Lowest levels were found in fish from Alaskan streams, the Colorado River system, and Mis- sissippi River tributaries in the Great Plains region. Total mercury residues exceeding the Food and Drug Administration action level of 0.5 ppm, set for edible portions of the fish only, were found in 8 samples from 8 of the 50 stations in 1969 and in 32 samples from 21 of 100 stations in 1970. Average values exceeded 0.5 ppm at 3 stations in 1969 and 6 stations in 1970. The frequency of occurrence of various residue levels is shown in Fig. 2. The range of values was comparable for 1969 and 1970 samples with the median residue level the same (0.15 ppm) for both sampling periods. High mercury levels occurred much more often in some species of fish than in others. With few exceptions, the highest levels were found in predatory species near the top of the food chain such as bass, perch, and squaw- fish. Generally, the residue results for the two com- posite samples of the same species collected at each station in 1970 were in close agreement indicating no great variation in similar samples. CONFIRMATORY ANALYSIS AND METHYL MERCURY The results of the initial analyses by Laboratory C of 40 selected samples from the 1970 collections and the analyses of subsamples of the same homogenates by Laboratory H for total mercury are shown in Table 2. Also shown are results of analyses for methyl mercury reported as mg/kg of Hg on 24 selected samples by Laboratory C. The samples selected for methyl mercury analyses were among those having the highest total mercury residues. The total mercury residue results for both laboratories are in very close agreement, although slightly different methods were used. From a comparison of the total mercury and methyl mercury results, it appears that at least 90% and pos- sibly more of the mercury in fish is methyl mercury. The significance of the mercury residue results with respect to possible adverse effects on fish and wildlife is unknown at the present time. Research is underway to determine possible correlation of residue levels in tissues with possible eff'ects such as mortality, repro- duction, etc. From the standpoint of the use of fish for human food, it may be significant that residue levels in some samples exceeded the FDA action level of 0.5 ppm. It is also possible that such levels may have an adverse effect on fish-eating birds or other animals. Monitoring for mercury and other residues in fish is a continuing program (5). Fish samples were collected at the same 100 sampling stations again in the fall of 1971 and are presently being analyzed for residues of mer- cury, other metals, organochlorine insecticides, and PCB's. A cknowledgment We greatly appreciate the help of the Bureau of Sport Fisheries and Wildlife biologists and fishery personnel in many of the States for collecting samples for the monitoring program. Without their assistance, such a program would not have been possible. 148 Pesticides Monitoring Journal LITERATURE CITED (/) American Fisheries Society. 1970. A list of common and scientific names of fishes from the United States and Canada. Washington, D.C. 20005. Spec. Publ. No. 6. 149 p. (2) Analytical Methods Committee Report. I960. Digestion procedure. Analyst 85:643-656. (3) Henderson, C, W. L. Johnson, and A. Inglis. 1969. Or- ganochlorine insecticide residues in fish (National Pesti- cide Monitoring Program). Pestic. Monit. J. 3(3):145-171. (4) Henderson, C, A. Inglis, and W. L. Johnson. 1971. Or- ganochlorine insecticide residues in fish — fall 1969 (Na- tional Pesticide Monitoring Program). Pestic. Monit. J. 5(1):1-11. (5) Inglis, A., C. Henderson, and W. L. Johnson. 1971. Ex- panded program for pesticide monitoring of fish. Pestic. Monit. J. 5(l):47-49. (6) Jeffiis. M. T., J. S. Elkins, and C. T. Kenner. 1970. De- termination of mercury in biological materials. J. Assoc. Off. Anal. Chem. 53(6):1172-1 175. (7) Joint Mercury' Residues Panel Report. 1961 . Analyst 86:608-614. 18) Kamps, L. R.. and B. McMahon. 1971. Utilization of the Westoo procedure for the determination of methyl mer- cury in fish by gas-liquid chromatography. J. Assoc. Off. Anal. Chem. 55(3):590-595. TABLE \.— Mercury residues in fish, 1969 and 1970 1970 1969 Station Number AND Location Species X iZ o 6 Z Average Size Total Mercury (PPM)' X iZ 0 6 Z Average Size 15 -J w Id Total Mercury (PPM)' ATLANTIC COASTAL STREAMS #1 Stillwater River White sucker 5 15.1 1.3 .43 5 15.0 1.5 .23 Old Town, White sucker (R) 5 15.3 1.3 .60 Maine Yellow perch 5 7.9 0.2 .29 5 7.7 0.2 .48 Chain pickerel 4 16.4 1.0 Avg. .64 .48 5 13.7 0.5 .42 Avg. .38 #51 Kennebec River Hinckley, Yellow perch Yellow perch (R) 5 5 9.3 9.0 0.4 0.4 1.20 .71 Maine White perch Smallmouth bass 2 8.9 11.3 0.5 0.9 Avg. .38 .64 .66 #52 Lake Champlain Burlington, Vt. Pumpkinseed Yellow perch Yellow perch (R) Chain pickerel 5 5 5 5 6.5 8.6 9.4 16.2 0.3 0.3 0.5 1.1 Avg. .38 .27 .49 .47 .41 #53 Merrimac River Lowell, Mass. White sucker White sucker (R) Pumpkinseed Yellow perch 5 5 5 3 12.0 10.4 5.6 7.9 0.6 0.5 0.1 0.2 Avg. .27 .28 .15 .33 .25 #2 Connecticut River Windsor Locks, White catfish White catfish (R) 5 5 12.6 12.9 0.9 I.O .22 .18 5 12.0 0.9 .14 Conn. Yellow perch 2 10.5 0.6 .30 3 8.8 0.4 .13 White perch 5 9.9 0.6 Avg. .51 .34 5 10.0 0.6 .80 Avg. 36 #3 Hudson River Poughkeepsie, Goldfish Goldfish (R) 5 5 8.4 10.5 0.5 1.0 .07 .11 2 11.7 1.5 .16 N. Y. Largemouth bass 4 12.8 1.3 .19 5 9.2 0.5 .25 Pumpkinseed 5 6.2 0.2 Avg. .10 .13 5 6.2 0.2 .19 Avg. .20 Vol. 6, No. 3, December 1972 149 TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location 0 6 Z Average Size Total Mercury (PPM)i £ 0 d Z Average Size Total Mercury (PPM)i ATLANTIC COASTAL STREAMS— Continued #54 Raritan River Golden shiner 5 5.9 0.1 .08 Highland Park, White perch 5 9.1 0.5 .28 N. J. White perch (R) Rock bass 5 3 8.3 6.9 0.3 0.2 Avg. .29 .25 .21 #4 Delaware River White sucker 5 14.7 1.41 .07 5 14.7 1.4 .08 Camden, N. J. Brown bullhead 5 10.6 0.6 .07 5 11.7 0.9 .05 White perch 5 9.8 0.6 .21 5 9.4 0.5 .22 White perch (R) 5 9.7 0.6 Avg. .17 .11 Avg. .12 #5 Susquetianna River Carp 3 21.6 5.0 .07 4 20.0 3.5 .05 Conowingo Dam. Channel catfish 4 12.1 0.6 .05 5 13.6 0.9 .06 Md. Yellow perch Yellow perch (R) 5 5 8.8 7.9 0.3 0.2 Avg. .09 .10 .07 5 9.1 0.4 .09 Avg. .07 #6 Potomac River Little Falls, Carp Carp (R) 3 3 13.8 14.1 1.3 l.I .08 .05 5 15.1 1.9 .10 Md. White sucker Black crappie Largemouth bass 5 11.5 8.7 0.7 0.3 Avg. <.05 .09 .05 5 5 12.7 10.5 0,8 0.5 .08 .09 Avg. .09 #55 James River Redhorse sucker 5 10.8 0.7 .11 Richmond, Channel catfish 4 18.8 2.5 .12 Va. Channel catfish (R) Largemouth bass 3 5 17.3 10.0 2.5 0.7 Avg. .20 .14 .14 #7 Roanoke River Redhorse sucker 3 21.7 3.7 .08 5 19.0 2.8 .10 Roanoke Rapids, Redhorse sucker (R) 3 20.0 3.2 .12 N. C. Brown bullhead 5 9.6 0.3 .21 5 9.6 0.4 .13 Largemouth bass 3 12.0 1.0 Avg. .12 .14 4 9.7 0.6 .09 Avg. .11 #8 Cape Fear River Gizzard shad 5 6.2 0.2 .25 5 12.0 0.6 .18 Elizabethtown, Channel catfish 2 21.5 3.9 .35 N. C. Brown bullhead Brown bullhead (R) Largemouth bass 5 5 5 8.2 8.2 13.2 0.3 0.3 1.3 Avg. .25 .25 .60 .37 5 10.8 0.6 .17 Avg. .23 #56 Pee Dee River White catfish 5 7.4 0.2 .19 Dongola, S. C. White catfish (R) Blue gill Largemouth bass 5 5 5 6.6 5.2 12.5 0.1 0.1 1.5 Avg. .20 .20 1.00 .47 #9 Cooper River Carp 2 17.5 3.5 .05 Summerton, Spotted sucker 5 12.6 1.2 .13 S. C. Bluegill 5 5.6 0.2 .20 5 6.8 0.2 .09 Largemouth bass 4 11.3 0.6 .20 5 13.4 1.3 .14 Largemouth bass (R) 4 12.0 0.7 Avg. .24 .16 Avg. .12 #10 Savannah River Carp 2 26.0 6.9 .17 4 15.8 1.8 .36 Savannah, Bluegill 4 8.3 0.5 .56 3 7.3 0.3 .45 Ga. Largemouth bass Largemouth bass (R) 3 3 11.3 9.0 1.0 0.5 Avg. 1.80 1.40 .78 4 10.5 0.8 1.00 Avg. .60 #57 Altamaha River Spotted sucker 5 15.2 1.4 .25 Doctortown, Spotted sucker (R) 5 11.2 0.7 .11 Ga. Bluegill Laj-gemouth bass 5 5 8.2 12.2 0.4 1.3 Avg. .15 .51 .28 #11 St. Johns River Striped mullet 3 16.3 1.7 .07 Welaka, Fla. Channel catfish Channel catfish (R) Redbreast sunfish 5 5 9.0 8.0 0.3 0.2 .06 <.05 5 4 11.0 5.8 0.9 0.2 <.05 .07 Largemouth bass 2 12.5 1.3 Avg. .43 .18 3 17.3 3.2 .08 Avg. .05 150 Pesticides Monitoring Journal TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 X £ o d Z Average Size Total Mercury (PPM)' s o d Z Average Size AND Location Id id Total Mercury (PPM)' ATLANTIC COASTAL STREAMS— Continued #12 St. Lucie Canal Indiantown, Channel catfish Channel catfish (R) 2 18.5 18.0 2.2 2.3 .27 .15 1 27.0 10.0 .23 Fla. Bluegill 5 5.6 0.2 .06 5 7.6 0.4 .13 Largemouth bass 5 11.2 0.9 Avg. .28 .18 5 13.4 1.6 Avg. .34 .23 GULF COASTAL STREAMS #58 Suwanee River Spotted sucker 4 15.8 1.7 .13 Old Town, Redbreast sunfish 4 7.0 0.5 .13 Fla. Redbreast sunfish (R) Largemouth bass 4 5 7.0 9.0 0.5 0.4 Avg. .21 .37 .22 #13 Apalachicola River Spotted sucker 3 17.3 2.5 .10 5 17.4 2.3 .23 Jim Woodruff, Channel catfish 5 11.0 0.7 .11 5 11.6 0.9 .08 Fla. Largemouth bass Largemouth bass (R) 5 5 10.8 9.4 0.7 0.5 Avg. .13 .10 .11 Avg. .16 #59 Alabama River Striped mullet 4 15.0 1.3 <.05 Chrysler, Striped mullet (R) 4 15.0 1.2 <.05 Ala. Bluegill Largemouth bass 5 3 6.6 17.3 0.3 2.6 Avg. .48 .60 .36 #14 Tombigbee River Carp 5 17.0 3.7 .15 5 20.8 4.6 .36 Mcintosh, Ala. Striped mullet Striped mullet (R) 4 4 15.8 15.8 1.6 1.6 .17 .35 5 16.0 1.8 .36 Largemouth bass 5 13.0 1.2 Avg. .92 .44 5 14.0 1.5 .65 Avg. .46 #15 Mississippi River Carp 4 15.3 2.1 <.05 5 13.4 1.7 .11 Luling, La. Carp (R) Freshwater drum Striped mullet 4 3 15.3 12.0 2.4 0.7 .05 .30 4 14.3 1.1 .14 Channel catfish 5 13.8 1.0 Avg. .10 .14 5 13.0 0.9 .22 Avg. .16 #60 Brazos River Smallmouth buffalo 3 17.2 3.2 .06 Richmond, Tex. Channel catfish Channel catfish (R) Longnose gar 3 3 5 20.9 17.1 25.1 3.4 1.8 1.5 Avg. .10 .08 .24 .13 #61 Colorado River Wharton, Tex. River carpsucker River carpsucker (R) Channel catfish Spotted bass 3 3 3 3 13.3 12.6 13.7 8.4 1.5 1.5 1.2 0.5 Avg. .15 .19 .18 .14 .16 #62 Nueces River Mathis, Tex. Gizzard shad Gizzard shad (R) Channel catfish Largemouth bass 5 5 4 5 11.4 10.0 12.9 10.9 0.5 0.4 0.7 0.9 Avg. <.05 .06 .06 .40 .17 #16 Rio Grande BrownsviUe. Gizzard shad Gizzard shad (R) 5 5 10.7 12.1 0.4 0.7 .08 .12 5 11.4 0.6 <.05 Tex. Channel catfish 2 16.8 1.5 .17 5 15.2 0.9 .06 Blue catfish - 16.2 1.3 Avg. <.05 .09 5 13.5 0.7 .06 Avg. .04 #63 Rio Grande Channel catfish 2 23.9 5.9 .35 Elephant Butte Bluegill 4 4.6 0.1 .10 Reservoir, Bluegill (R) 3 4.7 0.1 .13 N. Mex. Largemouth bass 2 18.6 4.5 Avg. .52 .33 Vol. 6, No. 3, December 1972 151 TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location s o 6 Z Average Size Total Mercury (PPM)> X £ o d Z Average Size Id b1 2 z 6 II Total Mercury (PPM)i GULF COASTAL STREAMS— Continued #64 Rio Grande Alamosa. Colo. Carp White sucker Wliite sucker (R) Brown trout 5 5 5 3 17.2 12.7 13.4 10.8 2.4 0.9 1.0 0.5 <.05 .16 .28 .18 Avg. .13 #65 Pecos River Red Bluff Lake, Tex. Gizzard shad Gizzard shad (R) Channel catfish Largemouth bass 5 I 12.3 12.4 15.8 10.6 0.8 0.8 1.4 0.7 .05 .05 .42 .06 Avg. .18 GREAT LAKES DRAINAGE #17 Genessee River White sucker 4 14.0 1.2 ,15 5 15.1 1.5 .13 Scottsville. Redhorse sucker (R) 4 13.2 0.9 ,19 N. Y. Rock bass Walleye Northern pike 4 4 8,1 13.7 0.5 n.7 Avg. .39 .17 .24 5 7.2 17.2 0.3 1.6 .22 .25 Avg. .20 #66 St, Lawrence River Massena, N. Y. White sucker Yellow perch Yellow perch (R) Northern pike 3 5 5 4 17.2 7.0 8.3 20.6 1.5 0.2 0.3 2.1 Avg. .20 .18 .39 .27 #18 Lake Ontario Port Ontario. Yellow perch Yellow perch (R) 5 5 8.5 8.4 0.4 0.4 ,86 1,00 4 10.4 0.6 .48 N. Y. White perch 5 8.3 0.4 1.30 5 9.5 0.5 .43 Rock bass 5 6.5 0.2 Avg. .30 .84 3 8.6 0.6 .65 Avg. .52 #19 Lake Erie White sucker S 18.0 2.7 .31 3 14.8 1.5 .10 Erie. Pa. Freshwater drum 5 14.1 1.3 .43 5 13.5 1.1 .15 Yellow perch 5 9.7 0.4 .23 s 9.4 0.4 .13 Yellow perch (R) 5 8.9 0.3 Avg. .15 .31 Avg. .13 #20 Lake Huron Carp 5 19.6 4.0 .07 5 16.3 2.1 <.05 Bay Port. Channel catfish 5 16.2 1.4 .07 5 15.9 1,5 .13 Mich. Yellow perch Yellow perch (R) 5 5 9.1 9.1 0.3 0.3 Avg, .08 .05 .07 5 9.9 0,5 .09 Avg. .07 #21 Lake Michigan Sheboygan, Bloater Bloater (R) 5 5 11.2 9.4 0.6 1.9 .09 .10 5 12.0 0,8 .09 Wis. Yellow perch 5 11.0 0,6 Avg, .07 .09 5 10.3 0.6 .27 Avg. .18 #22 Lake Superior Bloater 5 10.3 0.3 .15 5 11.2 0.4 .16 Bayfield, Lake whitefish S 17.6 1.7 .08 5 16.1 1.2 <.05 Wis. Lake whitefish (R) 5 18.1 1.9 .06 Lake trout 5 23.4 4.0 Avg, .29 ,17 4 22.0 3.0 .14 Avg. .10 MISSISSIPPI RIVER SYSTEM #67 Allegheny River Natrona. Pa, Carp Carp (R) Bluegill Walleye 5 5 5 5 14,8 14,8 5.5 12.7 2.0 2.0 0.2 0.6 .11 .05 .11 .18 Avg. .12 #23 Kanawha River Carp ■i 8.9 0.4 .08 4 8.6 0.4 <.05 Winfield. Brown bullhead 4 6.4 0.2 <.05 4 11,9 0.8 <.05 Brown bullhead (R) 4 6.5 0.2 <.05 White crappie 5 6.8 0.2 .11 Avg. .06 5 7.6 0.2 <.05 Avg, <,05 152 Pesticides Monitoring Journal TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 iZ 0 d Z Average Size Total Mercury (PPM)' X ll 0 d Z Average Size AND Location if Id 1^ -J c 15 Total Mercury (PPM)> MISSISSIPPI RIVER SYSTEM— Continued #68 Wabash River New Harmony, Ind. Carp Channel catfish White crappie White crappie (R) 5 3 5 16.8 12.4 8.6 7.6 2.3 0.7 0.3 0.2 Avg. .25 .15 .16 .15 .19 #24 Ohio River Carp 2 15.1 2.4 .24 4 10. 1 1.6 .22 Marietta, Redhorse sucker 4 11.7 0.6 .07 10 7.9 0.04 .20 Ohio Channel catfish Channel catfish (R) Largemouth bass 4 4 14.8 14.9 0.8 0.9 Avg. .83 .68 .36 1 5 15.7 11.3 1.3 0.7 .39 .50 Avg. .33 #69 Ohio River Cincinnati, Ohio Carp Carp (R) White crappie Sauger 3 3 18.5 18.6 8.6 13.9 3.1 3.3 0.3 0.9 Avg. .20 .09 .15 .30 .20 #70 Ohio River Metropolis, 111. Carp Channel catfish White crappie White crappie (R) 5 5 5 5 15.0 11.5 9.9 10.0 1.8 0.5 0.5 0.4 Avg. .14 .11 .43 .37 .22 #25 Cumberland River Carp 4 13.5 1.4 .11 5 II.8 0.8 .09 Clarksville, Bluegill 5 5.8 0.1 .05 s 6.2 0.1 .11 Tenn. Bluegill (R) 5 5.8 0.1 .05 Largemouth bass - 11.0 0.8 Avg. .15 .10 s 1 1.8 0.8 .27 Avg. .16 #71 Tennessee River Carp 5 16.0 1.9 .40 Savannah, Channel catfish 4 12.8 0.6 .28 Tenn. Channel catfish (R) Largemouth bass 4 5 13.0 15.2 0.6 2.2 Avg. .27 .67 .45 #72 Wisconsin River Carp 3 18.2 3.3 .37 Woodman, Carp (R) 2 19.3 4.0 .42 Wis. Channel catfish Smallmouth bass 3 3 16.7 11.7 2.1 1.0 Avg. .11 .60 .37 #73 Des Moines River Keosauqua, Carp Carp (R) 5 5 12.8 12.1 1.3 0.9 .07 .11 Iowa Channel catfish Walleye 3 10.3 12.6 0.4 0.9 Avg. .07 .24 .17 #26 niinois River Beardstown, Carp Carp (R) 5 5 14.2 16.3 1.4 2.1 .10 .10 5 15.3 1.9 .09 111. Bigmouth buffalo 3 18.6 3.9 .08 5 16.7 2.7 .07 White crappie 5 7.3 0.2 Avg. .21 .13 5 8.9 0.4 .13 Avg. .10 #74 Mississippi River White sucker 4 13.5 1.2 .21 Little Falls. White sucker (R) 4 13.8 1.2 .55 Minn. Yellow bullhead Northern pike 5 10.2 14.3 0.8 0.8 Avg. .68 .37 .48 #27 Mississippi River Carp 4 18.8 2.9 .11 5 13.9 1.4 .10 Gutenberg, Bluegill 4 8.3 0.4 .20 5 7.1 0.4 .13 Iowa Bluegill (R) 4 8.0 0.4 .12 Largemouth bass 3 15.3 2.1 Avg. .33 .20 5 12.0 1.0 .25 Avg. .16 #75 Mississippi River Cape Girardeau, Mo. Carp Channel catfish Channel catfish (R) White crappie 3 5 5 3 18.2 15.4 15.7 10.7 3.0 1.3 1.2 0.7 Avg. .20 .11 <.05 .15 .14 Vol. 6, No. 3, December 1972 153 TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 X iZ o d Z Average Size Total Mercury (PPM)' I o 1 Average Size AND Location si Id Total Mercury (PPM)' MISSISSIPPI RIVER SYSTEM— Continued #76 Mississippi River Carp 2 19.0 4.0 .17 Memphis, Carpsucker 2 16.5 2.4 .46 Tenn. Carpsucker (R) Freshwater drum 2 17.0 20.0 2.9 3.9 Avg. .14 .15 .21 #28 Arkansas River Carp 2 25.0 8.9 .09 3 21.0 3.8 .14 Pine Bluff, Smallmouth buffalo 2 16.5 2.9 .11 4 16.3 2.5 .08 Ark. Smallmouth buffalo (R) 2 19.5 4.8 .13 Flathead catfish - 23.5 5.5 Avg. .22 .14 2 21.0 4.6 .15 Avg. .12 #29 Arkansas River Keystone Reser- Carp Carp (R) 5 5 13.4 13.9 1.2 1.3 .06 .10 5 14.5 1.5 .08 voir, Okla. Bluegill 4 5.4 0.1 .13 5 6.2 0.2 <.05 Largemouth bass 1 14.3 1.7 Avg. .22 .14 5 15.0 2.5 .14 Avg. .07 #77 Arkansas River John Martin Reservoir, Colo. Carp Carp (R) Channel catfish Black bullhead 5 5 3 3 14.7 12.9 9.2 8.5 1.4 1.1 0.3 0.4 Avg. .05 .06 .05 .07 .06 #78 Verdegris River Carp 5 14.8 1.6 .13 Oologah, Carp (R) 5 15.0 1.7 .05 Okla. Bluegill Largemouth bass 5 3 4.7 14.3 0.1 2.3 Avg. .07 .44 .20 #79 Canadian River Carp 5 13.6 1.1 .06 Eufaula, Okla. Carp (R) Bluegill Largemouth bass 5 4 2 13.2 5.5 11.0 1.2 0.1 0.8 Avg. .21 .07 .10 .10 #30 White River Carp 2 18.0 2.9 .14 1 24.0 7.5 .27 DeValls Bluff, Bigmouth buffalo 2 17.0 2.6 .35 3 15.7 2.0 .22 Ark. Bigmouth buffalo (R) 2 21.0 4.8 .25 Channel catfish ' 15.5 1.4 Avg. .12 .19 4 14.5 0.8 .13 Avg. .21 #80 Yazoo River Redwood, Miss. Carp Smallmouth buffalo Smallmouth buffalo (R) Gizzard shad 5 20.0 16.5 15.5 5.8 4.5 3.0 2.3 0.1 Avg. .19 .16 .10 .15 .16 #81 Red River amallmouth buffalo 2 21.0 5.8 .10 Alexandria. Smallmouth buffalo (R) 2 20.0 5.2 .10 La. Freshwater drum White catfish 3 3 13.7 13.0 1.1 0.6 Avg. .24 .21 .18 #82 Red River Carp 5 20.5 4.5 .13 Lake Texoma, Carp (R) 5 20.2 4.3 .14 Okla. Bluegill Largemouth bass 4 4 6.6 13.2 0.4 0.9 Avg. <.05 .15 .10 #83 Missouri River Carp 2 19.4 3.7 <.05 Hermann. Mo. Carp (R) Bigmouth buffalo Channel catfish 3 18.8 17.9 18.3 2.9 3.7 2.0 Avg. .08 .14 .15 .11 #31 Missouri River Nebraska City, Carp Carp (R) 3 3 17.1 16.9 2.4 2.2 .06 .07 5 13.6 1.2 <.05 Nebr. Goldeye Channel catfish 4 13.0 0.9 Avg. .20 .14 5 5 12.5 13.0 0.8 0.8 .07 <.05 Avg. <.05 154 Pesticides Monitoring Journal TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location X £ 0 6 Z Average Size Total Mercury (PPM)i X £ 0 6 Z Average Size 2 2 II .J w Total Mercury (PPM)i MISSISSIPPI RIVER SYSTEM— Continued #32 Missouri River Carp 3 17.2 2.2 .11 2 15.2 1.6 .14 Garrison Dam, Goldeye 5 12.4 0.5 .24 5 10.8 0.3 .13 N. Dak. Goldeye (R) 5 11.9 0.5 .17 Walleye 3 15.8 1.3 Avg. .20 .17 4 17.6 1.4 .30 Avg. .19 #33 Missouri River Goldeye 5 11.2 0.5 .20 5 12.9 0.5 .14 Great Falls, Goldeye (R) 5 11.2 0.5 .13 Mont. Redhorse sucker Sauger 5 5 15.9 12.5 1.7 0.7 Avg. .16 .24 .19 5 16.9 2.0 .13 Avg. .14 #84 Big Horn River Hardin, Mont. Carp Goldeye Goldeye (R) Channel catfish 5 5 5 5 15.5 10.6 10.9 19.1 2.4 0.4 0.5 3.7 Avg. .35 .23 .25 .18 .26 #85 Yellowstone River Sidney, Mont. Carpsucker Goldeye Goldeye (R) Channel catfish 5 5 5 5 11.9 11.3 10.3 9.1 1.0 0.5 0.4 0.4 Avg. .11 .15 .15 .08 .11 #86 James River Carp 3 15.8 1.0 .13 Olivet, Carp (R) 3 15.3 0.9 .13 S. Dak. Goldeye Freshwater drum 5 4 11.0 9.0 0.8 0.3 Avg. .22 .08 .14 #87 North Platte River Lake McConaughy. Nebr. Carp Carp (R) Channel catfish Walleye Rainbow trout 3 3 3 5 3 15.8 15.9 16.5 16.2 19.6 1.2 1.2 1.0 1.8 3.2 Avg. .14 .10 .12 .09 .11 .11 #88 South Platte River Brule, Nebr. Carp White sucker White sucker (R) Green sunfish 5 5 5 3 5.6 12.0 10.2 4.8 0.1 0.7 0.5 0.1 Avg. .08 .11 .15 .10 .10 #89 Platte River Carp 3 19.7 3.7 .24 Louisville, Carp (R) 3 12.2 0.8 .11 Nebr. Channel catfish White crappie 5 3 12.6 7.6 0.6 0.3 Avg. .12 .13 .14 #90 Kansas River Carp 5 14.8 1.9 .10 Bonner Springs, Carp (R) 5 15.8 2.8 .13 Kans. Gizzard shad Freshwater drum 5 5 7.2 9.9 0.2 0.7 Avg. .08 .33 .18 HUDSON BAY DRAINAGE #34 Red River Noyes, Minn. Goldeye Goldeye (R) White sucker Channel catfish 5 3 12.3 12.4 15.6 0.6 0.7 0.7 .19 .19 .13 2 16.4 2.1 .36 Sauger 2 12.2 0.5 Avg. .60 .31 3 13.7 0.9 Avg. .41 .39 Vol. 6, No. 3, December 1972 155 TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location s £ 6 z Average Size Total Mercury (PPM)i I 0 d Z Average Size is II 5 = -J C- II Total Mercury (PPM)i COLORADO RIVER SYSTEM #35 Green River Carp 5 10,8 0.6 .14 5 11.0 0.9 <.05 Vernal, Flannelmouth sucker 5 16.7 1.4 .17 3 19.2 2.6 .10 Utah Flannelmouth sucker (R) Channel catfish Black bullhead 5 5 16.6 9.2 1.5 0.3 Avg. .24 .20 .18 3 5.4 0.2 <.05 Avg. <.05 #36 Colorado River Carp 5 16.4 3.9 <.05 5 16.9 2.5 <.05 Imperial Reser- Carp (R) 4 14.8 2.5 <.05 voir, Ariz. Channel catfish 5 12.3 0.9 <.05 3 9.2 0.2 <.05 Largemouth bass 5 14.5 0.9 Avg. .05 <.05 5 10.3 0.5 <.05 Avg. <.05 #91 Colorado River Havasu Lake, Ariz. Carp Carp (R) Channel catfish Largemouth bass 5 5 5 5 14.1 14.1 10.6 13.1 1.4 1.4 0.7 0.7 Avg <.05 .08 <.05 .08 .06 #92 Colorado River Lake Mead, Carp Carp (R) 4 3 15.8 16.1 2.8 3.0 .05 .05 Nev. Largemouth bass 4 14.7 2.0 Avg. .09 .07 #93 Colorado River Carp 3 12.7 0.5 .27 Lake Powell, Largemouth bass 4 13.9 1.2 .23 Ariz. Largemouth bass (R) Rainbow trout 4 5 13.0 13.4 0.9 1.1 Avg. .18 .10 .19 #94 Gila River Carp 6 14.5 1.0 .11 San Carlos Bluegill 6 4.7 0.1 .13 Reservoir, Ariz. Largemouth bass 3 13.1 1.2 Avg .22 .15 INTERIOR BASINS #37 Truckee River Fernley, Carp Carp (R) 5 5 13.2 12.7 1.1 1.1 .21 .23 5 14.6 1.5 .37 Nev. Brown bullhead 5 10.1 0.6 .35 5 10.2 0.7 .22 Largemouth bass 5 11.5 1.1 Avg. .65 .41 5 12.3 1.1 .53 Avg. .37 #38 Utah Lake Carp 5 16.7 2.4 <.05 5 17.0 2.1 .06 Provo, Black bullhead 5 10.2 0.6 .07 5 9.8 0.5 <.05 Utah Black bullhead (R) 5 9.9 0.6 .05 White bass 5 10.4 0.5 Avg. .06 .04 5 10.2 0.5 .06 Avg. .05 #95 Bear River Carp 3 18.6 3.8 .21 Preston. Idaho Largescale sucker Largescale sucker (R) Yellow perch 5 5 5 17.1 16.1 7.9 2.7 1.9 0.3 Avg. .34 .37 .13 .23 CALIFORNIA STREAMS #39 Sacramento River Sacramento, Carp Carp (R) 5 5 10.9 12.3 0.8 1.2 .18 .18 5 12.9 0.9 .11 Calif. White catfish 5 8.3 0.3 .20 5 14.1 1.3 .19 Largemouth bass 5 11.9 1.0 Avg. .22 .20 3 10.8 0.6 Avg. .13 .14 #40 San Joaquin River Carp 5 15.1 1.7 .23 5 14.7 1.3 .20 Los Banos, Channel catfish 5 16.6 2.3 .16 5 16.1 1.2 .20 Calif. Black crappie Black crappie (R) 5 5 11.6 10.8 1.2 1.1 Avg. .09 .11 .16 5 10.4 0.6 Avg. .14 .18 156 Pesticides Monitoring Journal TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location i Average Size Total Mercury (PPM)> s o 1 Average Size s 3 t 15 = 2 5^ II Total Mercury (PPM)» COLUMBIA RTVER SYSTEM #41 Snake River Largescale sucker 5 13.0 1.0 .08 5 15.0 1.4 .08 Hagerman. Largescale sucker (R) 5 12.6 0.9 .10 Idaho Rainbow trout 5 14,2 1.3 .18 5 13.2 1.0 .13 Northern squawfish 3 15.4 1.7 Avg. .43 .23 5 15.5 1.3 .37 Avg. .19 #42 Snake River Carp 4 15.3 2.3 .25 Lewiston, Largescale sucker 5 15.8 1.8 .23 5 15.9 2.0 .10 Idaho Largescale sucker (R) 5 15.3 1.6 .18 Smallmouth bass 5 11.0 0.8 .21 3 7.0 0.3 .15 Northern squawfish Avg. .22 ' 13.0 0.8 1.25 Avg. .50 #43 Salmon River Carp 4 13.1 1.5 .29 Riggins, Largescale sucker 4 17.4 2.3 .42 5 15.2 L6 .23 Idaho Largescale sucker (R) Northern squawfish 3 17.7 13.1 2.3 1.0 Avg. .39 1.70 .80 #96 Snake River Bridgelip sucker 5 12.1 0.8 .12 Ice Harbor Channel catfish 5 13.1 1.2 .90 Dam. Wash. Chaniiel catfish (R) Northern squawfish 5 4 14.3 12.6 1.3 0.7 Avg. .10 1.20 .61 #44 Yakima River Carp 5 11.2 1.1 .23 Granger, Carp (R) 5 11.3 1.0 .23 Wash. Black crappie 5 7.4 0.3 .13 Largescale sucker 5 14.0 1.2 .07 5 13.3 0.9 .30 Smallmouth bass 3 12.3 1.4 Avg. .27 .19 2 10.0 0.9 .14 Avg. .19 #45 Willamette River Carp 3 19.0 5.0 .17 Oregon City, Largescale sucker 5 15.3 1.8 .37 5 13.9 1.2 .18 Oreg, Largescale sucker (R) Chiselmouth White crappie 5 15.9 1.7 Avg. .33 .26 4 5 10.2 6.9 0.5 0.2 .13 .23 Avg. .18 #46 Columbia River Largescale sucker 5 16.9 2.0 .21 5 16.5 2.0 .27 Bonneville Chiselmouth 4 7.9 0.3 .15 Dam, Oreg. Northern squawfish Northern squawfish (R) 5 5 12.7 13.8 0.8 1.1 Avg. .67 1.10 .55 5 13.1 1.0 1.25 Avg. .56 #97 Columbia River Carp 5 12.6 13 .07 Pasco, Largescale sucker 5 17.2 2.6 .16 Wash. Largescale sucker (R) Mountain whitefish 5 3 16.3 12.0 2.1 0.5 Avg. .14 .19 .14 #98 Columbia River Bridgelip sucker 5 14.1 1.2 .07 Grand Coulee Walleye 5 14J 1.1 .11 Dam, Wash. Walleye (R) Northern squawfish 5 5 14.8 12.6 1.3 0.9 Avg. .12 .25 .15 PACIFIC COASTAL STREAMS #47 Klamath River Klamath sucker 5 15.7 2.1 .27 5 13.5 1.2 .12 Hombrook, Yellow perch 5 7.9 0.3 .20 5 8.9 0.4 .22 Calif. Yellow perch (R) Largemouth bass Rainbow trout 5 5 8.2 8.4 0.3 0.3 Avg. .19 .12 .20 5 11.6 0.8 Avg. .14 .16 #48 Rogue River Gold Ray Dam, Carp Bridgelip sucker 5 15.2 2.6 .18 5 14.0 1.5 .16 Oreg. Brown bullhead Brown bullhead (R) Black crappie Largemouth bass 5 5 2 10.8 10.8 9.5 0.7 0.6 0.6 Avg. .47 .51 .14 .27 5 4 9.5 7.0 0.5 0.3 Avg. .90 .25 .44 Vol. 6, No. 3, December 1972 157 TABLE 1. — Mercury residues in fish, 1969 and 1970 — Continued Species 1970 1969 Station Number AND Location s b 0 6 Z Average Size Total Mercury (PPM)' X £ o 6 Z Average Size a 2 i Id si Total Mercury (PPM)i ALASKAN STREAMS #49 Chena River Longnose sucker 2 13.5 1.7 .05 5 15.0 1.2 .09 Fairbanks, Round whitefish 3 11.7 1.0 .06 5 10.0 0.2 .06 Alaska Arctic grayling 3 10.2 0.6 Avg. .06 .06 5 11.7 0.5 Avg. .06 .07 #50 Kenai River Soldatna, Longnose sucker Round whitefish 5 12.1 0.7 .10 5 15.5 1.5 .08 Alaska Rainbow trout 5 16.3 1.5 .06 5 13.2 0.9 .06 Lake trout 5 13.7 0.9 Avg. .26 .14 5 14.6 0.9 Avg. .12 .09 HAWAIIAN STREAMS #99 Waikele Stream Tilapia - 2 6.1 0.1 .11 Waipahu, Cuban limia^ 13 2.6 0.1 .06 Hawaii Chinese catfish ' Chinese catfish (R) 3 2 8.1 9.4 0.1 0.2 Avg. .43 .22 .17 #100 Manoa Stream Tilapia = 3 8.0 0.3 .09 Honolulu, Cuban limia ^ 6 3.5 0.1 .13 Hawaii Chinese catfish * Chinese catfish (R) 3 3 10.3 8.8 0.3 0.2 Avg. .18 .15 .13 NOTE: (R) designates replicate field sample. To compute residue average, the replicate samples at a sampling station were averaged and this average used with the values tor the other species at a station to compute the average; values less than the sensitivity level of 0.05 ppm were considered to be zero in computing averages. ' mg/kg — wet-weight basis — whole fish. - Tilapia mossambica. ^ Limia vittata. ' Clarias fuscus (Identification uncertain). TABLE 2. — Results of analyses for total mercury and methyl mercury by Laboratory C and confirmatory analyses for total mercury by Laboratory H — 1970 Station Number AND Location Species Total Mercury (mg/kg)i Methyl Mercury - (mg/kg of Kg) Laboratory C Laboratory C Laboratory H #1 Stillwater River Chain pickerel .64 .69 #2 Connecticut River White perch .51 .54 .43 Yellow perch .30 .38 #3 Hudson River Goldfish .07 .13 #4 Delaware River White perch .21 .24 White perch (R) .17 .22 #8 Cape Fear River Largemouth bass .60 .61 Gizzard shad .25 .17 #10 Savarmah River Largemouth bass 1.80 1.73 1.70 #14 Tombigbee River Largemouth bass .92 .80 1.10 #15 Mississippi River Carp (R) <.05 .04 #16 Rio Grande Channel catfish .17 .15 #18 Lake Ontario White perch 1.30 .97 1.00 #20 Lake Huron Carp .07 .04 #21 Lake Michigan Bloater (R) -07 .09 158 Pesticides Monitoring Journal TABLE 2.— Results of analyses for total mercury and methyl mercury by Laboratory C and confirmatory analyses for total mercury by Laboratory H — 1970 — Continued Station Number AND Location Species Total Mercitry (mg/ko)i Methyl Mercury = (mg/kc of Hg) Laboratory C Laboratory C Laboratory H #23 Kanawha River Brown bullhead (R) <.05 .03 #24 Ohio River Channel catfish .83 .63 .65 Channel catfish (R) .68 .57 .56 #26 niinois River White crappie .21 .12 #28 Arkansas River Smallmouth buffalo (R) .13 .16 #30 White River Bigmouth buffalo (R) .25 .24 #31 Mississippi River Goldeye .20 .18 #34 Red River (North) Sauger .60 .48 #37 Truckee River Largemouth bass .65 .65 #39 Sacramento River Carp (R) .18 .20 #40 San Joaquin River Black crappie .09 .08 #43 Salmon River Northern squawfish 1.70 1.40 #45 Willamette River Largescale sucker (R) .37 .45 .36 #46 Columbia River Northern squawfish (R) I.IO .97 .88 #48 Rogue River Brown bullhead .47 .39 #51 Kennebec River Yellow perch 1.20 1.10 #52 Lake Champlain Yellow perch (R) .49 .48 #53 Merrimac River Yellow perch .33 .34 #54 Raritan River Golden shiner .08 .06 #55 James River Channel catfish .12 .07 #56 Pee Dee River Largemouth bass 1.00 1.00 1.00 #57 Altamaha River Spotted sucker .25 .23 Largemouth bass .51 .52 #59 Alabama River Largemouth bass .60 .74 .60 #63 Rio Grande Largemouth bass .52 .52 #67 Allegheny River Walleye .28 .19 #69 Ohio River Carp (R) .20 .10 White crappie .15 .19 #71 Tennessee River Largemouth bass .67 .69 #72 Wisconsin River Smallmouth bass .60 .56 #74 Mississippi River Yellow bullhead .68 .62 #75 Mississippi River Carp .20 .16 #76 Mississippi River Freshwater drum 15 .23 #80 Yazoo River Carp .19 .21 Smallmouth buffalo .16 .15 #81 Red River Smallmouth buffalo (R) .10 .06 #83 Missouri River Channel catfish .15 .19 #96 Snake River Northern squawfish 1.20 1.13 .94 NOTE: (R) designates replicate sample. ^ Confirmatory analyses at Laboratory H on 40 samples also analyzed at Laboratory C. 2 Analyses for methyl mercury at Laboratory C based on 24 samples. Vol. 6, No. 3, December 1972 159 Dursban® and Diazinon Residues in Biota Following Treatment of Intertidal Plots on Cape Cod — 1967-69 Vahe M. Marganian' and William J. Wall, it.' ABSTRACT The effects of the organophosphorous pesticides Dursban® and diazinon on intertidal biota were studied over a period of 3 years, 1967-69. One percent granular Dursban® applied manually at an optimum concentration of 0.05 lb/acre con- trolled Culicoides larvae efjectively with no noticeable harm to fiddler crabs or other organisms. Residues recovered ranged from trace amounts to 2.30 ppm in white oligochaete, 2.58 ppm in ribbed mussel, 4.62 ppm in fiddler crab, 14.0 ppm in horsefly, and 15.7 ppm in marsh snail. Two percent granular diazinon applied manually at 0.20 lb/acre controlled Culicoides effectively, hut killed small sand organisms. In general, concentrations of diazinon residues recovered were higher than those for Dursban® in the same organisms re- ported above. This report describes the sampling and gas chromatographic analytical procedures employed in this work, discusses data collected on residues in organisms at various periods after treatment, and gives persistence periods for these pesticides in substrates of intertidal sand, salt marsh sod, salt marsh mud, and sea water. Department of Chemistry, Bridgewater State College, Bridgewater, Mass. 02324. Department of Biology, Bridgewater State College, Bridgewater, Mass 02324. Introduction In recent years, the deleterious effects of organochlorine pesticides, particularly DDT, on intertidal biota have received much criticism from environmentalists and the public. In an effort to find alternate means to organo- chlorine pesticide control, the effects of a number of organophosphorous pesticides on the breeding patterns of bloodsucking insects in intertidal areas have been studied (7). This paper reports the results of a 3-year study (1967- 69) conducted on Cape Cod, Mass., to determine if the use of Dursban® and diazinon for control of larvae of Culicoides melleus breeding in intertidal sand, C. hol- lensis and C. furens breeding in salt marsh mud, and Tabanus nigrovittatus and T. lineola breeding in salt marsh sod, would result in harmful effects to nontarget organisms and to determine residue levels in the inter- tidal biota. Reports on the field tests and on the classifica- tion of organisms are being published separately. Because techniques for the chemical analysis of Durs- ban® and diazinon were not readily available, it was necessary to develop analytical methodology in the early 160 Pesticides Monitoring Journal phases of the study for the detection and quantitative measurement of both compounds. Treatment and Sampling Procedures The majority of the tests were conducted in small inter- tidal sand and salt marsh plots ranging from 0.08 to 0.25 acres in size. For each test, two plots were treated with a single concentration of Dursban® or diazinon and a nearby untreated plot was used as a control. These pesticides, in granular form, were applied by hand at low tide, and in some instances uncoated granules were added to the pesticide-coated granules to provide addi- tional materials for better distribution. During the latter phases of the program, two extended areas of intertidal sand or beach areas were treated using a Kiekens Whirl- wind gasoline-operated duster and a salt marsh was treated using a helicopter. Samples of intertidal biota, sand, and water were col- lected at regular intervals from treated and untreated areas before and after treatment as described by Wall and Marganian (/). When it was necessary to separate small organisms from the underlying sand, mud, or sod, the methods used for separation and counting of the larvae were based on that of Jamnback and Wall (2), Wall and Jamnback (.?), and Wall and Doane {4). The procedure for sample storage was based on method- ology recommended by Van Middelem (5), Beckman (6), and Lykken (7). All specimens were stored at low temperatures (about 0° C) to prevent possible decomposi- tion of the insecticides, and, when possible, samples were analyzed within 24 hours of their arrival at the laboratory. A nalytical Procedures Extraction and cleanup procedures were related to tech- niques outlined by Thornburg (5) and Morley and Chiba (9). The wet weight of analyzed samples, repre- senting composites of several specimens of the same species, as a rule, was in the following ranges: 1-10 g for claims, fiddlers, ribbed mussels, oysters, and shrimp; 0.1-1 g for mud snails, marsh snails, mud whelks, and periwinkles; 0.01-0.1 g for amphipods, crabs, tanai- daceans, horseflies, white oligochaetes, and red oliogo- chaetes; 15-20 g for sand; 50-55 g for sod; and 50 ml for water. Each sample of biota, sand, mud, and water was treated in a blender with 25 ml of reagent grade acetonitrile (density = 0.78 g/ml) for 5 minutes, and a 10-^1 solution of internal standard dissolved in petro- leum ether was added to the blender to insure uniform losses of insecticides during subsequent extractions. For the quantitative analysis of Dursban®, diazinon was used as an internal standard, and vice versa. This was followed by a second extraction of the sample with 15 ml of acetonitrile, and the two extracts were then combined. The combined extracts were next treated with an equal volume of petroleum ether (b.p. = 30°- 60° C, density = 0.62 g/ml) by shaking the mixture vigorously in a separatory funnel and removing the ace- tonitrile phase. This step was repeated twice using 25 ml of petroleum ether in each treatment of the ace- tonitrile phase, and all three petroleum ether extracts were combined. Five milliliters of a saturated NaCl solution and 25 ml of distilled water were added to the combined petroleum ether phase, shaken again, and the ether phase was transferred to a second separatory fun- nel, where it was washed again with distilled water. The two aqueous layers were treated together with small amounts of additional petroleum ether, and all ether phases were combined and dried over anhydrous NaoS04. The petroleum ether extracts were next con- centrated to about 0.3 ml with a gentle stream of nitro- gen, and 2-;il aliquots were subjected to gas chroma- tographic analysis. An F&M series Model 400 Biomedical gas chroma- tograph with a Honeywell strip chart recorder and a modified flame detector was used. This modification was achieved by coating a 27-gauge platinum wire with NaoS04 beads and mounting the coiled wire over the tip of the flame. The operating parameters were as fol- lows: Columns: Glass, 5' x Vi", o.d., packed with 5% UC-W98 on 60/80 mesh, acid-washed Diatoport S. Temperatures: Detector 245° C Injector 250° C Oven 185° C Flow rates: Carrier gas — He at 45 ml/min Oxygen (air) at 340 ml/min Hydrogen at 22 ml/min Retention times: Diazinon 4.2 min Dursban® 7.8 min The lower limit of sensitivity was 0.01 ppm (mg/kg, net fresh weight). Quantitative calculations were carried out on a computer. A 69f precision of results was ob- tained on several samples determined at random. Re- covery rates for both insecticides ranged from 80-85%. Data in this report do not include a correction factor for percent recovery. A few samples containing high concentrations of Dursban® and diazinon were analyzed by ultraviolet spectroscopy (at 23 1 myu. and 246 m^, respectively) and were found to give comparable results on gas chromatographic analysis. Results and Discussion The effects of applications of Dursban® and diazinon on nontarget intertidal biota are shown in Table 1. The applications listed in Table 1 effectively controlled Ciilicoides larvae. In addition, Dursban® and diazinon Vol. 6, No. 3, December 1972 161 TABLE 1. — Effects of Dursban® and diazinon on intertidal biota after effective control of Culicoidae larvae Application Rate lb/acre Means of Application Organism Controlled Effects on nontarget Organisms DURSBAN® 0.05 duster 0.5 mile of inter- tidal shoreline C. melleus larvae (up to 2 weeks following application ) Killed numerous fiddler crabs 0.05 manually Sand plots C. melleus larvae No visible effects 0.1 and 0.2 manually Sand plots C. melleus larvae Killed numerous fiddler crabs 0.20 manually 0.08— acre salt marsh plots Culicoides larvae, specifically C. furens and C. hollensis (for 18 days) Killed numerous larvae (75%) 0.20 helicopter 17 acres of salt C. hollensis larvae (up to 29 Numerous fish were found dead in the marsh days after treatment) tidal creek up to 3 days following treatment 0.2 duster 1.1 mile of inter- tidal sand C. melleus larvae Killed numerous marine fish including Fundulus spp. 0.2 manually Sand plots C. melleus larvae Killed small sand organisms such as naidids and dolichopodids 0.20 manually 0.12— acre salt marsh plots Culicoides larvae, specifically C. furens and C. hollensis (for 7 days) Killed numerous larvae (80%) applied by hand at low tide to 0.25-acre salt marsh plots at rates of 0.05 and 0.3 lb/ acre, respectively, failed to effectively control larvae of Tabamis sp.; numerous confined Fundulus spp. appeared to have died on the second day following this Dursban® treatment, and others placed daily in potholes were killed up to 4 days following the diazinon treatment. An optimum concentration of 0.05 lb/ acre of 1% granular Dursban®, applied manually, effectively con- trolled Culicoides larvae in small plots without visibly harming fiddler crabs or other organisms. However. Dursban® applied at the same rate by duster to 0.5 mile of intertidal sand shoreline controlled C. melleus larvae up to 2 weeks following treatment but also killed nu- merous fiddler crabs. Two percent granular diazinon applied manually at 0.20 lb/ acre controlled all Culicoides larvae effectively, but killed small sand organisms, such as naidids and dolichopodids. Table 2 gives the results of analyses of various species from sand and salt marsh plots for residues of Dursban® following treatment at 0.05 lb/ acre. Results of analyses of biota following diazinon treatments at 0.2 and 0.25 lb/ acre are given in Table 3. Some specimens from most of the species or groups (where species could not be determined) analyzed dur- ing the first 4 days after treatment were found to con- tain measurable amounts of Dursban® (Table 2) or diazinon (Table 3). Organisms taken from sand plots treated with diazinon applied at the rate of 0.2 pound of technical material per acre generally contained more residues than similar organisms taken from comparable plots treated with Dursban® applied at the rate of 0.05 pound of technical material per acre. Table 4 shows the periods of persistence of these pesticides in intertidal sand, salt marsh sod, salt marsh mud, and sea water. Each figure in Tables 2-4 represents one analysis per sample. With a few exceptions, no measurable residues of Durs- ban® or diazinon were found in the organisms from or the substrate of the treated or control plots prior to treatment, and none were found in organisms or substrate from control plots following treatment. In most of the species or groups analyzed, no obvious pattern of accumulation or disappearance of residues could be established for the two pesticides studied. In some specimens, residues up to 50 ppm were found dur- ing the first few days following treatment, gradually de- clining to immeasurable amounts at the end of 30 days. 162 Pesticides Monitoring Journal TABLE 2. — Dursban® residues in marine organisms at various intervals after treatment at a concentration of 0.05 lb/acre Substrate Dursban® Residues in PPM (fresh-weioht basis)' Organism Days 1 2 3 4 7 9 10 12 22 Oligochaeta Enchytraeidae (white oligochaete) Salt marsh mud 1.0 - 2.30 - Mya arenaria (clam) Intertidal sand T - - 0.01 Mollusca Modiolus demissus (ribbed mussel) Salt marsh mud — 2.58 0.12 — Nassarius obsotetus (mud snail) Intertidal sand T T 1.10 — 0.62 Melampus bidentatus (marsh snail) Salt marsh mud - T 2.24 — — 15.70 Anhropoda Lepiochelia sp. (tanaidacean) Salt marsh mud T - 16.70 - T Pataemonetes sp. (prawn) Intertidal sand — - Uca spp. (fiddler crabi Intertidal sand T T — 4.62 Culicoides spp. (gnat) SaJt marsh mud 0.43 - Tabanus spp. (horsefly) Salt marsh mud T ~ 3.80 0.43 14.00 ~ NOTE: Dursban® applied as 1% technical grade Dursban® in granular form; blank = no sample taken; — = no residue detected; T = trace <0.01 ppm. ' Represents one analysis per sample. In Other organisms of the same species or group, col- lected during the second or third week following treat- ment, residues over 20 ppm were found. From 1 to 7 days following treatment, many annelids, particularly Oligochaeta, did not contain measurable amounts of residues, but others were found to contain large quantities (over 10 ppm) of the particular f)esticide employed. From 1 to 21 days following treatment, samples of the Fundulus spp. (killifiish) as well as many samples of Pelecypcxla and Arthropoda analyzed con- tained small measurable amounts of residues (usually <1 ppm) of the pesicide distributed. In general, Mol- lusca (Gastropoda and Pelecypoda) were found to con- sistently contain more residues than the other organisms analyzed. Organisms taken from salt marsh habitats generally con- tained more residue of the pesticide employed than the same species or group taken from intertidal sand habi- tats. Dursban® applied at the rate of 0.05 pound of technical material per acre persisted in measurable amounts in the top one-half inch of intertidal sand for an average of 2 days with a maximum of 4 days; in the top inch of salt marsh sod for an average of 5 days with a maximum of 12 days: and in the top inch of salt marsh mud for an average of 15 days with a maximum of 22 days (Table 4). Diazinon applied at the rate of 0.2 pound of technical material per acre persisted in measurable amounts in the top one-half inch of intertidal sand for an average of 4 days with a maximum of 12 days: in the top inch of marsh sod for an average of 6 days with a maximum of 10 days: and in the top inch of marsh mud for an average of 10 days with a maximum of 22 days (Table 4). For both pesticides, residues on the day following treatment were greatest, gradually declining thereafter. With one minor exception, analysis of sea water taken from the bay or creek immediately adjacent to each treated plot showed no residues on the day following treatment. During the summer following the original application of Dursban® in small intertidal sand and marsh plots, organisms and substrates from these plots were analyzed, and no measurable amounts of residues of either pesti- cide were found. Vol. 6, No, 3, December 1972 163 '^ 1 1 d 1 s. 1 1 1 o m d s SO o a 00 1 ^ H 1 d ' m rj O o d d d _ so H "X rj d o d 1 aa ■^ 1 fS o S s g *" ' d d d 1 CT^ w-> Ov A -" o d d d i o r, a. z >- Ov o r-* d H z 00 S 3 o 1 r- d ■^^ 1 H d z o N 'O < 1 5 ■<*•' 1 m O ^ rs ^ o 1 r- ^. H d " ro d rj " d r- ^ ^ -N ^o vO «/^ -^ ' o d d s "■ d d ' d d d „ d 1 M ^ M ^ fS °'^. H q 1 rn vO 1 o\ ■* d o " \D o fN ^ r-i rj ■* o d 1 "■ o d d S ■ Average Maximum ' Intertidal sand 2 4 4 12 Salt marsh sod 5 12 6 10 Salt marsh mud 15 22 10 22 Sea water 0 0 ^ Time of last detectable trace A cknowledgment The authors gratefully acknowledge the help and co- operation of O. W. Doane, Jr., Superintendent of the Cape Cod Mosquito Control Project, and Donald Nye, Charles Pye, and Richard Benton for their assistance in the analytical laboratory, and Dr. H. O. Daley, Jr., for his assistance in computer programming. Special thanks are due to Dr. R. A. Coler of the University of Mas- sachusetts for establishing the basic gas chromatographic techniques employed in this study. See Appendix for chen paper. a! names of compounds discussed in this This work was supported by U.S. Public Health Service research grant CC00298 from the National Center for Disease Control, Atlanta, Ga. LITERATURE CITED (1) Wall. W. J., Jr., and V. M. Marganian. 1971. Control of Culicoides melleus (Coq.) (Diptera: Ceratopogonidae) with granular organophosphorous pesticides, and the direct effect on other fauna. Mosq. News 31:209-214. (2) Jamnback, H., and W. J. Wall. Jr. 1958. A sampling pro- cedure for Cluicoides melleus (Coq.) (Diptera: Heleidae) with observations on the life history of two coastal Culicoides. Mosq. News 18:85-88. (3) Wall. W. J.. Jr.. and H. Jamnback. 1957. Sampling methods used in estimating larval populations of salt marsh tabanids. J. Econ. Entomol. 50:389-391. (4} Wall. W. J., Jr.. and O. W. Doane, Jr. 1960. A prelimi- nary study of the bloodsucking Diptera on Cape Cod. Mass. Mosq. News 20:39-44. <5l Van Middelem, C. H. 1963. Principles of residue analysis. Vol. 1, p. 25-45. In G. Zweig, [ed.] Analytical methods for pesticides, plant growth regulators, and food additives. Academic Press, Inc., New York. (6) Beckman, H. F. 1963. Principles of formulations an- alyses. Vol. 1, p. 7-23. In G. Zweig, [ed.] Analytical methods for pesticides, plant growth regulators, and food additives. Academic Press, Inc.. New York. I7i Lykken, L. 1963. Important considerations in collecting and preparing crop samples for residue analysis. Residue Rev. 3:19-34. (8} Thornburg. W . W. 1963. Extraction and clean-up pro- cedures. Vol. 1, p. 7-108. In G. Zweig, [ed.] Analytical methods for pesticides, plant growth regulators, and food additives. Academic Press, Inc., New York. 19) Morley. H. V.. and M. Chiba. 1964. Thin-layer chrom- atography for chlorinated pesticide residue analysis with- out cleanup. J. Assoc. Off. Agric, Chem. 47(2):306-310. Vol. 6, No. 3, December 1972 165 PESTICIDES IN WATER Seasonal Variations in Residues of Chlorinated Hydrocarbon Pesticides in the Water of the Utah Lake Drainage System — 1970 and 1971 ' J. S. Bradshaw", E. L. Loveridge", K. P. Rippee", J. L. Peterson^ D. A. White", J. R. Barton*, and D. K. Fuhriman' ABSTRACT Definite surges of pesticides (1 ppb or more) enter Utah Lake three times per year — early spring, late spring, and fall, generally corresponding to the application times of pesticides by farmers in the area. The pesticides involved were mainly aldrin and BHC in the early spring: heptachlor (plus hepta- chlor epoxide) and methoxychlor in the late spring; and aldrin, heptachlor, and methoxychlor in the late fall. The fish samples collected from Utah Lake contained only small amounts of pesticides, the highest level being 956 ppb DDE. Introduction Utah Lake is a large freshwater lake in central Utah (Fig. 1), 25 miles long and 11 miles wide with an aver- age depth of 9 feet. The major inlets to Utah Lake are on the east side, and more than half of the estimated 600,000 acre-feet of water entering Utah Lake in an average year enters through the Provo, Spanish Fork, and American Fork Rivers. The rest of the water enters through agricultural drains, small creeks, and underground springs. The only outlet from Utah Lake is the Jordan River to the north. Utah Lake serves as a reservoir for the water users of the Utah Lake and Jordon River Irrigation System. Previous studies concerning the overall chemistry of Utah Lake were summarized by Bradshaw et al. (/, 2). The only previous pesticide residue studies of Utah ' Presented in preliminary form at the Arts and Letters Meeting of the Utah Academy of Sciences at Logan, Utah, September 10, 1971. - Chemistry Department, Brigham Young University, Provo, Utah 84601. {Mr. Rippee, National Defense Education Act Graduate Fel- low, 1970) ^ Zoology Department, Brigham Young University, Provo, Utah 84601. * Civil Engineering: E>epartment, Brigham Young University, Provo, Utah 84601. Lake showed that at least two surges of jjesticides enter Utah Lake every year (/, 3). Fish from Utah Lake were reported to contain minute amounts (0.1-0.8 ppm) of chlorinated hydrocarbon residues (4, 5). This study was undertaken to catalog the sources and types of pesticides entering the Lake in a given year and to determine the extent of pesticide residues in Utah Lake fish. Sampling and Analytical Procedures WATER SAMPLES Water from 15 tributaries and 1 outlet point (16 Sta- tions) was sampled biweekly from March 1 to July 1, 1970, and weekly or semi weekly through February 1971 (Fig. 1). Station 2 was soon abandoned because it dried up. One gallon of water was collected at each station in large mouth glass jars. The water (3 liters) was ex- tracted as soon as possible (within 3 days) with nano- grade petroleum ether (Mallinkrodt Chemical Co.) in a continuous liquid-liquid extractor for 24 hours. Care was taken to insure that a representative mixture of water and suspended material was extracted. The petro- leum ether extract was dried over anhydrous sodium sulfate, filtered, and evaporated to 10 ml. The sample was then analyzed on a dual glass column, Varian Aerograph 202 gas-liquid chromatograph (GLC) using electron capture detectors. Each sample was analyzed simultaneously on the two columns. One column (Vs" X 5') was packed with a mixture of 4% SE-30 and 6% QF-1 on Chromosorb W and the other, with a mixture of 1.5% OV-17 and 1.95% QF-1 on Chromosorb W. The columns were heated to 200° C. The GLC peak areas were determined using a Disc Integrator. Quantita- tion was accomplished by comparing the peaks with 166 Pesticides Monitoring Journal those of known standards. Only pesticides verified by the second column were evaluated (6). The final pesticide levels were calculated using a Hewlett-Packard 9100 B "programable" calculator. FISH SAMPLES Fish were caught from the east side of Utah Lake be- tween the Orem Pier and Provo Airport on July 21, 1970, by Utah State Wildlife Resources personnel. The fish were treated in a manner similar to that reported by Kleinert, Degurse, and Wirth (7). Each frozen fish sample was ground and homogenized in a heavy duty meat grinder. A 10-g portion of the homogenized fish was added to a blender and mixed with 60 g of an- hydrous sodium sulfate and 200 ml of hexane (distilled through a glass column in the laboratory). The solvent from the blended material was decanted through a filter pajjer into a 500-ml round-bottom flask. The fish sample was washed four times with 50-ml portions of hexane. The combined hexane extracts were evaporated at about 50-mm pressure to 5 ml using a rotary evapora- tor. This material was then placed on a column contain- ing 200 g of Florisil and eluted from the column with a mixture of 180 ml of hexane and 12 ml of ethyl ether which contained 2% ethyl alcohol. The solution was eluted at a rate of 5 ml/min. The resulting solution was evaporated at about 50-mm pressure to 10 ml and sub- jected to GLC analysis as reported above. RECOVERY STUDIES Spiked water samples treated as above gave 75-85% recovery of the various pesticide residues. The results were not corrected to reflect this recovery. Results and Discussion WATER SAMPLES The concentrations of pesticides detected in water sam- ples (aldrin, total alpha- and gamma-BHC, heptachlor and heptachlor epoxide, methoxychlor, and DDT-type compounds) by collection stations on Utah Lake are shown in Fig. 2. The results showed that definite surges of pesticides entered the Lake at specific times during 1970. Except for these surges, extremely low levels of pesticides were detected in the water entering the Lake. Aldrin and BHC were the main residues entering Utah Lake in the early spring (March-April); heptachlor or its epoxide and methoxychlor in the late spring (May-June); and aldrin, heptachlor or its epoxide, and methoxychlor in the late fall (October-November). These surges cor- responded to the times of application of the respective pesticides in Utah County. FIGURE 1. — Sampling stations on the Utah Lake tributaries. 1970 and 197] Most of the pesticide residues were detected in tribu- taries in valley locations, with the exception of residues detected in the early spring (probably resulting from forest runoff) and at one location in the fall (high aldrin at Station 4). Station 13 (Fig. 1) was also considered a valley location since there are many farms above this point. Aldrin (Fig. 2) was observed mainly in the northern part of the Utah Valley where it is used for grasshopper control. The spring and fall surges of this pesticide enter- ing Utah Lake were at levels over 1 ppb. The greatest surge of BHC, which is used extensively on livestock in Utah County, was observed in the early spring at a level of 1.3 ppb (Fig. 2) in the south cen- tral area where there is much livestock. The high incidence of heptachlor or its epoxide in the alfalfa-producing area (Fig. 2 — Stations 5, 6, and 13) was somewhat surprising, however, since heptachlor is no longer registered for use on alfalfa (S) and has not been sold in Utah County for 3-4 years. It is likely that the heptachlor used was that left over from previous purchases. Methoxychlor, due to its relatively rapid degradation (9), is finding wide use as a replacement for DDT and was used extensively throughout Utah County. It was never detected in samples at the Jordan River outlet from Utah Lake probably because of its degradation (Fig. 2). Vol. 6, No. 3, December 1972 167 FIGURE 2. — Pesticide residues in water samples from the Utah Lake drainage system, 1970 and 1971 ALDRIN Sampling Station Number Location 1 Jordan River 3 and 4 North Upper S and6 North Lower 7 North Central Upper 8 and 9 North Central Lower 10 South Central Upper 11 South Central Lower 12 South Central Upper 13 South Upper 14 South Lower IS and 16 South Central Lower TOTAL ALPHA- AND GAMMA-BHC HEPTACHLOR AND HEPTACHLOR EPOXTOE 168 Pesticides Monitoring Journal FIGURE 2. — Pesticide residues in water samples from the Utah Lake drainage system, 1970 and 1971 — Continued METHOXYCHLOR ,ected substances served as references. After removal of the corresponding zone and elution by 1 ml of benzene, gas chromatographic analysis using an elec- tron capture detector was repeated. As a rule, a particular insecticide was considered present only if corresponding peaks were obtained from all GC columns; therefore, a major number of peaks were considered unidentifiable. Preseparation by TLC was performed in addition when the comparatively low microcoulometric reading of less sensitive substances like DDT was obtained. The polychlorinated biphenyls were not considered present, however, without con- firmation by mass spectrometry even where typical fingerprints were observed. These compounds have not been detected in any samples taken during this series of studies. Results and Discussion Results of analyses of unfiltered water and suspended solids are given in Tables 1 and 2. Residue levels in water are expressed as ng 'liter (ppt) and values ob- tained from suspended solids as nanograms of insecti- cides in solids suspended in I liter of water, i.e.. the quantities obtained from the filter residues were divided by the number of liters of water that had been filtered. Generally, insecticide concentrations were low in both types of samples. In water samples, heptachlor, hep- tachlor epoxide, and dieldrin were found seven times, three times, and once, respectively. In the susp)ended solids heptachlor was detected only once, and aldrin, dieldrin. and heptachlor epoxide were not found in any of the samples. The results were similar to those from earlier studies. Concentrations of endosulfan. however, were clearly lower as compared with earlier studies; residues of this compound, originating from industrial effluents, were found in samples from the Rhine, the lower Main (downstream from its junction with the Rhine), and the Regnitz. The insecticides found most frequently were the hexa- chlorocyclohexane isomers. a-BHC and lindane (y- BHC); however, the proportion of these compounds Vol. 6, No. 3, December 1972 181 found in suspended solids was low because of their greater solubility in water. Because of technical dif- ficulties, only a few samples were analyzed for a-BHC and hexachlorobenzene (HCB), and concentrations were determined with certainty only in some samples of sus- pended solids. The results obtained, however, showed a notable increase of lindane and a-BHC concentra- tions in samples from the upper Rhine and at the Berlin Teltowkanal over values obtained in previous studies. DDT and its main metabolites. DDD and DDE, oc- cupied a subordinate rank with regard to the frequency of positive findings and concentrations in waters. Be- cause of extremely low solubility in water. DDT was found mainly adsorbed to suspended solids. Parathion, the only organophosphate analyzed in this study, was found in only a few samples and in very small amounts. In evaluating the degree of pollution of major German surface waters by organochlorine insecticides, results obtained in this study as well as former studies show that the Rhine River is the most contaminated. A cknowledgment A great number of samples were furnished regularly from various sources. The author wishes to express his gratitude, in particular, to the Hygienisches Institut. Hamburg; Wasserwerke Bremen AG; the Diisseldorf Field Station of this Institute; the Institut fiir Gaste- chnik, Feuerungstechnik und Wasserchemie, Technical University Karlsruhe, and Regierung von Niederbayern, Abt. Gewassergiiteaufsicht. Landshut. Special thanks for technical assistance are expressed to Mrs. H. Junge and Mrs. F. Reichert. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Breidenhach. A. W., and J. J. Lichtenberg. 1963. DDT and dieldrin in rivers: a report on the National Water Quality Network. Science 141:899-901. (2) Breidenhach, A. W., C. G. Gunnerson, F. K. Kawahara. J. J. Lichtenberg, and R. S. Green. 1967. Chlorinated hydrocarbon pesticides in major river basins. 1957-65. Public Health Rep. 82:139-156. (3) Breidenhach, A. W., J. J. Lichtenberg. C. F. Henke, D. J. Smith, J. W. Eichelberger, Jr., and H. Slierli. 1964. The identification and measurement of chlorinated hydrocarbon pesticides in surface waters. Public Health Serv. Piibl. No. 1241. 108 p. (4) Brown, E., and Y. A. Nishioka. 1967. Pesticides in selected western streams — a contribution to the national program. Pestic. Monit. J. l(2):38-46. (5) Cole. H., D. Barry, and D. E. H. Frear. 1967. DDT levels in fish, streams, stream sediments and soil before and after DDT aerial spray application for fall canker- worm in northern Pennsylvania. Bull. Environ. Contam. Toxicol. 2:127-146. (6) Croll, B. T. 1969. Orgrano-chlorine insecticides in water. Part I. J. Soc. Water Treat. Exam. 18:255-274. (7) Dcmini, R. J.. P. A. Frank, and R. D. Comes. 1970. Amitrole residues and rate of dissipation in irrigation water. Weed Sci. 18:439-442. (8) Epps, E. A., F. L. Bonner, L. D. Newsom, R. Carlton, and R. O. Smitherman. 1967. Preliminary report on a pesticide monitoring study in Louisiana. Bull. Environ. Contam. Toxicol. 2:333-339. (9) Faust. S. D., and I. H. Siifjel. 1966. Recovery, separa- tion, and identification of organic pesticides from natural and potable waters. Residue Rev. 15:44-116. (injFredccn. F. J. H.. and J. R. Duffy. 1970. Insecticide residues in some components of the St. Lawrence River ecosystem following application of DDD. Pestic. Monit. I. 3(4):219-226. (//) Grasso, C. 1967. Ricera degli antiparassitari nelle acque superficial! destinate alia potabilizzazione. L'Igiene Mod. 60:645-653. (12) Greve, P. A., and S. L. Wit. 1971. Endosulfan in Rijn- water. Chem. Weekblad 67:7-10. (13) Grzenda. A. R.. H. P. Nicholson, J. I. Teasley, and I. H. Patric. 1964. DDT residues in mountain stream water as influenced by treatment practice. I. Econ. Entomol. 57:615-618. (14) Giierrant, G. O.. L. E. Fetzer, Jr., and J. W. Miles. 1970. Pesticide residues in Hale County, Texas, before and after ultra-low volume aerial application of mala- thion. Pestic. Monit. J. 4(l):14-20. (15} Her-el, F. 1970. Untersuchungen von Oberfiachenge- wassern auf Insektizide. Bundesgesundh.-bl. 13:49-52. ( 16) Herzel, F. 1970. Chlorkohlenwasserstoff-lnsektizide in Oberfliichenwiissern. Bundesgesundh.-bl. 14:175-179. (17) Herzel, F. 1970. Schnellverfahren zur Spurenbestimmung von Chlorkohlenwasserstoff-Insektiziden in Wasser. Arch. Hyg. Bakteriol. 154:18-20. (15) Hindin. E.. D. S. May. and G. H. Dunstan. 1964. Col- lection and analysis of synthetic organic pesticides from surface and ground water. Residue Rev. 7:130-156. (19) Holden, A. V., and K. Marsden. 1966. The examination of surface waters and sewage efilents for organo- chlorine pesticides. I. Proc. Inst. Sew. Purif. p. 295-299. (20) Johnson. L. G.. and R. L. Morris. 1971. Chlorinated hydrocarbon pesticides in Iowa rivers. Pestic, Monit. J. 4(4):216-219. (21) Lichtenherger, J. J., J. W. Eichelberger, R. C. Dressnian, and J. E. Longhottom. 1970. Pesticides in surface waters of the United States — a 5-year summary. 1964-68. Pestic. Monit. J. 4(2):71-86. (22) Lowden, G. F., C. L. .Saunders, and R. W. Edwards. 1969. Organochlorine insecticides in water. Part II. Water Treat. Exam. 18:275-287. (23) Manigold, D. B., and J. A. Schulze. 1969. Pesticides in selected western streams — a progress report. Pestic. Monit. I. 3(2):124-135; Erratum 3(3):195. (24) Marston, R. B., D. W. Schidts. T. Shiroyama, and L. V. Snyder. 1968. Amitrole concentrations in creek waters downstream from an aerially sprayed watershed sub- basin. Pestic. Monit. I. 2(3):123-128. (25) Ministry of Technology. 1967. Notes on water pollution. Residues of organo-chlorine pesticides in surface waters. Water Pollut. Control 66:633-637. 182 Pesticides Monitoring Journal (26) Nicholson, H. P., A. R. Grzenda, and J. I. Teasley. 1968. Water pollution by insecticides. J. Southeast. Sect. Am. Water Works Assoc. 32:21-27. (27) Rowe. D. R.. L. W. Canter. P. J. Snyder, and J. W . Mason. 1971. Dieldrin and endrin concentrations in a Louisiana estuary. Pestic. Monit. J. 4(4):177-183. (28) Schafer. M. L.. J. T. Peeler. W. S. Gardner, and J. E. Campbell. 1969. Pesticides in drinking water: water from the Mississippi and Missouri Rivers. Environ. Sci. Tech- nol. 3:1261-1269. (29) Sheets. T. J.. M. D. Jackson, and L. D. Phelps. 1970. Water monitoring system for pesticides in North Caro- lina. U. S. Clearinghouse Fed. Sci. Techn. Inf. P. B. Rep. No. 189291, 109 p. (30) Warnick. S. L.. R. F. Gaiiffin. and A. R. Gauffin. 1966. Concentrations and effects of pesticides in aquatic en- vironments. J. Am. Water Assoc. 58:601-608. (31) Wojlalik. T. A.. T. F. Hall, and L. O. Hill. 1971. Moni- toring ecological conditions associated with wide-scale applications of DMA 2.4-D to aquatic environments. Pestic. Monit. J. 4(4): 184-203. 132) Vrochinsky, K. K.. and A. T. Ogalakowa. 1969. Hygienic assessment of the use of DDT. Gig. Sanit. 34:12-15. (33) Vrochinsky, K. K., S. S. Grebenjuk, and A. L. Burshlein. 1968. Contamination of water reservoirs with pesticides. Gig. Sanit. 33:69-72. (34) Wealherholtz. W. M., G. W. Comwell. R. W. Young, and R. E. Webb. 1967. Distribution of heptachlor resi- dues in pond ecosystem in southwestern Virginia. J. Agric. Food Chem. 15:667-675. (35) Weaver, L., C. G. Gunnerson, A. W. Breidenbach, and J. J. Lichtenberg. 1965. Chlorinated hydrocarbon pesti- cides in major U. S. river basins. Public Health Rep. 80:481-493. (36) Zweig, G., and J. M. Devine. 1969. Determination of organophosphorus pesticides in water. Residue Rev. 26:17-36. -Concentrations of insecticides in unfillered surface waters in the Federal Republic of Germany- May 1971 sampling excursion and monthly collections from April 1970-June 1971 [blank = not analyzed: — = not detected] Sampling Site No. (See Fig. 1 > Body of Water Insecticide Concentkations in nc/liter (ppt) Elbe Weser Lauenburg Bremen 5/21/70 6/11/70 7/23/70 8/70 9/01/70 10/28/70 11/05/70 12/14/70 1/27/71 2/25/71 5/03/71 6/15/71 5/10/71 4/13/70 5/11/70 6/08/70 7/13/70 8/10/70 9/07/70 10/12/70 11/09/70 12/07/70 1/11/71 2/08/71 3/08/71 — 215 250 395 310 175 125 160 185 810 255 1500 430 1050 275 690 250 Vol. 6, No. 3, December 1972 183 TABLE 1. — Concentrations of insecticides in unfiltered surface waters in tlie Federal Republic of Germany- May 1971 sampling excursion and monthly collections from April 1970-June 1971 — Continued Body of Water Date OF Sampling Insecticide Concentrations in ng/liter (ppt) iJXX QsoiQQQa. 30 — ____ — — — — 50 _________ 60 — — — __ — — — — 45 — — — — — — — — — 245 — — — 70 _ _ _ _ _ 215 — ________ 105 — _ — — — ____ 165 — _ _ 55 95 _ _ _ — 105 — — — 35 — — — _ — 140 — — — 15 20 — — 170 — 100 — _ _ 15 — — — _ — 220 — — — — — — — — — 115 205 — — — — — — — 55 175 — — — — — — — — 5 110 — — — — — — — — — 380 — — — — — — — — — 130 — — — — — — — — — 50_ — — — — — — — — 60 — — _ — — — __ — 225 — — — — — — — — — 455 — ___ — — ___ 125 __ — — — — — 55 _ 265 — — — — — — — — — 175 — — — — _____ 325 — — — — — 10 — — — 330 — — — — — — — — 5 330 — — — — — — — — — 260 — — — — — — — — — 535 __ — __ — — __ 240 — — — — — — — — — 155 — — — — — — — _ — 260 — — — — — — — — — Weser Rhine Achim Dusseldorf Rhine Rhine Rhine Danube Wesel St. Goar Oestrich Jochenstein 4/13/71 5/10/71 6/14/71 5/10/71 4/70 6/70 7/70 8/70 9/70 10/70 11/70 12/70 1/71 2/71 3/71 4/15/70 5/14/70 6/70 7/15/70 8/10/70 9/70 10/13/70 1 1 /09/70 12/10/70 1/13/71 2/71 3/16/71 4/71 5/71 5/12/71 5/11/71 5/11/71 5/12/71 4/15/70 5/13/70 6/10/70 7/08/70 8/19/70 9/16/70 10/14/70 1000 945 1100 1300 2400 890 115 184 Pesticides Monitoring Journal TABLE 1. — Concentrations of insecticides in iin filtered surface waters in tlic Federal Republic of Germany — May 1971 sampling excursion and monthly collections from April 1970-June 1971 — Continued Body of Water Datc OF Sampling Insecticide Concentkations in ng/liter (ppt) Danube Ulm Danube Ingolstadt Danube Geisingen Nord-Ostsee-Kanal Rendsburg Mittelland-Kanal . Bramsche Ems Rheine Ruhr Duisburg Sieg Siegburg Lahn Fachbach Moselle Koblenz Main Raunheim Main Bad Berneck Neckar Heidelberg Lake Constance Langenargen Regnitz Erlangen Saale Hof Havel Berlin-Gatow 11/11/70 12/09/70 1/20/71 2/17/71 3/17/71 4/14/71 5/12/71 6/09/71 5/13/71 5/14/71 5/13/71 5/10/71 5/11/71 5/11/71 5/11/71 5/11/71 5/11/71 5/11/71 5/12/71 5/14/71 5/12/71 5/13/71 5 14 71 5/15/71 4/29/70 5/22/70 6/24/70 7/08/70 8/12/70 9/17/70 10/27/70 11/02/70 12/01/70 1/21/71 2/10/71 3/25/71 4/21/71 5/12/71 6/21/71 Vol. 6, No. 3, December 1972 185 TABLE 1. — Concentrations of insecticides in unfillered surface waters in the Federal Republic of Germany — May 1971 sampling excursion and monthly collections from April 1970-June 1971 — Continued Body of Water Location Date OF Sampling Insecticide Concentrations IN NC/LITER (PPT) Sampling Site No. (See Fig. 1 ) U X n 0 Lindane Heptachlor Heptachlor epoxide DiELDRIN a-ENDOSULFAN z < 0 z W U Q oa D Q Q a Q z o I H < a. 28 Teltow-Kanal Berlin-LichterfeWe 4/29/70 5/11/70 6/24/70 7/08/70 135 515 170 — — — — 950 — — — — - - - 65 - 420 — — — — _ — 250 — 8/12/70 190 — — — — - - 95 - - 9/17/70 450 — — — — - - 190 - - 10/27/70 11/02/70 80 180 60 1350 _ _ _ _ — 35 _ 12/01/70 7100 _ _ _ _ — 85 - 135 - 1/21/71 415 1650 _ — _ _ - - 85 - - 2/10/71 3/25/71 1700 400 130 200 65 1750 _ _ _ — _ _ _ 4/21/71 530 715 — — — — - - 830 - - 5/12/71 545 540 — — — — — 70 775 - - 6/21/71 1245 80 — — — — - - - - - TABLE 2. — Concentrations of insecticides in suspended solids from surface waters in the Federal Republic of Germany — Mav 1971 Body of Water Location Date of Sampling Liters of Water Filtered Insecticide Concentrations in ng/Solids Suspended IN 1 Liter of Water (ppt)i Sampling Site No. (See Fig. 1) m X U X ga a Lindane Heptachlor o-Endosulfan ^-Endosulfan DDT 2 Parathion 2 Elbe Lauenburg 5/10/71 IS 57 — 37 — — — 36 — 4 Weser Achim 5/10/71 14 - - 53 — — — — — 6 Rhine Karlsruhe 5/12/71 18 - 2.5 21 — — — — — 7 Rhine Wesel 5/11/71 12 — - 53 — — — — 0.4 8 Rhine St. Goar 5/11/71 21 - 37 22 — — — — — 9 Rhine Oestiich 5/12/71 12 36 42 39 — — — — 0.15 11 Danube Ulm 5/13/71 34 - - 0.4 — — — — — 12 Danube Ingolstadt 5/14/71 24 0.6 - -- 2 - — 4.4 — 14 Rendsburg Bransche 32 13 15 Mittelland-Kanal 5/11/71 _ _ 3.1 — — — — — 16 Ems Rheine 5/11/71 12 - - 0.8 — — — — — 186 Pesticides Monitoring Journal TABLE 2. — Concentrations of insecticides in suspended solids from surface waters in the Federal Republic of Germany — May 1971 — Continued Body of Water Location Date of Sampling LrrERS of Water Filtered Insecticide Concentrations in ng/Solids Suspended IN 1 Liter of Water (ppt)' Sampling Site No. (See Fig. 1) HCB a-BHC Lindane Heptachlor ot-Endosulfan ^-Endosulfan DDT = Parathion 17 18 19 20 21 23 24 25 26 Ruhr Sieg Lahn MoseUe Main Neckar Lake Constance Regnitz Saale Duisburg Siegburg Fachbach Koblenz Raunheim Heidelberg Langenargen Eriangen Hof 5/11/71 5/U/71 5/11/71 5/11/71 5/12/71 5/12/71 5/13/71 5/14/71 5/15/71 20 20 12 25 13 32 25 11 13 1 — 2.1 — — — 8.7 — 0.6 _ 1.2 — — — 4.2 — 19 25 18 — 22 9.6 264 0.15 _ _ 0.15 _____ 21 — 159 — 24 _ 119 _ 6.5 _ 6.9 _ — _ 31 — NOTE: Aldrin, dieldrin. and heptachlor epoxide were not detected in samples of suspended matter. ' Quantities obtained from the filter residues were divided by the number of liters of water that had been filtered. - Only DDT was found in suspended solids; the presence of DDD and DDE could not be confirmed in any case Vol. 6, No. 3, December 1972 187 Insecticide Residues in Water and Sediment From Cisterns on the U.S. and British Virgin Islands — 1970 ' Herbert Lenon^ LaVerne Curry% Andrew Miller, and Daniel PatulsW ABSTRACT In the Virgin Islands the potential exists for pesticide con- tamination of water cisterns which supply and store all water used by local populations; cistern water and sediment samples on four islands were analyzed for pesticide residues in 1970 by gas-liquid chromatography. In the past, chlorinated hydro- carbon pesticides were used quite extensively on the Islands, however, malathion is more commonly used today. Evidence of an unknown malathion metabolite was found in all 49 water samples analyzed, wereas malathion was found in only two (0.01 and 0.14 ppb). DDT, its metabolites, and dieldrin were not commonly found in the water samples except those from St. John where dieldrin was detected in ap- proximately 50% of the samples (average concentration — 0.19 ppb). Sediment samples from cisterns, in general, contained much higher concentrations of pesticides than water, with DDT and its metabolites occurring most frequently. In many of these sediment samples, the residue levels were high enough to be concern. As a result it is strongly recommended that cisterns be cleaned frequently to remove sediment. Introduction Although the Virgin Islands receive an average annual rainfall of about 41 inches, much of this water is lost immediately by runoff and evaporation (1). Thus, the local populations depend on rain water for drinking and domestic use which is collected from roofs and stored in cisterns beneath their homes. With this type of rain catchment system, the nearby use of in- secticides in mosquito eradication programs has been of concern, since insecticides could be carried by wind Contribution 103 from the Virgin Islands Ecological Station. Great Lameshur Bay, St. John's, U.S. Virgin Islands. Department of Biology, Central Michigan University. Ml. Pleasant, Mich. 48858. 188 to roofs and then flushed into the cisterns during any of the Islands' frequent showers. Cistern water supplies from four of the Virgin Islands were surveyed for insecticide accumulations. The cis- terns sampled were on the three major U.S. Virgin Islands of St. Croix, St. Thomas, and St. John and one British Virgin Island, Anegada (Fig. 1). The Virgin Islands are at the end of a 1,300-mile chain of islands known as the Greater Antilles — including Cuba, Jamaica, and Puerto Rico — which begins off the south- ern tip of Florida and extends south and west toward Central America. ^^^ THE ANEGADA VIRGIN ISLANDS ^ r^ If VIRGIN GORDA ST THOMAS ^ -- - TOR TO LA SI JC HN CARIBBEAN \ SEA ^ ^-V,-,>^_V~N^ 22' 23 <£i_^ • .^"^i? ST THOMAS 0 1 """ FIGURE 3. — Sampling stations on the U.S. Virgin Island of St. Thomas FIGURE 5. — Sampling stations on the British Virgin Island of Anegada Vol. 6, No. 3, December 1972 189 living but now work for a British corporation preparing for a jet airport. There is no tourism, agriculture, or industry. Cisterns for catching rainwater are especially important for the basic supply of water since these islands have no other fresh water (7). The approximate average annual rainfalls for these four islands are: St. John, 47 inches; St. Thomas, 42 inches: St. Croix, 40 inches; and Anegada, 30 inches. Yet, these islands appear very dry, and as explained by Bowden et cil. (/) "In essence rain falling on most rain-days is evaporated and tran- spired almost immediately, and is obviously of little or no consequence for growth of crops and vegetation." Although no large-scale agricultural spraying is con- ducted on these islands, insecticides are used locally by individuals and by the U.S. Virgin Islands Health Department to control certain pest insects, especially mosquitoes. On St. Thomas and St. Croix, hotel owners spray areas to facilitate the tourist trade. The health department indicated that on St. Thomas DDT was used from 1960 to 1962 and dieldrin, from 1962 to 1964. Since then, malathion has been used, primarily because DDT and dieldrin were no longer effective against mos- quitoes. According to Director Francois of Environ- mental Health (personal communication, 1970). it is applied to the ground, shrubbery, exposed water con- tainers, and around the outside of water barrels and cisterns. Stored drinking water is often a source of mos- quitoes, and private cisterns may be treated directly with Abate or DDVP resin strips. A similar program has been followed on St. Croix. On St. John, all insecti- cide use appears to be by individuals who apply much malathion. All insecticides are prohibited inside the national park. Sampling Methods and Analytical Procedures Samples of water and sediment from cisterns were taken on the following dates: St. Croix Island — March 18 and 19, 1970; St. Thomas Island— March 10-12, 1970; St. John Island— February 23 and March 9, 1970; and Anegada Island— March 26, 1970. Each drinking water sample was collected in two 1-gal glass bottles. These were immediately extracted by liquid- liquid partitioning with purified petroleum ether using 70 ml per liter of water. This solvent was purified by twice distilling reagent grade petroleum ether with 10 g of dri-sodium per 3 liters at between 30° and 60° C. Each sample was extracted twice. Combined extracts were partially evaporated and sealed in screw-capped vials, packed, and sent by airmail to the biology labora- tory at Central Michigan University, Mt. Pleasant, Mich. They were then immediately dried with anhydrous sodium sulfate, further evaporated, and adjusted to 25 ml for analysis. It is believed that little if any break- down of the extracted pesticides occurred in the short period of transport as was also noted by Guerrant, Fetzer, and Miles (2) using hexane. Sediment samples were collected with a plankton net attached to a metal pole from the bottoms of cisterns containing significant amounts of sediment. They were then sent in screw-capped bottles directly to Central Michigan University for extraction and analysis. Water in the samples was removed by filtering on Whatman No. 1 paper with a Buchner funnel. Then the paper con- taining the sediment was oven-dried overnight at 50° C. The sample (3-7 g) was weighed on the pre-weighed filter paper and then shaken thoroughly several times with purified petroleum ether. The sediment was washed three times in petroleum ether, then the entire extract was dried with anhydrous sodium sulfate, evaporated, and adjusted to 25 ml. Sample extracts were identified and quantified by gas chromatography (Beckman GC-4) using electron cap- ture detection. Column packing and operating param- eters were based on those of Mills. Onley, and Gaither (5) and were very similar to those used later by Guerrant et al. (2) with malathion: Column: 6' x Va" stainless steel, packed with 3% SE-30 on 60/80 mesh Chromosorb W Temperatures: Detector 300° C Column 180° C Inlet 210° C Carrier gas: Helium at a flow rate of 40 ml/min Samples were verified by analysis using 3% OV-17 on Chromosorb W as described by Menzie and Prouty (4) and also used by Guerrant et al. (2) with good agree- ment of retention times between the two systems. Laboratory tests gave the following average recoveries: DDE, 76.1%; TDE (DDD), 72.8%; DDT, 82.2%; diel- drin, 83.5%; and malathion, 85%. Data in this report have been corrected using these recovery rates. The standards used were from: A. Beckman Poly-Science Quant-Kits. \% by weight in benzene, and included: Technical p,p'-DDT. 99.5% Technical p.p'-TDE, 99.5% Technical dieldrin, 99.5% Technical malathion. 99.5% B. Pesticide Repository. Perrine Primate Laboratory, Environmental Protection Agency, prepared 1% by weight in petroleum ether: Analytical Standard— p,p'-DDE. 99% Analytical Standard— o.p'-TDE 99% Analytical Standard— o.p'-DDT, 99% A given quantity of malathion standard was allowed to hydrolyze naturally at room temperature for 6 months in order to characterize its metabolite in gas chroma- tographic analysis. This common metabolite was not identified but was used as a "qualitative standard." 190 Pesticides Monitoring Journal Results and Discussion DDT, its metabolites, and dieldrin were not commonly found in the water samples (Tables 1-4). DDT was not present in any of the water samples and its metab- olites (DDE and TDE) were found in only one (Table 3). Dieldrin, which presents the greatest hazard in the water supply at levels found because of its toxicity and persistence, occurred in 48% (6 of 14) of the samples from St. John and 13% (2 of 15) of those from St. Thomas; however, no residues of dieldrin were found in samples from St. Croix and Anegada. Malathion was present in only two water samples (Sta- tions 19 and 34) and at low concentrations (0.14 and 0.01 ppb, respectively) (Tables 1-4). However, evidence of some metabolite of malathion was found in all water samples taken. Because this metabolite was not identi- fied, values are not reported. Detection of this com- pound is reported only to suggest the previous presence of its precursor, malathion. Since malathion is a short- term insecticide, it was expected that it would be found only as one of its hydrolyzed products (2). Widespread use of this insecticide is, nevertheless, suggested through the common appearance of its metabolite in every water TABLE 1. — Stations from which cistern water was sampled on St. Croix Island Cistern Source Approximate Age OF Cistern (YEARS) Sample Station ' Residence 75-100 Business 9 Business 3-4 Hotel >100 Residence 12 Museum <10 Residence 13 School 10-15 (not in use) 8 Agric, Exp. Stn. 100 (plastic liner) 9 Hotel 5 10 Business Unknown n Hotel >100 12 Residence Unknown 13 Residence 1 14 Hotel Unknown (cleaned often) 15 sample. The potential hazard of the insecticide would not appear to be great since hydrolysis occurs rather rapidly, especially under conditions of neutral-to-alkaline pH. Because the metabolite was not identified, however, the importance of its presence cannot be interpreted.. The highest indicated malathion occurrence, as evi- denced by the greatest relative quantities of its metab- olite, was on St. Thomas and St. John. It is reason- able to expect St. Thomas Island to have one of the highest levels of pesticide residues, since the local health department as well as individuals spray the area to reduce the annoyance of mosquitoes and the risk of malaria to both tourists and its large local population. It may be possible to explain the high occurrence of malathion in water samples from the cisterns of St. John on the basis of the large amounts of water for this island brought in from areas like Puerto Rico where insecticide use is probably more common. This would also perhaps, explain the more frequent occurrence of the chlorinated hydrocarbon pesticides, especially diel- drin (Table 3). Water samples from St. Croix were next highest in relative malathion metabolite, as might be expected, since it is also quite heavily populated and supports tourists interest. TABLE 2. — Stations from which cistern water was sampled on St. Thomas Island showing pesticide residue levels detected Approximate Age of C>"FfiN (YEARS) Sampie Station ■ Residues in ppb Source Mala- thion Diel- drin Estate >100 16 — — Estate 5 17 - - Estate 30 18 - - Residence >30 19 0.14 0.04 Dept. of Agric. >30 (artesian) 20 - - Nursery 39 21 - - Public 4 (open) 22 - — Hospital 40 (open) 23 - 0.10 Residence 3 24 - - Residence 200 25 - - Camp (Peace Corp) >30 27 - - Residence 5 28 - - Race track 1 29a - - Race track 21 29b - - School >30 30 - - NOTE: No residues of DDT, its metabolites, dieldrin, or malathion were detected. Evidence of some metabolite of malathion was found in all water samples taken. ' Sample station numbers correspond with those shown on map (Fig. 4). NOTE: — = no residue detected; no residues of DDT or its metab- olites were detected. Evidence of some metabolite of mala- thion was found in all water samples taken. ' Sample station numbers correspond with those shown on map (Fig. 3). Vol. 6, No. 3, December 1972 191 Sediment was found in cisterns and consequently sam- pled at 35 of the 46 stations where water samples were obtained. Pesticide residues were detected in sediment samples from only 15 of the Stations (Table 5). Gen- erally sediment samples had much higher residues with more variation in levels than water samples (Table 5 — values for sediment were reported in ppm rather than in ppb). This suggests that when sediment occurs, the insecticides tend to be bound and accumulate over longer periods of time. Of the pesticides detected, DDT, its metabolites, or both occurred most frequently and were present in 4 of 8 sediment samples from St. John and 9 of 14 from St. Thomas. The relative absence of these compounds in both sediment and water samples from St. Croix and Anegada indicates little usage of the pesticides on these islands. Many of the residue levels of DDT and its metabolites in sediment samples from St. John and St. Thomas were high enough to be of considerable concern, particularly two from Stations 19 and 41 (Table 5). It appears that DDT was used in these two situations in place of malathion because mala- thion was not available. Sediment from Station 41 con- tained a high amount of DDT and smaller amounts of TABLE 3. — Stations from which cistern water was sampled on St. John Island showing pesticide residue levels detected Sample Station - Residues in ppb Cistern Source ' o X z i H Q Q Q Q Q 5 Public 31 — _ — — — National park 32 - - - - - Camp ground 33 - - - - - Residence 34 0.01 - - - 0.02 Old commissary 36 - - - - 0.01 Laboratory 37 - - - - - Residence (Park Ranger) 38 — — — — 0.04 Camp 39a - - - - - Camp 39b - - - - - Laborator>' 40 - - - - 1.03 Residence 41 - - 0.15 0.02 - Clinic 42 - - - - 0.04 Church 43 - - - - 0.01 School 44 - - - - - Average 0.19 its degradation products indicating a short-term occur- rence of the pesticide in the sediment, while sediment from Station 19 contained very high amounts of metab- olites and little DDT, thus, indicating a longer presence of the pesticide. The fact that unusually high amounts were found only at these two locations suggests in- dividual sprayings and, [>erhaps, careless application. Dieldrin was not found in sediment as frequently (only one sample) as in water, a finding which remains un- explained. Malathion was found in only one sediment sample, while its metabolite was found in all but five (Stations 19. 22, 32. 41, and 43). It is interesting to note that even though evidence of this product was found in all water samples, it was absent in five of the sediment samples. Most sediment samples were composed of silty loam or organic matter and sometimes coral sand. DDT and its degradation products can accumulate in sediment, since they are bound to solid particles. Lichtenstein and Schulz (3) demonstrated that the persistence of residues in soils is dependent on various factors such as the insecticide itself, soil types, as well as climatic condi- tions. Soils of higher organic content tend to bind the greatest amount of chlorinated hydrocarbon pesti- cide. The survey and evaluation of pesticide levels in pri- vate and public cisterns on these islands were com- plicated for several reasons. The exact sources of the water are never known. Although rainwater is collected in all cisterns, these supplies are frequently insufficient and additional water must be purchased from various places, often as far away as Puerto Rico, but including other islands as well. This is known to be true, at least, for St. John where water arrives by barge and is then TABLE 4. — Stations from which cistern water was sampled on Anegada Island Approximate Cistern Age of Sample Source Cistern (■s-ears) Station > Business <1 ( open ) 45 Residence <1 46 Public well (plastic liner) very old 47 Public well Unknown 48 School >25 49 NOTE: — = no residue detected. Evidence of some metabolite of malathion was found in all water samples taken. ' Approximate ages of these cisterns are unknown. - Sample station numbers correspond with those shown on map (Fig. 2). •JOTE: No residues of DDT. its metabolites, dieldrin. or malathion were detected. Evidence of some metabolite of malathion was found in all water samples taken. Sample station numbers correspond with those shown on map (Fig. 5). 192 Pesticides Monitoring Journal trucked around the Island. Consequently, this may account for the occurrence in water of pesticides not used locally. Incomplete information was also a prob- lem. Data regarding the age and characteristics of the individual water supplies were often sparse. Some cis- terns were cleaned regularly and contained no sedi- ment, while others were never cleaned and contained several inches of bottom material. No apparent correlations are evident between the age of cisterns and residue levels, or between commercial or residential establishments and residue levels. It appears to be more a matter of the extent of individual use of pesticides, care in application, as well as, perhaps, the location where water was obtained. Results do not suggest a potential danger to the people who use water from the cisterns examined with the pos- sible exception of some on St. John containing signif- icant levels of dieldrin. Sediment, contained in many of the cisterns, represents a much greater potential hazard with accumulated levels of residues, represent- ing the past presence of insecticides at various stages of degradation. It is suggested that these sediment ac- cumulations be removed by frequent cleaning of the cisterns, thus keeping total i^esidue levels in the cisterns to a minimum. Acknowledgment We wish to thank the U.S. National Park Service, Mr. Bromberg, and Mr. Tony Cook for personnel and equipment; Drs. Edward Towle and Arthur Dammon for facilities at St. John; and Mr. John Yntema for help with field work. See Appendix for the chemical names of compounds discussed in this paper. LITERATURE CITED (1) Bowden, Martyn ].. Nancy Fischinan. Patricia Cook, James Wood, and Edward Omasta. 1970. Climate, water balance, and climatic change in the northwest Virgin Islands. Caribbean Res. Inst., College of the Virgin Islands, St. Thomas VI. p. 6. (2) Guerrant, G. O.. L. E. Fetzer, Jr., and J. W. Miles. 1970. Pesticide residues in Hale County, Texas, before and after ultra-low volume aerial application of malathion. Pestic. Monit. J. 4(l):14-20. 13) Lichtenstein, E. P.. and K. R. Schultz. 1959. Persistence of some chlorinated hydrocarbon insecticides as influenced by soil types, temperature, and rate of application. J. Econ. Entomol. 52(1):124. (4) Menzie, Calvin M., and Richard M. Proiity. 1968. Gas chromatographic analysis of gamma-BHC, the cyclodi- enes, and DDT analogs. J. Gas. Chromatogr. 6:64. (5) Mills, P. A., J. H. Onley, and R. A. Gaiiher. 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Agric. Chem. 46(2): 186-191. (6) Schiiclierl. Charles. 1935. Historical geology of the Antil- lean Caribbean Region. John Wiley and Sons, New York. 811 p. TABLE 5. — Stations where sediment of cisterns was sampled and pesticide residue concentrations detected Residues in ppm Mala- thion 3 _ — — — — 4 - - - - - 5 - - - - - 6 - - - - - 8 - - - - - 9 - - - - - 10 - - - - - 12 - - - - - 15 - - - — — ST. THOMAS 16 - 0.61 0.37 0.09 - 18 0.19 37.49 11.50 0.96 - 19 - 16.36 401.37 1,250.26 - 20 - 13.49 4.12 1.58 - 22 - - - - - 23 - - ~ - - 24 - - - - - 2."; - - - - - 26 - - - - - 27 - 0.96 0.43 0.17 - 28 - - - 0.07 - 29a - - 0.66 0.89 - 29b - 0.28 0.22 0.32 - 30 - 0.09 0.10 0.12 - 32 _ — — — - 33 - - - - - 34 - - - - - 35 — 1.82 0.21 0.05 — 36 _ — — - 0.08 41 - 271.29 34.11 6.27 - 43 — -. - 0.14 - 44 - 2.77 0.44 0.07 — 45 _ — — - - 47 - - - - - 48 ~ - - - — 49 - 7.18 1.79 3.68 — NOTE: — = no residue detected; evidence of some metabolite of malathion was found in all sediment samples with the excep- tion of the five samples from the following stations: Stations 19. 22. 32, 41, and 43. ■ Sample station numbers correspond lo those for water samples (Tables 1-4; Figs. 2-5). Vol. 6, No. 3, December 1972 193 PESTICIDES IN SOIL Pesticide Residue Levels in Soils, FY 1969 — National Soils Monitoring Program G. B. Wiersma', H. Tai=, and P. F. Sand' ABSTRACT This report is a summary of the FY 1969 results of the Na- tional Soils Monitoring Program, an integral part of the National Pesticide Monitoring Program (NPMP). Pesti- cide residues in cropland soil for 43 States and noncropland soil for II States are reported. Tables for each State give the number of samples collected, arithmetic means and ranges of residue levels detected, and the percent of sites with detectable residues. In addition, for selected pesticides and various States and State groupings, a frequency distri- bution of pesticide residues was determined. Use records for FY 1969 are given by the pesticides used, the percent of sites treated, the average application rates, and the average amounts applied per site. Comparisons are made between residue levels in different land-use areas. Introduction The National Soils Monitoring Program is an integral part of the National Pesticide Monitoring Program (NPMP), which was initiated as a result of a recom- mendation made by the President's Science Advisory Committee in its report of 1964 entitled "Use of Pesti- cides" that the appropriate Federal agencies "develop a continuing network to monitor residue levels in air, water, soil, man, wildlife, and fish." The NPMP as originally designed was described in the first issue of the Pesticides Monitoring Journal (I), and a revised description to reflect certain program realignments and Pesticides Regulation Division. Office of Pesticide Programs. Environ- mental Protection Agency. Washington, D. C. 20460. Pesticides Regulation Division. Office of Pesticide Programs. Environ- mental Protection Agency. Mississippi Test Facility, Bay St. Louis. Miss. 39520. Plant Protection and Quarantine Programs. Animal and Plant Health Inspection Service, U.S. Department of Agriculture, Hyattsville, Md. 20782. Other changes was published in the June 1971 issue of this Journal (2). The objectives of the NPMP are to determine levels and trends of pesticides in the various components of the environment (2). The establishment of baseline or back- ground levels of pesticide residues through the NPMP will provide a basis for comparison of subsequently identified pesticide residue levels in an environmental component. The Panel on Pesticides Monitoring of the Working Group on Pesticides (2) listed five bases for concern to be used in evaluating pesticide residue levels in the various environmental components. They are: (1) any concentration of a pesticide known to be potentially harmful; (2) increasing trends; (3) exceeding standards; (4) recognition of adverse effects on humans; and (5) erratic variability (a statistically oriented observa- tion that is potentially common to each stratum sampled). The results of this study serve to establish a baseline of pesticide residues in cropland and noncropland soils at a particular point in time (FY 1969). The present data and all future data will be evaluated using applicable criteria included in the five bases of concern outlined above. Sampling Procedures and Methods In general, sampling techniques involved in this study were the same as those described by Wiersma, Sand, and Cox (i). 194 Pesticides Monitoring Journal In FY 1969. cropland soil was sampled in every State except Alaska, Hawaii. Kansas. Minnesota, Montana. Oregon, and Texas. Noncropland was sampled in 1 1 States — Arizona, Georgia. Idaho. Iowa, Maine, Mary- land, Nebraska. Virginia, Washington, West Virginia, and Wyoming. Samples collected in FY 1969 included both soil and mature crops and/or those ready for harvest: however, results of crop analyses are not pub- lished in this report. A nalylical Procedures ORGANOCHLORINE AND ORGANOPHOSPHOROUS COMPOUNDS A subsample of soil weighing 300 g, wet weight, was placed in a 2-qt fruit jar with 600 ml of 3:1 hexane- isopropanol solvent. The jars were sealed and rotated for 4 hours. After rotation, the soil was allowed to settle, and 200 ml of the extract solution was filtered into a 500-ml separatory funnel. Isorpropanol was re- moved with two washings of distilled water, and the remaining solution was then filtered through a funnel containing glass wool and anhydrous sodium sulfate (NaoSOj). Further cleanup was normally not required before analysis. was partitioned three times with a portion of 150 ml of freon 113 for each partitioning. The freon 113 frac- tions were combined and concentrated to incipient dryness. The sample was then dissolved in hexane. adjusted to a 5-ml volume, and injected into a gas- liquid chromatograph. Gas-Liquid Chromatography A thermionic flame detector with rubidium sulfate coating on a helix coil was used. Instrument parameters were as follows: Column: Glass, 183 cm long by 6 mm. o.d.. and 4 mm. i.d., packed with 3rc Versamid 900 on 100 120 mesh Gas Chrom Q Carrier gas: Helium Detector fuel gas: Oxygen (200-300 ml min ) ; Hydrogen (20-30 ml, min) Temperatures: Detector 240° C Injection port 240° C Column 240° C Confirmation was made using a DC-200 column at 180" C and a Coulson detector (reductive mode) at the following temperature settings: pyrolysis tube — 850° C, transfer line— 220^ C. and block— 220° C. Gas-Liquid Chromatography Analyses were performed on gas chromatographs equippied with tritium foil electron affinity detectors for organochlorine compounds and thermionic or flame photometric detectors for organophosphorous com- pounds. A dual-column system employing polar and nonpolar columns was utilized to identify and confirm pesticides. Instrument parameters were as follows: Columns: d , Glass, 183 cm long by 6 mm, o.d., and 4 with one of the following packings: 3% DC-200 on 100 120 mesh Gas Chrom Q or 9% QF-1 on 100/120 mesh Gas Chrom Q Carrier gas: 5% methane-argon at a flow rate of 80 ml 'min Temperatures: Detector 200° C Injection port 250° C Column QF-1 166° C Column DC-200 170°-175° C When necessary, confirmation of residues was made by thin layer chromatography or p-values. The lower limit of detection was 0.01 ppm. The average recover>' rate for all pesticides was 100% (with a ±10% error); the data were corrected for recover^' and also adjusted to a dry-weight basis by determining the moisture content on a separate portion of each sample using the oven drying method. ATRAZINE After a 4-hour Soxhlet extraction of a 50-g subsample of soil with 25 ml of water and 300 ml of methanol, the sample extract was transferred to a 1 -liter separatory funnel and 200 ml of water added. The sample extract The minimum detection limit was 0.01 ppm. and re- covery was about 100%. 2.4-D Analyses were made following the procedure developed by Woodham et al. (4). The analytical method involved a diethyl ether extraction of acidified soil, an alkali wash to remove interfering substances, and an esteri- fication procedure using 10% boron trichloride in 2- chloroethanol reagent. The 2-chloroethyl ester of 2,4-D was then analyzed by gas chromatography. The minimum detection limit was 0.01 ppm. and the average recovery was 85%. Results were corrected for percent recovery. ARSENIC Arsenic was determined by atomic absorption spectro- photometry. The soil sample was first extracted with 9.6n hydrochloric acid (HCL) and reduced to trivalent arsenic with stannous chloride. The trivalent arsenic was partitioned from HCL solution to benzene, then further partitioned into water for the absorption meas- urement. A Perkin-EImer Model 303 instrument was used, and absorbance was measured with an arsenic lamp at 1972 A with argon as an aspirant to an air- hydrogen flame. The minimum detection limit was 0.1 ppm. and the recovery' value for arsenic averaged 70%. Results were corrected for percent recovery. Results The data in this report are for soils only (both crop- land and noncropland) and include results for all States Vol. 6, No. 3, December 1972 195 sampled in the study. Caution should be exercised when interpreting the arithmetic means presented in the tables, because pesticide residue data are not normally distrib- uted, and the arithmetic means for pesticide residues tend to be greater than the corresponding median. There- fore, they cannot be considered an indication of the central tendency of the data. Information accompanying the arithmetic means in this report such as the percent occurrence, range of detected residues, and number of observations can aid in evaluating the arithmetic mean. RESIDUES— ALL STATES Table I presents a summary of pesticide residues in cropland soils for all 43 States sampled. Percent occur- TABLE 1. — Summary of pesticide residues in cropland soil from 43 States — FY 1969 Number of Number of Percent Mean Residue Range of Compound Samples Positive Positive Level Detected Residues Analyzed ' Samples Sites = (PPM) (PPM) Aldrin 1,729 189 10.9 0.02 0.01-3.06 Arsenic 1,726 1,713 99.3 6.43 0.25-107.45 Atrazine 199 28 14.1 0.01 0.01-1.55 Carbophenothion 66 1 1.5 <0.01 0.23 Chlordane 1,729 151 8.7 0.04 0.01-6.30 2,4-D 188 3 1.6 <0.0I 0.01-0.03 DCPA (Dacthal®) 1,729 1 0.1 <0.01 0.54 o.p-DDE 1,729 79 4.6 <0.01 0.01-0.20 p,p'-DDE 1.729 429 24.8 0.06 O.01-6.99 o.p'-DDT 1,729 243 14.1 0.03 0.01-6.29 p,p'-DDT 1,729 384 22.2 0.17 0.01-35.92 DDTR 1,729 451 26.1 0.31 0.01-78.36 DEF 1,729 1 0.1 <0.01 0.12 Diazinon 66 2 3.0 <0.01 0.02-0.15 Dicofol 1,729 9 0.5 <0.01 0.03-1.07 Dieldrin 1,729 480 27.8 0.03 0.01-1.60 Endosulfan (I) 1,729 5 0.3 <0.01 0.01-0.24 Endosulfan (II) 1,729 9 0.5 <0.01 0.01-0.53 Endosulfan sulfate 1,729 11 0.6 <0.01 0.01-0.94 Endrin 1,729 39 2.3 <0.01 0.01-0.56 Endrin aldehyde 1,729 1 0.1 <0.01 0.03 Endrin ketone 1,729 9 0.5 <0.01 0.01-0.13 Ethion 66 1 1.5 <0.01 0.03 Heptachlor 1.729 68 3.9 <0.01 0.01-0.97 Heptachlor epoxide 1,729 139 8.0 <0.01 0.01-1.08 Isodrin 1,729 11 0.6 <0.01 0.01-0.03 Lindane 1,729 15 0.9 <0.01 0.01-0.35 Malathion 66 2 3.0 0.01 0.04-0.36 Methoxychlor 1,729 1 0.1 <0.01 0.28 Ethyl parathion 66 7 10.6 0.06 0.01-3.01 PCNB 1,729 1 0.1 <0.01 0.69 o,p'-TDE 1,729 49 2.8 0.01 0.01-4.52 p,p'-TDE 1,729 265 15.3 0.05 0.01-31.43 Toxaphene 1,729 73 4.2 0.07 0.10-11.72 Trifluralin 1,729 60 3.5 <0.01 0.01-0.25 ■ One sample per site. - Percent based on number of sites with residues greater than or equal to the sensitivity 111 196 Pesticides Monitoring Journal rence of residues is based on the number of sites with residues greater than or equal to the sensitivity limit. The data for atrazine, 2,4-D, and the organophosphates are not truly comparable with those determined for the organochlorines or arsenic, because analyses for atrazine and 2,4-D were made only when use records indicated that they had been applied — 199 and 188 times, respec- tively, and analyses for organophosphates were per- formed on only 66 of the 1,729 samples. Elemental arsenic residues were found most frequently, with 99.3% of the sites having detectable residues and a mean level of 6.4 ppm. It is probable that most of this arsenic was from natural sources, although agricultural sources cannot be ruled out at this time. The most widely distributed organochlorine pesticide was dieldrin, with 27.8% of the sites having detectable residues, followed by DDTR residues (a compilation of all members of the DDT group) found at 26.1% of the sites; aldrin, found at 10.9%; and chlordane, found at 8.7%. DDTR had the highest mean residue level, with 0.31 ppm found in cropland soils. With the exception of individual members of the DDT group, the other organochlorines had average residues ranging from <0.01 to 0.07 ppm. Based on the 66 samples analyzed for organophos- phates, ethyl parathion was detected 10.6% of the time, with a mean residue level of 0.06 ppm. Malathion and diazinon were each detected 3.0% of the time, with mean residue levels of 0.01 and <0.01 ppm, respectively. In the 188 samples analyzed for 2,4-D and other chlorophenoxy herbicides, 2,4-D was the only one de- tected; 2,4-D was found in 1.6% of 188 samples analyzed, with a mean residue level of <0.01 ppm. Atrazine was detected in 14.1% of the 199 samples analyzed, with a mean residue level of 0.01 ppm — the highest mean residue of the herbicides detected. Tri- fluralin was detected in 3.5% of the 1,729 samples, with a mean residue level of <0.01 ppm. The residues found in noncropland soils for the 1 1 States sampled are presented in Table 2. The mean arsenic residue level was 5.0 ppm, occurring in 98.5% of the samples. DDTR was detected in 16.1% of the noncropland soils at levels ranging from 0.01 to 0.62 ppm. with a mean level of O.OI ppm. With the excep- tion of members of the DDT group, dieldrin was the most widely distributed pesticide, occurring in 4.0% of the samples, with residues ranging between 0.01 to 0.09 ppm and a mean residue level of <0.0I ppm. RESIDUES— INDIVIDUAL STATES The p>esticide residue summaries for cropland by in- dividual States are given in Table 3. and similar results are shown for noncropland in Table 4. It would be impractical to attempt to comment on the results for each State: therefore, in order to facilitate summariz- ing the data. Figs. 1, 2, and 3 are presented. These are for three of the most commonly occurring residues — arsenic, DDTR. and dieldrin. Means for each pesticide in each State were calculated, and distribution of these averages are indicated on the corresponding Figures. TABLE 2. — Summary of pesticide residues in noncropland soil from 11 States — FY 1969 Aldrin Arsenic Chlordane o.p'-DDE p.p'-DDE o.p'-DDT p.p'-DDT DDTR Dicofol Dieldrin Heptachlor epoxide p,p'-TDE Tojtaphene Number of Samples Analyzed ' 199 199 199 199 Number of Positive Samples Percent Positive Sites - Mean Residl-e Range of Level Detected Residues (PPM) fPPM) <0.01 0.02 5.01 0.33-54.17 <0.01 0.04-0.50 <0.01 0.02 0.01 0.01-0.31 <0.01 0.01-0.05 O.OI 0.01-0.23 0.01 0.01-0.62 <0.0I 0.10-0.29 <0.0I 0.01-0.09 <0.01 0.01 <0.01 0.01-0.18 <0.01 0.52 ■ One sample per site. ' Percent based on number of sites with residues greater than or equal to the sensitivity limits. Vol. 6, No. 3, December 1972 197 FIGURE I. — Arsenic residues in cropland soil The class intervals for the keys accompanying each Figure were obtained in the following manner; The range of residues for the Nation was obtained, and the highest value was converted to a logarithm. This value was then divided by the number of desired classes. The resulting intervals were added to obtain the class bound- aries which, in turn, were converted to the untrans- formed dimensions. Essentially, this took advantage of the fact that most residue data are logarithmically distrib- uted. Distribution of arsenic residues across the United States is presented in Fig. 1. The highest residue levels were found in the New England States (Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont), Arkansas, Kentucky, New York, North Dakota, Ohio, and Pennsylvania; these individual States and the New England States had mean residues of arsenic >8.4 ppm. The remaining residues were distrib- uted primarily in the 2.0 to 8.4 ppm range, with Wyoming and Florida having less than 2.0 ppm. Those States left blank were not sampled. The distribution of DDT residues (DDTR) is shown in Fig. 2. Once again, the key indicates the range of residues for each of the class intervals. A similar map for diel- drin residues is presented in Fig. 3. The mean residue levels, the percent positive sites, and the range of residue levels for the 12 States with the highest arsenic residues are shown in Table 5. Residue data for the five States with the highest DDTR residues are presented in Table 6. Although Michigan had a mean residue of 2.09 ppm and a range of 0.01 to 78.36 ppm, only 23.5% of the samples had detectable residues, indicating that the residues were not widely distributed. By contrast, Mississippi had a mean residue of 2.06 ppm with 89.7% of its sites having detectable residues and a narrower range (0.03 to 13.14 ppm). Al- though the range was narrower, pesticide residues were more widely distributed in Mississippi than in Michigan. The seven States wth the highest dieldrin residues are listed in Table 7. The highest mean residue level. 0.11 ppm. was found in Illinois, with 61.3% of the sites hav- ing detectable residues. In general, the other si.\ States tended to have mean residues approximating one an- other, 0.06, 0.07, or 0.08 ppm. PESTICIDE USE RECORDS When soil samples were collected, an attempt was made to determine what pesticides had been used on the sites for the year of sampling. The summary tables for the use records show the percent of times a pesticide was 198 Pesticides Monitoring Journal FIGURE 2. — DDTR residues in cropland soil FIGURE 3.- — Dieldrin residues in cropland soil Vol. 6, No. 3, December 1972 199 used, the average application rate expressed in pounds per acre of the active ingredients, and the average amount applied per site. The average amount per site was determined by dividing the total amount of active ingredient of a pesticide used by the total number of sites surveyed. Table 8 shows 130 different pesticides reported to have been used on cropland in the year of sampling. Those most commonly used were atrazine, captan, 2,4-D, malathion, and methylmercury dicyandiamide. Technical DDT was used on 3.44% of the sites, aldrin on 4.16% of the sites, and dieldrin on 1.19% of the sites. On noncropland sites 2,4-D, malathion, and mirex were reported to have been used (Table 9). However, these should not be considered the only pesticides used on noncropland sites. In general, records of treatment of noncropland sites are less accurate than those kept for cropland. The breakdown of pesticide usage by in- dividual States for cropland and noncropland soils, respectively, are shown in Tables 10 and 11. Of the 43 States with cropland soil analyzed, use records for 4 showed no pesticides used on the sampling sites: Nevada (2 sites); New Hampshire {2 sites); Vermont (5 sites); and Wyoming (17 sites). Of the 11 States with noncropland soil analyzed. 8 reported no pesticides used on the sampling sites: Arizona (43 sites); Iowa (7 sites); Maine (11 sites); Maryland (3 sites); Virginia (14 sites); Washington (1 1 sites); West Virginia (9 sites); and Wyoming (37 sites). Because of the number of States and pesticides presented in Tables 10 and 11, it is difficult to make all possible comparisons between the use patterns indicated and the detected residues shown in Tables 3 and 4. There- fore, comparisons have been restricted to those States having the highest residues as shown in Figs. 1, 2, and 3 (arsenic. DDTR. and dieldrin, respectively). Table 12 compares those States having the highest arsenic residues with the average amount applied per site and the percent of sites which reported using an arsenic compound. The amount of arsenic applied did not seem to be directly related to the amount detected in the soil. Arkansas, Kentucky, North Dakota, and Ohio reportedly used no arsenic compounds, whereas New England, New York, and Pennsylvania reported using sodium arsenite and lead arsenate. The application rates were below the detected residue levels, and the percent of times used was below the percent of times residues were detected. It also must be considered that the application rates were for the active ingredients of sodium arsenite and lead arsenate, and not for elemental arsenic alone. A fair assumption would be that most arsenic residues detected in cropland soils probably resulted from natural levels of arsenic. A similar comparison for the five States with the high- est DDTR residues is found in Table 13. It is interesting to note that use records for four of the States listed (California, Michigan, Mississippi, and South Carolina) indicate that the amount applied was less than the mean level detected in the soil. Also, in all five States, the per- cent of sites positive for DDTR was approximately three or four times greater than the percent of sites reportedly treated with DDT. Unlike arsenic, the residues of DDTR could only result from the use of DDT either in the year of sampling or in previous years. Table 14 lists the seven States with the highest dieldrin residues. In most cases, the average amount of aldrin/ dieldrin applied approximated the mean residue of diel- • drin detected in the soil, but the percent of sites re- portedly treated with dieldrin or aldrin was always con- sideably less than the percent of sites with dieldrin residues. This wider distribution of dieldrin residues, when compared to use records for the year of sampling, probably indicates residues from previous years. PESTICIDE FREQUENCY DISTRIBUTION The statistics discussed thus far, namely the mean, the range, and the percent of sites at which residues were detected, do not describe their distribution. To describe this distribution, probit analysis was used. The residue levels were ranked from lowest to highest, accumulated, and the percentages computed. The residues were trans- formed to logarithms, the percentages to probits, and the relationship between the logarithms of the residues and the probits of the accumulated percentages was calculated by regression analysis. The computer program used was that of Daum. (5); the theory and techniques as applied in the cited reference were modified slightly. The residue levels at the fiftieth percentile f)oint (median) for the individual pesticides in soil for each State along with the upper and lower 95% fiducial limits are presented in Table 15. For example, in the State of Alabama, the fiftieth percentile point (median) for arsenic was 4.09 ppm. Thus, 50% of the sites had residues less than 4.09 ppm. The upper and the lower fiducial limits of the residues establish the 95% confi- dence interval about the residue value for the fiftieth percentile. It should be noted that the mean for a particular State is not the same as the fiftieth percentile point (median) from the frequency distribution. For example, the mean level of arsenic for Alabama was 6.1 ppm, while the frequency distribution indicated 4,09 ppm for the fiftieth percentile point. This is an example of the fact that residue data are not normally distributed and the mean and median are not identical. Not all pesticides are shown for all States. A cutoff point of six or more pairs of observations was used to eliminate 200 Pesticides Monitoring Journal situations where there were too few observations to calculate a reliable distribution. Space did not permit printing tables showing distribution of pesticide residues for percentiles other than the fiftieth. CROPPING REGIONS ANALYSIS The data were grouped by counties into various crop- ping regions, and these are shown in Tables 16 and 17. The boundaries for the various cropping areas were based on a major land-use map of the United States compiled by F. J. Marschner of the U.S. Department of Agriculture, Bureau of Agricultural Economics, 1950. No effort was made to make a land-use division within counties. This resulted in a good definition of the larger land-use areas such as the corn belt and cotton-growing areas. The land in the United States was grouped into several major land-use areas — corn, cotton, general farming, hay, small grain, vegetables, and fruit. In some cases, two areas overlapped. Irrigated land was deter- mined from information obtained at the time of sample collection in this study. It is of interest to make a few individual comparisons between the cropping regions and the national means. For example, note that in the corn region, aldrin oc- curred 23.5% of the time (Table 17) with a mean residue level of 0.05 ppm (Table 16). However, nationally, aldrin only occurred 10.9% of the time with a mean level of 0.02 ppm (Table 1), an indication of the heavier use of aldrin in the corn region. But, in the corn region, the mean residue level of DDTR was 0.14 ppm which is well below the national mean of 0.31 ppm. The vegetable and fruit cropping region had the high- est level of DDTR, over two times higher than the next highest cropping region and over six times higher than the national mean for DDTR. This might result from a high use of DDT in various orchard operations. The next highest residue was found in the cotton and vege- table region, with approximately equal amounts de- tected between them. The rest of the amounts of DDT in the cotton and general farming, general farming, hay and general farming, and irrigated land were simi- lar to one another. The two areas with the least amount of DDTR in the soil were the corn and small grains cropping regions. The corn, vegetable, and vegetable and fruit cropping regions had the heaviest residues of dieldrin. Residues of dieldrin in the other cropping regions were either equal to or below the mean residues detected for all States (Table 1). The cotton cropping region had the highest toxaphene residues. The cotton and general farming and general farming cropping regions had residue levels of about half those detected in the cotton cropping region. Acknowledgment It is not possible to list, by name, all the people who contributed to this study; however, special mention is made of the staff at the Monitoring Laboratory, Mis- sissippi Test Facility, Bay St. Louis, Miss., who proc- essed and analyzed the samples for chemical residues and contributed immeasurably to this study and of the in- spectors from the Animal Plant Health Inspection Service (APHIS) who collected the samples. Finally, recognition is due Dr. Edwin Cox, Biometrical Services Staff. USDA, for the sample allocation procedures and to Dr. Richard Daum of the Animal Plant Health In- spection Service, USDA. for the probit analyses. See Appendix for chen paper. al names and compounds discussed in this LITERATURE CITED f/)Pestic. Monit. J. 1967. Ul):l-22. (2) Pestic. Monit. J. 1971. 5(1):35-71. (3) Wiersma, G. B.. P. F. Sand, and E. L. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(I):63-66. (4) Woodham. D. W.. W. G. Mitchell. C. D. Loftis, and C. W. Collier. 1971. An improved gas chromatographic method for the analysis of 2,4-D free acid in soil. J. Agric. Food Chem. 19(1): 186-188. (5) Daum, R. L.. 1970. Revision of two computer programs for probit analysis. Bull. Entomol. Soc. Am. 16:10-15. Vol. 6, No. 3, December 1972 201 TABLE 3. — Pesticide residues in cropland soil from 43 Stales — FY 1969 Number of Samples Analyzed ' Number of Positive Samples Percent Positive Sites = Mean Residue Level (PPM) Range of Detected Residues (PPM) Arsenic Chlordane o,p'-DDE p,p'-DDE o.p'-DDT P.P'-DDT DDTR Dieldrin Endrin Hepiachlor Heptachlor epoxide Lindane D.p'-TDE P.P-TDE Toxaphene Trifluralin 86.4 72.7 90.9 90.9 22.7 59.1 27.3 31.8 6.11 0.04 <0.01 0.17 0.09 0.78 1.13 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.07 0.69 0.01 0.70-28.60 0.07-0.62 0.01 0.01-0.72 0.01-0.65 0.02-6.60 0.05-8.08 0.01-0.14 0.03-0.05 0.01 0.01-0.04 0.01 0.08 0.01-0.73 0.68-4.95 0.01-0.08 Arsenic 8 8 100.0 6.58 2.82-9.97 o,p'-DDE 8 4 50.0 0.02 0.01-0.07 P,P-DDE 8 8 100.0 0.46 0.06-0.84 o.p'-DDT 8 5 62.5 0.07 0.08-0.17 P.p'-DDT 8 7 87.5 0.20 0.03-0.57 DDTR 8 8 100.0 0.76 0.06-1.56 Endosulfan (I) 8 1 12.5 0.03 0.24 Endosulfan (II) 8 1 12.5 0.07 0.53 Endosulfan sulfate 8 1 12.5 0.04 0.29 Endrin 8 3 37.5 0.07 0.10-0.22 Endrin ketone 8 2 25.0 0.01 0.01-0.07 P,p'-TDE 8 2 25.0 0.01 0.03-0.06 Toxaphene 8 6 75.0 1.09 0.57-4.27 Trifluralin 8 I 12.5 0.02 0.13 Aldrin 47 7 14.9 <0.01 0.01-0.06 Arsenic 47 47 100.0 8.98 1.70-28.25 o,p--DDE 47 5 10.6 0.01 0.01-0.07 P,p'-DDE 47 32 68.1 0.24 0.01-2.81 o.p'-DDT 47 22 46.8 0.07 0.01-1.11 p.p'-DDT 47 32 68.1 0.29 0.01-3.28 DDTR 47 34 72.3 0.67 0.03-7.20 Dieldrin 47 12 25.5 0.02 0.01-0.24 Endrin 47 5 10.6 0.01 0.01-0.29 Endrin ketone 47 2 4.3 <0.01 0.10^.13 P,P'-TDE 47 27 57.5 0.07 0.01-1.19 Toxaphene 47 8 17.0 0.27 0.32-3.40 Trifluralin 47 4 8.5 0.01 0.01-0.20 CALIFORNIA Aldrin 65 1 1.5 <0.01 0.03 Arsenic 65 65 100.0 5.15 0.74-23.67 Carbophenothion 17 1 5.9 0.01 0.23 Chlordane 65 2 3.1 0.01 0.10-0.32 DCPA 65 1 1.5 0.01 0.54 o,p'-DDE 65 24 36.9 0.01 0.01-0.14 202 Pesticides Monitoring Journal TABLE 3. — Pesticide residues in cropland soil from 43 States — FY 1969 — Continued Number of Samples Analyzed' Number of Positive Samples Percent PosrrivE Sites = Mean Residue Level (PPM) Range of Detected Residues (PPM) CALIFORNIA— Continued p,p'-DDE 65 55 84.6 0.37 0.01-5.93 o,p'-DDT 65 32 49.2 0.08 0.01-1.33 p,p'-DDT 65 48 73.9 0.54 0.01-11.09 DDTR 65 55 84.6 1.47 0.01-41.81 Diazinon 17 1 5.9 <0.0I 0.02 Dicofol 65 6 9.2 0.02 0.03-1.07 Dieldrin 65 20 30.8 0.02 0.01-0.31 Endosulfan (I) 65 I 1.5 <0.01 0.01 Endosulfan (11) 65 5 7.7 <0.01 0.01-0.09 Endosulfan sulfate 65 5 7.7 0.01 0.02-0.15 Endrin 65 9 13.9 0.01 0.01-0.16 Heptachlor epoxide 65 8 12.3 <0.01 0.01-0.03 Lindane 65 2 3.1 <0.01 0.02 Ethyl parathion 17 1 5.9 <0.01 0.02 o.p'-TDE 65 13 20.0 0.09 0.01-4.52 p,p'-TDE 65 40 61.5 0.38 0.01-20.13 Toxaphene 65 10 15.4 0.16 0.16-2.07 Trifluralin 65 7 10.8 <0.01 0.0 1-0. 10 COLORADO Aldrin 60 1 1.7 <0.01 0.02 Arsenic 58 58 100.0 4.60 1.78-9.46 p,p'-DDE 60 7 11.7 0.01 0.01-0.17 o,p'-DDT 60 2 3.3 <0.01 0.01-0.03 p,p'-DDT 60 5 8.3 0.01 0.01-0.22 DDTR 60 8 13.3 0.01 0.01-0.42 Dieldrin 60 5 8.3 0.01 0.01-0.61 Endrin 60 3 5.0 <0.01 0.01-0.02 Endrin ketone 60 1 1.7 <0.01 0.05 p,p'-TDE 60 1 1.7 <0.01 0.01 CONNECTICUT Arsenic 2 2 100.0 3.96 2.33-5.59 p.p'-DDE 2 1 50.0 0.01 O.OI p,p'-DDT 2 1 50.0 0.03 0.05 DDTR 2 1 50.0 0.03 0.06 Dieldrin 2 1 50.0 0.01 0.01 DELAWARE Arsenic 3 3 100.0 2.97 0.95-5.88 p,p'-DDE 3 1 33.3 <0.01 0.01 DDTR 3 1 33.3 <0.01 0.01 Dieldrin 3 1 33.3 <0.01 0.01 Aldrin Arsenic Chlordane o,p'-DDE P.p'-DDE o,p'-DDT P.P'-DDT DDTR 50.0 II. 1 72.2 50.0 77.8 77.8 0.03 0.77 0.36 O.OI 0.25 O.IO 0.37 0.85 0.47 0.25-3.08 0.04-3.32 0.03-0.06 0.01-2.40 0.01-0.98 0.01-2.08 0.01-5.03 Vol. 6, No. 3, December 1972 203 I TABLE 3. — Pesticide residues in cropland soil from 43 Stales — FY 1969 — -Continued Number of Samples Analyzed ' Number of Positive Samples Percent PosiTivr Sites = Mean Residue Level (PPM) Range of Detected Residues (PPM) FLORIDA— Continued Diazinon 5 1 20.0 0.03 0.15 Dieldrin 18 7 38.9 0.08 0.01-0.52 Endrin 18 2 11.1 0.03 0.13-0.38 Endrin aldehyde 18 1 5.6 <0.01 0.03 Endrin ketone 18 1 5.6 <0.01 0.03 Ethion 5 1 20.0 0.01 0.03 Heptachlor 18 1 5.6 <0.01 0.05 Heptachlor epoxide 18 3 16.7 0.01 0.01-0.07 Ethyl parathion 5 2 40.0 0.60 0.01-3.01 o,p'-TDE 18 1 5.6 0.02 0.34 p.p'-TDE 18 11 61.1 0.11 0.01-0.64 Toxaphene 18 2 11.1 l).08 0.62-0.77 Trifluralin 18 ' 5.6 <0.01 0.03 Arsenic Chlordane 2.4-D o,p-DDE P.p'-DDE o.p-DDT P,P'-DDT DDTR DEF Dieldrin Endrin Heptachlor epoxide PCNB o,p'-TDE p.p'-TDE Toxaphene Trifluralin 90.9 59.1 36.4 13.6 2.61 0.01 <0.0I 0.01 0.18 0.09 0.56 0.96 0.01 <0.01 0.02 <0.0I 0.03 0.02 0.10 0.60 <0,01 0.37-10.72 0,19 0.01 0.01-0.08 0.01-1.04 0.01-0.73 0.01-4.64 0.01-6.31 0.12 0.01-0.03 0.42 0.02 0.69 0.34 0.01-1.23 0.43-5.63 0.02-0.04 Arsenic Chlordane p.p'-DDE o,p'-DDT p.p'-DDT DDTR Dieldrin Heptachlor epoxide o.p'-TDE p.p'-TDE Trifluralin 24.2 18.2 24.2 24.2 3.22 <0.0I 0.01 0.01 0.04 0.07 0.01 <0.01 <0.01 0.01 0.01 0.47-8.58 0.03-0.07 0.01-0.09 0.01-0.13 0.01-0.67 0.02-1.03 0.03-0.11 0.01 0.01 0.01-0.15 0.01-0.24 Aldrin Arsenic Atrazine Chlordane p.p'-DDE o,p'-DDT P,p-DDT DDTR 42.3 100.0 25.4 11.3 0.13 8.05 <0.01 0.23 <0.01 <0.01 <0.01 0.01 0.01-2.24 1.54-33.40 0.02-0.10 0.02-5.20 0.01-0.05 0.01-0.02 0.01-0.06 0.01-0.29 204 Pesticidbs Monitoring Journal TABLE 3. — Pesticide residues in cropland soil from 43 Stales — FY 1969 — Continued Number of Number of Percent Mean Residue Range of Compound Samples Positive Positive Level Detected Residues Analyzed ' Samples Sites = (PPM) (PPM) ILLINOIS— Continued Dieldrin 142 87 61.3 0.11 0.01-1.42 Heptachlor 142 31 21.8 0.03 0.01-0.59 Heptachlor epoxide 142 36 25.4 0.02 0.01-1.08 Isodrin 142 2 1.4 <0.01 0.02 o,p-TDE 142 1 0.7 <0.01 0.06 p,p'-TDE 142 5 3.5 <0.01 0.01-0.16 Trifluralin 142 2 1.4 <0.01 0.05-0.16 INDIANA Aldrin 78 13 16.7 0.07 0.01-3.06 Arsenic 78 78 100.0 7.88 1.28-19.65 Chlordane 78 4 5.1 0.02 0.07-0.53 p,p'-DDE 78 I 1.3 <0.01 0.03 o,p-DDT 78 2 2.6 <0.01 0.01-0.03 p.p-DDT 78 2 2.6 <0.01 0.02-0.09 DDTR 78 2 2.6 <0.01 0.06-0.14 Dieldrin 78 21 26.9 0.03 0.01-0.58 Heptachlor 78 2 2.6 <0.01 0.02-0.08 Heptachlor epoxide 78 I 1.3 <0.0I 0.02 Isodrin 78 1 1.3 <0.01 0.03 p.p-TDE 78 2 2.6 <0.01 0.01 Trifluralin 78 1 1.3 <0.01 0.03 IOWA Aldrin 151 48 31.8 0.04 0.01-1.37 Arsenic 152 152 100.0 7.51 0.86-107.45 Atrazine 48 13 27.1 0.05 0.01-1.55 Chlordane 151 32 21.2 0.13 0.04-6.30 p,p'-DDE ISl 21 13.9 0.01 0.01-0.18 o.p'-DDT 151 6 4.0 <0.01 0.01-0.05 p.p-DDT 151 23 15.2 0.01 0.01-0.34 DDTR 151 25 16.6 0.03 0.01-0.60 Dieldrin 151 81 53.6 0.06 0.01-0.42 Heptachlor 151 14 9.3 0.02 0.01-0.97 Heptachlor epoxide 151 31 20.5 0.01 0.01-0.33 Isodrin 151 2 1.3 <0.01 0.01-0.02 o,p'-TDE 151 I 0.7 Number of Positive Samples Percent Positive Sites = AN Residue Level (PPM) Range of Detected Residues (PPM) MICHIGAN— Continued Dieldrin 11 21.6 0.05 0.01-1.01 Endosulfan (I) 2 3.9 0.01 0.03-0.24 Endosulfan sulfate 2 3.9 0.02 0.25-0.94 Endrin 1 2.0 <0.0I 0.01 p,p-TDE 5 9.8 0.65 0.02-31.43 MISSISSIPPI Arsenic 30 30 100.0 5.70 1.10-16.90 o.p'-DDE 29 9 31.0 0.01 0.01-0.08 p.p'-DDE 29 26 89.7 0.31 0.01-1.43 o,p'-DDT 29 22 75.9 0.20 0.02-1.35 p.p-DDT 29 26 89.7 1.36 0.01-9.28 DDTR 29 26 89.7 2.06 0.03-13.14 Dieldrin 29 10 34.5 0.01 0.02-0.10 Endrin 29 1 3.5 0.01 0.19 Endrin ketone 29 1 3.5 <0.01 0.1 1 Lindane 29 2 6.9 <0.01 0.01-0.04 o,p-TDE 29 2 6.9 0.03 0.33-0.49 p.p-TDE 29 20 69.0 0.15 0.01-0.81 Toxaphene 29 14 48.3 0.78 0.10-8.80 Trifluralin 29 6 20.7 0.02 0.02-0.25 Aldrin Arsenic Chlordane P.p-DDE o,p-DDT p,p-DDT DDTR Dieldrin Endrin Heptachlor Heptachlor epoxide Isodrin Toxaphene Trifluralin 22.0 98.8 0.05 5.99 0.03 <0.01 <0.01 <0.01 <0.01 0.04 <0.01 <0.01 <0.01 <0.01 0.04 <0.01 0.01-1.59 0.49-24.51 0.17-0.60 0.01 0.01-0.02 0.02-0.09 0.03-0.12 0.01-0.55 0.01 0.01-0.04 0.01-0.06 0.03 3.15 0.02-0.10 Aldrin 106 2 1.9 <0.01 0.01 Arsenic 106 106 100.0 5.81 0.33-15.80 Atrazine 72 12 16.7 <0.01 0O1-O.12 Chlordane 106 11 10.4 0.0 1 0.03-0.18 p,p-DDE 106 14 13.2 0.01 0.01-0.10 o.p-DDT 106 6 5.7 <0.01 0.01-0.08 p,p-DDT 106 12 11.3 0.01 0.01-0.19 DDTR 106 16 15.1 0.01 0.02-0.31 Dicofol 106 2 1.9 <0.01 0.10 Dieldrin 106 37 34.9 0.02 0.01-0.19 Endrin 106 1 0.9 <0.01 0.02 Heptachlor 106 1 0.9 <0.01 0.01 Heptachlor epoxide 106 12 11.3 <0.01 0.01-0.03 Malathion 2 1 50.0 0.18 0.36 p,p-TDE 106 4 3.8 <0.01 0.01-0.05 Vol. 6, No. 3, December 1972 207 TABLE 3. — Pesticide residues in cropland soil from 43 States — FY 1969 — Continued Number of Samples Analyzed ' Number of Positive Samples Percent Positive Sites = Mean Residue Level (PPM) Range of Detected Residues (PPM) NEW HAMPSHIRE Arsenic 2 2 lOO.O 5.35 t. 31-9.38 p,p'-DDE 2 I 50.0 0.02 0.03 DDTR 2 ' 50.0 0.02 0.03 NEW JERSEY Arsenic 5 100.0 11.72 4.55-17.21 o,p'-DDE 5 20.0 ■CO.OI 0.02 P.p'-DDE 5 40.0 o.n 0.18-0.66 o,p'-DDT 5 20.0 0.06 0.28 p,p'-DDT 5 40.0 0.24 0.05-1.17 DDTR 5 40.0 0.55 0.26-2.48 Dieldrin 5 40.0 0.05 0.05-0.21 Endosulfan (II) 5 20.0 <0.01 0.02 Endosulfan sulfate 5 20.0 0.02 0.11 Heptachlor epoxide 5 20.0 <0.0I 0.01 Lindane 5 20.0 0.01 0.03 Ethyl parathion 1 lOO.O 0.02 0.02 o,p'-TDE 5 20.0 0.02 0.09 p,p'-TDE 5 2 40.0 0.06 0.03-0.26 NEW MEXICO Arsenic 10 10 100.0 4.64 0.66-15.82 P.p'-DDE 10 4 40.0 0.02 0.01-0.11 o,p'-DDT 10 1 10.0 <0.01 O.OI p,p'-DDT 10 4 40.0 0.01 0.01-0.03 DDTR 10 4 40.0 0.02 0.02-0.15 Dieldrin 10 1 10.0 <0.01 0.01 NEW YORK Arsenic Chlordane o,p'-DDE p.p'-DDE o,p'-DDT P,p'-DDT DDTR Dieldrin Endrin Endrin ketone Lindane Methoxychlor o,p'-TDE p,p-TDE 39.5 29.0 34.2 39.5 34.2 9.38 0.08 <0.01 0.23 0.07 0.53 0.91 0.05 0.01 <0.01 0.01 0.01 0.01 0.07 1.24-43.90 3.19 0.01-0.06 0.01-3.70 0.01-1.45 0.02-7.67 0.01-13.29 0.01-0.96 0.56 0.05 0.01-0.23 0.28 0.06-0.37 0.01-1.49 NORTH CAROLINA Aldrin 31 3 9.7 0.05 0.01-1.12 Arsenic 27 27 100.0 6.18 0.73-22.00 Chlordane 31 1 3.2 <0.01 0.11 208 Pesticides Monitoring Journal TABLE 3. — Pesticide residues in cropland soil from 43 Stales — FY 1969 — Continued Number of Samples Analyzed • Number of Positive Samples Percent PosmvE Sites - AN RESIDLT Level (PPM) Range of Detected Residues (PPM) NORTH CAROLINA— Continued o,p-DDE p.p-DDE o.p-DDT p,p-DDT DDTR Djeldrin Endrin Heptachlor Heptachlor epoxide Isodrin Ethyl parathion o,p-TDE p,p'-TDE Toxaphene Trifluralin 19.4 71.0 45.2 61.3 71.0 32.3 16.7 35.5 61.3 22.6 <0.01 0.08 0.07 0.28 0.53 0.08 <0.0I <0.01 <0.01 <0.01 <0.01 0,03 0.07 0.28 <0.0I 0.01-0.03 0.01-0.44 0.03-0.83 0.01-1.75 0.02-2.88 0.01-1.53 0.01-0.08 0.01-0.02 0.01-0.03 0.01 0.02 0.03-0.17 0.01-0.27 0.34-3.20 0.03-0.11 NORTH DAKOTA Aldrin Arsenic Chlordane p.p'-DDE o.p'-DDT P.P-DDT DDTR Dieldrin Endrin Heptachlor epoxide p.p-TDE <0.01 8.50 <0.01 <0.01 <0.0I 0.01 0.01 ^0.01 <0.01 <0.01 <0.01 0.03 0.98-37.53 0.08-0.15 0.01-0.14 0,01-0.19 0.01-0.56 0.01-0.95 0.01-0.20 0.01 0.02-0.07 0.01-0.06 Aldrin 68 10 14.7 0.03 0.01-0.74 Arsenic 69 69 100.0 11.23 1.15-41.49 Chlordane 68 4.4 0.01 0.01-0.71 o,p-DDE 68 1.5 <0.01 0.20 P.P'-DDE 68 11 16.2 0.03 0.01-1.77 o.p-DDT 68 2.9 0.01 0.19-0.22 p.p-DDT 68 8.8 O.M 0.01-1.27 DDTR 68 11 16.2 0.08 0.01-3.38 Dieldrin 68 19 27.9 0.02 0.01-0.30 Endosulfan (1) 68 1.5 <0.0I 0.07 Endosulfan (11) 68 1.5 <0.OI 0.29 Endosulfan sulfate 68 1.5 0.01 0.40 Heptachlor 68 2.9 <0.0I 0.01 Heptachlor epoxide 68 1.5 <0.01 0.01 Isodrin 68 2.9 <0.01 0.01-0.03 Lindane 68 1.5 0.01 0.35 P.p-TDE 68 4.4 <.0005 Corn silage .0098 .0047 .0061 .0028 .0032 .0038 .0014 .0021 Com soil ^ .4507 .3590 .2583 .0095 .0008 .0006 .0027 .0013 Soybean feed = '.0062 5 .0133 5.0444 5 .0458 5.0081 •.0064 Concentrate feed ' .0024 .0011 .0007 .0009 .0008 .0038 .0051 .0009 '.0017 .0010 <.0005 .0009 Commercial protein supplement .0030 .0037 <.0005 .0037 .0016 .0038 <.0005 .0052 Permanent pastures 6-inch composite core Surface sample " .0251 .0397 .0173 .0277 .0009 .0081 .0046 .0104 <.O0O5 .0065 <.0005 .0109 Soil average for all fields » .3859 .2183 .3558 .3153 .3515 .1344 .0219 .0566 .0047 .0009 .0020 .0010 NOTE: Residues of heptachlor, heptachlor epoxide, DDT, and DDE found only at trace levels in some samples. Residues of aldrin found at trace levels in some soil samples. Each of the 12 water samples, one from each farm, had a dieldrin level of <.0005 ppm. ' Dry lot operation. = Soil samples taken with a standard soil sampling probe to a depth of 6 inches. ' Purchased, no field history. * Soybean meal. "' Roasted soybeans. ** Made from home-grown com and oats plus commercial protein supplement and minerals. ' Commercial concentrate feed. » Sampled May 25, 1971. » Represents an average of residue levels in 6-inch soil samples from every field on each of the 12 farms. samples as expected. There was a drop in the dieldrin milk residue level on most of the farms between the February 2 and March 17 samplings. Indications are that this general downward trend continued on at least 8 of the 12 farms through the spring and summer months as shown by the September 24 samples. It can be speculated that these findings are attributable to an overall decrease in dieldrin residues in crops and soils, but with a peak being reached during the winter months due to the fol- lowing factors: 1 . November and December are the months of heavy freshening of cattle on these farms. Dry stock and young stock could release higher than normal amounts of dieldrin in thir milk for a time after freshening. 2. Cattle subjected to extremely cold temperatures could draw on body fat reserves (dieldrin storage site) at a faster than normal rate and release greater amounts of dieldrin into their milk. Significant amounts of dieldrin milk residues occurred even on dairy farms (Farms 8 through 12) where no aldrin was used in the 10-year period, 1961-70. Only trace levels of dieldrin existed in the soil on these farms. The dairyman on Farm 7 had used aldrin from 1961 to 1964. Soil residues after 7 years showed just trace levels 236 of dieldrin, and dieldrin milk residues were also low. There is some indication from the data that dairy cattle on a farm having a history of aldrin soil treatments within the last 6 to 7 years will produce milk with dieldrin resi- dues near or above the Food and Drug Administration's current administrative guideline of 0.3 ppm dieldrin in milk (fat basis). Decker, Bruce, and Bigger (5) showed that 75% of the aldrin applied to soil dissipates by the end of the first year. The remaining residue in the form of dieldrin in the soil dissipates more slowly (about 12% per year) with a half-life of 4 years. All the samples of hay and oat straw contained significant levels of dieldrin residues (Table 2). Farms 1 through 6 had slightly higher levels of dieldrin in these materials than Farms 7 through 12. However, the dieldrin in the hay and oat straw on these latter farms could still ac- count for a significant part of the dieldrin residue occur- ring in the milk. Gannon, Link, and Decker [4) demonstrated that dairy cattle fed 0.05 ppm of dieldrin in their total diet produced milk with a dieldrin residue (butterfat basis) of 0.25 ppm. Pesticides Monitoring Journal Roasted soybeans being fed to cattle on Farms 6 and 7 had high dieldrin residues. Significant dieldrin residues were also present in the roasted soybeans from Farm 3, while only trace levels of dieldrin occurred in the roasted soybeans from Farm 8. The two samples of soybean meal obtained from Farms 1 and 12 showed only trace levels of dieldrin. This is to be expected since the oil (main storage site for dieldrin in soybeans) is extracted in the preparation of meal. All soybean feed had been pur- chased. Corn silage, commercial feed concentrates and protein supplements, and the water on all 1 2 farms showed only trace amounts of dieldrin (Table 2). There was no ap- parent correlation between the dieldrin soil residue and the dieldrin residue in the silage. The silage was cut at heights varying from 4 to 7 inches above ground. Farms 1, 2, and 3 had the highest dieldrin soil residues, and the silage on these farms was cut at 4, 7, and 6 inches above ground, respectively. The overall dieldrin milk residue is still increased slightly by feeds with trace residues of dieldrin. In addition, cattle can absorb dieldrin directly through their skin. The amount of dieldrin absorbed by cattle lying on contaminated soil and from consuming dieldrin-contaminated soil is currently not predictable. The soil type, soil moisture level, and other factors would vary greatly the amount of dieldrin cattle obtain directly from the soil. As already pointed out, there is a fivefold increase from the level of dieldrin in the diet to the level of dieldrin occurring in the milk fat. There was no good correlation between the dieldrin soil residues and the dieldrin residues in hay and oat straw (Table 2). Levels of dieldrin in hay and oat straw exceeded 0.01 ppm on all farms including those where no aldrin had been used for at least 10 years. The waxy coating on hay and straw can readily absorb dieldrin; therefore, it is suggested that direct contact with con- taminated ground soil or blowing soil particles could account for the dieldrin residues in the hay and straw. A higher dieldrin soil residue was present at the soil surface than in a 6-inch deep composite core sample in permanent pastures on six farms (Table 2). Aldrin had never been applied to this land, and no soil erosion from adjacent fields had occurred at the sampling sites. This would indicate that soil particles contaminated with dieldrin were transported by the wind to these fields. Cohen and Pinkerton (5) in a study conducted at Cincinnati. Ohio, reported the average monthly dust fall to be 15 tons per square mile. The dust source was from the southern high plains of Texas and contained 0.003 ppm dieldrin. They further stated that the movement of soil particles by air within a localized area is a certainty. Conclusions 1 . The chances of dieldrin residues in milk exceeding the FDA's current administrative guideline of 0.3 ppm (fat basis) are greatest on dairy farms having a history of aldrin soil treatment within the last 6 or 7 years. Therefore, it can be expected that additional herds, but in lessening numbers, will be found producing milk with illegal residues for about 4 to 6 more years. 2. Hay and oat straw supply significant amounts of dieldrin to dairy cattle. In addition, roasted soybeans, a relatively new feed for dairy cattle, could be an im- portant source of dieldrin contamination in milk. 3. Corn silage, commercial feed concentrate, and well water are usually not important sources of dieldrin con- tamination to dair>' cattle. See Appendix for chemical names of compounds discussed this paper. LITERATURE CITED (/) Duggan, R. E. 1967. Chlorinated pesticide residues in fluid milk and other dairy products in the United States. Pestic. Monit. J. l(3):2-7. (2) Kuhlman, D. E., and R. Randell. 1971. Insect situation, 1971. Twenty-third Illinois Custom Spray Operators Training School. Summary of Presentation, p. 66-85. 13) Decker, G. C. W. N. Bruce, and J. H. Bigger. 1965. The accumulation and dissipation of residues resulting from the use of aldrin in soils. J. Econ. Entomol. 58(2):266- 271. (4} Gannon, N., R. P. Link, and G. C. Decker. 1959. Storage of dieldrin in tissues and its excretion in milk of dairy cows fed dieldrin in their diets. J. Agric. Food Chem. 7(12):824-826. (5) Cohen. J. M.. and C. Pinkerton. 1966. Widespread trans- location of pesticides by air transport and rain out. Organic Pesticides in the Environment (Symposia) Am. Chem. Soc: Adv. Chem. Ser. 60:163-176. Vol. 6, No. 4, March 1973 237 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Organochlorine Residues in Estuarine Mollusks, 1965-72 — National Pesticide Monitoring Program^ Philip A. Butler" Part I. General Summary and Conclusions Part II. Residue Data — Individual States SECTION A: SECTION B: SECTION C: SECTION D: SECTION E: SECTION F: SECTION G: SECTION H: SECTION I: SECTION J: SECTION K: SECTION L: SECTION M: SECTION N: SECTION O: ALABAMA CALIFORNIA DELAWARE FLORIDA GEORGIA MAINE MARYLAND MISSISSIPPI NEW JERSEY NEW YORK NORTH CAROLINA SOUTH CAROLINA TEXAS VIRGINIA WASHINGTON ABSTRACT This paper describes the development of the national program for monitoring estuarine mollusks in 15 coastal States and reports the findings for the period 1965-72. The report is presented in two parts: Part I. General Summary and Conclusions, and Part II. Residue Data — Individual States. ' Contribution No. 155 from the Gulf Breeze Environmental Research Laboratory, U.S. Environmental Protection Agency. Gulf Breeze, Fla. 32561, an Associate Laboratory of the National Environmental Research Center, Corvallis, Oreg. ^ Ecological Monitoring Branch, Technical Services Division, Office of Pesticide Programs. U.S. Environmental Protection Agency, Gulf Breeze, Fla. 32561. 238 Analyses of the 8,095 samples for 15 persistent organo- chlorine compounds showed that DDT residues were ubiqui- tous: the maximum DDT residue detected was 5.39 ppm. Dieldrin was the second most commonly detected compound with a maximum residue of 0.23 ppm. Endrin, mirex, toxa- phene, and polychlorinated biphenyls were found only oc- casionally. Results indicate a clearly defined trend towards decreased levels of DDT residues, beginning in 1969-70. At no time were residues observed of such a magnitude as to imply damage to mollusks: however, residues were large enough to pose a threat to other elements of the biota through the processes of recycling and magnification. Pesticides Monitoring Journal Part I. General Summary and Conclusions Introduction Initial investigations of the effects of pesticides on estuarine fauna were undertaken at the Gulf Breeze Laboratory in 1958 to determine if the pesticide lindane might be safely used directly in estuarine waters to con- trol crabs preying on shellfish populations. The un- expected acute toxicity of this chemical, not only to crabs but also to nontarget organisms, revealed by these early experiments prompted a broad investigation of both the direct and indirect effects of persistent synthetic pesticides. The extent of the problem was not known, and the investigators were concerned about the potential harm to estuarine fauna exposed to drainage waters from large river basins where significant quantities of pesticides were used. Marine commercial fisheries were recognized as being especially vulnerable since a major portion of their catch, both in tonnage and dollar value, is made up of estuarine-dependent species. The acute toxicity of a broad spectrum of pesticides was determined under laboratory conditions (14-17). These data, however, could be most useful only if there were information on the actual levels of organochlorines reaching the estuarine environment. Accordingly, a search was undertaken for meaningful tools to measure this type of pollution (6). The decision to use mollusks as bioassay tools was based on the findings of laboratory experiments designed to measure the uptake and flushing rates of an array of organochlorine pesticides under controlled conditions. Various species of mollusks. but primarily the eastern oyster, Crassostrea virginica. were exposed to appro- priate concentrations of pesticides added continuously to a flowing seawater system. Results indicated that oysters detect DDT in the ambient water supply at levels as low as 10 parts per trillion (10^"). By the process of biomagnification, residues of DDT as high as 25 ppm accumulate in oyster tissues within 96 hours at a level of environmental contamination of only 1.0 ppb (/). Oysters tolerate tissue residues of DDT at least as high as 150 ppm without apparent ill effect provided residues are accumulated slowly. However, as little as 0.1 ppm of DDT in the oyster's water supply terminates feeding activities and at summer water temperatures (31 °C) will cause death. Organochlorine residues are flushed rapidly from mol- luscan tissues when the water supply is no longer contaminated. In one experimental series, for example. DDT residues of about 25 ppb in oysters and soft Vol. 6. No. 4, March 1973 clams, Mya arenaria, diminished by 50-90% after a week of flushing in clean water. Consequently, it is possible to learn much about the periodicity of organo- chlorine pollution in estuaries from samples of sedentary species collected at appropriately brief intervals. As a result of these studies, it was possible for the Bureau of Commercial Fisheries to undertake a program for monitoring pesticide residues in estuarine mollusks to determine the extent of organochlorine pollution. The collection of samples was not begun immediately in some areas, while in others, sample collection was terminated at an early date. The program was continu- ously operative, however, from July 1965 through June 1972. In 1971, the Gulf Breeze Laboratory and the monitoring program became a part of the U.S. Environ- mental Protection Agency. The following report describes the 7-year ( 1965-72) data collection and discusses, specifically, the well-defined trends in the magnitude of DDT residues in estuarine mollusks. Except where noted, the term DDT includes the metabolites TDE and DDE. All residue analyses are presented, by State, in Part II of this report. A report summarizing the first 3 years of this program was pub- lished in 1969 (i). Data Interpretation Although the eastern oyster has a wide distribution, it was obvious that some other species might be more available for monitoring in different geographical areas or salinity regimes; thus, different species of mollusks were tested in the laboratory- to determine their relative capabilities in the uptake and retention of organochlorine pollutants (2). Such information is all important for the understanding of these monitoring data. In the tests, all species were exposed to the same hydrographic conditions with low turbidity and a salinity level about 80% that of seawater. It is probable that species accustomed to different ecological conditions would react more efficiently in nature than in the Laboratory. Caution must be exercised in the extrapola- tion of laboratory results to field conditions, and, at best, such data serve only as guidelines for the interpretation of residue levels in monitored samples. In general, any of three species of oysters, four species of mussels and two species of clams were found to be reliable indicators of the magnitude of organochlorine pollution (Table 1). In some areas it was necessary to use the hard clam, M. mercenaria. although it is the least satisfactory of the species evaluated. Under similar 239 laboratory conditions, for example, hard clams ac- cumulated pesticide residues less than half as large as those in oysters. Moreover, the residues were flushed from the clam much more quickly than from the oyster when clean water was restored. Sample Collection and Preparation The management of estuarine molluscan resources is the responsibilir\' of the individual States: therefore, in each coastal area there is a cadre of specialists who are not only interested in estuarine pollution but who also have the knowledge and equipment necessary to collect sheMsh samples. Without the continuing cooperation TABLE 1. — Pelecypod moUusks used to monitor organo- chlorine residues in 15 States — 1965-72 Scientific and Coximon Names of Mollusks Crassoscrea gigas Crassostrea virginicu Osirea lurida Modiolus demlssus Modiolus modiolus Mytilus californianus Mytilus edulis Mercenaria mercenaria Mya arenaria Corbicula fiuminea State Pacific oyster eastern oyster 01>-mpia oyster ribbed mussel northern horse mussel Califomian mussel blue mussel bald clam soft clam Asiatic clam, fresh water Species Collecieb Alabama C. virginica California C. gigas a. lurida M. demissus M. californianus M. edulis C. fiuminea Delaware C. virginica M. demissus M. mercenaria Florida C. virginica Georgia C. virginica Maine M. modiolus M. edulis M. arenaria Maryland C. virginica Mississippi C virginica New Jersey C. virginica New York C. virginica M. demissus M. edulis M. mercenaria U. arenaria North Carolina C. virginica South Carolina C. virginica Texas C. virginica Virginia C. virginica Washington C. gigas 240 of these agencies (see Acknowledgment), this program could not have achieved its objectives. Estuaries with well defined drainage basins and bays that could be considered "nursery areas" for estuarine fauna were selected for monitoring. Some sites were monitored because of suspected pollu- tion problems. To insure continuit>' of data, permitting detection of not only seasonal but yearly trends in pesticide pollution levels, it was essential, too, that the stations selected have shellfish populations large enough for monthly collections over a number of years. Dupli- cate samples of 15 or more mature mollusks were collected and prepared for shipment at about 30-day intervals. About 109f of all samples were analyzed in replicate; the remaining duplicates were discarded after satisfactors- analysis of the sample. Sample collections were interrupted by the loss of shellfish populations to vandals, floods, and hurricanes, but the overall continuity of the data was good. Coverage of coastal estuaries was incomplete in this program because other agencies were monitoring shell- fish in some states, notably Alabama, Louisiana, and Massachusetts. The number of sample collections by State and year is tabulated in Table 2. The original plan was to monitor each area for 5 years so that trends in pesticide residue levels could be detected. The general absence of residues in Washington estuaries, however, prompted an earlier termination of monitoring in that State. In addition to the samples tabulated, about 2,000 miscellaneous samples of other species of vertebrates and invertebrates were collected and analyzed. These fre- quently had more varied pesticide residues and at higher levels than mollusks but are omitted from this report because of difficulty in determining their source. The analysis of all samples by a single laboratory to insure uniformity seemed important in planning the program. Various potential preservatives were examined to find a method for shipping samples without resorting to refrigeration. Eventually, it was discovered that by dehydrating the homogenized tissues of mollusks or other marine animals with a desiccant mixture, the dry samples could be wrapped in aluminum foil and held without refrigeration for 15 or more days without degradation or loss of organochlorine residues (2). This made it possible to ship the samples by regular mail. In practice, samples of 15 or more mature oysters or other mollusks were collected and taken to the cooperat- ing agency's laboratory'. Samples not to be processed immediately could be refrigerated for 2 or 3 days in the shell. If longer storage was necessary, animals were shucked and the undrained meats frozen in mason jars. The shucked meats were homogenized in an electric blender, and approximately 25-g aliquots were blended Pesticides Monitoring Journal with precisely three times their weight of desiccant to yield a total sample weight of about 100 g. Alternate blending and chilling (not freezing) of sample is re- quired to achieve a dry. free-flowing product. The amount of desiccant used depends on the moisture con- tent of the sample. Less desiccant is required for fish (two times body weight), while up to nine times as much desiccant may be used with small samples, plankton for example, to achieve a 100-g final weight of the sample to be processed. The desiccant is made up of about 90% sodium sulfate and 10% Quso (Quso G30. manufactured by Philadelphia Quartz Co., Philadelphia, Pa.), a micro fine precipitated silica. Analytical Procedures Throughout the monitoring program samples were routinely screened for the following substances: aldrin. chlordane, p.p'-DDT, p.p'-TDE (DDD), p.p'-DDE, dieldrin, endrin, heptachlor. heptachlor epoxide, lindane, methoxychlor, mirex. and toxaphene. On the few oc- casions when the o.p' isomers of DDT were detected in quantifiable amounts, they were included with the p.p' residues. On receipt in the laboratory, samples were extracted for 4 hours with petroleum ether in a Soxhlet apparatus. Extracts were concentrated and transferred to 250-mI separatory funnels. The extracts were diluted to 25 ml with petroleum ether and partitioned with two, 50-ml portions of acetonitrile previously saturated with petro- leum ether. The acetonitrile was evaporated just to dry- ness, and the residue eluted from a Florisil column (12). The sample was then identified and quantitated by electron capture gas chromatography. Three columns of different polarity (DC-200, QF-1. and mixed DC-200/QF-1) were used to confirm identification Operating parameters on Varian Aerograph gas chrom- atographs were as follows: Columns: Pyrex glass 6' x '/»" (o.d.) packed with 3TJ. DC-200. 5% QF-1. and a 1:1 ratio of 3% DC-200 and S% QF-1. all on 80/100 mesh Gas Chrom Q Temperatures: Detector — 210° C Injector — 210^ C Oven— 190° C Carrier gas: Prepurified nitrogen at a flow rate of 40 ml/min A few samples were analyzed by thin layer chromatog- raphy. All residues are reported on a wet-weight basis. The lower limit of quantification was 10 ppb. Laboratory tests conducted during the sampling period gave the following recovery rates: p.p'-DDE, 80-85%: p.p'-JDE. 92-95% ; p,p' -DDT, 91-95% . Data in this report do not include a correction factor for percent recovery'. Toxaphene sometimes interfered with the quantification of DDT residues which, in these cases, are reported as approximate values. The lower limit of quantification of toxaphene was 250 ppb. The presence of polychlorinated biphenyls (PCB's) also interfered with the quantifica- tion of DDT residues. In most instances. DDT was calculated as though PCB's were not present. Acquisition TABLE 2. — Summary of sample collections by Stale and year — 1965-72 Statb Principal Species MoNrroRED Number of Sample Collections 1965 1966 1967 1968 1969 1970 1971 1972 Totals Alabama C. virginica 13 20 33 California C. gigas 136 180 167 139 45 75 30 772 Delaware M. mercenaria 16 101 99 71 287 Florida C. virginica 6 80 102 82 44 35 19 6 374 Georgia C. virginica 112 127 124 121 120 60 664 Maine M. arenaria 6 95 89 79 83 44 396 Maryland C. virginica 18 20 26 9 15 88 Mississippi C. virginica 30 71 72 72 63 66 60 36 470 New Jersey C. virginica 23 44 45 39 33 27 8 219 New York M. mercenaria 148 183 175 174 148 143 88 1,059 North Carolina C. virginica 96 201 204 204 124 136 66 1,031 South Carolina C. virginica 72 142 143 145 108 610 Texas C. virginica 53 133 125 93 97 103 95 29 728 Virginia C. virginica 56 117 123 120 112 105 27 9 669 Washington C. gigas 40 218 223 214 695 Total 263 1,293 1,718 1,661 1,287 839 702 332 8,095 Vol. 6, No. 4, March 1973 241 of the appropriate standards permitted the identification of Aroclor 1254® in sainples from California, Florida, Georgia, Texas, and Virginia, and Aroclor 1242® in samples from Virginia. Since 1970, PCB residues have been approximately quantified in samples from Florida and, more recently, from Virginia. There is some question as to how much interference hy PCB's exists in the sample analyses reported in the early years of the monitoring program. At this time there is no way of knowing with certainty. It is considered sig- nificant that in the period 1965-70 there was a 3-S% annual increase in the domestic sale of these chemicals, and total domestic sales in 1970 were more than double sales in 1960; however, PCB residues were identified in samples from relatively few estuaries in 1971. During the course of the program, several States ex- tended the monitoring of their estuaries and collected more samples than the Gulf Breeze Laboratory was equipped to process. Analytical equipment similar to that used at Gulf Breeze was provided to these agencies as well as a manual of operations (Prepared by A. J. Wilson, Jr., Research Chemist, Gulf Breeze Laboratory), to insure similar methodology in analytical techniques. For the first few collections under the new arrangement, samples were split and analyses made by both the State and Federal laboratories. Excellent comparability in data was obtained (13) and thereafter, the State agency sub- mitted only the monthly data reports to the Gulf Breeze Laboratory. Such arrangements were in effect during portions of the monitoring program in California, Georgia, Maine, New York, and Virginia. Data Summaries and Discussion DDT with its analogs was the most commonly identified pesticide and occurred in 63% of all samples analyzed (Table 3). Dieldrin was the second most commonly detected residue with an incidence of 15%. DDT and dieldrin were detected in some samples from all States monitored (Tables 4 and 5). Other organochlorine residues were encountered infrequently and generally at low levels, with the exception of toxaphene. The large number of Georgia samples containing toxaphene re- flects the direct contamination of the marine environ- ment by the effluent from a single manufacturing plant. The incidence of DDT residues varied markedly from one drainage basin to another and was not correlated with the magnitude of the residues. Only in New Jersey and Alabama, for example, did all samples contain detectable residues of DDT, but the size of DDT resi- dues was greater in several other States (Table 4). It is true that in both Alabama and New Jersey, monitored oyster populations were exposed primarily to the runoff from a single, although complex, drainage basin. In other States, samples were collected from several distinct drainage basins. TABLE 3. — Summary of organochlorine residues detected in estuarine moUusks hy State — 1965-72 State Total Number OF Samples Number of Samples with Residues >5 PPB (wg/kg) and Maximum Residue ( ) Detected in PPB (ag/kg) DDT Dieldrin Endrin Mirex Toxaphene PCB'S Alabama 33 33 (616) 6 (21) California 772 712 (3.970) 194 (57) 14 (19) 4 (11,000) 121 Delaware 287 216 (205) 37 (25) Florida 374 230 (5,390) 27 (28) 25 (390) Georgia 664 96 (96) 141 (230) 128 (54,000) 1 16 Maine 396 72 (359) 14 (38) Maryland 88 71 (70) 11 (22) Mississippi 470 285 (135) 19 (20) New Jersey 219 219 (278) 52 (26) 16 New York 1,059 858 (596) 456 (132) North Carolina 1,031 768 (566) 12 (19) South Carolina 610 332 (154) 24 (154) 12 (540) Texas 728 530 (1,249) 134 (87) 22 (32) ' 1 ' 5 Virginia 669 585 (678) 112 (40) 19 (2.800) Washington 695 78 (176) 1 (120) 1 Present but not quantified. 242 Pesticides Monitoring Journal TABLE 4. — Listing of States in order of frequency and maximum value of DDT residues in mollusks TABLE 5. — Listing of States in order of frequency and maximum value of dieldrin residues in mollusks State Frequency OF Resi- DITES (%) State Maximum Value IN PPB Alabama 100 Florida 5,390 New Jersey lOO California 3.970 California 92 Texas 1,249 Virginia 87 Virginia 678 New York 81 Alabama 616 Maryland 81 New York 596 Delaware 75 North Carolina 566 North Caiolina 75 Maine 359 Texas 73 New Jersey 278 Florida 62 Delaware 205 Mississippi 61 Washington 176 South Carolina 54 South Carolina 154 Maine 18 Mississippi 135 Georgia 15 Georgia 96 Washington 11 Maryland 70 NOTE: These comparisons are limited in that the number of samples, number of sampling stations, periods (years) of sampling, and species of mollusks differ for each State. The magnitude of all DDT residues was low compared to residues reported in carnivores such as fish-eating birds. By extrapolation from laboratory' experiments, the monitoring data indicate that, in most cases, estuarine pollution with DDT was intermittent and at levels in the low parts-per-trillion range. In only 38 samples (0.5%) did the residue exceed 1.0 ppm. These samples were collected in California, Florida, and Texas in drainage basins having intensive agricultural development. The single highest residue of 5.39 ppm (DDT-3.7() ppm. TDE-0.76 ppm, DDE-0.93 ppm) was observed in oysters from the Caloosahatchee River drainage basin in Florida where the seasonal pattern of residue fluctuations indicated an agricultural or at least a scheduled use of the pesticide (Fig. 1). It is significant that extensive acreage in this drainage basin was devoted to sugarcane and sweefcorn that would be maturing and receiving fairly heavy applications of pesticides during the peak residue periods indicated in Fig. 1 (R. G. Curtis, 1972. Florida Cooperative Extension Service, personal com- munication). In controlled feeding experiments in the laboratory, from 50 to 100% mortality was observed in small populations of commercial species of shrimp, crabs, and fish fed exclusively diets containing less than 3.0 ppm of /7,p'-DDT (4). In a survey of 7,000 analyses of mollusk samples com- pleted in the period 1965-71, the mean residue com- position was 24% DDT, 39% TDE, and 37% DDE. Exceptions to this average picture were Station 2 in New Jersey where DDT comprised only 4% (mean of 47 samples in 5 years) and Station 18 in Washington where DDT made up 75% of the residues (mean of Vol. 6, No. 4, March 1973 State Frequency OF Resi- dues (%) State Maximum Value IN PPB New York 43 Georgia 230 California 25 South Carolina 154 New Jersey 24 New York 132 Georgia 21 Washington 120 Alabama 18 Texas 87 Texas 18 California 57 Virginia 17 Virginia 40 Delaware 13 Maine 38 Maryland 13 Florida 28 Florida 7 New Jersey 26 Mississippi 4 Delaware 25 South Carolina 4 Maryland 22 Maine 4 Alabama 21 North Carolina 1 Mississippi 20 Washington <1 North Carolina 19 NOTE: These comparisons are limited in that the number of samples, number of sampling stations, periods (years) of sampling, and species of mollusks differ for each State. 36 samples in 3 years). Biotic recycling of persistent residues is usually associated with the high percentages of DDT metabolites found in dominant carnivores. It is of interest that the metabolites were the only residues detected in many of these analyses of filter-feeding mollusks. Results of a study by Johnson el al. (10) indicated that there are some animals, however, such as aquatic insects, in which direct exposures to DDT result in tissue residues that are more than 80% DDE. The large percentage of the parent compound DDT in residues from Washington mollusks does imply a direct contamination of the estuarine environment, perhaps, for insect control. But in general, the percentage distri- bution of DDT metabolites in these samples revealed little about the kinetics of DDT in the estuary. FIGURE 1. — DDT residues in the eastern oyster from the Caloosahatchee River Basin, Lee County, Fla.. by month of collection— 1967 and 1968 243 Trends in DDT Residues Many of the estuaries were monitored over a sufficient period of time to pennit detection of clearly defined trends in DDT residue patterns. Average DDT residue levels detected in the first 2 to 5 years and average levels in the final year of monitoring in each State are pre- sented in Table 6. The overall picture is that of a pronounced decline, about 55%, in the number of samples containing DDT residues in excess of 100 ppb. There was a 20% decrease in the 10-100 ppb range, and a concomitant 44% increase in the number of samples having negligible or undetectable DDT residues. There are important exceptions to this average picture. In California, New York, and Virginia, for example, more samples had residues in excess of 10 ppb in 1971 than in earlier years. On the other hand, the percent of samples having residues higher than 100 ppb declined in these States. It would appear that in some areas, DDT pollution has become more widespread, but has resulted in residues of lower magnitude in the estuarine food web. Since organochlorine residues in mollusks showed a continuing decline in most areas during the years that domestic sales and presumably usage of PCB compounds were increasing, PCB's were not considered to be a significant factor in the early monitoring data. Too few samples from Alabama were analyzed in this program to indicate any trend in residue magnitude. The mean value of 88 ppb of DDT in 33 samples col- lected in 1969-70 may be compared, however, with a mean residue level of 330 ppb in a series of 82 samples of oysters collected in 1965-66 (7). Exact comparisons by States of the data in Table 6 are not valid since in succeeding years there were different numbers of samples and occasionally different species of mollusks collected at the same station. A more critical review of data on DDT residues is possible for 10 sta- tions in North Carolina. These stations were selected for the continuity of sampling of the eastern oyster at monthly intervals for more than 5 years. The number of samples containing less than 1 1 ppb of DDT increased steadily until, in 1971, 76% of all residues were in this category as compared to only 8% in 1966 and 1967. The corresponding decrease in the number of samples containing larger residues is shown in Fig. 2 and Table 7. TABLE 6. — Percent distribution of DDT residues of different magnitude in estuarine mollusks by State — 1965-71 (7,000 samples) Percent Distribution of Samples State <11 PPB 11-100 PPB 101-1,000 PPB > 1,000 PPB First 2 to First 2 to First 2 to First 2 to 5 Years 1971 5 Years 1971 5 Years 1971 5 Years 1971 Alabama 69 31 California 14 7 30 64 51 28 5 1 Delaware 23 30 62 67 15 3 Florida (1 station) 43 100 57 Georgia 85 96 15 4 Maine 82 98 17 2 1 Maryland 19 50 81 50 Mississippi 42 72 56 27 2 1 New Jersey 7 69 74 31 19 New York 26 22 60 74 14 4 North Carolina 22 76 68 24 10 South Carolina 52 82 47 18 1 Texas 34 52 53 45 13 3 <1 Virginia 18 67 95 15 5 Washington (1 station) 92 94 8 6 Mean 39 56 49 39 11 5 <0.5 244 Pesticides Monitoring Journal TABLE 7. — Trends in magnitude of DDT residues in oysters, 10 stations. North Carolina Total Number of Samples <11 PPB 11-100 PPB 101-1,000 PPB Year Number of Percent Samples DisTRiBirrioN Number of Percent Samples Distribution Number of Percent Samples Distribution 1966 60 5 8 45 75 10 17 1967 119 9 8 90 76 20 16 1968 120 26 22 70 58 24 20 1969 120 29 24 77 64 14 12 1970 109 61 56 46 42 2 2 Subtotal S28 130 25 328 62 70 13 1971 115 87 76 26 22 2 2 Percent change in from average fo 1966-70 1971 r +204% -65% -85% 1967 1968 1969 1970 1971 FIGURE 2. — Percent of eastern oyster samples containing more than 10 ppb of DDT, average of monthly samples collected at 10 stations in North Carolina (Numbers in bars indicate total number of samples) Conclusions The data demonstrate that in most estuaries monitored, detectable DDT residues have declined in both number and magnitude in several species of estuarine mollusks in recent years. DDT pollution in many estuaries, as judged by the magnitude of the residues in mollusks, peaked in 1968 and has been declining markedly since 1970. The sensitivity of mollusks to organochlorine pollutants plus the fact that they are filter-feeders warrant the as- sumption that the contribution of particulate DDT to estuaries from one or more primary sources such as drainage basin runoff waters, atmospheric fallout, and persistent reservoirs in bottom sediments, has declined significantly. Vol. 6, No. 4, March 1973 In view of the efficiency of mollusks in detecting and storing residues of the persistent organochlorines. it is clear that relatively low levels of this type of pollution were present in the monitored areas during the period 1965 to 1972. Appropriate correlations of the residue data reported here with available records of drainage-basin discharge rates, precipitation, and hydrographic factors in the various types of estuaries should provide a useful model for predicting the effects of future introductions of un- specified synthetic substances chemically similar to DDT. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Butler, P. A. 1966. Pesticides in the marine environ- ment. L Appl. Ecol. 3(Suppl.): 253-259. (2) . 1968. Pesticide residues in estuarine mollusks. Proc. Natl. Symp. Estuarine PoUut. Stanford University, Stanford, Calif., 1967. p. 107-121. (3) . 1969. Monitoring pesticide pol- lution. BioScience 19(10): 889-891. (4) . 1969. Significance of DDT residues in estuarine fauna, p. 205-220. In Chemical Fallout. Charles C. Thomas, Springfield, 111. (5) Butler. P. A., A. J. Wilson, Jr., and R. Childress. 1972. The association of DDT residues with losses in marine productivity, p. 262-266. In Marine pollution and sea life. Fishing News (Books) Ltd., London, Eng. (6) Butler, P. A., A. J. Wilson, Jr., and A. J. Rick. 1960. Effect of pesticides on oysters. Proc. Natl. Shellfish. Assoc. 51:23-32. (7) Casper, V. L., R. J. Hammerstrom, E. A. Robertson, Jr., J. C. Bugg, Jr., and J. L. Gaines. 1969. Study of chlorinated pesticides in oysters and estuarine environ- ment of the Mobile Bay area. USDHEW, Consum. Prot. Environ. Health Serv. 47 p. (8) Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr. 1970. A polychlorinated biphenyl (Aroclor 1254®) in the water, sediment, and biota of Escambia Bay, Florida. Bull. Environ. Contam. Toxicol. 5(2): 171-180. 245 (9) Foehrenbach, J., G. Mahmood, and D. Sullivan. 1971. Chlorinated hydrocarbon residues in shellfish (Pele- cypoda) from estuaries of Long Island, New York. Pestic. Monit. J. 5(3): 242-247. (10) Johnson, B. T., C. R. Saunders, H. O. Sanders, and R. S. Campbell. 1971. Biological magnification and deg- radation of DDT and aldrin by freshwater inverte- brates. J. Fish. Res. Board Can. 28(5): 705-709. (//) May, E. B. 1971. A survey of the oyster and oyster shell resources of Alabama. Ala. Mar. Resourc. Bull. 4:1-53. (12) Mills, P. A., J. H. Onley, and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Agric. Chem. 46(2): 186- 191. (13) Modin, J. C. 1969. Chlorinated hydrocarbon pesticides in California bays and estuaries. Pestic. Monit. J. 3(1): 1-7. (14) U.S. Department of the Interior. 1962. Effects of pesti- cides on fish and wildlife in 1960. Fish Wildl. Serv. Circ. 143. Washington. D.C. 52p. (15) 1963. Pesticide-wildlife studies: a review of Fish and Wildlife Service investiga- tions during 1961 and 1962. Fish Wildl. Serv. Circ. 167. Washington, D.C. 109p. (16) 1964. Pesticide- wildlife studies 1963: a review of Fish and Wildlife Service investigations during the calendar year. Fish Wildl. Serv. Circ. 199. Washington, D.C. 129p. (17) 1965. The effects of pesti- cides on fish and wildlife. Fish Wildl. Serv. Circ. 226. Washington, D.C. 77p. A cknowledgments I should like to but cannot acknowledge individually the many people in administrative and technical positions whose interest in this program made its efficient conduct possible. It is my pleasure to thank especially Louis D. Stringer, Thomas C. Carver. Chester E. Danes. Anne Gibson, now of the National Marine Fisheries Service, and my secretary, Madeleine Brown, for their continuing cooperation and assistance. We are greatly indebted to the graduate students and technicians whose diligence in the collection and proces- sing of samples made the program a reality. I trust that the results will make them pleased with their participa- tion. The program could not have been developed without the interest and skills of Alfred J. Wilson, Jr., Research Chemist at the Gulf Breeze Laboratory. Lastly, I thank the administrators and professional staffs of the cooperating agencies who kindly let me think that the monitoring program had the number one priority on their busy schedules. In view of the volume of data in this report, it is in- evitable that there are sins of both omission and com- mission. The writer would be most grateful to have these called to his attention so that the record can be appropriately emended. 246 COOPERATING AGENCIES— This alphabetical listing by Slates in- cludes the names of investigators and, where appropriate, chemists and their titles at the time Ihey were participating in the program. Where chemists are not listed, the samples were analyzed at the Gulf Breeze Laboratory under the supervision of Alfred J. Wilson, Jr., with the assistance of Jerrold Forrester and Johnny Knight. The listing of more than one principal investigator or agency in any one State reflects changes talcing place during the monitoring period 1965-72. Operational funds were provided by the LI.S.F.W.S.. Bureau of Commercial Fish- eries (BCF) for the collection of samples and for analytical equipment where contracts are indicated. In States participating by agreement, the BCF provided equipment and chemicals. In 1971-72, the program was jointly funded by the National Marine Fisheries Service (NMFS) and the Environmental Protection Agency. ALABAMA Alabama Marine Resources Laboratory Johnie H. Crance, Director; E. B. May, Principal Investigator. Agreement. CALIFORNIA California Dept. of Fish and Game, Marine Resources Operations Dr. H. C. Orcutt. Laboratory Supervisor; John Modin, Chemist. Contracts. BCF: 14-17-0007- 332: 14-17-0002-211; -265; -337; -532. California Department of Fish and Game, Resources Agency W. H. Griffith, Principal Investigator. Contract, NMFS: N-042-10-72(N). DELAWARE University of Delaware Dr. F. C. Daiber, Principal Investigator. Con- tracts. BCF: 14-17-0002-117; -261; -326. FLORIDA State Board of Conservation Marine Laboratory R. M. Ingle, Director of Research. Agreement. Bureau of Commercial Fisheries — Environmental Protection Agency, Gulf Breeze Laboratory. Dr. T. W. Duke, Director. Agreement. GEORGIA The University of Georgia Dr. T. L. Linton. Principal Investigator. Con- tracts, BFC: 14-17-0002-220; -267. C. J. Durant, Principal Investigator and Chemist. Contracts, BFC: 14-17-0002-344; -454. Dr. R. J. Reimold. Principal Investigator. Con- tract, NMFS: N-042-12-71(N). MAINE Department of Sea and Shore Fisheries L. Varney, Principal Investigator; John Hurst, Laboratory Director and Chemist. Contracts, BCF; 14-17-0007-333; 14-17-0002-206; -263; -332; -434. BCF Biological Laboratory Dr. A. Rosenfield, Principal Investigator. Agree- ment. Gulf Coast Research Laboratory Dr. W. P. Abbott, Principal Investigator. Con- tracts, BCF: 14-17-0002-133; -172; -235; -341. Dr. G. Gunter. Laboratory Director. Contract, NMFS: N-042-ll-71(N). Rutgers — The State University, Oyster Research Laboratory Dr. H. H. Haskin and D. E. Kunkle, Principal Investigators. Agreement. New York State Department of Environmental Conservation D. H. Wallace, Director of Marine Fisheries; J. Foehrenbach, Chemist. Contracts. BCF: 14-17- 0002-163; -219; -268; -345; -455; NMFS: N-042- 14-71(N). University of North Carolina, Institute for Marine Sciences Dr. A. F. Chestnut, Principal Investigator. Con- tracts, BCF: 14-17-0002-182; -239; -343; NMFS: N-042-15-71(N). Bears Bluff Laboratories, Inc. Dr. G. R. Limz, Director (deceased). Contracts, BCF: 14-17-0002-130; -171; -234; -340; -426. TEXAS State of Texas, Parks and Wildlife Department T. R. Leary, Coastal Fisheries Coordinator; R. Childress, Principal Investigator. Agreement. VIRGINIA Virginia Institute of Marine Science Dr. M. L. Brehmer, Principal Investigator; Dr. R. J. Huggett, Principal Investigator and Chemist. Contracts, BCF: 14-17-0002-138; -174; -237; -342; -452; NMFS: N-042-13-71(N). WASHINGTON State of Washington, Department of Fisheries C. Lindsay, R. E. Westley, Principal Investi- gators. Contracts. BCF: 14-17-0002-134; -173; -236. PESTICIDES MONITORING JOURNAL MARYLAND MISSISSIPPI NEW JERSEY NEW YORK NORTH CAROLINA SOUTH CAROLINA Part II. Residue Data — Individual States The following sections present residue data for the 15 coastal States where estuarine mollusks were monitored for organochlorine residues. A map showing sampling sites in the respective States together with a discussion of the findings are included in each section. SECTION A.— ALABAMA Samples of the eastern oyster, Crassostrea virginica. were collected in Alabama at 3-month intervals during 1968- 69 from four commercial reefs in or near Mobile Bay. Samples were processed at the Alabama Marine Re- sources Laboratory and mailed to the Gulf Breeze Laboratory for chemical analysis. Approximate station locations are shown in Fig. A- 1. Stations 1 and 2 on the eastern shore of Mobile Bay are influenced more by the presumably cleaner Gulf of Mexico waters than Stations 3 and 4 which are more exposed to drainage waters from the Alabama-Tombig- bee River Basin. Both Stations 1 and 4 are influenced to an unknown extent by small drainage basins in the coastal areas of Alabama. A summary of data on or- ganochlorine residues in the monitored species, C. virginica, is presented in Table A-1, and the distribution of residues in this species for each sampling station by date of collection in Table A-2. Many of these data have already been published by the cooF>erating agency {10). All 33 samples contained detectable amounts of DDT. but the sampling series was conducted in Alabama for too few years to indicate annua! trends in pollution levels. An earlier study of pesticide residues in Mobile Bay oysters (7) also reported a 100% incidence of DDT in 82 samples analyzed; however, maximum DDT residues at Shell Bank and Cedar Point reefs were 13 and 25 times higher in 1965 than those observed in this study in 1969. Because of differences in sample preparation in the two studies, 1965 residues could be expected to be only about 10% higher than the 1969 data had there been no change in DDT pollution levels in the bay. Alabama and New Jersey were the only States of the 15 monitored in which 100% of the samples contained detectable residues of DDT. The maximum level of DDT in Alabama oysters (616 ppb) was lower than residues found in four other States. Dieldrin residues were small, but the 18% incidence was significantly higher than the average incidence for all States of 15%. The incidence and magnitude of dieldrin residues in the 1965 study (7) were significantly higher. GULF OF MEXICO FIGURE A-1. — Diagram of coastal Alabama showing approximate location of monitoring stations 1. Shellbank — Bon Secour Bay 2. Klondike— Mobile Bay 3. Whitehouse — Mobile Bay 4. Cedar Point Reef — Mississippi Sound TABLE A-L — Summary of data on organochlorine residues in the monitored species (C. virginica), 1968-69 — Alabama Station Number Location Monitoring Period Number of Samples ' Number of Posttive Samples and Maximum Residue ( ) Detected IN PPB (ag/kg) DDT Dieldrin I 2 3 4 SheUbank Klondike White House Cedar Point Occasional stations (2) 1968-69 1968-69 1968-69 1968-69 1968-69 8 8 7 8 2 8 (214) 8 (445) 7 (616) 8 (372) 2 (237) 1 (14) 1 (14) 2 (21) 2 (13) Total number of samples 33 Percent of samples positive for indicated compound 100 18 ■ Each sample represents IS or more mature mollusks. Vol. 6, No. 4, March 1973 247 TABLE A-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Alabama [Blank = no sample collected; — = no residue detected above 5 ppb; T = >5 but <10 ppb] Residues in PPB (/ig/ko) STATION 1— SHELL BANK— 8 SAMPLES' 1968 DDE 110 110 33 TDE 88 52 15 DDT 16 12 - 1969 DDE 48 94 48 26 T TDE 31 70 25 17 T DDT - - - 13 - Dieldrin - 14 - - - STATION 2.— KLONDIKE— 8 SAMPLES' 1968 DDE 230 210 45 TDE 180 130 37 DDT 35 34 12 1969 DDE 120 18 170 73 22 TDE 100 94 110 53 18 DDT - 44 23 62 - Dieldrin - 14 - - - STATION 3.— WHITE HOUSE— 7 SAMPLES' 1968 DDE 320 120 32 TDE 240 57 20 DDT 56 11 - Dieldrin 20 - - 1969 DDE no 15 56 46 TDE 83 98 37 40 DDT - 36 — 36 Dieldrin - 21 - - STATION 4.— CEDAR POINT— 8 SAMPLES' 1968 DDE 180 86 41 TDE 160 51 23 DDT 32 17 23 1969 DDE 84 77 110 26 30 TDE 55 71 78 22 23 DDT - 30 — 26 T Dieldrin - 13 - - T ' Each sample represents 15 or more mature mollusks. 248 Pesticides Monitoring Journal SECTION B.— CALIFORNIA The monthly collection of mollusks to monitor pesticide p>ollution in 12 estuaries in California was initiated in January 1966. Some of these stations were terminated and other estuaries were added during the course of the program. Samples were analyzed at the Gulf Breeze Laboratory until May 1968: from then until May 1970 they were analyzed at the Marine Resources Operations Laboratory of the Department of Fish and Game, Menlo Park, Calif. During the period July 1970 - June 1972, samples were collected and analyzed at approximately 3-month intervals by the Department of Fish and Game, Pesticides Investigations at Sacramento, Calif. Six different mollusks {Crassostrea gigas. Corhicula fiuminea, Modiolus denissus. Mytilus calif orniaiius. Mytilus edulis. and Ostrea lurida) were utilized for monitoring; for the most part, a single species was collected at each station. The relative ability of these different mollusks to store organochlorine residues ap- pears to be reasonably similar and, thus, comparisons of the magnitude of residues in different estuaries can be made with some confidence. In general, residue levels at different stations followed patterns of suspected pollu- tion loading in the associated drainage basin, regardless of the species monitored. The approximate station locations are shown in Fig. B-1. A summary of data on organochlorine residues in the monitored species is presented in Table B-1, and the distribution of residues in these species for each sampling station by date of collection in Table B-2. Results of some of the analyses conducted by the Gulf Breeze Laboratory during the period January 1 966 - December 1967 have been published by the cooperating agency (/i). DDT residues in mollusks were consistently larger in California than in any other area monitored with the exception of a single station in south Florida. There is a clear pattern of maximum pesticide residues being correlated with proximity of the monitoring station to runoff from agricultural lands. In southern California, where most samples contained typically large residues, residues were consistently higher at Hedionda and Mugu Lagoons, the recipients of agricultural runoff waters, than at Anaheim Slough which receives intermittent runoff from the urban and industrialized sections of Los Angeles. Residues in samples from estuaries draining the intensely cultivated central and southern parts of the State were larger, by one order of magnitude usually, than those in samples collected from watersheds north of San Francisco Bay where dairy land predominates. The incidence of dieldrin residues (25%) was second only to New York samples although residues were lower in magnitude than in five other States. California and Texas were the only States where endrin and toxaphene Vol. 6, No. 4, March 1973 . ig \l3 / ] »' k i'^ ft^ 1 'X h- y^ CALIFORNIA 6^ n Francisco Bav ^ 0 JO mi \ \ N \ bV M PACIFIC OCEAN ^~\ 3 \^ 2\ "BOm. 0 FIGURE B-1. — Diagram of coastal California and the San Francisco Bay area showing approximate location of monitoring stations 1. Hedionda Lagoon 2. Anaheim Slough 3. Point Mugu 4. Baywood Park — Morro Bay 5. Los Osos Creek — Morro Bay 6. Elkhorn Slough 7. Coyote Point — San Francisco Bay, South 8. Guadalupe Slough — San Francisco Bay, South 9. Alviso Slough — San Francisco Bay, South 10. West Island — Sacramento-San Joaquin River Basin 1 1 . False River — Sacramento-San Joaquin River Basin 12. Napa River — San Pablo Bay 13. Petaluma River— San Pablo Bay 14. Point San Quentin — San Francisco Bay, North 15. Bolinas Lagoon 16. Schooner Bay — Drakes Estero n. Berries Bay — Drakes Estero 18. Tomales Bay — Tomales Bay 19. Nicks Cove — Tomales Bay 20. Gunther Island— Humboldt Bay 21 . Bird Island — Humboldt Bay from presumably agricultural sources were detected. Polychlorinated biphenyl compounds were detected in samples beginning in 1971, but were not quantified. They occurred in a few samples from nearly all drainage basins monitored. Late in 1970 or early 1971, there was a sharp decline in DDT residues in samples collected in estuaries draining predominantly agricultural areas, i.e., San Francisco Bay and the southern parts of the State. Decreased frequency 249 of sample collection in 1970-71 makes it impossible to pinpoint when this decline in DDT pollution oc- curred. The typically small DDT residues in samples from drainage basins north of San Francisco Bay remained about the same throughout the monitoring period. TABLE B- -Summary of data on organochlorine residues in the monitored species, 1966-72 — California Station Number Location Monitoring Period Principal Monitored Species Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (/ig/kg) DDT DiELDRIN Endrin TOXAPHENE PCB's 2 , Hedionda Lagoon 1967-72 M. edulis 31 31 (3,970) 4 (T) 2 (11,000) 2 2 Anaheim Slough 1967-72 M. edulis 33 33 (833) 10 (31) 1 (T) 2 3 Point Mugu 1967-72 M. edulis 29 29 (1,758) 9 (16) 1 (T) 2 4 Baywood Park 1966-72 C. gigas 52 52 (601) 3 (24) 5 Los Osos Creek 1966-72 C. gigas 52 52 (412) 4 (27) 1 6 Elkhorn Slough 1966-72 C. gigas 57 57 (2,305) 24 (57) 2 (19) 2 7 Coyote Point 1966-72 O. lurida 55 54 (362) 26 (43) 2 (19) I 8 Guadalupe Slough 1968-72 M. demissus 27 25 (407) 9 (37) 1 9 Alviso Slough 1968-72 M. demissus 28 28 (328) 6 (25) 1 10 West Island 1967-72 C. fluminea 28 28 (2,280) 23 (22) 3 (T) I II False River 1967-71 C. fluminea 25 26 (1,850) 12 (24) 1 (18) 12 Napa River 1968-72 M. demissus 28 26 (210) 5 (T) 2 (T) 1 13 Petaluma River 1968-72 M. demissus 28 25 (268) 4 (10) 1 14 Point San Quentin 1966-70 C. gigas 50 49 (440) 22 (23) 15 BoUnas Lagoon 1966-68 C. gigas 17 14 (45) 16 Schooner Bay 1966-72 C. gigas 33 25 (43) 2 (T) I 17 Berries Bar 1966-68 C. gigas 27 25 (44) 1 (19) 18 Tomales Bay 1966-72 C. gigas 34 28 (45) 2 (T) 1 (T) 19 Nicks Cove 1966-68 C. gigas 25 20 (37) 20 Gunther Island 1966-72 C. gigas 33 31 (78) 5 (T) 1 21 Bird Island 1966-68 C. gigas 25 3 (T) Occasional stations (15) 1966-72 Mixed 54 51 (1,144) 25 (26) 2 (1,000) 4 Total nu nber of samples 772 Percent c f samples positive for inc licated compo und 92 25 2 <1 3 NOTE: T = >5 but < 10 ppb. 1 Each sample represents 15 or more matu - Present but not quantified. TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California (Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] Residues in PPB (mo/ko) STATION 1.— HEDIONDA LAGOON— M. EDULIS UNLESS OTHERWISE INDICATED— 31 SAMPLES' DDE TDE DDT Toxaphene M30 = 90 240 84 3,600 740 11,000 970 250 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (ag/kg) Sept. Oct. STATION 1.— HEDIONDA LAGOON— Af. EDVLIS, UNLESS OTHERWISE INDICATED— 31 SAMPLES i— Continued 1968 DDE 130 52 200 210 91 130 120 168 3 105 120 136 TDE 73 31 88 220 103 154 80 171 74 73 58 DDT 920 200 440 300 42 86 59 129 63 120 164 1969 DDE 52 211 242 118 227 95 139 347 466 76 TDE - 207 101 172 124 53 35 99 115 64 DDT 123 291 486 214 99 91 34 61 68 108 1970 DDE TDE DDT Dieldrin 114 102 54 T 1971 DDE TDE DDT Dieldrin PCB's 19 n 16 T 36 58 T 54 56 285 18 13 10 1972 DDE TDE DDT Dieldrin PCB's 14 T 10 T 31 31 10 T «> STATION 2.— ANAHEIM SLOUGH— Af. EDVLIS, UNLESS OTHERWISE INDICATED— 33 SAMPLES' 1967 DDE TDE DDT 360 100 85 330 150 120 200 87 120 1968 DDE 270 ° 110 ' 170 310 464 203 265 432 3 464 440 354 TDE 91 45 62 110 186 102 68 109 127 170 118 DDT 160 43 110 77 108 52 33 51 65 110 70 Dieldrin - 31 - - - T T - - 12 - Endrin - - - - - - T - - - - 1969 DDE 157 273 127 51 388 547 323 466 451 168 494 TDE 37 55 - 136 172 189 107 115 107 129 130 DDT 123 217 94 222 131 97 37 60 64 282 88 1970 DDE TDE 157 49 305 126 VOL. 6, No. 4, March 1973 251 TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB ((ic/kg) Mar. STATION 2.— ANAHEIM SLOUGH— M. EDVLIS. UNLESS OTHERVMSE INDICATED— 33 SAMPLES i— Continued DDE TDE DDT Dieldrin PCB's 75 103 185 92 53 164 10! 41 23 T 22 10 T T T T - - - <« 1972 DDE 64 80 TDE 24 53 DDT 18 10 Dieldrin T T PCB's Ml STATION 3.— POINT MUGU— M. EDVLIS. UNLESS OTHERWISE INDICATED— 29 SAMPLES ^ DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin Endrin DDE TDE 250 230 460 370 170 366 350 180 494 790 430 749 465 = 269 388 278 432 566 '298 116 160 220 230 280 440 650 360 443 955 DDT 161 391 248 120 92 40 580 176 185 1970 DDE TDE DDT «238 141 56 1971 DDE TDE DDT Dieldrin PCB's *49 24 45 T •65 73 11 T •22 T '112 SO 20 T u> 1972 DDE TDE DDT Dieldrin PCB's 1 M 12 T T = 24 ID 10 T 252 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (/ig/ko) STATION 4,— BAYWOOD PARK— C. GIGAS—il SAMPLES' 1966 DDE 54 74 82 75 76 52 55 62 59 69 69 100 TDE 26 34 35 25 32 19 22 25 35 34 33 37 DDT 25 25 26 20 24 14 - 18 26 24 25 46 Dieldrin - - - 24 16 - - - - - - - 1967 DDE 110 110 62 130 80 120 51 82 55 48 35 46 TDE 29 42 50 47 34 49 29 40 23 21 10 13 DDT 58 73 96 130 67 70 37 49 46 26 15 10 1968 DDE 96 43 40 160 48 49 48 48 44 74 TDE 24 13 T 40 17 19 - 13 - - DDT 25 13 30 61 - T T T - - 1969 DDE 123 111 139 180 148 119 110 97 165 184 162 TDE 23 38 - 70 57 40 57 31 53 70 75 DDT 24 164 131 351 189 150 43 31 58 64 69 1970 DDE TDE DDT 220 74 69 226 87 64 215 58 46 56 21 1971 DDE TDE DDT 22 11 21 16 10 1972 DDE TDE DDT Dieldrin 33 12 T T STATION 5— LOS OSOS CREEK— C. GIG AS. UNLESS OTHERWISE INDICATED— 52 SAMPLES' 1966 DDE 83 58 43 88 65 40 43 53 73 10 71 72 TDE 33 27 17 39 25 16 16 22 34 27 33 31 DDT 23 21 14 30 20 - - 14 23 23 25 37 Dieldrin - - - 27 10 - - - - - - - 1967 DDE 62 120 63 110 93 130 64 81 56 43 37 29 TDE 29 47 43 42 57 56 46 44 33 20 14 10 DDT 41 96 130 120 92 80 52 49 72 25 20 12 1968 DDE 100 61 42 70 '65 42 31 25 55 69 TDE 32 21 13 24 T T - 11 T - DDT 37 21 T 36 T - T - - - 1969 DDE 66 70 126 104 155 144 201 115 223 137 TDE T 37 - 56 61 80 83 43 72 51 DDT T 72 131 239 183 188 128 34 93 35 Vol. 6, No. 4, March 1973 253 T.\BLE B-;. -Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (oo kg) STATION 5— LOS OSOS CREEK— C. GICAS. UN1.ESS OTHERWISE INDICATED— 52 SAMPLES i— Continued DDE TDE DDT DDE TDE DDT DDE TDE DDT Dieldrin I PCB's STATION 6— ELKHORN SLOUGH— C. GICAS. UNLESS OTHERWISE INDICATED— 57 SAMPLES' DDE TDE DDT Dieldrin 220 220 290 DDE TDE DDT Dieldrin 220 200 230 210 300 160 200 190 230 200 260 340 390 200 260 210 440 390 690 860 920 390 500 390 190 250 150 230 340 370 DDE TDE DDT Dieldrin Esdiin DDE TDE DDT DDE TDE DDT Dieldiir Endrin DDE TDE DDT Dieldrin PCB's 214 212 129 237 191 126 280 215 324 424 338 156 393 223 253 358 441 346 808 304 96 704 230 445 270 353 325 300 582 2S5 276 236 444 308 491 411 375 J73 237 191 502 171 117 630 284 '31 19 26 T T ^28 37 17 189 254 Pesticides Monitoring Joltinal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by dale of collection — California — Continued RESXCES is PPB (iC KC) 11 COMPOU>1) Jan. Fa. Ma«. Api. May Jcse July Aix. Sept. Oct. Nov. D STATION 6.— ELKHORN SLOUGH— C. GIGAS. UNLESS OTHERWISE INTJICATED— 5" S.^IPLES ^— Cortmaed 1972 DDE ■« "T TDE 2S T DDT 36 10 Dieldrin T 57 PCB's - •e STATION 7.— COYOTE POINT— O. LURID A— 55 SAMPLES- DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin Endrin DDE TDE DDT Dieldni! Endrin DDE TDE DDT DDE TDE DDT 102 102 DDE TDE DDT Dieldrii! DDE TDE DDT DieldTiii PCBs Vol. 6. No. 4. M.\rch 1973 255 TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued RESroUES IN PPB (/iC/KO) STATION 8.— GUADALUPE SLOUGH— Af. DEMISSUS—n SAMPLES 1 1968 DDE 36 77 48 74 67 34 24 19 24 34 T TDE 90 180 100 185 140 68 53 57 58 T 24 DDT 110 150 60 91 130 34 T 40 26 - T Dieldrin 18 23 14 - 14 - - - - - - 1969 DDE _ _ 34 70 26 11 10 24 - 29 TDE 42 — - - 27 108 22 34 48 50 1970 DDT - — — — — 204 T T T T 1971 DDE TDE DDT Dieldrin T 40 28 T T 26 10 T - T T 10 37 1972 DDE TDE DDT Dieldrin PCB's 11 12 10 T T T 10 T (« STATION 9. -ALVISO SLOUGH — M. DEMISSUS- -28 SAMPLES i 1968 DDE 43 46 69 74 47 26 28 18 11 — 13 TDE 140 59 170 169 95 72 80 45 79 T 30 DDT 93 78 77 85 66 35 34 35 11 T 27 Dieldrin 18 12 25 - - - - - - - - 1969 DDE 38 — 55 98 52 12 17 30 - 39 TDE 59 61 55 - 73 161 42 45 56 27 DDT - 88 - 108 HI T 20 T T 1970 DDE TDE DDT 42 76 33 1971 DDE TDE DDT Dieldrin 13 38 17 T 15 T T T T T 10 1972 DDE TDE DDT Dieldrin PCB's T T 10 T T T 10 T 256 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California— ConXinued Residues in PPB (ag/ko) STATION 10— WEST ISLAND— C. FLUMlSEA—2$ SAMPLES ' 1967 DDE 280 330 320 270 320 230 170 140 170 180 690 390 TDE 250 370 350 250 250 210 130 93 150 150 490 310 DDT 210 300 310 250 260 270 150 130 230 270 1,100 770 Dieldrin 20 20 22 17 12 18 T 15 20 10 20 18 Endrin T T T - - - - - - - - - 1968 DDE 390 500 280 370 251 196 134 104 41 71 TDE 290 400 200 220 224 183 160 182 97 138 DDT 240 290 190 210 320 223 150 235 150 184 Dieldrin 16 22 15 16 - 21 19 13 - - 1969 DDE TDE DDT 177 168 1970 1971 DDE 198 91 15 TDE 126 71 T DDT 173 111 - Dieldrin T T T 1972 DDE TDE DDT Dieldrin PCB's 11 10 10 T T 10 T STATION II— FALSE RIVER— C, FLUMINEA—26 SAMPLES" 1967 DDE 470 460 320 420 270 400 TDE 410 320 200 260 180 350 DDT 970 910 640 780 500 210 Dieldrin 24 19 20 16 16 17 1968 DDE 470 500 340 330 315 199 250 122 53 96 TDE 400 590 230 230 281 167 190 212 109 144 DDT 220 420 200 190 312 225 290 296 92 103 Dieldrin 17 22 19 23 - - - 16 - - Endrin 18 - - - - - - - - - 1969 DDE 151 54 93 41 88 139 57 42 - TDE 152 66 75 47 88 165 91 76 91 1970 DDT 378 167 214 46 135 136 61 43 44 """""""""""""" Vol. 6. No. 4, March 1973 257 TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (ao/ko) STATION 11.— FALSE RIVER— C. FLVMINEA— 26 SAMPLES i— Continued 1971 DDE 21 TDE 41 DDT 20 Dieldiin T STATION 12.— NAPA RTVER- Af. DEMISSUS—2S SAMPLES ' 1968 DDE T 25 21 24 23 15 21 18 T TDE 22 46 72 100 83 38 42 62 24 DDT T 26 39 45 47 - 23 18 T 1969 DDE 10 — 100 62 — 10 13 T — T 12 TDE 30 - 48 - - 24 45 30 58 24 37 DDT T - - - - T T T - T T 1970 DDE TDE DDT Dieldrin EndriD 11 33 T 16 93 46 T T 1971 DDE TDE DDT Dieldrin Endrin 27 143 41 T T 13 68 10 T T T T T T T 1972 DDE TDE DDT Dieldrin PCB's T 21 23 T T T 10 T STATION 13— PETALUMA RIVER— Af. DEMISSVS—li SAMPLES' 1968 DDE — 27 27 26 47 19 — — 92 TDE - 58 63 72 104 35 T 13 68 DDT - 15 19 31 41 T - - 108 1969 DDE T — 124 49 12 T 17 — — 22 10 TDE T - 37 - 28 T 38 - 57 37 22 DDT - - - - - T T - - T T 1970 DDE TDE DDT Dieldrin T T T 28 71 26 10 258 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (iic/tio) May June July Aug. STATION 13— PETALUMA RIVER— M. DEMISSUS—2S SAMPLES '—ConUnued 1971 DDE T T — T TDE 18 24 T T DDT 10 T - - Dieldrin T - - — 1972 DDE T T TDE T T DDT 10 10 L Dieldrin T T \ PCB's - tt) STATION 14. -POINT SAN QUENTIN— C . GIGAS- -50 SAMPLES > 1966 DDE 12 30 47 52 69 59 37 52 57 51 55 55 TDE 20 37 60 83 120 92 47 82 90 88 84 110 DDT 14 12 19 23 45 38 24 43 49 33 40 98 Dieldrin - - - 14 20 - - - - " 15 20 1967 DDE 52 34 30 42 23 39 45 53 30 31 100 45 TDE 130 65 59 75 55 85 120 130 74 68 50 84 DDT 88 49 49 70 34 64 89 63 38 36 85 45 Dieldrin 23 n i; 19 13 21 19 17 11 - 10 11 1968 DDE 43 44 43 43 36 59 59 25 38 40 ■ TDE 79 96 78 97 95 110 no 60 86 120 [ DDT 44 89 67 63 69 100 100 T 52 82 1 Dieldrin 12 17 17 12 - - 12 - - 18 r 1969 DDE 74 53 62 47 143 25 13 30 — — 31 TDE 80 149 134 - 143 54 23 41 - 55 51 DDT 130 193 76 182 154 24 T T - 32 26 1970 DDE TDE DDT 18 18 T 19 T T 54 31 37 66 64 45 51 39 23 STATION 15.— BOLINAS LAGOON— C. GIGAS— V SAMPLES i 1966 DDE TDE DDT 10 T T T 10 - 1967 DDE T T 10 10 11 T 11 13 - T T T TDE n 13 16 17 16 14 21 20 - 15 11 T DDT T T T 11 14 12 13 11 - 11 - - Vol. 6. No. 4, March 1973 259 TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued REsrouES IN PPB (ao/kg) STATION 15.— BOLINAS LAGOON— C. GIGAS—ll SAMPLES >— Continued STATION 16.— SCHOONER BAY— C. GlGAS—33 SAMPLES ' STATION 17.— BERRIES BAR— C. GIGAS—ll SAMPLES i 1966 DDE — T T — T T T T — T T — TDE - T - T - - - - T T - DDT - - - - - - - - - - - - 1967 DDE T T 10 11 T 11 T 15 - - T - TDE - - T 13 13 13 T 18 - - - - DDT - - - 10 - T - 10 - - - - 1968 DDE TDE - 1969 DDT — 1970 DDE TDE DDT 11 T T 10 11 10 1971 DDE TDE DDT Dieldrin 14 16 10 T T T T T T T T T 10 1972 DDE TDE DDT Dieldrin PCB's T T 10 T T 10 T 1966 DDE — 13 T 10 13 10 17 11 12 T T 11 TDE - 15 T 17 16 10 13 11 T T T 10 DDT - T - - T - - - - - - - 1967 DDE T 11 17 14 16 12 13 T 13 15 14 T TDE T 14 20 18 17 14 15 12 16 18 17 T DDT - - T 10 11 10 T - 10 T T - 260 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (;ig/kg) STATION 17— BERRreS BAR— C. GIG AS— 21 SAMPLES J— Continued STATION 18— TOMALES BAY— C. GIGAS—i* SAMPLES" 1966 DDE T T — — T — 14 11 14 14 T T TDE DDT - T - - 11 T - T T 11 12 — — 1967 DDE T 12 11 11 T 11 T T T _ 11 _ TDE - T T 12 T 14 T - - - T - DDT T 10 T " T 13 T - - - T - 1968 DDE TDE DDT : 11 10 T T 1969 DDE TDE DDT 22 T 18 T T T 1970 DDE TDE DDT Dieldrin Endrin T T 10 T T 1971 DDE TDE DDT 12 T 10 T T 10 T T 10 1972 DDE TDE DDT Dieldrin T T in T STATION 19.— NICKS COVE— C. GIG AS— 25 SAMPLES' 1966 DDE — 12 „ — T T n 11 T T T T 1 TDE - T - - - — — T — - T - DDT - T - - - - - - - - - - 1967 DDE 12 13 13 14 10 T u T T — 14 — TDE T 10 12 12 T T T - T - - - DDT T 11 T 11 T T T - - - - - Vol. 6, No. 4, March 1973 261 TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Residues in PPB (ao/kg) May June July Aug. STATION 19— NICKS COVE— C. GIGAS— 25 SAMPLES i— Continued STATION 20.— GUNTHER ISLANI>— C. GIGAS— ii SAMPLES ' STATION 21.— BIRD ISLAND— C. GIGAS— 25 SAMPLES » 1966 DDE — — _ - — T 11 T T T T T TDE - - - - - T 17 - 21 T T T DDT T 10 - 47 II 14 — II - 18 14 20 1967 DDE 10 T T T T T T T - T T T TDE T - - T - T T - T T T T DDT 30 28 12 19 19 19 24 12 16 15 21 22 1968 DDE TDE - 13 n 1969 1970 DDT — 54 DDE 11 TDE 11 DDT 10 Dieldrin T 1971 DDE TDE DDT Dieldrin T 13 17 T T T 10 T T T T 10 T 1972 DDE TDE DDT Dieldrin PCBs T T 10 T T 10 a> DDE TDE DDT DDE TDE DDT 262 Pesticides Monitoring Journal TABLE B-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — California — Continued Year Compound Residues in PPB (/io/ko) Jan. Feb. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 21— BIRD ISLAND— C. GIG AS— 25 SAMPLES > — Continued Each sample represents 15 or more mature moUusks. DDE, TDE, and DDT values approximated because of presence of toxaphene. C. gigas. Present but not quantified. '' M, demissus. " M. calilo " M. edulis SECTION C— DELAWARE Samples were collected at nine stations at monthly intervals during the period October 1966 - August 1969. The eastern oyster (Crassostrea virginica) ribbed mussel {Modiolus demissus). and hard clam (Mercenaria mercenaria) were each collected at three stations. All samples were analyzed at the Gulf Breeze Laboratory. The approximate locations of the stations are shown in Fig. C-1. The Cape Henlopen station was in Delaware Bay, the other stations were adjacent to the Bay but exposed primarily to the runoff from large agricultural areas in separate drainage basins. A sum- mary of data on organochlorine residues in the moni- tored species is presented in Table C-l. and the distribu- tion of residues in these species for each sampling station by date of collection in Table C-2. The use of three different species for monitoring ob- scured pollution patterns in Delaware estuaries to some extent. The relative inefficiency of hard clams in storing organochlorine residues makes Rehoboth Bay (Stations 7 and 8) appear to be generally free from this type of pollution. The first samples of clams collected in adjacent Indian River Bay (Station 9) also were free of detectable residues: however, subsequent monitoring, using the ribbed mussel, showed Indian River Bay to be moderately but continuously polluted. It is probable that Rehoboth Bay was similarly polluted during the monitoring period. This same reasoning suggests that the waters at Cape Henlopen were continually more polluted with DDT than the small residues in the hard clanT- would imply. The magnitude of DDT residues in clams and oysters showed no trend towards increased or decreased levels during the 3-year monitoring period. In ribbed mussels, however, there was a marked decline in the average level Vol. 6, No. 4, March 1973 of residues in the final year at Stations 1 and 2 as well as Station 9. Delaware monitoring samples ranked 6th in frequency and 10th in magnitude of DDT residues in comparison with the other 14 States. The 13% inci- dence of dieldrin residues was about the average for all States. FIGURE C-I. — Diagram of coastal Delaware showing approximate location of monitoring stations I. Leipsic River 2. Simons River 3. Bowers Beach — Murderkill River 4. Mispillion River 5. Broadkill River 6. Cape Henlopen — Delaware Bay 7. Thompson Island — Rehoboth Bay 8. Arrowhead Point — Rehoboth Bay 9. West Gables — Indian River Bay 263 TABLE C-1. — Summary of data on organocMonne residues in the monitored species, 1966-69 — Delaware Station Location MoNrroRiNG Period Principal Monitored Species Number of Samples • Number of Positive Samples and Maximum Residue ( ) Detected in PPB (;ig/ko) DDT DmLDRIN I 3 4 5 6 7 8 9 Lejpsic River Simons River Bowers Beach Mispillion River Broadkill River Cape Henlopen Thompson Island Arrowhead Point West Gables 1967-69 1967-69 1966-69 1966-69 1966-69 1966-69 1966-69 1966-69 1966-69 M. demissus M. demissus C. virginica C. virginica C. virginica M. mercenaria M. mercenaria M. mercenaria M. demissus 27 25 J4 35 34 32 33 34 33 23 (156) 23 (205) 34 (172) 33 (90) 34 (90) 30 (65) 5 (16) 4 (35) 30 (96) 4 (13) 6 (19) 25 (25) 2 (10) Total number of samples 287 Percent positive for indicated compound 75 13 Each sample represents 15 or more mature mollusks. TABLE C-2 — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Delaware [Blank = no sample collected: — = no residue detected above 5 ppb; T = >5 but <10 ppb] Residues in PPB (/iO/KG) STATION 1— LEIPSIC RIVER— Af. DEMISSUS— 21 SAMPLES' 1967 DDE 12 25 26 47 33 21 17 22 18 32 TDE II 53 46 91 77 51 47 29 47 77 DDT - T 12 18 23 51 47 - T 17 Dieldrin - 10 13 - 10 - 10 - - - 1968 DDE 27 30 32 26 33 T 12 23 19 TDE 68 69 91 4! 45 20 18 29 37 DDT 17 17 14 - 22 - - T 18 1969 DDE — — T 15 T — 17 — TDE — — 14 18 T - 33 - DDT - - - - 19 - STATION 2.— SIMONS RIVER— Af. DEMISSUS— 25 SAMPLES ' 1967 DDE 13 17 31 31 43 37 25 18 29 29 TDE 43 37 65 150 89 79 47 88 75 66 DDT — - 15 24 19 28 38 29 18 16 Dieldrin - - 15 19 12 T - 12 - - 1968 DDE 28 23 39 23 — 20 11 TDE 65 78 100 30 - 26 16 DDT 18 39 16 - - 22 - Dieldrin - - 10 - - - - 264 Pesticides Monitoring Journal TABLE C-2 — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Delaware — Continued Residues in PPB (;io/kg) STATION 2.— SIMONS RIVER— M. DEMISSUS— 25 SAMPLES i— Continued 1969 DDE _ 13 T 21 14 21 13 21 TDE - 22 T 23 19 29 26 35 DDT - - - - - 24 26 31 STATION 3. —BOWERS BEACH- -C. VIRGINICA- -34 SA\ IPLES' 1966 DDE TDE DDT Dieldrin 25 29 16 19 17 1967 DDE 27 25 n. .., 42 43 41 40 40 42 41 32 TDE 35 26 ,,. «, 65 70 66 64 56 98 51 38 L DDT - - T 10 24 68 17 25 14 10 1 Dieldrin 18 14 20 25 24 18 II 13 16 16 13 15 1968 DDE 50 46 48 52 66 75 82 49 41 52 57 41 TDE 56 42 47 48 73 78 53 34 32 44 57 35 DDT T - T - 10 T 25 T T 13 18 T Dieldrin 12 13 14 15 12 16 - - - - 16 15 1969 DDE 52 48 42 49 41 79 60 39 TDE 37 47 36 39 39 70 57 29 L DDT - - - - - 20 29 11 Dieldrin 14 15 II - II - - - STATION 4.— MISPILLION RIVER— C. VIRGINICA— 35 SAMPLES ■ 1966 DDE TDE DDT 31 27 15 21 24 22 24 1967 DDE 17 24 25 35 23 22 16 20 T 32 27 b TDE IS 22 ,=, 31 41 26 30 20 23 44 36 32 1 DDT - ,.. - - - T II T T - T 1 Dieldrin - 10 - 10 - - - - - - - 1968 DDE 23 28 Lost 41 39 39 47 34 32 25 39 38 TDE 40 31 40 36 34 33 23 25 18 32 27 DDT T - ~ 15 - - - - - - - 1969 DDE 40 50 36 29 36 26 35 28 TDE DDT 29 31 28 25 32 26 22 20 Vol. 6, No. 4, March 1973 265 TABLE C-2 — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Delaware — Continued Residues in PPB (/ig/ko) STATION 5— BROADKILL RIVER— C. VIRGINICA— 34 SAMPLES ' 1966 DDE TDE DDT 18 20 T 22 17 1967 DDE 28 18 23 17 23 24 16 30 27 35 35 37 TDE 23 II 17 13 18 21 19 30 27 27 31 33 DDT - - - - - T T 16 11 T T T 1968 DDE 25 29 23 32 39 43 36 48 37 31 44 51 TDE 21 22 16 21 45 32 20 32 25 22 33 39 DDT - - - - - - - - - - - - 1969 DDE 40 38 43 41 39 42 43 35 TDE 24 28 26 20 28 28 24 15 DDT - - - - - - - - STATION 6.— CAPE HENLOPEN— M. MERCENARIA— 32 SAMPLES' 1966 DDE TDE DDT 12 11 1967 DDE 12 13 - ,=, 14 12 20 12 T 14 16 16 TDE DDT 16 12 - '=' 14 14 24 14 T 13 15 15 1968 DDE 13 15 IS 18 28 39 25 25 19 13 T 21 TDE 12 14 14 15 24 26 16 15 12 T T 11 DDT - - - - - - - - - - - - 1969 DDE 12 14 22 Lost 16 19 22 35 TDE - - T II T 10 20 DDT - - - - - - - STATION 7.— THOMPSON ISLAND— Af. MERCENARIA— 33 SAMPLES i 266 Pesticides Monitoring Journai TABLE C-2 — Dislribiilion of organochlorine residues in the monitored species for each sampling station by dale of collection—Delaware — Continued Residues in PPB (mg/kg) STATION 7.— THOMPSON ISLAND— M. MERCENARIA—i3 SAMPLES" — Continued STATION 8— ARROWHEAD POINT— M. MERCENARIA—3A SAMPLES" 1966 1967 1968 1969 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT III III III III III 1 H H III III = K 1 III III III III III 1 H H STATION 9.— WEST GABLES— M. DEMISSUS UNLESS OTHERWISE INDICATED— 33 SAMPLES" 1966 DDE TDE DDT "" (3> 1967 DDE 11 18 17 22 19 15 18 13 19 19 21 TDE 25 37 32 33 24 21 29 13 29 30 33 DDT 32 19 14 24 13 14 41 21 21 22 26 1968 DDE 19 24 18 20 18 23 T T - T 12 13 TDE 29 35 28 32 30 37 11 T - T 16 18 DDT 21 30 22 26 23 36 T - -- - T - 1969 DDE in 16 13 16 17 21 13 • 11 TDE 14 16 17 20 22 27 IS T DDT - - - T 10 T 11 - ' Each sa mple represents 15 o r more mature moUusks. ' Present but not quantified. ' M. mer "enar:a. Vol. 6, No. 4, March 1973 267 SECTION D.— FLORIDA Investigation of the effects of pesticide pollution on estuarine fauna in Florida was initiated at the Gulf Breeze Laboratory, Gulf Breeze, Fla., in 1959. During the next 5 years, sufficient headway in the understand- ing of uptake and flushing rates of persistent synthetic compounds as well as the technology for handling samples made a continuing monitoring program feasible. Local oysters (Station 9, East Bay) were analyzed monthly during 1964, and the concept of a national monitoring program was developed and implemented in 1965. The eastern oyster, C. virginica. was the only species monitored in Florida; all samples were analyzed at the Gulf Breeze Laboratory. The approximate loca- tions of monitoring stations are shown in Fig. D-1. A summary of data on organochlorine residues in the monitored species, C. virginica. is presented in Table D-1, and the distribution of residues in this species for each sampling station by date of collection in Table D-2. Oyster samples from Florida contained the highest levels of DDT residues and the most persistent contamination with PCB's observed in the entire monitoring program. The polychlorinated biphenyl, Aroclor 1254®, was identified in studies of estuarine fauna following a 1969 fish kill in Escambia Bay, Fla., (8). Station 9 is about 25 miles from the presumed source of this PCB pollution and is in a contiguous but distinct drainage basin. Monitoring samples from this station contained PCB residues about one-third the magnitude of residues in Escambia Bay oysters and continued to have residues of similar magnitude for at least 3 years after the pre- sumed primary source of PCB's had been eliminated. The trend in DDT residues is most clearly shown in the Station 9 data. Some DDT had been used in this geographic area for agricultural purposes. However, its primary use had been for the control of stable-fly larvae, Stomoxys calcitrans. that develop in seaweed windrows on estuarine beaches. In 1969. methoxychlor was substituted for this purpose, and DDT residues virtually disappeared from all succeeding monitoring samples. Methoxychlor residues were not detected in the monitored samples. There are not enough recent data to determine DDT pollution trends in other estuaries along the Florida Gulf coast. The incidence of DDT in Florida samples (62%) is about the average for all States monitored. The incidence of dieldrin (1%) may be compared with the average incidence of 15% for all States. FIGURE D-1.- — Diagram of coastal Florida showing approximate location of monitoring stations 1. lona Point — Caloosahatchee River 2. Charlotte Harbor — Peace River 3. Coral Cove — Little Sarasota Bay 4. Manatee River 5. Crystal River 6. Suwanee River 7. St. Vincents Bar (North) — Apalachicola Bay 8. St. Vincents Bar (South) — Apalachicola Bay 9. East Bay — Blackwater River TABLE D-1. — Summary of data on organochlorine residues in the monitored species (C. Virginica), 1965-72 — Florida Station 1 OCATION Monitoring Period Number of Samples ' Number of PosrrivE Samples and MAxiMinrf Residue ( ) Detected in PPB (ag/kg) DDT Dieldrin PCB'S ' 1 lona Point 1967-69 31 31 (5,390) 1 (11) : Charlotte Harbor 1966-69 31 28 (338) 13 (27) J Coral Cove 1966-69 3: 32 (129) 4 Manatee River 1966-69 3: 32 (159) 5 Crystal River 1966-71 43 7 (27) 6 Suwanee River 1966-69 32 6 (22) 268 PEsncroES Monitoring Journal TABLE D-\.— Summary of data on organochlorine residues in the monitored species (C. Virginica), 1965-72- Florida — Continued Station Number Location Monitoring Pekiod Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (iic/kc) DDT DiELDRIN PCB's = 7 8 9 St. Vincents Bar (North) St. Vincents Bar (South) East Bay Occasional stations (21) 1966-67 1966-67 1965-72 1966-71 17 16 M 56 12 (50) 10 (70) 46 (65) 26 (101) 3 (28) 3 (22) ^ (12) 25 (390) Total number of samples 374 Percent of samples positive for indicated compound 62 7 7 Each sample represents 15 f Calculated as Aroclor 1254®. mature mollusks. TABLE D-2 — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Florida [Blank = no sample collected; — =; no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] REsrouES IN PPB (^/KO) STATION 1.— lONA POINT— 31 SAMPLES' 1966 DDE TDE DDT 30 39 13 20 24 48 35 79 28 T T 1957 DDE 91 320 930 1.450 290 110 53 60 87 72 140 240 TDE 94 no 760 705 310 200 no 160 160 150 220 310 DDT 190 630 3.700 2.550 350 68 57 32 97 110 68 520 1968 DDE 760 1.200 1.100 1.500 780 340 180 - T 77 84 82 TDE 44 560 580 560 390 310 190 T 16 160 120 120 DDT 2.800 3.600 2.300 1.200 650 220 33 - - 69 140 60 Dieldrin - - - - - - - - " - - - 1969 DDE TDE DDT 710 1.400 1.700 940 400 1.100 STATION 2.— CHARLOTTE HARBOR— 31 SAMPLES" 1966 DDE TDE DDT T 10 T 16 17 23 15 — 52 91 41 1967 DDE 83 14 15 39 18 30 13 T T - T 18 TDE 85 20 24 33 27 43 20 13 T - 11 28 DDT 170 T 13 - T 13 T - - - - 21 Dieldrin - - - - - - 14 11 19 - - 15 Vol. 6, No. 4, March 1973 269 TABLE D-2. — Distribution of organocMorine residues in C. virginica for each sampling station by date of collection — Florida — Continued Residues in PPB (ag/kg) Nov. Dec. STATION 2.— CHARLOTTE HARBOR— 31 SAMPLES >— Continued 1968 DDE 19 23 18 34 27 22 20 — T — T T TDE 22 28 18 36 29 18 26 T 17 - 11 T DDT 14 13 - 20 16 10 T - - - - - Dieldrin - 11 - 18 11 - 27 - 16 - 13 19 1959 DDE TDE DDT 14 19 17 22 12 STATION 3.— CORAL COVE— 32 SAMPLES' 1966 DDE TDE DDT 24 21 T 10 T 25 33 T 17 16 T 1957 DDE 34 26 24 25 20 24 25 23 12 16 13 10 TDE 28 23 22 26 21 21 24 20 16 16 10 10 DDT 12 12 T 13 T 10 17 T T T T T 1968 DDE 29 27 21 35 49 39 31 19 20 28 21 23 TDE 30 30 14 36 43 40 26 16 23 28 23 29 DDT 10 14 - 13 37 49 32 22 14 28 11 T 1959 DDE TDE DDT 30 38 T 41 40 20 36 40 STATION 4.— MANATEE RIVER— 32 SAMPLES » 1966 DDE TDE DDT 23 39 37 47 13 25 33 11 T T 30 33 12 1957 DDE 37 39 22 3! 18 T 19 21 23 33 34 13 TDE 30 45 24 41 23 T 20 42 46 59 45 14 DDT 19 19 10 13 T - T 20 17 13 14 14 1968 DDE 26 24 18 42 16 18 31 16 18 18 17 24 TDE 24 29 30 65 19 61 88 37 38 15 19 27 DDT 26 13 10 22 T 25 40 T 13 - - 14 1969 DDE TDE DDT 22 33 32 46 17 24 26 T 270 Pesticides Monitoring Journal TABLE D-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of Florida — Continued Residues in PPB (/ig/kg) May June July Aug. Nov. Dec. STATION 5.— CRYSTAL RIVER— 43 SAMPLES > STATION 6.— SUWANEE RIVER— 32 SAMPLES ' STATION 7.— ST. VINCENTS BAR (NORTH)— 17 SAMPLES' DDE TDE DDT Dieldxin 11 T 10 T Vol. 6, No. 4, March 1973 271 TABLE D-2. — Distribution of organochlorine residues in C. virginica for each sampling station by dale of collection — Florida — Continued Residues in PPB (^g/ko) STATION 7.— ST. VINCENTS BAR (NORTH)— 17 SAMPLES i— Continued STATION 8.— ST. VINCENTS BAR (SOUTH)— 16 SAMPLES > 1966 DDE 18 25 17 — — — — TDE 21 30 T - - - - DDT - 15 - - - - - Dieldrin - 13 - - - - - 1967 DDE T — 14 21 T 13 T T — TDE - - 13 22 T 12 T - - DDT - - - T 38 T - - - Dieldrin - - 15 22 - - - - - STATION 9.— EAST BAY— 84 SAMPLES ■ 1965 DDE TDE 19 18 T I T T - T T T DDT 13 T T - T - 1966 DDE 12 13 13 17 26 24 15 14 T - T T TDE - 14 - 15 24 19 11 - - - - T DDT - - - 15 15 14 - - - - - - 1967 DDE T 18 21 18 18 12 20 T T T T T TDE - 18 17 22 24 13 23 - - - - - DDT - 14 16 15 15 - 18 - 10 - - - 1968 DDE 16 12 17 22 15 15 — T 20 — T — TDE 15 20 - - - - - T - - - - DDT 10 12 - - - - - - - - - - 1969 DDE T 16 11 — 13 14 — — 10 T - - TDE T 14 10 - 13 - - - T - - - DDT - T - - - - - - 14 - - - 1970 DDE TDE - T - T - - - - - - - - DDT PCB's = ~ — — _ 380 180 170 73 92 50 55 140 1971 DDE - - - - — - - - - - - - TDE - - - - — — - - - - — — DDT - — - — — — - - — - - - PCB's ' 160 160 200 220 230 390 190 230 100 55 120 - 272 Pesticides Monitoring Journal TABLE D-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Florida — Continued Residues in PPB (#g/kg) May June STATION 9.— EAST BAY— 84 SAMPLES ' — Continued Each sample represents IS or more mature mollusks. Calculated as Aroclor 1254®. SECTION E— GEORGIA Monthly collections of the eastern oyster (C. virginica) were made at 1 1 estuarine areas in Georgia during the period February 1967 - June 1972. Analyses were done at the Gulf Breeze Laboratory until September 1969, and thereafter at the Marine Institute of the University of Georgia. The approximate locations of monitoring stations are shown in Fig. E-1. A summary of data on organochlorine residues in the monitored species, C. virginica. is presented in Table E-1, and the distribution of residues in this species for each sampling station by date of collection in Table E-2. The 15% incidence of DDT residues in Georgia samples was next to the lowest of all States monitored (Washington, lowest at 11%). The maximum level of DDT observed was also next to the lowest of any of the other States monitored. By contrast, the largest dieldrin residue detected in the nationwide program was in Georgia, (230 ppb) and the incidence of dieldrin residues (21 % ) was well above the average incidence (15%) for all States. The occurrence of substantial toxaphene residues in the samples collected in St. Simons Sound was unexpected. A special sampling program was initiated in the area that included the placement of trays of oysters in creek beds where oysters did not normally occur. Analyses of these samples pinpointed the industrial source of the toxaphene and precipitated a schedule for control of the effluent discharge by the manufacturer. The magnitude of toxaphene residues at Stations 8-11 illustrates well the importance of dilution (distance) in the abatement of pollution. Polychlorinated biphenyl residues were analyzed for beginning in 1969. A few samples collected in the Ogeechee and Satilla River basins contained residues of Aroclor 1 254®, but the amounts were not quantified. DDT residue levels were generally low and there was an approximate increase of 13% in the number of samples Vol. 6, No. 4, March 1973 with negligible residues in 1971 as compared to earlier years. Stations 1 and 2 in the Savannah River basin, however, showed a reversal of this trend in 1972 when oysters contained substantially higher residue levels than in 1971. GEORGIA ATLANTIC OCEAN 7o FIGURE E-1. — Diagram of coastal Georgia showing approximate location of monitoring stations 1 . Lazerelta Creek— Savannah River Basin 2. Wilmington River— Savannah River Basin 3. Ogeechee River— Ogeechee River Basin 4. St. Catherine Sound— Ogeechee River Basin 5. Sapelo Sound— Ogeechee River Basin 6. Doboy Sound — Ogeechee River Basin 7. Egg Island — Altamaha River Basin 8. St. Simons Sound— Satilla River Basin 9. Terry Creek— Satilla River Basin 10. Jekyll Island— Satilla River Basin 11. Satilla River— Satilla River Basin 273 TABLE E-1 — Summary of data on organochlorine residues in the monitored species (C. virginica), 1967-72 — Georgia Station Number Location Monitoring Period Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (^o/kg) DDT Dieldrin TOXAPHENE PCB's = 1 Lazerclta Creek 1967-72 64 -10 (96) 58 (230) 2 Wilmington River 1967-72 65 21 (86) 27 (901 3 Ogeechee River 1967-72 65 LI (50) 15 (261 1 4 St. Catherine Sound 1967-72 65 7 (15) 2 (T) I 5 Sapelo Sound 1967-72 65 12 (50) 6 (12) 2 6 Doboy Sound 1967-72 64 7 (27) 8 (14) 1 7 Egg Island 1967-72 65 -1 (52) 22 (23) 8 St. Simons Sound 1967-72 65 ,3. 3 (T) 64 (7,500) 2 9 Terry Creek 1967-70 16 - 16 (54,000) 10 Jekyll Island 1967-72 62 ,„ 37 (3,500) 8 11 Satilla River 1967-72 64 3 (15) 8 (1,000) 1 Occasional stations (2) 1968-69 4 ,3, 3 (13,000) Total number of samples 664 Percent of samples positive for indica ed compound 15 21 19 2 NOTE: T = >5 but <10 ppb. ' Each sample represents 15 or more mature mollusks. ' Present but not quantified. ' Presence of toxaphene prevented quantification of DDT and its metabolites. TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Georgia RESIDUES IN PPB (Ag/kg) [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION :.— LAZERETTA CREEK— 64 SAMPLES' 1967 DDE 14 13 21 T T 53 - — — — 12 TOE 17 14 29 13 11 25 14 - - - 16 DDT - - T - T 18 II - - - T Dieldrin 98 65 56 32 30 30 33 18 42 33 46 1968 DDE - 13 12 17 - — 15 - - - T TDE - 16 12 23 - - 23 - - - T DDT - - - T - - 28 - - - - Dieldrin 22 42 37 46 - 20 39 22 18 42 56 1969 DDE - — — — — T — - - - - T TDE - - - - - 13 - - - - - - DDT -. - - - - - - - - - - - Dieldrin 39 23 47 51 16 35 28 23 20 180 230 20 1970 DDE T 13 — T T — - T - 23 - - TDE - - - T T - - - - - - - DDT - - - - - - - - - - - - Dieldrin 30 31 40 32 17 23 80 T — — T T Pesticides Monitoring Journal TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Georgia — Continued Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. RESIDUES IN PPB (»g/kg) [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION 1.— LAZERETTA CREEK— 64 SAMPLES i— Continued 1971 DDE _ _ 20 _ _ — _ — — T T — TDE - - - - - - - - - T T - DDT - - - - - - - - - - - - Dieldrin 19 19 T 17 1.1 10 T T - - 13 1972 DDE T T 2.1 18 T T TDE - T 14 12 T T DDT - - T T - T Dieldrin 15 13 T T 22 T STATION 2.— WILMINGTON RIVER— «5 SAMPLES ' 1967 DDE T T T _ — T 12 — — — — TDE T T T - - T - - - - - DDT - - - - - - - - - - - Dieldrin 17 19 22 - - - - - - - - 1968 DDE TDE DDT - - T T : : - - - - - - Dieldrin 10 21 12 - - - - - - - - - 1969 DDE TDE DDT - - - ": : - - - - - - Dieldrin - - - 10 - - - - - - 90 T 1970 DDE TDE DDT - 11 - T T - - - T 86 - - - — — — _ _ _ _ — _ — _ Dieldrin T T 10 25 - T - - - - - T 1971 DDE - - 10 - — - - - T T T TDE - - - - - - - - - T T - DDT - - - - - - - - - - - - Dieldrin T 12 i; T T - - - - - T T 1972 DDE r 12 15 i: T T TDE - 13 T 11 T T DDT - - - - T T Dieldrin 10 17 15 - T T Vol. 6, No. 4, March 1973 275 TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Georgia — Continued ('EAR Compound I Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. D [Blank = no sample collected; RESIDUES IN PPB (/ig/kg) no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION 3.— OGEECHEE RIVER— 65 SAMPLES > DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin PCBs DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT T T T STATION 4.— ST. CATHERINE SOUND— 65 SAMPLES' 276 Pesticides Monitoring Journal TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Georgia — Continued May June RESIDUES IN PPB (/ig/kg) [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION 4— ST. CATHERINE SOUND— 65 SAMPLES i— Continued 1970 1971 1972 DDE TDE DDT DDE TDE DDT Dieldrin DDE TDE DDT III 1 1 1 1 III III Hill III 1 1 H 1 1 1 1 III III Hill III 1 1 H 1 1 1 1 III 1 H H 1 1 1 1 III 1 1 1 1 III 1 1 1 1 III 1 1 1 1 III 1 1 1 1 III 1 1 1 1 III STATION 5.— SAPELO SOUND— 65 SAMPLES • DDE TDE DDT Dieldrin DDE TDE DDT DDE TDE DDT Dieldrin PCB's DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Vol. 6, No. 4, March 1973 277 TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Georgia — Continued ITear I Compound H Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. D RESIDUES IN PPB (/ig/kg) [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION 6.— DOBOY SOUND— 64 SAMPLES ■ DDE TDE DDT DDE TDE DDT DDE TDE DDT Dieldrio PCB's DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT 14 14 13 STATION 7.— EGG ISLAND— 65 SAMPLES ' DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin 278 Pesticides Monitoring Journal TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection- Georgia — Continued Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. RESIDUES IN PPB (dg/kg) [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] STATION 7.— EGG ISLAND— 65 SAMPLES »— Continued DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin T T T T T T II T T T [Blank = no sample collected; — RESIDUES IN PPM (mg/kg) : no residue detected above 0.1 ppm or no residue detected (PCB's): T = >0.1 but 0.1 but <0.25 ppm] STATION 9.— TERRY CREEK— 16 SAMPLES' 1967 Toxaphene 12.0 4.7 18.0 13.0 1968 Toxaphene 23.0 6.0 54.0 5.0 6.3 12.0 1969 Toxaphene 9.0 12.0 17.0 8.0 1970 Toxaphene 6.2 8.2 Vol. 6, No. 4, March 1973 279 TABLE E-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Georgia — Continued I Blank = no sample collected; RESIDUES IN PPM (mg/kg) - = no residue detected above O.I ppm; T = >0.1 but <0.26 ppm] STATION 10.— JEKYLL ISLAND— 62 SAMPLES ' Toxaphen 1968 Toxaphene PCB's 1969 Toxaphene PCBs 1970 Toxaphene PCB's 1971 Toxaphene PCB's 1972 Toxaphene — T 0.5 0.4 0.4 11.7 2.1 0.7 0.7 0.5 T I.O 1.0 1.0 1.0 0.6 O.f 1.0 0.6 RESIDUES IN PPM (mg/kg) [Blank — no sample collected; — ^ no residue of DDT detected above 0.005 ppm or no residue detected above 0.1 ppm (toxaphene and PCB's); t = >0.1 but <0.25 ppm; T = >0.005 but <0.010 ppm] STATION 11— SATILLA RIVER— 64 SAMPLES' 1967 DDE TDE DDT Toxaphene 1968 DDE TDE DDT Toxaphene 1969 DDE TDE DDT 1970 DDE TDE DDT 1971 DDE TDE DDT PCB's 1972 DDE TDE DDT i.n 0.5 n.7 ' Each sample represents 15 or more mature molluskii. 2 Aroclor 1254® present but not quantified. ■> Presence of toxaphene prevented quantification of DDT and its metabolites in these samples. 280 Toxaphene present but not quantified. ■ One sample each in April 1969, April 1970, and February 1972 contained a trace of dieldrin. DDT and its metabolites not detected in any samples. Pesticides Monitoring Journal SECTION F.— MAINE The monthly monitoring of Maine estuaries for per- sistent synthetic residues was initiated in December 1 965 and continued until November 1970. There were 10 principal stations; about 40 other sites were sampled occasionally. Samples were analyzed at the Gulf Breeze Laboratory until June 1969 and. thereafter, at the Fisheries Research Station. Maine Department of Sea and Shore Fisheries. The soft clam (Mya arenaria) and the blue mussel (Mytilus edulis) were the principal mollusks monitored and, on occasion, both eastern oysters (Crassostrea virginica) and horse mussels (Modiolus modiolus) were collected at the same sites. In the laboratory, the uptake of DDT was greater in the soft clam than in other species tested as was the flushing rate, and 90% of DDT residues was lost within 7 days after the toxicant was removed. This may explain why in simultaneous collections of two or more species of mollusks, DDT residues in soft clams examined at 30- day intervals were usually lower than those in the oyster or horse mussel. A summary of data on organochlorine residues in the monitored species, is presented in Table F-1, and the distribution of residues in these species for each sampling station by date of collection in Table F-2. The Maine samples are characterized by the low in- cidence (18% ) of detectable DDT residues as compared to most other monitored areas, despite the fact that substantial amounts of DDT are reported to have been used agriculturally in some watersheds in Maine. The maximum magnitude of DDT residues detected was, however, larger than that found in seven other States. Analysis of occasional collections of fish and inverte- brates other than mollusks revealed DDT residues larger than those in mollusks. Presumably organochlorine pollution in Maine estuaries was usually too low and too transitory to be detected except in animals that retain residues for a long period of time. Despite the generally low incidence of DDT residues at most stations, there was sufficient continuity in detect- able DDT residues at Station 10 on the Piscataqua River to show a gradual decline from an average of about 28 ppb in 1966 to an undetectable level in 1970. A similar trend is clearly shown in samples collected at Station 7, Small Point. 6 •, 8 •^'-' FIGURE F- 1 . — Diagram of coastal Maine showing approximale location of monitoring stations Mill Cove— St. Croix River MachUsporl — Machias River Millbridgc — Narraguagus River Fort Point — Penobscot River Thomaston — St. George River Medomak — Nfedomak River Small Point — Kennebec-Androscoggin River Phippsburg — Kennebec- Androscoggin River Biddeford Pool— Saco River Eliot — Piscataqua River TABLE F-1 — Summary of data on organochlorine residues in the monitored species, 1965-70 — Maine Vol. 6, No. 4, March 1973 Station- Number Location monitorino Period Principal MONITOREn Species Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (iio/kc) DDT Dieldrin 1 ,( J 6 7 Mill Cove Machiasporl Millbridgc Fort Point rhomaston Medomak Small Point 1965-66 1965-7n 1966-70 1965-7(1 1965-70 1967-70 1968-70 M. arenaria M arenaria M arenaria M. arenaria M arenaria M. arenaria M. edulis 12 52 .17 42 42 23 18 : (15) I (12) 1 (15) 1 (80) 2 (11) 12 (359) 1 (11) 281 TABLE F-1. — Summary of data on organochlorine residues in the monitored species. 1965-70 — Maine — Continued Station NVMBEa MosrTO«i>G Peiioo PHINCIPAl movttoied Species Nl"Mbe» of Posimi Samples and Maximum Number of Residue ^ ) Detected in PPB (»g kg) Samples ' PhiFPsburi: Bidacford Pool Eliot Occaskmal sotiaas (40 1965-69 1968-70 1966-70 1965-69 M. arenaria M.edulls M. areruiria Mued (24) (M) (67) (93) (38) (18) Tocal nmnber ot samp4es Percent of sampfes positive for indicated cofupoand Each sample rerresents 15 or more mature monosks. TABLE F-I. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Maine [Blank = no sample collected: — = no residue detected above 5 ppb: T = >5 bm <10 ppb.] Residues in PPB (»g ko) STATION 1— NniX CO\'E—M. ARESARIA— 12 SAMPLES ^ DDE TDE DDT DDE TDE DDT STATION 2.— MACHIASPORT— -W. ARENARIA— 52 SAMPLES ' DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT 282 Pesticides Monitoring Joltlnal TABLE F-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Maine — Continued Yeai Compound Residues in PPB (ac kg) Feb. Mas. Apr. May June JutY Aug. Sept. Oct. Not. Dec STATION 2.— MACHIASPORT— M. ARESARlA—52 SAMPLES J— Contmned 1970 DDE TDE STATION 3 — MILLBRIDGE— .W. ARENARIA—il SAMPLES ^ DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT STATION 4.— FORT POTST—M. ARE\ARIA—*2 SAMPLES ' Vol. 6, No. 4. March 1973 283 TABLE F-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Maine — Continued Residues in PPB (/io/kg) Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 4.— FORT POINT— M. ARENARlA—^2 SAMPLES "—Continued STATION 5.— THOMASTON— M. ARENARIA, UNLESS OTHERWISE INDICATED— 42 SAMPLES" DDE TDE DDT DDE TDE DDT Dieldrin DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT STATION 6— MEDOMAK— Af. ARENARIA— 2i SAMPLES" 284 Pesticides Monitoring Journal TABLE F-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Maine — Continued Residues in PPB ((ig/kg) Nov. Dec. STATION 7.— SMALL POINT— Af. EDVLIS—IS SAMPLES ' 1968 DDE .15 21 17 12 25 19 TDE 44 25 20 14 27 18 DDT 280 77 68 18 26 26 1969 DDE 11 T T T 12 - - — - TDE 14 T T T 21 - - - - DDT 18 15 13 T 1.1 49 - - - 1970 DDE TDE DDT _ _ - STATION 8.— PHIPPSBURG— Af. ARENARIA—Z9 SAMPLES' 1965 DDE TDE DDT 1966 DDE TDE DDT 1967 DDE TDE DDT 1968 DDE TDE DDT 1969 DDE TDE DDT STATION 9.— BIDDEFORD POOL— M. EDULIS—24 SAMPLES ' 1968 DDE — — T — T T T T TDE - - T - T T T T DDT - - 21 - 54 22 15 13 1969 DDE T — T — — - — — TDE T - - - - - - - DDT 21 - 12 - - - - - 1970 DDE - - - - - - - - DDT - - - - - - - - VOL. 6, No. 4, March 1973 285 TABLE F-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — Maine — Continued Residues in PPB (mo/ko) June July STATION 10.— ELIOT— M. ARENARIA. UNLESS OTHERWISE INDICATED— »5 SAMPLES' DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT DDE TDE DDT ' Each sample represents 15 or - Af. edulis. " M. demissus. mature moUusks. 286 Pesticides Monitoring Journal SECTION G.— MARYLAND Eastern oysters, Crassostrea virginica. were collected in upper Chesapeake Bay and its tributaries at irregular intervals (usually twice yearly) from August 1966 to November 1970. The sampling was made possible be- cause of oyster surveys being conducted for other pro- grams. All samples from the 10 locations in Maryland were analyzed at the Gulf Breeze Laboratory. The ap- proximate station locations are shown in Fig. G-1. A summary of data on organochlorine residues in the monitored species. C. virginica. is presented in Table G-1, and the distribution of residues in this species for each sampling station by date of collection in Table G-2. Maryland was fifth among all States, in the incidence of DDT residues (81%), but the magnitude of residues in oysters was surprisingly low in view of the size of the Susquehanna River watershed and the extent of its agricultural development. More selective monitoring might show that the major pesticide burden of the river is precipitated with silt in the headwaters of the Bay and does not enter the trophic web of the estuarine system extensively. DDT residues detected at monitoring stations probably reflected pollution primarily in the adjacent and usually small drainage basins. Despite the small number of samples, the decline in average DDT residues from 26 ppb in 1966 to 10 ppb in 1970 together with a more than 150% increase in samples containing less than 1 1 ppb suggests a real change in average pollution levels. FIGURE G-1. — Diagram of coastal Maryland showing approximate location of monitoring stations loteaguc Bay Franklin City— Pocomoke Sou Tangier Sound Honga River Choptank Rive Eastern Bay Tollys Bar — Chesapeake Bay Herring Bay — Chesapeake Baj Cedar Point — Chesapeake Bay St. Marys River TABLE G-1. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1966-70 — Maryland Station Number Location Monitoring Period Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB ((ig/kg) DDT Dieldrin Franklin City 1966-70 8 8 (43) Pocomoke Sound 1966-69 6 5 (47) Tangier Sound 1966-70 10 5 (48) Honga River 1966-70 10 8 (43) Choptank River 1966-70 8 4 (30) Eastern Bay 1966-70 10 8 (70) Tollys Bar 1967-70 8 8 (44) 7 (22) 8 Herring Bay 1966-70 10 9 (46) 4 (18) 9 Cedar Point 1966-70 in 9 (70) 10 St. Marys River 1966-70 « 7 (33) Total number of samples 88 Petcent of samples positive for indicated compound 81 13 ' Each sample represents 15 or more mature moUusks. Vol. 6, No. 4, March 1973 287 TABLE G-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Maryland [BlanJc = no sample collected: — = no residue detected above 5 ppb: T = >S but <10 ppb] Yeak CoMFOlRiD REsmi^ES IN PPB (/IC/KG) STATION 1— FRANKLIN dTY— 8 SAMPLES' 1966 DDE TDE DDT 10 14 T T 1967 DDE TDE DDT 11 10 13 196« DDE 26 T T TDE 17 T - 1969 1970 DDT — 16 No Samples Collected T DDE 14 TDE — DDT - STATION 2.— POCOMOKE SOUND— 6 SAMPLES ' 1966 DDE — T TDE 17 T DDT T - 1967 DDE T T TDE T T DDT - T 1968 DDE TDE DDT 11 12 24 1969 DDE TDE DDT STATION 3— TANGIER SOUND— 10 SAMPLES' 1966 DDE TDE DDT 13 24 11 T T 1967 DDE TDE - T DDT - 10 288 Pesticides Monitoring Journal TABLE G-2. — Distribution of organochlorine residues in C. virginica jor each sampling station by date of collection — Maryland — Continued DDE TDE DDT DDE TDE DDT DDE TDE DDT Residues in PPB (/ig/kg) Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 3.— TANGIER SOUND— 10 SAMPLES' — Continued STATION 4.— HONGA RTVER— 10 SAMPLES • 1966 DDE TDE DDT T 12 11 12 20 11 1967 DDE TDE DDT T 12 T T T 1968 DDE TDE DDT T T T 28 T 10 1969 DDE TDE DDT - 1970 DDE TDE DDT - T 10 STATION 5.— CHOPTANK RTVER— 8 SAMPLES i 19M. DDE TDE DDT T 11 T 13 12 1967 DDE TDE DDT T 11 T T 196» DDE TDE DDT — Vol. 6, No. 4, March 1973 289 TABLE G-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Maryland — Continued Residues in PPB (/ig/ko) STATION 5.— CHOPTANK RIVER— 8 SAMPLES i— Continued STATION 6.— EASTERN BAY— 10 SAMPLES » 1966 DDE TDE DDT - 14 17 1967 DDE TDE DDT 11 15 T 11 T 1968 DDE TDE DDT - 11 11 48 11 16 1969 DDE TDE DDT 10 T 1970 DDE TDE DDT 11 T 10 10 STATION 7— TOLLYS BAR— 8 SAMPLES" 1967 DDE TDE DDT Dieldrin 18 19 T 13 13 17 11 13 1968 DDE 14 12 15 TDE 11 14 13 DDT - T 16 Dieldrin 15 - 11 1969 DDE TDE DDT Dieldrin 15 14 16 290 Pesticides Monitoring Journal TABLE G-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Maryland — Continued Residues in PPB (mo/ko) STATION 7.— TOLLYS BAR— 8 SAMPLES i— Continued 1970 DDE 16 T TDE 17 10 DDT - - Dieldrin 22 15 STATION 8 —HERRING BAY— 10 SAMPLES ' 1966 DDE TDE DDT 10 15 T T 1967 DDE TDE DDT Dieldrin 12 11 10 17 T 13 1968 DDE TDE DDT T T 12 14 20 12 11 11 1969 DDE TDE DDT Dieldrin 10 11 13 1970 DDE TDE DDT Dieldrin 14 16 18 12 STATION 9— CEDAR POINT— 10 SAMPLES > 1966 DDE TDE DDT 18 27 25 20 24 15 1967 DDE TDE DDT 22 20 T 15 16 13 1968 DDE T 21 T TDE - 13 T DDT - 16 24 1969 DDE TDE DDT T T 11 12 Vol. 6. No. 4, March 1973 291 TABLE G-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Maryland — Continued i Residues in PPB (ag kg) STATION 9.— CEDAK POINT— 10 SAMPLES »— Continued DDE TDE DDT STATION 10.— ST. MARYS RTVER— 8 SAMPLES ' 1966 DDE TDE DDT - 12 16 T 196- DDE TDE DDT 15 17 T T T 1968 DDE T 11 T TDE — 11 - DDT - 11 12 1969 1970 DDE TDE DDT 15 11 Each sample represents 15 or more mature mollusks. SECTION H.— \nSSISSIPPI MississippM Sound and tributaries were monitored for organochlorine residues in eastern oysters, C. virginica. during the period August 1965 - June 1972. AH samples from the eight sampling stations were anal>"zed at the Gulf Breeze Laborator>". Approximate station locations are shown in Fig. H-1. A summan.' of data on organo- chlorine residues in the monitored species. C virginica. is presented in Table H-1. and the distribution of resi- dues in this species for each sampling station by date of collection in Table H-2. Only four States had a lower incidence of DDT residues in oysters, and the maximum residue detected in Mississippi f 135 ppb) was lower than that in 12 of the other 14 States. Maximum DDT residues appeared to be more directly related to runoff from urban and in- dustrialized centers rather than frcMn agricultural areas. In 1971, there was a more than 70*^ increase in the number of DDT residues of less than 10 ppb as com- 292 pared to earlier years. This trend was reversed in the first 6 months of 1972 when 44<~c of the residues were more than 10 ppb as compared to only 25% in 1971. Golf of mexco FIGURE H-1. — Diagram of coastal Mississippi showing approximate location of monitoring stations 1. Pascagoula — Pascagoula River 2. Gravelioe — Graveline Bay 3. Deer Island — BDoju Bay 4. BQoxi Bay — BUo» Bay 5. Pass Christian f Inshore ) — Mississippi Sovmd 6. Pass Christian (Offshore) — Mississippi Sound 7. Bay St. Louis — St. Louis Bay 8. St. Joseph Point — Mississippi Sound Pesticides Monitoring Joltlnal TABLE H-1. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1965-72 Mississippi Station Number Pascagoula Grave line Deer Island Total number of samples MoNrro«ivG Period 1965-72 1965-72 1965-69 4 BQoxi Bay 1965-72 5 Pass Chrisuan ( Inshore ) 1965-66 6 Pass Christian (Ofishore) 1965-72 7 Bay St. Louis 1966-72 8 St Joseph Point 1969-72 Percent of samples positive for indicated compound Each sample represents 15 or more mature moUusks. Nlmber of Samples - Nl-mber of Posnri-E Samples and NLociml-m REsroL-E ' ) Detected i>- PPB fao kg) DDT Dieldbd.- 47 f74) 56 (99) 33 (105) 71 (135) 7 (S3) 29 (42) 31 11 (124) (69) 8 (19) 3 (16) 7 (20) I (18) TABLE ni— Distribution of organochlorine residues in C. virginica for each sampling station b\ date of collection — Mississippi [Blank = no sample collected: — = no residue delected above 5 ppb; T = >5 but <10 ppb] CoMFoimo DDE TDE DDT REsmuEs rs PPB (as EC) May Jl>-e July Auc. STATION 1— PASCAGOULA— -8 SAMPLES - DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT Vol. 6, No. 4, March 1973 293 TABLE H-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Mississippi — Continued Residues in PPB (/io/Ko) Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 1.— PASCAGOULA— 78 SAMPLES >— Continued STATION 2.— GRAVELINE— 79 SAMPLES i 1965 DDE TDE DDT T T T T T T T T T 20 1966 DDE 10 T 12 29 21 22 16 12 18 T 13 13 TDE 27 T 10 10 60 68 19 31 69 13 17 36 DDT T - - T T - - - - - - - 1967 DDE 14 12 23 24 T T T — T 12 14 15 TDE II 10 66 36 T 18 T - 12 23 18 23 DDT 13 - 10 T - - - - 21 29 10 T 1968 DDE 15 16 13 11 16 22 10 _ — — — T TDE 22 23 19 18 23 25 14 - T — — — DDT T 12 - T T T - - - - - - 1969 DDE — — 11 T 15 T — — — 11 17 TDE - - 14 T 15 12 - — - 13 20 DDT - - - - T - - - - - 10 1970 DDE - 14 14 15 10 T — — — _ — TDE - 16 17 14 11 10 - - - - - DDT - 10 T - - T - - - - - 1971 DDE 15 — — — 12 _ _ _ _ T TDE DDT 17 - - - 23 - - - - T 1972 DDE T T _ 15 T 16 TDE T T — — T — DDT - - - - - - STATION 3.— DEER ISLAND-49 SAMPLES ' 1965 DDE 10 T T T TDE 21 T 17 17 DDT T - - - 294 Pesticides Monitoring Journau TABLE H-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Mississippi — Continued Residues in PPB (^o/ko) STATION 3.— DEER ISLAND— 49 SAMPLES i— Continued 1966 DDE 14 20 15 22 27 23 17 T - T - T TDE 27 43 25 45 62 65 38 T - T - 11 DDT T 16 T 12 16 - - - - - - - 1967 DDE 10 15 14 15 11 - - — — - - T TDE 12 T 14 11 17 - - - - - - T DDT T - - - - - - - 12 - - - 1968 DDE T 11 T 12 12 — — — - — - - TDE 13 13 T 12 12 - - - - - - - DDT - T - - - - - - - - - - 1969 DDE T T 11 T T — T T TDE T - 13 13 T - 27 34 DDT - - - - - - - 22 STATION 4.— BILOXI BAY— 78 SAMPLES' 1965 DDE TDE DDT 14 23 T T 11 : T 23 T 18 1966 DDE 14 16 16 29 32 — 20 19 — T 15 T TDE 43 30 33 73 87 - 47 48 - T 27 15 DDT 14 T 11 15 16 - - - - - T - 1967 DDE 16 19 23 28 15 13 T T - - T T TDE 31 40 43 50 33 21 43 25 17 17 19 22 DDT 15 23 15 20 - T - - T T - - Dieldrin - - - 13 - - - - - - - - 1968 DDE 12 14 16 20 30 17 T — — — T 16 TDE 32 30 39 34 94 61 52 25 24 T 43 49 DDT - T - T T - - - - - - - 1969 DDE T 18 17 14 20 17 T — 14 14 20 TDE 28 46 47 46 67 54 22 25 42 28 53 DDT - 1 T It T - - - 18 - 12 Dieldrin - - - - - - - - - 16 18 1970 DDE 18 19 28 — - — - — — - TDE 60 50 78 - 77 40 - 12 12 17 DDT 15 T 14 - - - - - - - Dieldrin 19 16 15 - n - 16 - - - 1971 DDE T 24 16 24 T - 22 - - T TDE 26 65 43 69 85 - 81 - 19 27 DDT - - - - - - - - - - Vol. 6, No. 4, March 1973 295 TABLE H-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Mississippi — Continued Residues in PPB (/u}/ko) Nov. Dec. STATION 4.— BILOXI BAY— 78 SAMPLES "—Continued 1972 DDE T 10 12 18 17 T TDE 20 28 35 58 63 30 DDT - - - - - - STATION 5.— PASS CHRISTIAN (INSHORE)— 13 SAMPLES ' 1965 DDE TDE DDT T T T i T : 1966 DDE T — _ T 11 19 _ — TDE T - - T 12 34 - — DDT - - - - 11 - - - STATION 6.— PASS CHRISTIAN (OFFSHORE)— 78 SAMPLES ' 1965 DDE TDE DDT T T : ; T T T : 1966 DDE T — — 11 14 — — — — — TDE T - - 12 15 - - - - - DDT - - - T 13 - - - - - 1967 DDE — — T — — — — — — T TDE - - T - - - - - - T DDT - - - - - - - - - - 1968 DDE T T T T T — — — — — TDE - T T 11 11 - - - - - DDT - T - - - - - - - - 1969 DDE — — — T T — - T T TDE - - - T 13 - - T T DDT - - - T - - - - - 1970 DDE 12 13 15 11 T — — — — TDE T 22 22 16 T - - - - DDT - T - T — - - - - Dieldrin 11 16 - - - - 15 - - 1971 DDE — — — _ T — — — — T TDE - - - - 14 - - - - T DDT - - - - - - - - - - 1972 DDE T T 12 12 T 11 TDE T T 10 16 T - DDT - - - T - - 296 Pesticides Monitoring Journal TABLE H-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Mississippi — Continued Residues in PPB (/iO/KO) STATION 7— BAY ST. LOUIS— «6 SAMPLES ■ 1966 DDE TDE DDT : : - - 1967 DDE T T T T T — — — — - 11 T TDE T T 14 T T - - - - - - - DDT - - - - - - - - 10 - - - 1968 DDE T T T T 10 - — — — - - - TDE T T T T 11 - - - - - - - DDT - T - - T - - - - - - - 1969 DDE — T T — T T - - - T 10 TDE T - 12 - T 11 - - - 11 12 DDT - - - - T - - - - T 11 Dieldrin T 14 >' T - - - - - - - 1970 DDE T 12 17 34 32 — - - - - - TDE 13 15 21 76 12 - - - - - - DDT - - T 14 - - - - - - - Dieldrin 17 20 - 14 - - - - - - - 1971 DDE - - - — - - - - - T TDE - - - - 13 - - - - - DDT - - - - - - - - - - 1972 DDE TDE T T T T - 11 11 T - DDT - - - T - - STATION 8.— ST. JOSEPH POINT— 29 SAMPLES' DDE TDE DDT DDE TDE DDT Dieldrin DDE TDE DDT DDE TDE DDT ' Each sample represents 15 or more mature mollusks. Vol. 6, No. 4, March 1973 297 SECTION I.— NEW JERSEY Samples of eastern oysters, Crassostrea virginica, were collected at five principal stations in the New Jersey waters of Delaware Bay during the period June 1966 - June 1972. All samples were analyzed at the Gulf Breeze Laboratory. TTie approximate station locations are shown in Fig. I-l. A summary of data on organo- chlorine residues in the monitored species, C. virginica. is presented in Table I-l, and the distribution of residues in this sjjecies for each sampling station by date of collection in Table 1-2. Oyster samples collected in Delaware Bay were characterized by a 100% incidence of DDT residues and a relatively high incidence (24%) of dieldrin residues as compared to other areas monitored. The maximum DDT residue observed, 272 ppb, is low compared to that in many other estuaries; most residues, from New Jersey were less than half this amount. The fact that DDE was the principal component of these residues suggests that the pesticide had been metabolized in other links of the trophic web before its acquisition by the oyster. DDT residues appear to have been somewhat higher in the 1968-69 period than earlier, but the 1971 data show a clear-cut trend towards decreased residue levels. FIGURE I-l. — Diagram of coastal New Jersey showing approximate location of monitoring stations Drum Beds — Delaware River Maurice River — Delaware River Dividing Creek — Delaware River Lease 564/496D — Delaware River Cohansey — Delaware River TABLE I-l. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1966-72 — New Jersey Station Location Monitoring Period Number op Samples i Number of Positive Samples and Maximum Residue ( ) Detected in PPB (/iO/KO) DDT Dieldrin PCB'S' . Drum Beds 1966-72 49 49 (213) 3 (12) 2 2 Maurice River 1966-72 50 50 (143) 1 (T) 1 3 Dividing Creek 1966-71 7 7 (125) 1 (12) 4 Uase 564/496D 1966-72 52 52 (278) 28 (26) 2 5 Cohansey 1966-72 49 49 (245) 16 (23) I Occasional Stations (7) 1966-71 12 12 (166) 3 (29) Total number of samples 219 Percent of samples positive for indicated compound 100 24 3 NOTE: T = >5 but <10 ppb. » Each sample represents 15 or more mature mollusks. > Present but not quantified. 298 Pest ICIDES MONITORIN o Journal TABLE 1-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — New Jersey [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] Yeai Compound Resdues in ppb (/uj/ko) STATION 1.— DRUM BEDS-^9 SAMPLES' 196« DDE TDE DDT 19 18 33 38 15 24 24 11 28 26 10 17 14 1967 DDE 43 39 30 31 27 18 27 37 42 TDE 34 28 27 30 40 25 33 46 50 DDT 11 T - - 21 16 13 22 14 1968 DDE 43 50 55 50 110 110 55 44 75 52 TDE 43 43 54 57 98 83 38 35 48 44 DDT 10 T T - T 13 13 T " - 1969 DDE 49 19 48 51 73 52 63 67 56 58 TDE 35 18 15 45 44 30 34 32 41 28 DDT - - - - - T - T T T 1970 DDE 99 100 110 34 37 46 38 TDE 42 52 47 12 15 21 16 DDT 11 - - - - - - Dieldrin - - 12 - - - - 1971 DDE 35 59 70 38 27 33 TDE 10 35 30 26 14 28 DDT - - - - - - 1972 DDE TDE DDT Dieldrin PCB's MO 20 52 T »52 29 T STATION 2— MAURICE RIVER— 50 SAMPLES' 1966 DDE TDE DDT 11 IS T 12 14 15 13 16 T T 1967 DDE 12 12 13 15 12 T 18 26 19 TDE T T 19 28 23 10 30 40 31 DDT 17 - - - T - 13 13 - 1968 DDE 19 24 22 21 45 37 17 20 16 24 TDE 27 31 32 43 68 38 21 24 17 19 DDT T - - - — 16 T 10 T T Vol. 6, No. 4, March 1973 299 I TABLE 1-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — New Jersey — Continued Residues in PPB (lua/m) STATION 2.— MAURICE RIVER— 50 SAMPLES "—Continued 1969 DDE 21 16 77 75 13 22 12 T 19 13 TDE 21 15 26 68 14 23 18 11 14 T DDT - - - - - T - - - - 1970 DDE 16 24 25 32 17 13 18 13 TDE T 22 36 34 16 15 19 10 DDT - - - - - - - - 1971 DDE 12 T 26 23 14 T TDE T — 29 29 13 — DDT - - - - - 1972 DDE TDE DDT Dieldrui PCB's 14 M7 17 T STATION 3— DIVIDING CREEK— 7 SAMPLES' 1966 DDE T TDE 13 DDT - 1967 DDE 26 41 22 TDE 28 66 33 DDT — 18 11 Dieldrin — 12 - 1968 DDE 49 TDE 64 DDT T 1969 DDE 60 TDE 35 DDT - 1971 DDE 13 TDE 13 DDT - STATION 4— LEASE 564/496D— 52 SAMPLES i 1966 DDE 34 29 41 51 58 TDE 42 39 53 53 110 DDT _ T 12 67 15 300 PESTICIDES Monitoring Journal TABLE 1-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — New Jersey — Continued Residues in PPB (/io/ko) STATION 4.— LEASE 564/496D— 52 SAMPLES "—Continued 1967 DDE 47 41 48 41 44 29 38 26 39 39 TDE 48 39 86 81 72 47 56 41 56 56 DDT T - - - 18 17 19 10 - - Dieldrin 10 - 18 20 18 - 12 - - - 1968 DDE 35 38 37 23 no 77 51 69 67 57 TDE 50 54 60 45 140 82 46 57 57 56 DDT T T T - 18 23 16 T T T Dieldrin II 14 15 - - 14 - - - 11 1969 DDE 100 66 95 27 82 47 72 84 72 TDE 87 51 74 34 68 39 45 48 56 DDT 13 - - - 17 T 13 14 14 Dieldrin 13 12 18 21 - - 19 13 11 1970 DDE 130 140 180 75 35 62 95 120 42 12 TDE 61 67 98 92 18 33 36 33 36 43 DDT 15 16 - - - - - - - - Dieldrin 14 16 20 26 - - - - - 12 1971 DDE 150 180 180 190 49 56 TDE 45 87 62 78 25 18 DDT - T - - - - Dieldrin 13 19 19 T - - 1972 DDE TDE DDT Dieldrin PCB's »67 42 11 T »46 35 14 en STATION 5.— COHANSEY^»9 SAMPLES ' 1966 DDE TDE DDT 12 24 17 37 20 35 22 33 11 23 1967 DDE 29 35 41 54 24 29 17 17 32 TDE 45 53 19 150 59 66 39 38 59 DDT T T 22 25 10 13 - T - Dieldrin - - 23 18 12 T - - 11 1968 DDE 20 30 22 49 81 68 32 33 52 28 TDE 41 62 66 12 150 110 60 50 70 32 DDT - - - - 14 11 15 T T - Dieldrin - 12 14 13 19 12 - - - - Vol. 6, No. 4, March 1973 301 TABLE 1-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — New Jersey — Continued Residues in PPB (/to/KO) STATION 5.— COHANSEY— 49 SAMPLES i— Continued 1969 DDE 33 59 57 36 37 29 24 42 38 TDE 46 43 76 49 46 45 44 48 42 DDT - - - - T T - - T Dieldrin - - 16 - - - - - - 1970 DDE 45 41 55 30 27 53 36 42 TDE 46 51 98 30 34 54 42 36 DDT - - - T - - - - Dieldrin - 11 21 - - - - - 1971 DDE 52 28 38 27 21 22 TDE 42 24 61 30 20 17 DDT - - T - - - Dieldrin 13 - 16 - - ,- 1972 DDE TDE DDT Dieldrin PCB's 23 114 •40 49 T Each sample represents 15 or more mature mollusks. DDT values are approximate twcause of presence of unidentified PCB's. ' Present but not quantified. 302 Pesticides Monitoring Journal SECTION J.— NEW YORK Several diflferent species of mollusks (Crassotrea vir- ginica, Modiolus domissus, Mytilus edulis, Mercenavia mereenaria, and Mya arenaria) were collected at 16 principal sites in New York's coastal waters to monitor organochlorine pollution during the period March 1966 - June 1972. Samples were analyzed at the Gulf Breeze Laboratory until February 1969 and thereafter by the New York Conservation Department. Analyses of aliquots of some of the samples collected during the period October 1968 - July 1970 have been reported by the cooperating agency (9) and do not differ sig- nificantly from the data reported here. Approximate station locations are shown in Fig. J-1. A summary of data on organochlorine residues in the monitored sp)ecies is presented in Table J-1, and the distribution of residues in these species for each sampling station by date of collection in Table J-2. The hard clam, M. mereenaria. was the principal species collected because of its ubiquity and despite its recog- nized inefficiency in storing organochlorine residues. This lack of sensitivity to low levels of DDT pollution is especially well documented in the analytical record of samples collected in Conscience Bay, Station 6. Hard clams were the only mollusk of four species collected there in which DDT residues were undetected. DDT pollution apparently disappeared at this station during the period July 1968 - March 1969, but this was be- cause of the substitution of hard clams for the blue mussel as monitors. These data emphasize the fact that in areas where hard clams did show DDT residues, there were probably significant levels of DDT in the water or food supply. This parallels the situation in Delaware, where hard clams collected in Delaware Bay (Cape Henlopen) consistently had DDT residues while residues were FIGURE J-1. — Diagram of coastal New York showing approximate location of monitoring stations 9. Mecox Bay 10. Shinnecock Bay 11. Moriches Bay 12. Bellport — Great South Bay 13. SayviUe— Great South Bay 14. Amityville— South Oyster Bay 15. East Bay 16. West Bay 1. Mamaroneck 2. Hempstead Harbor 3. Oyster Bay Harbor 4. Huntington Bay 5. Nissequogue River 6. Conscience Bay 7. Southold — Gardiners Bay 8. Flanders Bay usually not detected in hard clams collected in inner bays. TTiere was generally good agreement in the magnitude of residues in two or more species, other than the hard clam, collected at the same station on the same day. The New York samples ranked fifth among the States in incidence and sixth in magnitude of DDT residues. More samples (43%) contained dieldrin residues than in any other area monitored. PCB's were present in some samples in 1972, but they were not identified or quantified. Despite the large number of samples collected over a p>eriod of 7 years, no clearly defined trends in pollution levels can be identified. This may be the result of having used a variety of species. The overall impression is one of no significant change in DDT residue levels in mollusks. TABLE J-1. — Summary of data on organochlorine residues in the monitored species, 1966-72 — New York Station Number Location Monitoring Period Principal Monitored Species Number of Samples i Number of Positive Samples and Maximum Residue ( ) Detected in PPB (ag/Ro) DDT Dieldrin 6 7 8 9 Mamaroneck Hempstead Harbor Oyster Bay Huntington Bay Nissequogue River Conscience Bay Southold Flanders Bay Mecox Bay 1966-69 1966-72 1966-72 1966-72 1966-72 1966-72 1969-72 1966-72 1966-72 M. mereenaria M. mereenaria M. mereenaria M. edulis M. edulis M. edulis C. virgtniea M. mereenaria C. virgtnica 36 69 67 34 (96) 70 (201) 54 (99) 72 (588) 70 (138) 61 (112) 32 (149) 63 (199) 65 (596) 27 (29) 61 (132) 48 (86) 52 (104) 58 (117) 52 (75) 26 (78) 15 (107) 14 (22) Vol. 6, No. 4, March 1973 303 TABLE J-1. — Summary if data on organochlorine residues in the monitored species, 1966-72 — New York — Continued Station Number Location Monitoring Period Principal Monitored Species Number of Samples ' Number op Positive Samples and Maximum Residue ( ) Detected in PPB (jug/ko) DDT Dieldrin 10 11 12 13 14 15 16 Shinnecock Bay Moriches Bay Bellport Bay Sayville Amityville East Bay West Bay Occasional stations 1966-72 1966-72 1966-72 1966-72 1966-72 1966-72 1966-72 8) 1967-72 M. mercenaria M. mercenaria M. mercenaria M. mercenaria M. mercenaria M. mercenaria M. mercenaria Mixed 7.1 71 71 74 73 57 57 9 43 (188) 49 (83) 51 (132) 41 (107) 49 (64) 43 (98) 51 (111) 9 (159) 19 (46) 13 (49) 10 (53) 16 (59) 13 (42) 13 (38) 19 (20) 3 (31) Total number of samples 1,059 Percent of samples positive for indicated compound 81 43 Each sample represents 15 or more mature moUusks. TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York (Blank = no sample collected; — = no residue detected above 5 ppb; T = >5 but <10 ppb) Residues in PPB (/ig/kg) STATION 1.— MAMARONECK— Af. MERCENARIA— 36 SAMPLES' 1966 DDE — T — — — — T 16 T TDE - T - 13 T 12 18 49 29 DDT - - - - - - - 14 13 Dieldrin - - - - - - - 29 12 1967 DDE T 19 12 11 11 11 T T T 12 T T TDE 35 50 31 27 27 28 20 15 26 28 32 30 DDT 24 27 11 11 11 15 T T - T 14 T Dieldrin 16 21 16 16 15 15 15 14 14 13 14 15 1968 DDE T T T 11 10 T - - - - - T TDE 27 25 27 30 27 26 22 20 20 18 23 19 DDT T - - T 12 15 T - - - - - Dieldrin 11 12 14 11 12 - 10 12 12 11 15 14 1969 DDE TDE DDT Dieldrin 18 11 10 24 11 13 304 Pesticides Monitoring Journal TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (ag/ko) STATION 2— HEMPSTEAD HARBOR— M. MERCESARIA, UNLESS OTHERWISE INDICATED— 74 SAMPLES' 1966 DDE — — — T — 3 24 T 11 15 13 TDE - - - 29 - 48 17 29 39 35 DDT - - - 13 - 26 - - 17 14 Dieldrin - - - - - - - - 17 15 1967 DDE T 14 13 12 12 14 T T 12 13 12 10 TDE 17 36 35 30 33 39 23 25 29 30 32 30 DDT - 13 13 11 15 28 15 16 - T 11 11 Dieldrin - 15 16 17 15 19 15 17 15 16 14 16 1968 DDE II 13 13 13 10 T — — — T — T TDE 29 31 31 34 26 27 17 18 17 24 22 23 DDT 11 - 10 10 10 - T - - - - - Dieldrin 12 16 14 15 20 16 - - 11 50 93 65 1969 DDE — 10 = 15 ^ 16 18 15 T — = 34 = 30 = 23 = 26 TDE 12 29 33 34 18 19 22 10 93 62 57 57 DDT - T 34 38 12 T T - 74 49 47 46 Dieldrin 47 70 22 86 85 13 33 38 132 28 40 31 1970 DDE J 41 11 5 24 ■'13 = 12 = 18 10 10 = 21 = 18 = 18 = 20 TDE 71 33 51 28 33 48 22 35 71 40 48 50 DDT 76 15 62 29 54 70 17 18 28 35 43 51 Dieldrin 29 30 30 25 30 33 20 18 26 22 19 25 1971 DDE ' 10 M3 = 13 = 15 = 20 - = 16 ' 13 = 22 = 23 TDE 22 26 33 38 27 16 37 31 46 58 DDT 18 31 34 44 23 10 30 17 32 51 Dieldrin 10 14 16 31 - 13 21 19 23 20 1972 DDE .-. ]9 ' 17 = 23 = 34 = 9 — TDE 41 - 48 67 15 T DDT 22 24 44 53 9 - Dieldrin 19 14 19 21 - T STATION 3.— OYSTER BAY HARBOR— Af. MERCENARIA. UNLESS OTHERWISE INDICATED— 73 SAMPLES" 1966 DDE — — _ — — — — — T T TDE - - - - - T - - 22 11 DDT - - 13 - - - - - T - Dieldrin - - - - - - - - 13 11 1967 DDE 13 T T T T T — T T T T T TDE 50 15 19 14 20 22 26 17 13 T 13 15 DDT 18 - - - - 13 T 12 - - - - Dieldrin 10 - 14 13 14 14 11 14 - 12 11 - Vol. 6, No. 4, March 1973 305 TABLE J-2. — Distribution of organocMorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (;io kg) STATION 3— OYSTER BAY HARBOR— M. MERCESARIA. UNLESS OTHERWISE INTDICATED— 73 SAMPLES i— Continued DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin = 13 32 22 ♦27 48 55 20 15 29 30 DDE TDE DDT Dieldrin STATION 4— HL^TTNGTON BAY— M. EDULIS. UNLESS OTHERWISE INDICATED— 74 SAMPLES ■ 1966 DDE •T s_ = 32 98 53 40 5 — 3 — = 21 5 29 TDE 16 — 75 280 190 110 - T 64 71 DDT - — 81 210 60 25 - - 17 16 Dieldrin _ _ _ _ 18 13 _ _ 12 T DDE TDE DDT Dieldrin DDE TDE UUl — T — T 14 — T — — — T 11 Dieldrin t II 11 - 12 - - - - - - 11 T 1969 DDE '11 'T 18 ^T •30 29 5 15 34 24 28 30 TDE 26 28 32 35 24 104 100 23 127 73 84 80 DDT - - - 21 21 46 50 - 47 28 55 50 Dieldrin 7 T T 11 14 104 26 T 18 - 23 34 306 Pesticides Monitoring Journal TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residi;es in PPB (#g/eg) Jan. Feb. Mas. Apb. NUy June July Aug. Sept. Oct. STATION 4.— HUNTINGTON BAY— M. EDULIS. UNXESS OTHERWISE INDICATED— 74 SAMPLES i— Continued 1970 DDE 38 15 23 _ 20 13 21 20 19 20 24 21 TDE 90 58 60 22 50 59 146 70 40 66 89 73 DDT 61 40 49 12 40 40 55 29 44 28 28 29 Dkldrin 18 16 17 38 22 21 26 21 26 22 17 17 1971 DDE 21 18 15 11 21 15 26 33 21 19 TDE 70 57 50 37 51 63 74 14 56 60 DDT 35 30 24 22 22 22 27 T 23 28 Dieldrin 17 18 22 14 - 21 14 13 - 14 1972 DDE — 14 17 15 10 14 TDE T 33 40 36 20 41 DDT - 20 15 18 - 15 Dieldrin - 13 15 12 - 60 STATION 5— NISSEQUOGUE RIVER— W. EDVLIS. UNLESS OTHERWISE INDICATED— 74 SAMPLES ' 1966 DDE 21 21 24 18 T 19 17 22 42 40 TDE 33 47 45 49 17 43 38 48 76 59 DDT 23 37 50 34 13 30 29 22 20 30 Dieldrin 16 20 23 - - - - - 31 17 1967 DDE — 23 24 21 23 21 18 14 20 19 17 18 TDE 33 53 59 50 18 51 42 38 49 42 35 44 DDT 13 27 29 33 45 42 33 32 33 27 18 32 Dieldrin 13 17 27 27 27 22 18 19 15 15 14 17 1968 DDE 14 16 13 17 17 13 11 - 5- '- = - '- TDE 32 33 36 40 44 49 44 31 - - - T DDT 20 18 21 23 42 51 47 25 - - - - Dieldrin 14 18 16 18 - - - - - - - 12 1969 DDE ^- = T 'T 12 »T 3 — »I5 .- 10 14 18 20 TDE - T 14 30 12 T 22 T 34 35 49 42 DDT - - T 22 11 T 14 - 17 30 36 25 1970 DDE 16 17 = T - 21 14 18 15 'T 14 11 •T TDE 37 44 18 16 46 37 48 46 17 38 29 14 DDT 25 33 T T 38 26 34 30 - 22 17 - Dieldrin 27 17 10 16 23 20 24 25 T 24 12 T 1971 DDE 14 T 'T J- : — 10 »17 '14 11 »- TDE 30 16 17 15 12 38 T 10 34 T DDT 24 12 T T - 20 - - 13 - Dieldrin 14 T 17 20 T 27 - 13 10 — Vol. 6, No. 4, March 1973 307 TABLE J-2. — Distribution of organochtorine residues in the monitored species for each sampling station by date . collection — New York — Continued Residues in PPB (/ic/kg) Jan. Feb. Mar. STATION 5.— NISSEQUOGUE RIVER— M. EDULIS. UNLESS OTHERWISE INDICATED— 74 SAMPLES ' — Continued 1972 DDE ." — 15 -T = - T T TDE 12 33 12 T 20 14 DDT - 18 T - 10 T Dieldrin 10 13 T - T 12 STATION 6.— CONSCIENCE BAY— M. EDULIS, UNLESS OTHERWISE INDICATED— 73 SAMPLES' 1966 DDE 3T ' — = - 5 18 = — = - 20 21 24 «17 TDE 18 - - 26 - - 35 34 46 40 DDT 15 12 - 15 - - 22 22 30 17 Dieldrin - 12 - - - - - - 25 - 1967 DDE 18 23 18 18 20 22 21 21 20 18 17 16 TDE 48 43 33 34 42 44 48 44 36 31 29 31 DDT 24 23 18 21 29 41 36 35 24 21 18 20 Dieldrin 17 20 20 30 24 22 21 16 13 15 14 13 1968 DDE 14 16 14 15 T 12 '- = - '- = - 3- '- TDE 23 24 22 27 24 24 - - - - - - DDT 14 13 17 19 21 21 - - - - - - Dieldrin 15 14 14 14 - - - - - - - T 1969 DDE = — = - ' — 16 15 "16 3 18 J 14 ' 13 17 23 21 TDE - - - 23 24 36 22 20 14 29 39 36 DDT - - - 14 32 48 20 - T 15 26 17 Dieldrin - T T 14 15 - T - 15 26 18 13 1970 DDE 17 22 ' — 25 21 24 26 = - 24 23 18 TDE 37 37 11 49 45 59 59 17 46 37 26 DDT 25 36 - 36 29 28 27 - 24 15 14 Dieldrin 16 19 20 26 20 23 23 T 16 T 10 1971 DDE 3T ^T 3- 16 ' 10 •T » — »- T 12 'T TDE 12 15 13 29 15 24 13 13 16 23 11 DDT T 10 - 13 - 10 - T T 11 - Dieldrin T 14 22 18 - 10 10 17 T T 11 1972 DDE TDE DDT Dieldrin 10 18 14 T T 11 75 13 21 49 308 Pesticides Monitoring Journal TABLE J-2. — Dislribulion of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (/ig/kg) STATION 7.— SOUTHOLD— C. VIRGIN IC A. UNLESS OTHERWISE INDICATED— 34 SAMPLES' 1969 DDE •22 6T s — '22 = T = T •20 TDE 48 11 T 38 14 T 41 DDT 28 - - 89 - - 63 Dieldiin - 78 T - - - T 1970 DDE •16 29 27 27 = 10 21 19 17 22 20 TDE 32 30 32 35 13 18 19 21 21 21 DDT 21 26 23 22 - 22 23 18 15 12 Dieldrln - 21 20 26 T 11 27 14 15 14 1971 DDE °T 17 17 18 5 — 10 <■ — » — = - M5 = — TDE 16 19 19 17 - 10 T T - 18 16 DDT - 14 11 12 - 13 - - - 13 - Dieldiin 21 12 14 16 14 - - 12 - T T 1972 DDE 16 17 18 16 = 10 21 TDE 27 17 22 21 18 28 DDT 16 T T 11 - 31 Dieldrin 14 11 T 10 T 39 STATION 8— FLANDERS BAY— Af. MERCENARIA, UNLESS OTHERWISE INDICATED— 69 SAMPLES ' 1966 DDE 56 28 22 24 — 11 T T 10 17 TDE 54 25 21 44 - 23 14 - 15 23 DDT 89 29 15 - - - - - - - 1967 DDE 15 18 25 23 = 23 '20 17 17 16 17 16 15 TDE 20 27 42 32 58 53 46 47 36 42 37 33 DDT - - - - 12 12 - T - - - - 1968 DDE 13 10 12 17 10 19 10 T 10 - T 10 TDE 25 17 25 41 24 59 44 38 38 18 39 34 DDT - - - - - - - - - - - - 1969 DDE - T 12 '33 15 14 10 12 "20 - 13 TDE 12 32 25 84 33 28 19 23 49 T 28 DDT - - - 27 - - - - 75 - - Dieldrui - - - - 17 107 11 - 14 93 - 1970 DDE 14 «T 13 M4 a 14 3T T »T TDE 26 22 30 29 29 19 T 14 DDT - 12 - - T - - - Dieldrin U - - - T T - - Vol. 6, No. 4, March 1973 309 TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued RESroUES IN PPB (/lO/KG) STATION 8.— FLANDERS BAY— M. MERCENARIA, UNLESS OTHERWISE INDICATED— 69 SAMPLES "—Continued 1971 DDE _ T — T •16 3 — T 13 ' — — TDE 10 16 - 16 50 16 12 24 - 11 DDT - - - - 15 - - - - - Dieldrin 10 T 12 13 T - - T - - 1972 DDE T — - - - - TDE 12 - - 10 T - DDT - - - - - - Dieldrin T - - - — — STATION 9.— MECOX BAY— C. VIRGINICA, UNLESS OTHERWISE INDICATED— 67 SAMPLES ' 1966 DDE 300 120 3 22 3T 3 27 3 21 3 — 46 42 83 TDE 240 120 41 13 45 29 - 46 37 83 DDT 56 22 20 - 19 - - 12 - - 1967 DDE 63 67 77 T '37 190 3 15 49 64 69 93 no TDE 66 60 62 11 67 180 22 52 74 74 100 73 DDT - - - - 29 27 T 18 17 11 15 T 1968 DDE 100 53 130 150 130 68 32 34 37 75 30 TDE 81 48 87 120 85 48 29 18 32 50 18 DDT - - 20 38 48 T - - - - - 1969 DDE 44 62 26 60 3 20 3 21 3 19 3T 3 10 3- 3 12 TDE 31 45 20 39 31 29 21 10 10 - 23 DDT - - - T 24 10 - - - - - Dieldrin - - - - 12 - - 22 - - - 1970 DDE 3 19 3 21 16 32 = 16 21 22 36 3T 3T TDE 27 27 14 45 36 25 38 48 10 12 DDT 52 49 10 - 32 T 13 13 - - Dieldrin - - - T 10 - - 16 - 10 1971 DDE 30 41 34 T 14 37 35 TDE 24 32 34 10 15 40 46 DDT - T T - - 15 T Dieldrin - 12 T - 10 19 - 1972 DDE 45 37 26 34 26 35 TDE 52 39 26 40 27 38 DDT 13 T - T - 12 Dieldrin 10 T 10 - T - 310 Pesticides Monitoring Journal TABLE J-2. — Dislribuiion of organochlorine residues in the monitored species for each sampling station by date collection — New York — Continued Residues in PPB (^o/kg) Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. STATION 10.— SHINNECOCK BAY— M. MERCESARIA, UNLESS OTHERWISE INDICATED— 73 SAMPLES 1966 DDE _ — — 3T — T — — - T TDE - - - T - 14 - - - 13 DDT - - - - - - - — — — 1967 DDE T T T 59 T T — T - T - - TDE 12 12 12 50 T T - T - T - - DDT - - - - - T - - - - - — 1968 DDE TDE DDT - - - - - - - - - 10 - T 1969 DDE _ — — T »20 — — =12 = 14 = 10 '- = 13 TDE — T - T 38 T T 21 20 16 - 24 DDT - - - - 21 - - 12 T T - 22 DieldriD - - - - 14 T - - T 46 - - 1970 DDE "11 3 — 3 — 3 — '10 3 18 = 10 = 12 '- »- 8T TDE 18 13 T - 19 34 18 22 - T 11 DDT - - - - T 21 24 20 T - - Dieldrin 14 - 12 - - 12 T T 12 - - 1971 DDE = 10 JT = — ' — = — - - = - = - '- TDE 17 18 10 10 - - T - - T DDT 12 14 T - - - - - - - Dieldrin 10 10 - - - 44 18 T T - 1972 DDE TDE T T = - = II 22 11 = 11 165 DDT - - - 12 T 12 STATION 11.— MORICHES BAY— M. MERCEN^RM, UNLESS OTHERWISE INDICATED— 71 SAMPLES ' 1966 DDE _ — — T — — — — = 15 T TDE - - - 10 - - - - 33 14 DDT - - - - - - - - - — 1967 DDE T T T T T T T T T T T - TDE 13 14 18 13 18 17 10 T 17 T 18 - DDT - - - - - - - - - - - - 1968 DDE T — T T — - — — - - - - TDE 10 - 14 T - - - T - 12 T T DDT - - - - - - - - - - - — 1969 DDE — — — — — - — - - - - TDE - 11 — — 13 - T T - - T DDT - - - - - - - - - 24 — Vol. 6, No. 4, March 1973 311 TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (/iC/KO) STATION 11.— MORICHES BAY— M. MERCENARIA. UNLESS OTHERWISE INDICATED— 71 SAMPLES i— Continued 1970 DDE - T — T T 3T 2 20 = 25 = 25 = 13 TDE T 13 - 14 20 21 40 29 19 13 DDT - T - - - 11 23 17 17 T Dieldrin - - - - T - - 14 T - 1971 DDE T = 20 "18 - — — — = 22 = 10 = 21 TDE 10 27 25 11 - - T 15 26 34 DDT - 15 14 - - - - 17 T 25 Dieldrin T T 16 - - 17 18 - T T 1972 DDE = 17 = 16 M7 = 20 = 17 = 25 TDE 27 20 27 26 13 33 DDT 19 T - 15 - 22 Dieldrin T - - T - 49 STATION 12— BELLPORT BAY— M. MERCENARIA. UNLESS OTHERWISE INDICATED— 71 SAMPLES i 1966 DDE 57 — - 12 T T T 14 16 10 TDE 44 - 10 27 18 13 16 28 30 20 DDT 31 - - T - - - - - - 1967 DDE 20 21 24 19 12 12 11 10 15 T 13 14 TDE 42 40 45 36 30 31 25 19 26 20 22 27 DDT - - - - T - - T - - - - 1968 DDE 15 13 15 30 10 T T — T _ — — TDE 28 24 27 50 23 14 12 - T - - T DDT - - - - - - - - - - - - 1969 DDE - T — »25 T — T — — — — TDE - 10 - 50 10 15 18 - - - - DDT - - - 33 - - - - - - - 1970 DDE T — 11 10 T T — — — TDE 13 - 25 17 21 17 - 11 - DDT - - - T - - - - - Dieldrin - - - T - - 37 T - 1971 DDE — T T — — — - — — — — TDE DDT Dieldrin 10 12 11 13 10 - - - - - T - - 12 T T T - 10 - - 53 1972 DDE — - — — — T TDE - T T T - — DDT — - — — — — Dieldrin 16 - - - - 312 Pesticides Monitoring Journal TABLE J-2. — Distribution of organocMorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (ag/kg) STATION 13.— SAYVILLE— M. MERCENARIA. UNLESS OTHERWISE INDICATED— 74 SAMPLES ' 1966 DDE — — — T — — — — — T TDE - - T 10 - - - - - 10 DDT - - T T - - - - - - 1967 DDE T T 11 T T T T T T - T T TDE 14 19 24 16 24 14 T 10 T - 16 19 DDT T - - - T - - T - - - - 1968 DDE TDE DDT - - - - - - T T - - - - - - - - - - - - - - - - 1969 DDE — — — — — — — — — — »1! T TDE - - - - - - - - T T 24 13 DDT - - - - - - - - - - - - Dieldrin - - - - - - - - 59 - 19 12 1970 DDE — — - — — T — T 1 10 - T TDE T 13 11 - T 16 T 14 16 12 T 20 DDT - - - - - T 10 - T T - 10 Dieldrin - T - - - T - - - T 10 T 1971 DDE T - — — — — — — — TDE 12 T 11 11 10 - - - - 16 DDT - - - - - - - - - 12 Dieldrin T T - - - 13 - 41 T 11 1972 DDE •22 •22 - 17 — — TDE 56 38 - 16 - - DDT 29 T T 10 - T Dieldrin 15 - - 11 - - STATION 14— AMITYVILLE— M. MERCENARIA— 73 SAMPLES" 1966 DDE — _ — — _ _ — — T T TDE - - - 18 - - - - 10 17 DDT - - - - - - - - - - 1967 DDE T T T T T T — — - - T - TDE 20 15 16 16 18 14 17 13 T 11 14 - DDT T - - - T - - T - - - - 1968 DDE — — — T — — T _ T — — — TDE - - - 13 - — 11 T T - 13 T DDT — - - - - - - - - - - - Vol. 6. No. 4, March 1973 313 TABLE J-2. — Dislribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (/ug/ko) STATION 14.— AMITYVILLE— M. MERCENARIA—13 SAMPLES i— Continued 1969 DDE _ _ _ _ _ _ _ _ _ — 20 — TDE - T - T 14 - T - 11 T 11 - DDT - - - - - - - - - T 33 - Dieldrin - - - - T - - - T - T T 1970 DDE — — — 10 T T T - - - - TDE DDT Dieldrin 11 - T 20 19 15 15 10 T T 10 - T - T - - - - 18 - T 1971 DDE — — — — — — — - - - TDE 11 12 T 16 - T T 10 - 10 DDT - - - - - - T - - - Dieldrin - - 10 10 - - T - 42 ■- 1972 DDE T — _ — — _ TDE 16 T T T - - DDT T - - - - - Dieldrin 11 - - - - - STATION 15.— EAST BAY— M. MERCENARIA, UNLESS OTHERWISE INDICATED— 57 SAMPLES ' 1966 DDE — — — — — — - - T T TDE - - T - - - - - 18 19 DDT - - T - - - - - T - 1967 DDE T - T T - T - - - T T T TDE 21 12 13 15 19 19 15 T T 13 T 14 DDT T - - - T T T T - - - T 1968 DDE T T T — — - — — - - TDE 16 10 12 - - T - 12 - T DDT - - - - - - - - - - 1969 DDE - - — — — — — — — — T TDE DDT Dieldrin 16 10 - - 16 14 14 T T T T 14 16 - - - - T 10 16 17 T 14 1970 DDE TDE DDT Dieldrin T 12 T T 3 10 21 18 16 314 Pesticides Monitoring Journal TABLE J-2. — Distribution of organochlorine residues in the monitored species for each sampling station by date of collection — New York — Continued Residues in PPB (ag/ko) STATION 15.— EAST BAY— Af. MERCENARIA. UNLESS OTHERWISE INDICATED— 57 SAMPLES »— Continued 1971 DDE = 12 "T = 18 3_ — T TDE 29 21 57 19 15 26 DDT 29 11 23 12 10 23 Dieldrin 15 11 38 11 - — 1972 DDE TDE T = T 14 T - DDT - T - - STATION 16.— WEST BAY— M. MERCENARIA, UNLESS OTHERWISE INDICATED— 57 SAMPLES ' 1966 DDE _ T _ — — — — T T TDE - 15 - - 13 - - 26 22 DDT - T - - - - - 14 13 1967 DDE T T T — T 10 T T - T T T TDE 20 17 24 24 27 32 - 17 T 20 14 19 DDT 13 T 12 IS 17 14 - 13 - - - 13 Dieldrin - - 11 12 10 - - - - - - - 1968 DDE — T T T ._ - — - - - TDE 20 18 13 17 T 15 14 16 15 14 DDT - T - - - - - - - - 1969 DDE — T - — II — — — — — 10 TDE 19 20 T - 28 13 18 19 14 21 21 DDT - - - - 33 T - - - 12 43 Dieldrin - - - - T T 18 17 20 12 17 1970 DDE TDE DDT Dieldrin 1.? T 20 II 14 19 40 T = T 15 15 T 1971 DDE = 11 "T - 15 s — - 10 TDE 23 2: 47 15 14 25 DDT 28 12 44 - T 20 Dieldrin T 10 16 - T 10 1972 DDE TDE DDT Dieldrin 10 18 14 T T ■'.30 59 22 » 13 28 T ^ Each sample represents 15 or mon - M. edulis. 3 M. arenaria. * C. rirginica. •' A/, mercenaria. " M. demissus. Vol. 6, No. 4, March 1973 ature mollusks. 315 SECTION K— NORTH CAROLINA The monthly collection of eastern oysters, Crassostrea virginica. to monitor pollution was initiated in July 1966 and continued until July 1972. During the program, 17 stations were sampled routinely for periods ranging from 3 to 6 years. All samples were analyzed by the Gulf Breeze Laboratory. Approximate station locations are shown in Fig. K-1. A summary of data on organochlorine residues in the monitored species. C. virginica, is presented in Table K-1, and the distribution of residues in this species for each sampling station by date of collection in Table K-2. North Carolina samples are noteworthy for the con- tinuity of collections of a single species of moUusk at short intervals over a relatively long period of time. For this reason the data present a good picture of annual and seasonal trends of a persistent synthetic pollutant in this estuarine environment. The incidence of DDT residues (75%) and maximum magnitude (566 ppb) are about the median of the 15 States monitored. The 1% incidence of dieldrin residues was somewhat lower than most other states. PCB com- pounds were not detected. Although there are exceptions from one estuary to an- other, the magnitude of DDT residues in oysters showed little seasonal variation during the period 1967-69 when maximum levels of DDT pollution were detected. The overall decline in DDT residues (Part I. Table 7 and Fig. 2) is notable and undoubtedly associated with the decreased agricultural use of this chemical in North Carolina. NORTH CAROLINA ^p LANTIC OCEAN FIGURE K-1. — Diagram of coastal North Carolina showing approximate location of monitoring stations Wanchese — Croatan Sound Salvo — Pamlico Sound Wysocking Bay Rose Bay Bay River Neuse River Point of Marsh — Neuse River West Bay Back Bay — Core Sound Jarrett Bay — Core Sound North River Newport River Bogue Sound White Oak River New River Wrightsville Beach — Wrightsville Sound Southport — Cape Fear River Shallotte River TABLE K-I. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1966-72 — North Carolina Station Monitoring Number of Number of Positive Samples and Maximum Residue ( ) Detected in PPB (^g/kg) DDT Dieldrin 1 ' Wanchese 1966-72 72 49 (264) 2 ■' Salvo 1966-72 71 58 (566) y Wysocking Bay 1966-70 4.1 35 (64) 4 ' Rose Bay 1966-72 71 46 (121) 3 (14) 5 « Bay River 1966-72 71 69 (310) 2 (12) 6 Neuse River 1966-70 4.1 43 (176) 7 « Point of Marsh 1966-72 71 53 (139) 2 (19) 8 West Bay 1967-72 58 34 (74) 9 Back Bay 1966-67 9 8 (103) 10 • Jarrett Bay 1966-72 66 42 (106) 11 " North River 1966-72 64 48 (172) 2 (10) 12 • Newport River 1966-72 68 54 (121) 3 (13) Pesticides Monitoring Journal TABLE K-1. — Summary of data on organochlorinc residues in the monitored species (C. virginica). 1966-72- Nortli Carolina — Continued Station Number Location Monitoring Period Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (jho/kg) DDT DlELDRIN 13 14 15 • 16 17 • 18 Bogue Sound White Oak River New River Wrightsville Beach Southport Shallotte River 1967-72 1966-70 1966-72 1966-70 1966-72 1966-70 51 43 72 43 72 43 33 (71) 30 (60) 61 (118) 35 (57) 32 (116) 38 (51) Total number of samples 1,031 Percent of samples positive for indicated compound 75 1 Data from these stations summarized in Part I. Tab'e 7. and Fi^;. 2, Each sample represents 15 or more mature mollusks. TABLE K-2. — Distribution of organocMorine residues in C. virginica for each sampling station by date of collection — North Carolina [Blank = no sample collected; — = no residue detected above 5 ppb; T = >5 but <10 ppb] Residues in PPB ((ig/kg) STATION 1.— WANCHESE— 72 SAMPLES' 1966 DDE 19 20 12 22 20 20 TDE 12 17 T 17 18 32 DDT 13 - T 22 - 11 1967 DDE 14 25 28 16 26 21 21 19 20 24 43 28 TDE 16 20 32 17 32 31 35 15 15 11 57 10 DDT 15 10 17 - 29 21 64 17 13 17 64 53 1968 DDE 140 140 85 78 62 T 30 - 43 35 29 21 TDE 56 51 59 16 32 T 13 - 22 27 16 15 DDT 68 29 37 42 86 - 12 - 60 49 57 - 1969 DDE 40 17 13 10 37 11 T 10 — T T 12 TDE 15 16 18 10 44 21 21 10 - T 13 15 DDT T T 11 - 43 T 19 13 - - - T 1970 DDE T T 13 T 17 — — — — — - - TDE 11 T 15 - 19 - - - - 11 - - DDT - - T - - - - - - - - - 1971 DDE TDE DDT - : : - : T : - - - - - 1972 DDE ^ — — T — T TDE - - - - - 10 DDT - - - - - - Vol. 6. No. 4, March 1973 317 TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (/iO/KO) STATION 2— SALVO— 71 SAMPLES' t966 DDE 12 14 14 14 32 23 TDE - 17 - 17 28 17 DDT - - - - 28 15 1967 DDE 26 24 31 35 24 21 17 24 120 74 87 TDE 11 13 21 25 21 30 21 19 56 45 29 DDT T T T n 19 21 29 44 390 190 66 1968 DDE 35 85 66 85 65 34 58 28 95 45 58 66 TDE 16 26 20 24 37 29 38 21 40 33 37 35 DDT 20 50 36 21 28 19 87 36 240 76 120 80 1969 DDE 100 73 100 59 120 39 27 — 15 13 10 15 TDE 31 31 38 27 51 38 37 - 21 15 19 13 DDT 87 35 50 22 67 16 28 - T T - 11 1970 DDE 23 34 24 19 27 14 — 12 11 _ 10 19 TDE 25 27 20 16 33 20 - 17 - — — 16 DDT 14 20 13 10 19 - - 14 - - - 11 1971 DDE 16 15 — 17 21 _ 12 _ _ _ _ _ TDE 17 16 - 18 21 — 14 — — — — — DDT T - - - 11 - - - - - - - 1972 DDE TDE - - - T 13 T 13 22 DDT - - - - - - STATION 3.— WYSOCKING BAY-43 SAMPLES ' 1966 DDE 17 17 T T T TDE 17 — 18 13 12 11 DDT - - 20 - - - 1967 DDE T 14 15 17 16 12 15 T _ _ T 10 TDE 12 17 17 22 29 22 35 T — — T 15 DDT T 10 - - 14 13 14 T - - T T 1968 DDE T T T 18 13 15 — T T — T — TDE T T - 20 20 13 - T T — 13 — DDT - - - - T 13 - - 21 - - - 1969 DDE T — T 12 T T T T _ T T 14 TDE 14 - - 16 T T T — T 12 19 DDT - - - T - - T 12 - - - 12 1970 DDE TDE T T DDT T Pesticides Monitoring Journal TABLE K-2. — Distribution of organoclilorine residues in C. virginica for each sampling station by dale of collection — North Carolina — Continued Residues in PPB (yao/KG) STATION 4.— ROSE BAY— 71 SAMPLES » 1966 DDE 28 16 19 18 16 20 TDE 34 13 22 23 23 36 DDT 21 - 32 16 T 14 1967 DDE 12 T 23 15 16 15 35 T T — 14 12 TDE 18 14 32 26 32 30 63 15 10 - 30 15 DDT T T T 11 16 40 23 13 T - 19 T 1968 DDE T T 13 15 21 14 T — T T T 16 TDE T T 12 15 27 25 T - T 17 17 17 DDT - - - 22 13 T - - T T T 29 1969 DDE 11 16 11 T 12 T T T 12 T - 10 TDE 15 18 12 - 17 T T 13 17 T - 14 DDT 20 - - - T - T 69 - - - T 1970 DDE 17 13 14 T T 11 - — — - — TDE 19 19 19 - 15 19 - - - - - DDT 15 10 10 - - 12 - - - - - Dieldrin - - 14 - - - - - - - - 1971 DDE TDE - - - - T 13 - - - - - - - DDT Dieldrin — — 10 ~ 12 — — — : — 1972 DDE TDE - - - - - - DDT - - - - - STATION 5— BAY RIVER— 71 SAMPLES' 1966 DDE 36 55 52 23 30 26 TDE J6 78 73 46 61 60 DDT 29 25 34 19 11 20 1967 DDE 36 30 81 39 32 29 22 15 T 28 25 24 TDE 69 49 100 56 65 56 46 48 T 43 34 46 DDT 23 16 35 20 27 19 27 27 - 51 - 16 1968 DDE 35 44 37 52 75 22 18 23 13 T 24 16 TDE 35 43 24 49 71 33 24 28 15 - 36 21 DDT 26 32 28 47 55 T 13 18 12 - 29 T 1969 DDE 19 29 36 43 54 45 37 18 T 13 T 20 TDE 25 39 36 56 59 80 71 16 T T 20 35 DDT T 20 37 37 32 17 26 18 14 - — 21 Vol. 6, No. 4, March 1973 319 TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (ag/ko) STATION 5.— BAY RIVER— 71 SAMPLES "—Continued 1970 DDE 24 40 36 42 55 10 15 11 13 — 23 TDE 33 43 29 31 94 27 23 12 22 16 39 DDT 17 33 18 14 22 - 18 - 14 - 13 1971 DDE 12 16 — 22 110 16 52 49 18 17 13 T TDE 15 13 - 21 170 19 97 96 34 26 11 - DDT - 10 - - 30 - 27 22 - 18 12 - Dieldrin - - - - 10 - - - - - - - 1972 DDE TDE 16 11 41 37 - 71 48 85 130 43 91 DDT - 21 - 37 87 43 Dieldrin - - - - 12 - STATION 6.— NEUSE RIVER— 43 SAMPLES ' 1966 DDE 29 18 32 36 24 29 TDE 46 24 48 57 55 60 DDT 13 15 49 30 13 18 1967 DDE 17 16 24 29 21 16 19 14 20 25 24 24 TDE 29 28 41 50 42 30 37 33 32 47 49 46 DDT - T T T T 16 25 14 14 13 T T 1968 DDE 19 20 15 30 49 32 26 29 13 T 19 25 TDE 24 25 15 44 110 68 42 56 22 T 32 25 DDT II T - 27 17 15 19 39 T - T 20 1969 DDE 20 17 23 16 37 29 30 13 T 10 T 16 TDE 17 13 26 23 56 75 40 23 T 17 19 35 DDT 10 T 11 - 20 21 20 11 - - - 16 1970 DDE TDE DDT 27 45 17 STATION 7.— POINT OF MARSH— 71 SAMPLES' 1966 DDE 33 26 15 29 16 20 TDE 37 26 20 31 33 40 DDT 38 28 25 19 16 16 Dieldrin T - - - - - 1967 DDE 15 17 22 20 20 33 13 22 11 12 11 18 TDE 29 24 28 32 39 82 26 24 19 19 18 25 DDT 15 10 - 11 45 24 27 33 10 27 15 10 .^20 Pesticides Monitoring Journal TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Caro/ina— Continued Residues in PPB (/ig/kg) STATION 7.— POINT OF MARSH— 71 SAMPLES ■—Continued 1968 DDE 11 — 12 18 11 15 10 15 _ T 14 11 TDE 15 - 18 23 18 20 13 19 - T 21 16 DDT T - - 21 10 16 11 21 - - - - 1969 DDE 13 T 12 T T T 10 37 - T T T TDE 14 14 17 13 T 11 16 27 - T 11 10 DDT - T T - - - 18 48 - T 12 - Dieldrin - - - - - - - 19 - - - - 1970 DDE 11 22 20 T T — — _ — T — TDE 21 29 21 12 17 - - - - T - DDT T 15 - - - - - - - - - 1971 DDE — T T T T — — — — — — T TDE - T T 32 - - - - - - - T DDT - - - - - - - - - - - T 1972 DDE 1. — — T T — TDE 20 - - - T - DDT - - - - - - STATION 8.— WEST BAY— 58 SAMPLES ' 1967 DDE 18 25 22 14 T _ 16 T 15 TDE 25 39 22 19 T - 22 10 24 DDT T 11 13 11 T - 17 12 15 1968 DDE T n 25 T 16 11 — T - T — 10 TDE - 11 30 T 13 T - T - - - 16 DDT - - 19 - T - - 15 - - - - 1969 DDE 16 T 20 16 II T 12 — — — T T TDE 10 T 17 19 T 12 16 - - - 16 17 DDT T - 12 12 10 T T - - - - T 1970 DDE — — — — — — — T T TDE DDT — - — - - - - T 16 1971 DDE _ T T T TDE DDT - T - - - - - - - T T - 1972 DDE TDE DDT - 13 10 14 T 11 T - Vol. 6, No. 4, March 1973 321 TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (/ig/kg) STATION 9.— BACK BAY— 9 SAMPLES ' 1966 DDE 10 — 15 17 24 10 TDE 12 - 11 32 74 14 DDT U - 12 15 T - 1967 DDE TDE DDT 10 10 26 23 17 10 13 T STATION 10.— JARRETT BAY— 66 SAMPLES' 1966 DDE 22 — 13 14 T 12 TDE 22 - 11 16 T 18 DDT 15 - 19 16 - 14 1967 DDE 11 17 14 29 19 17 10 12 12 14 10 21 TDE T 12 19 24 22 18 12 T T 18 17 17 DDT - T - 17 14 10 T 12 T 39 13 12 1968 DDE 18 13 47 T 10 T — 13 T 18 — T TDE 14 10 44 T - - - T T 13 - 15 DDT T T 15 - - - - T T 66 - T 1969 DDE 12 T 12 21 13 T 10 — — — 10 12 TDE T 11 16 22 12 10 15 - - - 18 22 DDT - T T - T - - - - - - 11 1970 DDE T _ _ — — — _ — _ TDE T — — — — — — — — DDT T - - - - - - - - 1971 DDE — T — — 11 — _ _ — T — TDE DDT - T - - 10 - - - - T - 1972 DDE TDE DDT - 12 T - STATION 11.— NORTH RIVER— 64 SAMPLES' 1966 DDT 64 43 43 47 36 35 TDE 50 33 41 47 33 29 DDT 58 36 31 30 10 - Dieldrin 10 - - - - - 1967 DDE 27 26 45 11 52 53 34 21 16 17 10 20 TDE ■ 15 18 40 12 46 49 28 20 12 12 10 16 DDT 10 16 27 — 29 31 15 26 T 10 — T Dieldrin - - 10 - - - - - - - - - 322 Pesticides Monitoring Journal TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (/«j/ko) STATION 11.— NORTH RIVER— 64 SAMPLES i— Continued 1968 DDE 18 14 T 35 34 T 32 21 T 22 38 27 TDE 13 - - 25 26 - 27 19 T 17 20 - DDT T - - 43 36 - 57 26 T 36 27 - 1969 DDE 18 13 16 32 16 T - - 12 53 - T TDE T - T 15 12 - - - T 73 - T DDT - - 12 14 - - - - II 34 - T 1970 DDE T It — — — — — - T TDE T 11 - - - - - - - DDT T - - - - - - - - 1971 DDE TDE - — 12 T T - - — - 1972 DDT DDE TDE DDT 20 11 10 T - STATION 12.— NEWPORT RIVER— «8 SAMPLES > 1966 DDE 20 17 14 16 24 14 TDE 21 13 19 26 44 22 DDT - T T - 11 - Dieldrin T - - - - - 1967 DDE 14 18 25 20 21 19 T T 14 16 12 16 TDE 21 24 85 27 29 30 12 15 25 18 17 26 DDT T T II T - T 10 T 15 23 - T 1968 DDE n 16 17 25 — T T T 11 18 19 15 TDE 14 16 23 31 - - T T 13 24 29 18 DDT - - T - - - - - T 23 11 T 1969 DDE 21 21 20 27 17 12 T — T 13 15 18 TDE 21 22 21 29 23 19 T - T 16 15 17 DDT - 10 T 13 T T - - - 25 17 17 Dieldrin - - - - - - - - - T - - 1970 DDE 16 12 12 18 T — T — — T TDE 14 T 10 23 T - - - - T DDT 13 - T 10 - - - - - - 1971 DDE — 11 — 13 — _ 17 — — — — TDE - 11 - 18 - - 16 - - - - DDT - - - - - - - - - - — Vol. 6, No. 4, March 1973 323 TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (/ig/ko) STATION 12.— NEWPORT RIVER— 68 SAMPLES i— Continued STATION 13— BOGUE SOUND— 51 SAMPLES' 1967 DDE 31 20 15 T 10 10 13 15 15 TDE 26 23 17 T 12 12 14 - T DDT 12 T T - 11 16 24 T T 1968 DDE 12 T 16 15 T — T T 13 13 18 TDE T — — T — — - T 13 13 11 DDT - - - - - - - T 21 T 11 1969 DDE 20 29 17 25 19 T 15 — — 12 12 TDE 15 23 11 20 19 11 16 - - 14 - DDT T 19 T 12 11 11 37 - - T - 1970 DDE TDE DDT - 1971 DDE TDE DDT : : T : : : - - - - 1972 DDE TDE - - T - - - DDT - - - - - - STATION 14.— WHITE OAK RIVER— 43 SAMPLES ' 1966 DDE T 20 T 29 T T TDE — 25 T 31 T T DDT - T - - - - 1967 DDE — — T — T _ T — T T T T TDE - - - — T — 13 - T - T T DDT - - - - - - 10 - T - - - 1968 DDE T T 13 T — — — T 11 T T 14 TDE T T 13 T - - - T 11 - T T DDT T - - - - - - T T - - T 1969 DDE r 12 14 T T — — _ — T T — TDE - - T - T - - — - T T - DDT - - - - - - - - - - - - 324 Pesticides Monitoring Journal TABLE K-2. — Dislribulion of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Year Compound Residues in PPB (/ig/ko) Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 14.— WHITE OAK RIVER— 43 SAMPLES '—Continued STATION 15.— NEW RIVER— 72 SAMPLES > 1966 DDE 25 T 23 21 28 36 TDE 21 T 27 26 34 44 DDT 28 - T - - 14 1967 DDE 39 16 30 45 20 16 11 19 16 28 21 28 TDE 49 18 30 59 23 13 13 28 20 34 26 37 DDT 16 T T 14 - - - 11 - - - 21 1968 DDE 42 16 35 39 25 15 T 10 14 15 15 14 TDE 38 14 31 29 25 15 - T 14 12 12 T DDT 31 T T - - - - T T - - - 1969 DDE 25 18 21 28 13 15 11 13 14 19 23 27 TDE 19 19 27 35 13 15 15 13 12 22 26 27 DDT - T T T - - - T - 11 - 11 1970 DDE 21 28 29 26 26 T — — — — — 17 TDE 19 24 22 31 20 - - - - - - - DDT - T T 12 - - - - - - - - 1971 DDE 11 T 15 T T — — - - 12 - 20 TDE - T 12 - — - - - - 11 - 22 DDT - - - - - - - - - T - T 1972 DDE 19 17 24 11 T - TDE 18 21 21 - - - DDT — - — — - — STATION 16— WRIGHTSVILLE BEACH— 43 SAMPLES' 1966 DDE 11 14 15 15 19 12 TDE 12 18 12 16 24 10 DDT - - - 13 14 - 1967 DDE 11 16 19 14 T T T 10 — T - 11 TDE 14 18 15 14 T T 14 18 - 12 - 13 DDT - T T - T - T 14 - 22 - T 1968 DDE T T 10 13 T — — 10 T T T T TDE T - - 10 T - - - - - 12 - DDT T - - - - - - T - — — — Vol. 6, No. 4, March 1973 325 TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (^g/bg) STATION 16— WRIGHTSVILLE BEACH— 43 SAMPLES >— Continued 1969 DDE T T T T T _ _ _ _ T T 12 TDE DDT - - - T T - - - — T 11 16 a 1970 DDE TDE DDT T STATION 17— SOUTHPORT— 72 SAMPLES' 1966 DDE 11 21 11 29 T T TDE T 16 10 25 T T DDT 12 - - - - - 1967 DDE T 13 II T — T 10 14 11 T — T TDE - 12 T T - - 10 T - - - T DDT - T - - - - 17 30 15 - - - 1968 DDE 18 13 T T 11 — — 10 11 T 17 17 TDE 13 T T T 14 - - - T 11 - T DDT T - - - - - - 13 T - 21 10 1969 DDE T — 12 T n — — — — — — — TDE - - 17 - 12 - — — - — - - DDT - - 87 - T - - - - - - - 1970 DDE TDE DDT - T - - - T - - - 1971 DDE TDE DDT - ~ ~ — — - - — - - 1972 DDE ^ _ _ _ _ _ TDE - - — — — — DDT - - - - - - STATION 18.— SHALLOTTE RIVER— »3 SAMPLES i 1966 DDE _ T T T 19 T TDE — - T - 18 T DDT - - - - 11 - 1967 DDE T 16 11 14 19 T T T 10 T 12 T TDE - 13 T 15 22 T 11 T T — 11 T DDT — T - - 10 - 10 T T - T - 326 Pesticides Monitoring Journal TABLE K-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — North Carolina — Continued Residues in PPB (iiig/kg) STATION 18.— SHALLOTTE RIVER— 43 SAMPLES i— Continued 1968 DDE 13 14 16 15 — — — T T 13 - 17 TDE 11 10 11 12 - - - - - T - 10 DDT T T - - - - - - - 11 - T 1969 DDE T T 12 II 15 T 14 T T 11 T T TDE - - 10 T 19 - 14 T - T 13 - DDT - - 19 - T - 16 16 12 T - - 1970 DDE TDE DDT T Each sample represents 15 or more mature moUusks. SECTION L— SOUTH CAROLINA Monthly collections of eastern oysters, Crassostrea virginica, to identify estuarine pollution were made from August 1965 through November 1969. The 17 stations (Fig. L-1) were monitored for periods ranging from 1 to 5 years. All samples were analyzed at the Gulf Breeze Laboratory. A summary of data on or- ganochlorine residues in the monitored species, C. virginica, is presented in Table L-1, and the distribution of residues in this species for each sampling station by date of collection in Table L-2. South Carolina samples are characterized by the uni- formly low level of DDT residues and moderately low incidence of positive samples. Samples from only three other States indicated generally lower levels of DDT contamination. In those areas with adequate numbers of samples for annual comparison, there was an obvious decline at most stations in the magnitude and incidence of DDT resi- dues in 1968-69 as compared to earlier years (Part I. Table 6). South Carolina was the only State in which mirex residues were detected in mollusks. These residues were observed only in the period March - May 1969. They were found at nine stations widely distributed along the South Carolina coast. Largest residues were found in samples collected in the Charleston area, i.e.. Stations 8 and 9. Vol. 6, No. 4, March 1973 SOUTH CAROLINA ATLANTIC OCEAN FIGURE L-1. — Diagram of coastal South Carolina showing approximate location of monitoring stations 1. North Sanlee Bay — Santee River 2. South Santee Bay — Santee River 3. Bull Creek 4. Price Creek 5. Inlet Creek 6. Hog Island Channel— Ashley, Cooper, and Wando Rivers 7. Wando River — Ashley, Cooper, and Wando Rivers 8. Ashley River — Ashley, Cooper, and Wando Rivers 9. Fort Johnson— Ashley, Cooper, and Wando Rivers 10. Steamboat Creek — North Edesto River 11. Toogoodoo Creek — North Edesto River 12. Big Bay Creek — South Edesto River 13. St. Pierre Creek— South Edesto River 14. Whale Branch— Broad River 15. Skull Creek— Broad River 16. May Creek 17. New River 327 TABLE L-1. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1965-69 — South Carolina Station Number Location MoNrroRiNO Period Number of Samples i Number of Positive Samples and Maximum Residue ( ) Detected in PPB (ag/kg) DDT Dieldrin Mirex 1 North Santee Bay 196S-68 41 10 (19) 4 (19) 2 South Santee Bay 1965-68 40 14 (80) 3 (19) Bull Creelc 1969 12 2 (10) 2 (13) 2 (35) 4 Price Creek 1965-68 42 25 (81) 2 (12) Inlet Creek 1965-68 42 21 (52) Hog Island Channel 1965-68 41 33 (73) Wando River 1965-68 42 31 (44) 8 Ashley River 1965-69 54 45 (154) 8 (90) 1 (190) 9 Fort Johnson 1969 12 4 (10) 1 (540) 10 Steamboat Creek 1965-69 54 26 (32) 1 (38) 11 Toogoodoo Creek 1965-69 53 40 (98) 1 (38) 12 Big Bay Creek 1965-69 54 32 (91) 1 (T) 13 St. Pierre Creek 1969 12 7 (88) 1 (38) 14 Whale Branch 1965-68 41 21 (79) 15 Skull Creek 1965-68 39 12 (30) 1 (35) 16 May Creek 1969 12 3 (15) 1 (11) 3 (37) 17 New River 1969 12 1 (16) 1 (21) 1 (27) Occasional stations (6) 1965-68 7 5 (201) 2 (15) Total number of samples 610 Percent positive for indicated compound 54 4 2 NOTE: T = >5 but <10 ppb. ^ Each sample represents 15 or more mature mollusks. TABLE L-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — South Carolina [Blank = no sample collected; — = no residue detected above 5 ppb; T = >5 but <10 ppb] Residues in PPB (^g/ko) STATION 1.— NORTH SANTEE BAY^tl SAMPLES" 1965 1966 1967 DDE TDE DDT DDE TDE DDT DDE TDE DDT Dieldrin T T T — — — T T T — — — ___ _TTT — — — — — — 15 ________ 328 Pesticides Monitoring Journal TABLE L-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — South Carolina — Continued Residues in PPB (#g/kg) May June STATION 1.— NORTH SANTEE BAY-^1 SAMPLES »— Continued DDE TDE DDT Dieldrin STATION 2.— SOUTH SANTEE BAY^»0 SAMPLES' DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT Dieldrin STATION 3.— BULL CREEK— 12 SAMPLES' DDE TDE DDT Dieldrin Mirex STATION 4.— PRICE CREEK— 42 SAMPLES' 1965 DDE TDE T T - T - - - DDT - - - - - - 1966 DDE T - T — — — - - 19 T — T TDE - - - — — - — - 36 - - T DDT - - — - - - - - 26 - - - Dieldrin - - 12 - - - - - - - - - 1967 DDE T 11 12 T T T T 13 T — 10 T TDE - T - - - 10 T 12 - - T T DDT - T - - T 11 10 11 T - T — Vol. 6, No, 4, March 1973 329 --—Oimammmmt PPB«' E Bc ns Okie SSi DOE STAHOK 5— 3"LZT ZySZS.—^-. 5-JC?135 K — T T T 3 — 16 — 14 — r A3SDO «1>'E»— «2 SAMPLES ^ ME DDE 330 Pesticides Ma9>TroKC«c Jocks al STATION - — WAXDO il3"ES^I SiJ-G^lZi DDE UK MJT J>UE TDE DDT TDE IffiT TDE DOT ixe TDE 1ST DOE TIX DOT DDE TDE DDT Dieiars Tt>E DDT Vrex DDE TDE DOT _£i jLTV-ER— 5i SA3£?LES - STAuas •— i=oia" xessos— :: sam?i.es- Vo«_ 6- No. -i. March 197? TABLE L-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — South Carolina — Continued Residues in PPB (mo/ko) STATION 10. -STEAMBOAT CREEK— 54 SAMPLES ■ 1965 DDE T T T - T - TDE T T - - — — DDT - T — - — — 1966 DDE T T — 14 — 11 — T - T - - TDE - - - 11 — 11 — - T T - - DDT - - - - - - - T — — — 1967 DDE T n 10 — 13 T — - T - - - TDE T T 10 — 14 T — - T - - T DDT - — T — T 16 — - T - - T 1968 DDE TDE DDT T T T T — T T — T - - - - - 1969 DDE TDE DDT - T — : ! : : - - - T T Mirex - — 38 - - - - - — — — — STATION 11.— TOOGOODOO CREEK— 53 SAMPLES i 1965 DDE 32 14 18 16 20 16 TDE 43 20 19 20 33 16 DDT T T T - T - 1966 DDE 27 18 15 38 24 19 - 15 13 18 11 22 TDE 25 20 13 36 33 20 - 16 13 18 12 26 DDT - T T 24 16 - - - 11 10 - T 1967 DDE 10 20 21 25 21 14 T - 12 T 30 TDE T 17 18 23 22 15 - - - - 26 DDT - - T - 14 T - - - - 12 1968 DDE 17 20 16 18 25 21 T 18 11 T T 13 TDE 14 16 - 16 20 16 T 19 10 - - T DDT T - - - - - - 17 T - - - 1969 DDE TDE DDT : : -_ - - : - : - - T - Mirex - - 38 - - - - - - - - - STATION 12.— BIG BAY CREEK— 54 SAMPLES' 332 Pesticides Monitoring Journal TABLE L-2. — Distribution of organocMorine residues in C. virginica for each sampling station by date of collection — South Carolina — Continued REsrouES IN PPB (ag/kg; STATION 12— BIG BAY CREEK— 54 SAMPLES i— Continued 1966 DDE 11 _ — — T T 12 T — — — T TDE T - - - T T T - - - - - DDT - - - - - - - - - - - - 1967 DDE 11 14 14 12 12 T 13 - T - - T TDE T 12 14 11 15 T 14 - - - - - DDT T T U 12 13 21 31 - - - - - 1968 DDE T T T 13 12 - - T — - - - TDE 11 - T T - - - T - - - - DDT T - - - - - - T - - - - 1969 DDE — — — T T 24 — — - 12 14 17 TDE - - - - - 23 - - - 13 T 13 DDT - - - - 33 44 - - - 27 13 13 Mirex — — T - — — — — — — — — STATION 13.— ST. PIERRE CREEK— 12 SAMPLES' STATION 14.— WHALE BRANCH— 41 SAMPLES' STATION 15.— SKULL CREEK— 39 SAMPLES ' Vol. 6, No. 4, March 1973 333 TABLE L-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — South Carolina — Continued Residues in PPB (iia/t.a) May June July Aug. STATION 15.— SKULL CREEK— 39 SAMPLES >— Continued DDE TDE DDT DDE TDE DDT DDE TDE DDT Dieldrin STATION 16.— MAY CREEK— 12 SAMPLES" DDE TDE DDT Dieldrin Mirejt STATION 17.— NEW RIVER— 12 SAMPLES' DDE TDE DDT Dieldrin Mirex Each sample represents IS or more mature mollusks. 334 Pesticides Monitoring Journal SECTION M.— TEXAS The eastern oyster, Crassostrea virginica. was used to monitor pollution in Texas estuarine waters during the period July 1965 - June 1972. All samples were an- alyzed at the Gulf Breeze Laboratory. Approximate locations of the 13 sampling stations are shown in Fig. M-1. A summary of data on organochlorine residues in the monitored species, C. virginica, is presented in Table M-1, and the distribution of residues in this species for each sampling station by date of collection in Table M-2. In some instances, more than one reef was sampled at different times in a particular bay. In these instances, the data have been integrated to reflect bay conditions as a whole. At some times, floods resulting from tropical storms decimated oyster reefs and inerrupted routine monitoring. On at least one occasion, sample preparation reagents were contaminated with chlordane leading to spurious analytical results. Consequently, all findings of chlordane have been omitted from the data tabulations. In conjunction with oyster monitoring in Texas, many samples of fish and other vertebrates were analyzed throughout the monitoring program. These analyses indicated, as might be expected, more kinds of pollutants and of greater magnitude than those found in oysters. PCB's, for example, were commonly found in fish samples but were detected in only five collections of oysters. In the Arroyo Colorado, Station 12, findings of consistently large DDT residues in oysters were par- alleled by DDT residues about 10 times larger in fish. A causal relationship between DDT residues in the eggs and reproductive failure of the spotted sea trout. Cynoscion nebulosus. there in 1969, has been postu- lated (5). Although the incidence of DDT residues was higher in eight other States, samples from monitoring stations in Texas bays that receive runoff from the agricultural areas were consistently contaminated with DDT. The maxi- mum DDT residue detected, 1 ,249 ppb. was in an isolated sample; more typically the residues in contaminated areas were in the range of 100 - 500 ppb of DDT. Toxaphene of presumably agricultiu-al origin was de- tected in only one sample. There is a clearly defined trend of declining DDT resi- dues in oysters. In 1971, there was a more than 50% increase in the number of samples containing negligible DDT residues (i.e., <11 ppb) over previous years and a 75% decrease in the number of samples in the 100 - 1 .000 ppb range. FIGURE M-1. — Diagram of coastal Texas showing approximate location of monitoring stations Trinity Bay — Trinity-San Jacinto River basins Galveston Bay — Trinity-San Jacinto River basins Tres Palacios Bay — Lavaca River Basin Lavaca Bay — Lavaca River Basin San Antonio Bay, North — Guadalupe-San Antonio River Basin San Antonio Bay, South — Guadalupe-San Antonio River Basin St. Charles Bay — San Antonio-Nueces Coastal Area Aransas Bay — San Antonio-Nueces Coastal Area Copano Bay — San Antonio-Nueces Coastal Area Red Fish Bay. — San Antonio-Nueces Coastal Area Nueces Bay — Nueces River Basin Arroyo Colorado^Rio Grande Coastal Area Lower Laguna Madre — Rio Grande Coastal Area TABLE M-1. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1965-72 — Texas Number of Positive Samples and Maximum Station Number Location Monitoring Period Number of Samples ' Residue ( ) Detected in PPB (/ig/kg) DDT Dieldrin Endrin PHENE^ PCB'S = I Trinity Bay 1965-69 47 28 (51) 1 (20) 2 Galveston Bay 1965-72 71 60 (88) 31 (87) 3 Tres Palacios Bay 1965-72 74 71 (974) 6 (18) 4 Lavaca Bay 1965-72 66 59 (400) 4 (24) 2 5 San Antonio Bay, North 1965-72 59 38 (78) 8 (27) 6 San Antonio Bay, South 1965-72 75 40 (488) 3 (56) 1 (10) Vol. 6, No. 4, March 1973 335 TABLE M-1. — Summary of data on organochlorine residues in the monitored species (C. virginica), 1965-72- Texas — Continued Station monttoring Pemoo Number of Samples' Number of PosrrrvE Samples and Maximum REsmuE ( ) Detected in PPB (5 but <10 ppb.] Year CoMPotniD Residues in PPB (fiG/KG) STATION 1— TRINITY BAY— 47 SAMPLES' 1965 DDE T _ T T T 11 TDE T - - T 10 16 DDT - - - - - - 1966 DDE 12 18 15 18 — — — — — T T TDE DDT 17 27 28 33 — — — — — T 12 1967 DDE T T 12 _ _ T _ _ _ T T T TDE T 12 18 - - T - - - T T - DDT - - - - - T - - - T - - 1968 DDE T T T T T — — T — 10 T TDE 11 T T 11 T - — - - T - DDT - - - - - - - - - - - 1969 DDE _ T _ _ _ — T TDE - 13 - - - - - DDT - - - - - - - Dieldrin - 20 - - - - — 336 Pesticides Monitoring Journal TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues is PPB (»c kg) STATION 2— GALV-ESTON BAY— 71 SAMPLES" DDE TDE DDT DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin 1971 DDE T 11 - - — - T T TDE 39 38 48 - - - 17 17 DDT - - - - - - T 11 Dieldrin 16 23 30 65 46 - - 26 1972 DDE T T T T — TDE 18 T 26 15 T DDT - - - - - Dieldrin 42 26 87 24 36 STATION 3.— TRES PALACIOS BAY— 74 SAMPLES » 1965 DDE „ It T T 21 93 TDE T T - - T 29 DDT - - — — T 65 Vol. 6. No. 4. M.\rch 1973 TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues in PPB (ag/kg) STATION 3.— TRES PALACIOS BAY— 74 SAMPLES >— Continued 1966 DDE 78 78 250 190 300 47 210 97 21 11 23 26 TDE 36 36 44 53 89 22 97 29 T - T T DDT 43 53 80 59 130 12 23 - - - - - 1967 DDE 42 42 67 51 34 58 18 12 18 72 150 240 TDE 14 17 31 19 14 24 - - - 41 52 57 DDT - T 11 T 15 11 - - - T 71 38 1968 DDE 270 220 230 320 300 91 62 43 20 19 22 24 TDE 66 57 23 590 77 62 95 10 42 13 19 15 DDT 83 21 81 64 22 T 17 - T - - - Dieldrin - 18 - - - - - - - - - - 1969 DDE 25 24 83 91 55 95 58 43 25 TDE 19 18 35 44 62 15 56 T 40 DDT - T 27 21 15 - - - 12 Dieldrin - - - - - - - 10 - 1970 DDE 70 36 110 230 44 33 41 — 50 16 TDE 48 29 51 44 38 55 72 - - 12 DDT 31 - 19 56 31 - - - - - Dieldrin - 13 17 13 - - - - - - 1971 DDE — 43 14 13 10 13 15 T — 14 T TDE DDT — 30 12 12 23 27 44 — — 15 T 1972 DDE TDE DDT Dieldrin 100 25 15 59 20 T T STATION 4.— LAVACA BAY— 66 SAMPLES ' 1965 DDE TDE DDT T - T 13 T T 22 T 10 1966 DDE 33 40 43 56 51 140 39 26 17 T T 11 TDE 12 17 T 27 25 30 16 11 - - - - DDT 11 18 T 16 21 23 - - - - - - 1967 DDE 22 16 20 25 14 T 25 14 14 T 19 26 TDE 13 T 12 14 T - 13 - - - - 12 DDT - - - T 14 - 34 - - - - T 338 Pesticides Monitoring Journal TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues in PPB (#o/ko) STATION 4.— LAVACA BAY— 66 SAMPLES i— Continued 1968 DDE 39 38 39 69 46 140 24 TDE 16 17 22 62 39 120 13 DDT 26 40 18 49 34 140 - Dieldrin - - - - - 24 — 1969 DDE 20 19 33 41 33 — 12 — 26 40 TDE T - 11 19 22 - - - 18 33 DDT - - - 14 16 - - - 15 48 1970 DDE — 120 30 o, 37 „> — - 16 TDE - 42 16 «. 53 (» - - T DDT - 26 11 "' - ,., - - - Dieldrin - - 10 - - - - - - PCBs - - - '" - '" - - - 1971 DDE 48 43 43 22 T T - 12 T 13 TDE 29 15 - - - - - 25 - - DDT T - - - - - - - - - Dieldrin - - - - - - - - - 14 1972 DDE TDE DDT Dieldrin 18 T T 21 STATION 5.— SAN ANTONIO BAY (NORTH)— 59 SAMPLES • 1965 DDE T T T T 11 30 TDE T T T T T 25 DDT — T - T T 16 Dieldrin - - - - 11 1966 DDE 31 30 32 29 33 29 16 — T 13 15 19 TDE 24 27 30 23 27 22 10 — - - T 14 DDT 14 16 15 - 18 13 — — - - - - Dieldrin - - 17 - - - - - - - - - 1967 DDE 17 20 22 29 13 12 T — 11 14 TDE 13 18 18 30 T - - - T 13 DDT - - - T - _ _ _ 14 - 1968 Dieldrin — 10 — — — — — — — — 1969 DDE TDE DDT - : T T 18 12 T Vol. 6, No. 4, March 1973 TABLE M-2. -Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues in PPB (ag/ko) STATION 5.— SAN ANTONIO BAY (NORTH)— 59 SAMPLES "—Continued DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin DDE TDE DDT Dieldrin STATION 6.— SAN ANTONIO BAY (SOUTH)— 75 SAMPLES' 1965 DDE — T T T 12 17 TDE - — T T 10 T DDT - - T T T T 1966 DDE 13 13 14 19 14 T — — — T 15 10 TDE T - - 14 10 - - - — — T T DDT T - - - 10 - - - - - T - 1967 DDE 17 20 20 14 T — — — T TDE 11 10 11 - - — — — T DDT 10 - 11 - - - - - T 1968 DDE 21 T — — 110 _ — _ T TDE 19 - - - 310 - - — T DDT 13 — — — 68 — — — — Dieldrin 56 — — — 14 — — — — Endrin 10 - - - - - - - - 1969 DDE T 16 20 16 T — — — T T 12 TDE - - - 14 T — — — T T 15 DDT - - — T — — — — — _ T Dieldrin 14 - - - - - - - - - - 1970 DDE - — — — 11 — _ _ _ _ 13 _ TDE — — — — 25 — _ _ _ — 41 _ DDT - - - - - - - - - - - - 1971 DDE TDE DDT _ : T : _= - - - T 13 10 T 340 Pesticides Monitoring Journal TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues in PPB ( 1966 DDE 29 24 12 T T T T TDE 25 21 18 T 11 T T DDT 12 12 - - - - - 1967 DDE T 15 17 - T 14 T — TDE T 21 32 - 14 39 19 - DDT - T T - - 13 14 - 1968 DDE 23 25 18 12 10 10 11 — — 10 TDE 14 26 43 18 21 18 15 21 - 17 DDT - 12 21 - - T 23 T - T 1969 DDE 15 T 10 15 — T — — 12 — 11 17 TDE 27 T 19 27 18 T - - - - 15 22 DDT 13 - T 19 - - - - - - T 13 342 Pesticides Monitoring Journal TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued Residues in PPB (/«;/kg) STATION 10.— RED FISH BAY— 67 SAMPLES i— Continued 1970 DDE 16 14 18 17 10 12 14 12 — — — T TDE 20 19 29 25 23 38 25 18 - - - 29 DDT T 10 13 12 - - - 10 - - - 15 PCB's - - - - - - - - - "' - - 1971 DDE _ — 17 — T — — 13 T T T 12 TDE - - 14 - - - - 13 - T T 11 DDE - - - - - - - 17 26 17 22 26 1972 DDE TDE 14 11 20 15 16 16 18 12 - T 14 DDT 22 30 45 42 - 34 PCB's - - - - - »> STATION 11.— NUECES BAY— 20 SAMPLES ^ 1965 DDE TDE DDT T 1966 DDE 34 22 32 120 18 18 T T TDE 30 17 26 200 20 16 - 12 DDT 12 - 14 130 - - - - Dieldrin - - - 33 - - - - 1967 DDE 31 30 43 46 34 29 20 32 57 51 TDE 36 61 110 110 48 52 20 20 25 22 DDT T 22 20 26 22 49 17 37 35 15 Dieldrin - n 13 19 - - - - - - Endrin - 18 12 II - - - - - - 1968 DDE TDE 45 28 DDT 15 STATION 12.— ARROYO COLORADO— 48 SAMPLES' 1965 DDE TDE DDT Dieldrin Endrin 170 520 20 19 24 33 T T 55 80 17 29 32 64 80 16 34 19 1966 DDE 80 120 120 74 96 230 300 270 98 12 180 63 TDE 110 140 130 70 69 140 230 93 57 - 50 58 DDT 21 19 17 - 26 31 53 24 - - 19 12 Dieldrin 32 23 24 18 16 30 45 27 14 - 18 20 Endrin 18 17 14 - 22 23 28 13 - - 14 12 Vol. 6, No. 4, March 1973 343 TABLE M-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Texas — Continued RESroUES IN PPB (/iO/KG) STATION 12.— ARROYO COLORADO-^8 SAMPLES i— Continued 1967 DDE 120 140 210 170 110 160 160 79 TDE 73 110 180 75 49 63 92 49 DDT 27 - 28 19 26 24 23 16 Dieldrin 23 16 42 46 19 33 30 16 Endrin U 29 19 - - - 12 - 1968 DDE TDE DDT Dieldrin 48 150 160 68 49 33 1969 DDE 260 330 220 320 180 260 280 86 100 110 210 54 TDE 110 100 48 100 35 63 55 28 33 30 T 21 DDT 15 57 35 110 77 48 22 - - T - 24 Dieldrin 14 16 17 IS 14 25 18 17 12 T 16 - 1970 DDE 23 120 140 no 130 96 TDE 35 20 25 29 25 54 DDT 32 19 22 T T 60 Dieldrin 21 18 23 25 13 25 Endrin T T - - - 12 1971 DDE TDE DDT Dieldrin Toxapliene 65 14 11 280 61 27 380 46 24 220 78 38 STATION 13.— LOWER LAGUNA MADRE— 24 SAMPLES i DDE TDE DDT DDE TDE DDT Dieldrin DDE TDE DDT Each sample represents 15 or more mature mollusks. DDT present but not quantified due to presence of PCB'- Present but not quantified. Dieldrin data omitted because of possible sample contam 344 Pesticides Monitoring Journal SECTION N.— VIRGINIA The eastern oyster, Crassostrea virginica, was monitore(i at 10 principal stations in estuarine areas of Virginia during the period July 1965 - February 1972. Samples were analyzed at the Gulf Breeze Laboratory until June 1968, and thereafter at the Virginia Institute of Marine Science. The approximate station locations are shown in Fig. N-1. A summary of data on organochlorine res- idues in the monitored species, C. virginica. is presented in Table N-1, and the distribution of residues in this species for each sampling station by data of collection in Table N-2. The 87% incidence of DDT residues in Virginia samples and the maximum residue of 678 ppb were fourth highest of the States monitored. The higher residues were clearly associated with intensive truck farming (Station 2) and a combination of urban and industrial development (Station 9). The presence of PCB's was noted in 1970 samples, but not until 1971 was equipment acquired to identify and quantify these compounds. The residue of 2,800 ppb of Aroclor 12545 but < 10 ppb. ^ Each sample represents 15 or more mature mollusks. TABLE N-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia [Blank = no sample collected; — = no residue detected above 5 ppb or no residue detected (PCB's); T = >5 but <10 ppb] Residues in PPB (/to/KO) Nov. Dec. STATION 1.— MACHIPONGO RIVER— 67 SAMPLES i 1965 DDE 34 15 18 T 13 15 tde 20 13 28 T T T DDT 73 T 24 - - - Dieldrin 11 - - - - - 1966 DDE 12 T 11 14 19 17 19 — T T — T TDE - - - T 14 18 17 - - - - - DDT - - - - - - - - - - - - 1967 DDE — 34 T T 17 14 T T - — T 11 TDE - 59 - - 12 13 - T - - - - DDT - 10 - - - T - T - - - - 1968 DDE T — T — T 18 15 T — T 11 T TDE - — - — — 10 20 T - T T - DDT - - - - - - 10 - - - - - 1969 DDE T T T T T 13 — 11 T 20 T TDE - T - - T 13 - 16 T 27 T DDT - T - - - T - - - 16 - Dieldrin - - - - - - - - T - - 1970 DDE 15 10 — — It 24 T T T 11 TDE 14 T - — T 35 13 T T T DDT - 11 - - - 17 T - - - 1971 DDE TDE DDT PCB's 10 18 T 17 T "390 346 Pesticides Monitoring Journal TABLE N-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (juo/kg) STATION 1.— MACHIPONGO RIVER— 67 SAMPLES i— Continued STATION 2.— CHERRYSTONE INLET— 68 SAMPLES ' 1965 DDE 60 35 16 24 25 45 TDB 89 60 14 42 32 55 DDT 230 71 T 35 20 35 1966 DDE 45 42 33 43 36 32 90 41 14 25 19 36 TDE 49 46 45 40 36 37 110 86 35 66 62 73 DDT 23 26 25 15 11 16 130 59 T 20 11 14 1967 DDE 49 31 32 37 45 37 34 44 55 26 24 20 TDE 74 52 36 53 75 68 61 63 81 42 29 18 DDT 17 14 - 12 10 21 110 110 120 22 13 T 1968 DDE 19 27 35 59 42 40 146 63 20 33 33 T TDE 18 20 46 58 55 52 210 172 76 31 31 15 DDT T - T 21 12 17 322 42 12 T T T 1969 DDE 24 11 21 17 12 T 15 35 17 24 16 35 TDE 16 14 22 16 13 14 10 31 22 34 10 39 DDT - - - - - - - 20 " 13 - 17 1970 DDE 32 33 — 20 28 24 T 22 18 19 TDE 30 42 — 21 29 26 T 34 19 22 DDT T 16 - - - 23 T T - T 1971 DDE TDE DDT PCB's 30 30 22 14 14 29 23 T = 350 1972 DDE TDE DDT PCB's 43 18 '510 STATION 3.— BOWLERS ROCK— 70 SAMPLES" 1965 DDE 16 T T T T 11 TDE 23 T T T T 12 DDT 21 T T T - - 1966 DDE 11 10 — 13 11 13 13 T — - T - TDE T T - T 11 15 15 T - - T - DDT - - - - - T - - - - - - Vol. 6, No. 4, March 1973 347 TABLE N-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (/«}/ko) STATION 3.— BOWLERS ROCK— 70 SAMPLES '—Continued 1967 DDE — T T 10 T T 10 — — T T T TDE - - T 11 T 11 14 15 - T T T DDT - - - - - - 11 18 - T T - 1968 DDE - T T T T 13 10 10 - 17 T 12 TDE - - T - - 14 12 15 - 17 T T DDT - - - - - - - T - T - - 1969 DDE T T 11 12 10 T T T T 11 T 11 TDE 10 T 10 14 10 T T T 10 18 14 13 DDT - - - - T - - T T 14 T T 1970 DDE 16 10 T T 10 10 T T - T - T TDE 14 T - 11 10 17 12 T T 12 T T DDT T 32 - - - T - - T T - .- 1971 DDE TDE DDT = PCB's u T T T 14 12 400 1972 DDE TDE DDT 17 12 STATION 4.— URBANA— 69 SAMPLES' 1965 DDE T 10 T T T 13 TDE 13 16 T - - 10 DDT 14 19 T - - - 1966 DDE TDE DDT 10 T T - - 10 T 15 - T - - T T T 1967 DDE 12 10 11 T T T T T - T 11 11 TDE - T T T T T T T - 11 T 12 DDT - - - - - - - T - 12 - T 1968 DDE T T T 11 T 11 14 T - T T T TDE T - T T - — 13 T - T 12 T DDT - - - - — — T - - - T - 1969 DDE T T - T T T T T T 11 T T TDE T 11 — — T T T 13 T 18 10 10 DDT T T - - - - - - - 16 - - 1970 DDE T — T 10 15 T — 10 - T T TDE 10 - T T 17 T T 17 - T T DDT 16 - - - T T - 14 - - T 348 Pesticides Monitoring Journal TABLE N-2. — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (/ig/kg) STATION 4.— URBANA— 69 SAMPLES' — Continued 1971 DDE 10 T 10 TDE T - T DDT - - - » PCB's T - 270 1972 DDE TDE DDT 10 T STATION 5.— BELL ROCK— 69 SAMPLES i 1965 DDE 11 T T T 11 16 TDE 24 T 13 10 13 21 DDT 19 T 10 T - 13 1966 DDE TDE DDT - - - - - - - - - - - T 1967 DDE - T - T - - - - - - - T TDE - T - - - - - - - 12 - T DDT - - - - - - - - - - - - 1968 DDE - - - - - T T - T T 11 TDE - - - - - - 10 T - T T T DDT - - - - - - - - - - - 11 1969 DDE - - - - - T - T T 11 17 TDE - - - - - T - T 14 20 T DDT - - - - - - - - - 10 - 1970 DDE T T - T T 10 10 - - - - T TDE T 12 11 11 T 18 13 T T - - T DDT - - - - - - T - - - - - 1971 DDE TDE DDT PCB's T T T T '390 1972 DDE TDE DDT PCB's T T M50 STATION 6.— PAGES ROCK— 68 SAMPLES' 1965 DDE 10 T 11 11 17 19 TDE 15 12 17 14 20 16 DDT 17 14 14 12 24 13 Vol. 6, No. 4, March 1973 349 TABLE N-2. — Distribution of organocMorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (^g/ko) STATION 6.— PAGES ROCK— 68 SAMPLES" — Continued 1966 DDE 14 — — T 10 11 — T — T - T TDE 13 - - - T 11 - T - T - T DDT T - - - - - - 11 - - - - 1967 DDE - - T 10 - T T — T T T 13 TDE - - - T - T T - 16 14 11 14 DDT - - - - - - - T 14 T - - 1968 DDE T T — T — 12 13 T — T T 10 TDE - T - - - - 14 10 - 10 T 11 DDT - - - - - - - - - - - T 1969 DDE — - T - T 13 - 14 18 T TDE — — T - T T - 12 16 T DDT - - T - - - - T T ■- Dieldrin - - - - - - - - T - 1970 DDE — T — T T T T T — 10 90 T TDE T 20 - T T 29 12 T - T 10 T DDT - - - - - 11 T - - - - - 1971 DDE TDE DDT PCB's T 3T - T T >400 1972 DDE TDE DDT T T STATION 7 —DEEP WATER SHOALS— 69 SAMPLES i 1965 DDE 21 18 10 13 30 40 TDE 52 31 17 22 41 56 DDT 63 35 T 13 17 23 Dieldrin 14 T - - 11 13 1966 DDE 37 11 24 26 30 40 37 23 11 18 19 17 TDE 43 15 24 32 45 63 57 41 21 29 28 32 DDT 15 - - — 14 20 30 22 T 16 15 10 Dieldrin - - - 23 34 38 16 17 - 12 - - 1967 DDE 21 26 19 31 19 20 20 T 17 13 21 19 TDE 29 30 21 41 25 32 37 25 33 20 23 20 DDT 12 13 - 19 13 12 18 24 28 10 11 24 Dieldrin - 14 - 40 28 21 22 11 12 - - - 1968 DDE 15 14 17 15 15 23 18 14 T 15 12 19 TDE 15 12 15 15 19 29 26 25 T 20 T 18 DDT — - - - 11 14 15 18 - T T T Dieldrin — — 12 12 16 16 T T — - T — 350 Pesticides Monitoring Journal TABLE N-2.- — Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (/ig/ko) STATION 7— DEEP WATER SHOALS— 69 SAMPLES i— Continued 1969 DDE T T 10 11 T 10 18 14 17 20 28 TDE 10 T 12 T T 16 12 16 23 28 40 DDT - - - - T T - 16 21 20 29 Dieldrin - Lost - - T 11 13 T - T 14 1970 DDE 41 19 10 27 10 12 T 40 20 25 12 17 TDE 43 22 11 12 T 21 22 71 40 43 17 28 DDT 60 - T - - 17 T 10 14 25 T 12 Dieldrin T - 14 - - 12 16 - - - - - 1971 DDE TDE DDT Dieldrin ' PCB's 40 35 T 31 1,000 T 13 T 16 21 17 560 1972 DDE TDE DDT Dieldrin PCB's 15 15 10 3 760 STATION 8.— NANSEMOND RIDGE— 64 SAMPLES » 1965 DDE 16 17 17 T 27 36 TDE 59 43 29 14 37 49 DDT 53 39 25 T 24 31 Dieldrin 17 T - - T 11 1966 DDE 28 14 16 30 30 36 34 13 10 11 11 TDE 35 14 17 34 29 52 55 18 15 16 19 DDT 15 - - 13 13 29 29 - 10 16 10 Dieldrin - - - 17 14 22 14 - - - - 1967 DDE 14 17 22 18 15 14 14 18 T 13 17 20 TDE 17 16 20 18 17 20 24 35 16 24 24 25 DDT T T 11 T T 12 11 20 T 10 13 10 Dieldrin - - - 15 12 T 12 14 - - 10 11 1968 DDE 12 15 14 12 32 24 23 14 - T 16 16 TDE 14 16 15 12 47 32 38 29 - 12 13 22 DDT - T T - 45 27 23 15 - - T T Dieldrin - 11 - 10 21 15 T - - - - - 1969 DDE - T 10 T T 11 T 50 11 16 16 TDE T T 11 T T 23 T 37 14 28 26 DDT - - — - - 10 - 23 T 13 12 Dieldrin - - - - - 10 - - - 11 T Vol. 6, No. 4, March 1973 351 TABLE N-2.- -Distribution of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (ag/ko) TDE DDT Dieldrin DDE TDE DDT Dieldrin » PCB's STATION 8.— NANSEMOND RIDGE— 64 SAMPLES > — Continued 1970 DDE 12 15 — 10 16 10 T T TDE 18 40 13 27 23 14 12 14 DDT 22 11 35 - 13 11 10 T Dieldrin T - T T - - - - 1971 DDE TDE DDT Dieldrin PCB's 22 18 T 15 '1,000 11 13 T 16 15 20 a 440 1972 DDE TDE DDT Dieldrin 16 14 STATION 9.— HOSPITAL POINT— 58 SAMPLES" 1966 DDE 140 82 63 83 66 37 20 24 26 27 TDE 120 73 60 130 96 63 36 53 42 40 DDT 40 32 31 89 39 43 22 35 27 24 Dieldrin 13 18 15 20 - - - - - T 1967 DDE 42 52 26 34 33 37 29 11 20 39 43 54 TDE 48 53 17 25 42 76 67 55 59 83 78 64 DDT 31 29 T - 20 58 36 31 62 63 100 37 Dieldrin T 16 - - 11 16 - - 10 15 16 19 1968 DDE 68 92 60 57 48 50 30 20 14 13 11 26 TDE 79 67 48 49 48 93 67 62 30 24 17 21 DDT 52 55 18 20 34 83 35 19 12 10 T T Dieldrin 13 19 15 12 12 13 10 T - 10 11 - 1969 DDE 12 17 31 22 15 15 15 28 33 32 29 TDE T 11 32 21 28 28 33 70 84 92 56 DDT - - 11 19 11 27 15 41 46 71 36 Dieldrin - T 10 10 T T 10 T 19 10 T 1970 DDE 15 32 15 T 18 24 13 T 15 40 20 T 2,800 24 960 352 Pesticides Monitoring Journal TABLE N-2. — Distribulion of organochlorine residues in C. virginica for each sampling station by date of collection — Virginia — Continued Residues in PPB (iia/KO) STATION 9.— HOSPITAL POINT— 58 SAMPLES i— Continued 1972 DDE 34 TDE 32 DDT - Dieldrin Lost 3 PCB's 1,440 STATION 10.— LYNNHAVEN BAY— 62 SAMPLES" 1965 DDE 26 18 13 14 13 31 TDE 49 33 10 24 14 40 DDT 17 12 T - T T Dieldrin 10 - - - - - 1966 DDE 19 20 17 32 16 25 36 16 16 14 17 14 TDE 25 29 20 39 20 41 59 21 24 22 27 26 DDT - - - T - 11 15 - - T - T 1967 DDE 16 22 19 29 15 24 34 17 21 20 20 18 TDE 19 27 21 36 18 35 57 33 33 32 27 25 DDT T T - T T 20 22 17 16 17 11 10 Dieldrin - - - 16 - - - - - - - - 1968 DDE 19 T 29 18 27 30 15 14 11 16 15 19 TDE 22 - 43 18 28 45 T 21 13 20 12 20 DDT T - 12 - 10 27 12 T - T - T Dieldrin - - 13 - - - - - - - - - 1969 DDE 18 16 12 11 16 12 27 14 11 20 18 TDE 16 22 21 11 21 16 28 18 20 28 23 DDT - T T - T - 17 T 10 - - Dieldrin - - - - - - - - - 10 - 1970 DDE — 20 — T 11 28 18 18 14 TDE - 26 - - - 29 20 12 23 DDT T - - - - T 10 T T Each sample represents 15 or more mature mollusks. Calculated as Aroclor 1242®. Calculated as Aroclor 1254®. Vol. 6, No. 4, March 1973 353 SECTION O.— WASHINGTON The Pacific oyster, Crassostrea gigas, was used to moni- tor 19 estuarine sites at monthly intervals in the period October 1965 - December 1968. All samples were analyzed at the Gulf Breeze Laboratory. The approxi- mate station locations are shown in Fig. O-l. A summary of data on organochlorine residues in the monitored species, C. gigas, is presented in Table O- 1 , and the distribution of residues in this species for each sampling station by date of collection in Table 0-2. The monitoring program was terminated in Washington after 3 years because of the absence of detectable DDT residues in most samples. This was due to the absence of DDT pollution and not because of any lack of sensitivity on the part of the monitored species. Analyses of samples of the Pacific oyster in California waters had demonstrated its ability to store organochlorine residues at levels comparable to other molluscan species in the same estuary. The overall incidence of DDT residues in Washington samples was only 11%. The maximum residue detected. 176 ppb, was the obvious result of a single pollution incident. Station 18 was the only one demonstrating a continuing, but low-level pollution problem. The fact that residues at this station were primarily DDT rather than one of its metabolites suggests a direct application of the pesticide to coastal waters. Analytical data are too few, even at Station 18. to indicate any trend in DDT pollution. The overall picture is that of an estuarine area of the United States that was remarkably free from DDT pollution in the period 1965-68. FIGURE O-l. — Diagram of coastal Washington showing approximate location of monitoring stations Stackpole Harbor — Willapa Bay Olson Slough— Willapa Bay Bear River — Willapa Bay Naselle River — Willapa Bay Netnah River — Willapa Bay Stony Point— Willapa Bay South Bend— Willapa Bay Beardslee Slough — Grays Harbor Oyehut — Grays Harbor Sequim Bay North Bay Reserve — Puget Sound Oakland Bay Reserve — Puget Sound Mud Bay — Puget Sound Padilla Bay— Padilla Bay Swinomish — Padilla Bay Scott Point — Samish Bay Rock Point — Samish Bay Lummi — Luinmi Bay Blaine — Drayton Harbor TABLE O-l. — Summary of data on organochlorine residues in the monitored species (C. gigas), 1965-68 — Washington Number of Positive Samples and Maximum Station Number Location Monitoring Period Number of Samples ' Residue ( ) Detected in PPB (ao/ko) DDT Dielorin 1 Stackpole Harbor 1965-68 38 9 (25) 2 Olson Slough 1966-68 30 7 (55) 3 Bear River 1965-68 38 3 (17) 4 Naselle River 1965-68 38 1 (11) 1 (120) 5 Nemah River 1965-68 39 4 (21) 6 Stony Point 1965-68 39 10 (176) 7 South Bend 1965-68 39 6 (23) 8 Beardslee Slough 1965-68 37 2 (27) 9 Oyehut 1966-68 36 10 luim Bay 1966-68 31 11 North Bay Reserve 1965-68 33 12 Oakland Bay Reserve 1965-68 33 354 Pesticides Monitoring Journal TABLE O-l. — Summary of data on organochlorine residues in the monitored species (C. gigas), 1965-68- Washington — Continued Station Number Location Monitoring Period Number of Samples ' Number of Positive Samples and Maximum Residue ( ) Detected in PPB (/io/kg) DDT DiELDRm 13 Mud Bay 1965-68 32 14 Padilla Bay 1965-68 39 8 (17) 15 Swinomish 1965-68 38 1 (T) 16 Scott Point 1965-68 39 4 (10) 17 Rock Point 1965-68 37 18 Lummi 1965-68 38 23 (99) 19 Blaine 1965-68 38 Occasional stations (2) 1966 3 Total number of samples 695 Percent of samples positive for indicated compound 11 5 but <10 ppb. ' Each sample represents 15 or more mature mollusks. TABLE 0-2. — Distribution of organochlorine residues in C. gigas for each sampling station by date of collection — Washington [Blank = no sample collected; — = no residue detected above 5 ppb; T = >5 but <10 ppb] Residues in PPB (mg/kg) STATION l.—STACKPOLE HARBOR— 38 SAMPLES » 1965 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT T T — T — — T — — — — T T T 13 11 — T — — — STATION 2.— OLSON SLOUGH— 30 SAMPLES > Vol. 6, No. 4, March 1973 355 TABLE 0-2. — Distribution of organochlorine residues in C. gigas for each sampling station by date of collection — Washington — Continued Residues in PPB (^/ko) Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 2.— OLSON SLOUGH— 30 SAMPLES i— Continued STATION 3.— BEAR RIVER— 38 SAMPLES i 1965 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT III III III ill III III III III III III III III III III III III H H H 1 M H ill III III III III III III III III III III III III III III III III III' III 1 1 H STATION 4.— NASELLE RIVER— 38 SAMPLES > STATION 5.— NEMAH RIVER— 39 SAMPLES ' 356 Pesticides Monitoring Journal TABLE 0-2. — Distribution of organocMorine residues in C. gigas for each sampling station by date of collection — Washington — Continued Residues in PPB (;io/kg) Feb. Mar. May June July Aug. Sept. Oct. Nov. Dec. STATION 5— NEMAH RIVER— 39 SAMPLES i— Continued 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT _ — — __n T — — — — — — _ — __10 — _ — _ — — T_ — — — — — — — — — — STATION 6.— STONY POINT— 39 SAMPLES ' 1965 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT T T — 14 T — T — — T — — T TT 13 — — — — — T — — T — 11 11 — — — — — T — T — — — — — — — — — STATION 7.— SOUTH BEND— 39 SAMPLES ' 1965 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT T — T T T — 10 — — — — — T — 16T — — 13 — — — — — — T — — — — — — — — — — _T — — — — — — — — — — — T — — — — — — — — — — Vol. 6, No. 4, March 1973 357 Ifrssiwifr^ 7& ??S .a£ V£.' OCE Nil* ---THHTT— 5» SiSetJ ssaoaxc s.— ^ascnc s&t— :-: &>3£?^ jsa, TABLE 0-2. — Distribution of organochlorine residues in C. gigas for each sampling station by date of collection — Washington — Continued Residues in PPB (;ig/ko) Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 13.— MUD BAY— 32 SAMPLES i— Continued STATION 14.— PADILLA BAY— 39 SAMPLES ■ STATION 15.— SWINOMISH— 38 SAMPLES > STATION 16.— SCOTT POINT— 39 SAMPLES ' 196S 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT _T — — — — — — — — — — 360 Pesticides Monitoring Journal TABLE 0-2. — Distribution of organochlorine residues in C. gigas for each sampling station by date of collection — Washington — Continued Residues in PPB (ao/ko) STATION 16.— SCOTT POINT— 39 SAMPLES i— Continued STATION 17.— ROCK POINT— 37 SAMPLES ' 1965 1966 1967 1968 DDE TDE DDT DDE TDE DDT DDE TDE DDT DDE TDE DDT STATION 18.— LUMMI— 38 SAMPLES' 1965 DDE TDE DDT — - — 1966 DDE — - - - - — - - - - T T TDE - — - — - - - - - - 15 — DDT - - - - - T - - - - - 18 1967 DDE T — T T T 11 T T — T - T TDE 10 - T II T 14 T T T T - T DDT 25 19 29 44 42 74 34 14 15 21 21 19 1968 DDE T - — - 10 T T T — - — TDE - - - - T T - - - - - DDT 17 19 22 33 25 24 14 17 - - — Vol. 6, No. 4, March 1973 361 TABLE 0-2. — Distribution of organochlorine residues in C. gigas for each sampling station by date of collection — Washington — Continued Residues in PPB (/ig/ko) Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. STATION 19.— BLAINE— 38 SAMPLES' 1965 DDE _ TDE — — — DDT - - - 1966 DDE TDE DDT — - 1967 DDE TDE DDT — - 1968 DDE TDE DDT - Each sample lepresents IS or more mature mollusks. 362 Pesticides Monitoring Journal PESTICIDES IN WATER Organochlorine Insecticide Residues in Streams Draining Agricultural, Urban- Agricultural, and Resort Areas of Ontario, Canada — 1971' J. R. W. Miles and C. R. Harris ABSTRACT Organochlorine insecticide residues in water systems drain- ing agricultural, urban-agricultural, and resort areas of Ontario, Canada, were compared by analysis of water, bot- tom mud, and fish, collected during the period from mid- April to mid-October 1971. Insecticides detected were p,p'-DDT, o.p'-DDT. p.p'-TDE, o.p'-TDE, p,p'-DDE, y-cMordane, dieldrin. endrin, endosulfan, heptachlor, hepta- chlor epoxide, lindane, and aldrin. Insecticide concentra- tions in water from all three areas were less than the "Maximum Reasonable Stream Allowances" for growing fish that are safe for human consumption. The concentrations of total DDT in the water were com- bined with water flow data to calculate the weekly rate of transport of total DDT at each sampling time. The greatest transport of total DDT was by the Muskoka River which drains the Muskoka Lakes resort area where DDT was used until 1966 for control of biting flies; a peak of 11.8 lb total DDT per week was recorded in May, but this trans- port quickly lessened, resulting in a May to October average of 1.9 lb total DDT per week. Corresponding figures for the Thames River (urban-agricultural) were peak 2.5 lb and average 0.4 lb total DDT per week and for Big Creek (agricultural), peak 0.5 lb and average 0.2 lb per week. The ratio of concentration of total DDT in mud to total DDT in water was as great as 800; total DDT in fish to total DDT in water was as great as I million. The ratio of p,p'-TDE to p,p'-DDT was / in bottom mud. indicating possible dechlorination of p.p'-DDT to p,p'-TDE in the bottom mud. Polychlorinaled hiphenyls (PCB's) were present in the urban-agricultural area samples of bottom mud and fish at levels up to 217 ppm and about 0.4 ppm. respectively. ' Contribution No. 528 from the Research Institute, Canada Depart- ment of Agriculture, University Sub Post Office, London 72, Ontario. Vol. 6, No. 4, March 1973 Introdi4Ction In a previous issue of this Journal (4), this laboratory reported on the transport of insecticides into Lake Erie by two water systems draining agricultural areas in southwestern Ontario ( Big Creek, which flows into Lake Erie, and a controlled drainage system near Erieau, Ontario, the water of which is pumped into Lake Erie). In 1971, in order to compare residue contributions from differing areas of insecticide usage, the present study was made of insecticides transported by water systems draining agricultural, urban-agricultural, and resort areas. The agricultural area studied (Fig. 1, Area 1) was the same 280 square miles of predominantly tobacco farms in Norfolk County, Ontario, reported in the earlier study, whose drainage enters Lake Erie by Big Creek. DDT has been used extensively in this area for many years primarily for cutworm and hornworm control. Since January 1970, use of DDT has been restricted to cutworm control on tobacco and requires a provincial government permit prior to its use. The urban-agricul- tural area (Fig. 1, Area 2) was the City of London, Ontario, (population 200,000) on the Thames River which drains 1,200 square miles of mixed agricultural land (chiefly dair>' cattle) before flowing through Lon- don; the Thames River flows into Lake St. Clair which empties into Lake Erie via the Detroit River. DDT usage in this area has also been subject to the provincial ban of 1970. The resort area (Fig. I. Area 3) was the Muskoka Lakes region of Ontario. 1.700 square miles which drains into Georgian Bay and Lake Huron by the Muskoka River. DDT had been used extensively in this area for biting fly control until 1966 when this use was discontinued. Average water flow for the three streams during 1971 was Big Creek (agricultural) 190 cubic feet per second (CFS), Thames River (urban-agricultural) 1.030 CFS, and Muskoka River (resort) 2,421 CFS. 363 FIGURE 1. — Partial map of Ontario, Canada, showing drainage areas of I — Big Creek (agricultural), 2 — Thames River (urban-agricultural), and 3 — Muskoka Lakes (resort) In Big Creek drainage area, the overburden consists mainly of glacial till of Pleistocene age with dominantly coarse-textured soil formed on sand and gravel. The adjacent Thames River drainage area is also of glacial till but is dominantly fine-textured soil formed on very fine sands and silts. The Muskoka Lakes region is a Pre- cambrian area with little or no true soil and consists of lakes and rock outcrops with conifers growing on shal- low soils and detritus trapped between rocks. Materials and Methods SAMPLE COLLECTION Water, bottom mud, and fish samples were collected be- tween mid-April and mid-October 1971. Water and botton mud samples in Big Creek and the Thames River were taken every 2 weeks. Depth-integrated water sam- ples were collected in 32-fluid ounce, narrow-necked glass bottles clamped to a 24-ft long aluminum pole. The contents of two bottles were combined for one water sample. Bottom mud samples were collected using a sampler (authors' design) consisting of a steel con- tainer, 3!4 inches in diameter and 1% inches deep, attached to the end of a 24-fl aluminum pole. Five samples of mud were taken, ranging from near the bank to mid-stream, and combined into one composite sam- ple. Water and bottom mud samples from the Muskoka River were taken at monthly intervals by personnel of the Ontario Water Resources Commission and shipped .^64 to London, Ontario, for analysis. The difference in frequency from the other two rivers was necessitated by the greater distance of the Muskoka Lakes from the laboratory. Water samples were collected from 10 feet below the surface using Kemmerer bottles. Bottom mud samples were collected with an Eckmann Dredge. Water depth at sampling points was about 30 feet. Stream flow data were measured and compiled by per- sonnel of the Water Survey of Canada using the "Gen- eral Procedure for Gaging Streams" (6). Fish were collected in the fall of 1971 by personnel of the Ontario Department of Lands and Forests, using electric shockers and gill nets. EXTRACTION AND FRACTIONATION Water plus any suspended matter was analyzed "as is" without filtration. The contents of the bottles were measured by weighing bottles before and after emptying the contents into a 2-liter separatory funnel. The empty bottles were rinsed with 10 ml acetone to remove any insecticide adsorbed on the walls, and the acetone rinse was added to the separatory funnel. The bottles were then rinsed with 100 ml of hexane which was also added to the separatory funnel. The funnel was shaken for 2 minutes, and the layers allowed to separate. The aqueous layer was withdrawn into a second 2-liter separatory funnel and extracted twice more with 50-ml portions of hexane, the first separatory funnel being used twice. The three hexane extracts were combined in a 500-ml round- bottom flask and concentrated for fractionation on a Florisil column. Extraction of bottom mud and fish and fractionation of extracts on Florisil have been previously described (4). GAS-LIQUID CHROMATOGRAPHY Two Model 1400 and one Model 1200 Varian Aero- graph gas chromatographs were used. The column of one Model 1400 was packed with 5% XE-60, the other with mixed 3% DC-200/4.5% QF-1. The column of the Model 1200 was packed with 5% DC-200. Solid support in all columns was 80/100 mesh Chromosorb W. A.W. DMCS treated; all columns, 6 ft long x 2 mm (i.d.), were operated at 180° C. Nitrogen was the car- rier gas at a flow rate of 40 ml/min.. Tritium electron capture detectors were used on all three gas chroma- tographs. All samples were run on all three columns. In the samples of bottom mud and fish from the urban- agricultural area (Thames River), interference from polychlorinated biphenyls (PCB's) measured as Aroclor 1254® (up to 217 ppm in bottom mud, about 0.4 ppm in fish) was too great to allow direct GLC determina- tion of p.p'-DT)T, o./7'-DDT, and p.p'-DDE. In these samples the DDT compounds were converted to di- chlorobenzophenones, separted from the PCB's on the Florisil column, and then assessed by GLC (5). Pesticides Monitoring Journal RECOVERY Recoveries of reported insecticides from water fortified at 100 parts per 10'- (American trillion) ranged from 75% to 102%. Recoveries of the insecticides added to bottom mud at 0.2 ppm were 91 % to 103%. Recoveries of the reported insecticides added directly to fish muscle at 0.1 ppm before extraction ranged from 91 % to 95% . Results and Discussion The concentrations of insecticides found in water sam- ples are given in Table 1. In all three water systems, residues of p.p'-DDT were the highest, followed by dieldrin and o.p'-DDT. Peak concentrations for all in- secticides occurred during spring runoff in May, with subsequent leveling off at lower concentrations during the rest of the sampling period. For these uniform periods, data have been condensed by reporting aver- age concentrations and ranges (Table 1). For the sam- pling period, the averages for total DDT in water were similar for the three areas — 28, 23, and 18 parts per IQi- (American trillion) for agricultural, urban-agricul- tural, and resort areas, respectively. All insecticide con- centrations in water were below the "Maximum Reason- able Stream Allowances" (2) in which it is presumably safe to grow fish for human consumption. The concentrations of total DDT in the water were combined with water flow data measured in cubic feet per second (CFS) to calculate the weekly rate of trans- port of total DDT at each sampling time (Fig. 2). Although the peak transport (in May) for the Muskoka River (resort area) was 11.8 lb total DDT per week, the average for the period sampled was 1.9 lb per week. TABLE 1. — Insecticide concentrations in water of three streams in Ontario, Canada — 1971 Date (1971) REsrouES IN Parts per 10" (American ttiillion) Total DDT Diel- drin 7-Chlor- Endo- dane sulfan Hepta- chlor BIG CREEK (AGRICULTURAL) Apr. 13 30 5 13 10 2 3 <1 2 <1 <1 — — 26 31 5 13 10 41 <1 2 <1 <1 - — May 4 75 15 13 40 11 23 <1 II <1 2 — — 11 79 5 12 58 11 <1 Average 16 2 9 4 » Thames River Big Creek v.. .7>^^ N^ "'^•»'-T.Tr.;?:T.»nlll.^r.ll„JU..mmi«T.*TS ■jwm.i'Jtr^?: •,~.T..Tr.t'— — ■ April I May June July I Aug 1971 Sept Oct FIGURE 2. — Transport of total DDT per week by water of Big Creek (agricultural), Thames River (urban-agricultural), and Muskota River (resort) Similarly, the Thames River (urban-agricultural) aver- aged 0.4 lb total DDT per week and Big Creek (agricul- tural) averaged 0.2 lb total DDT per week. To properly relate these data, the size of the three drainage areas must be considered, i.e. resort, 1,700 square miles; urban- agricultural, 1,200 square miles; and agricultural, 280 square miles. Average amounts of total DDT trans- ported per week per 100 square miles were: Muskoka River (resort)-O.ll lb; Big Creek (agricultural) -0.05 lb; and Thames River (urban-agricultural) -0.03 lb. It is surprising that based on area the resort district is still the largest contributor of DDT, since the last offi- cial use of DDT for biting-fly control was in 1966. In part, this difference may be explained by the different techniques used in these areas for insect control. In the agricultural area (Big Creek), DDT, applied pri- marily for cutworm control on tobacco, was incorpo- rated into the soil. By contrast, in the resort area (Muskoka River), DDT was applied by ground or air application over land and water. As noted in the intro- duction, the Muskoka district has little or no true soil, thus the insecticide would tend to accumulate in the surface detritus with the possibility of greater surface erosion. The concentrations of insecticides found in the bottom mud are listed in Table 2. These concentrations were uniform for each compound, and results for each month have been averaged for presentation in this table. Con- centrations of total DDT in the bottom mud of Big Creek (agricultural) were 604 times those in the water, while the ratios of total DDT in bottom mud/water for the Thames River (urban- agricultural) and the Muskoka River (resort) were 109:1 and 863:1, respectively. The .Ui6 reason for the low bottom mud/ water ratio for total DDT in the Thames River is that the Thames had the lowest insecticide concentration in the bottom mud, average total DDT ^ 2.5 parts per 10^ (American billion). These data may be interpreted to mean that the DDT contamination in the Thames River did not result from erosion of treated soil into the stream, but rather from domestic DDT usage with direct contamina- tion of the water. Ratios of /7,p'-DDE:p,/7'-TDE:/7,p'-DDT in bottom mud may indicate the metabolic history of residues in specific areas. These ratios were as follows: Big Creek (agricultural) 0.7:1.0:1.0; Thames River (urban-agri- cultural) 1.9:5.7:1.0; and Muskoka River (resort) 2.5:1.8:1.0. The higher DDE/ DDT ratios in the Thames and Muskoka Rivers compared to Big Creek could indicate that these residues are older (the last official use of DDT in the resort area was in 1966). The high TDE/DDT ratio in the Thames River bottom mud suggests greater anaerobic dechlorination of DDT (1 ,3) and may indicate the presence of sewage. Residues found in fish from the three areas are listed in Table 3. Magnification of total DDT concentration from water to fish was greatest (1 million times) in the lake trout from the resort area. No direct comparisons can be made because the same species of fish were not obtained from all three areas, but it is interesting to note the differences in the ratios of p,p'-DDE: p.p'-TDE: p,p' -DDT in fish from Big Creek (agricultural) -3.6: 0.7:1.0 and from Muskoka River (resort) -0.6: 1.0:1.0, indicating more metabolism to DDE in the smaller fish from the agricultural area than in the larger fish from Pesticides Monitoring Journal the resort area. In the fish from the urban-agricultural area (Thames River), levels of total DDT were very low (0.02-0.04 ppm), and the major part of this residue was p,p'-DDE and p,p'-TDE; levels of p,p'-DDT were <0.01 ppm. Summary Insecticide residues in water, bottom mud, and fish were compared in streams draining agricultural, urban-agri- cultural, and resort areas during spring runoff and sum- mer of 1971. Transport of total DDT was calculated by combining insecticide concentrations in water with stream flow measurements. Average transports (April- October) of total DDT were Muskoka River (resort) 0.1 1 lb per week per 100 square miles. Big Creek (agri- cultural) 0.05 lb per week per 100 square miles, and Thames River (urban-agricultural) 0.03 lb per week 100 square miles. The heaviest contributor of DDT among these three water systems was the resort area in spite of the fact that official DDT usage in that area ceased in 1966. Fish from the resort area contained up to 19 ppm total DDT compared to a high of 1.3 ppm from the agricultural area stream. Bottom mud and fish from the urban-agricultural river contained PCB's (up to 217 ppm in the mud and about 0.04 ppm in the fish). The very small concentration of DDT in the bottom mud of the urban river indicated that the DDT in this water system did not come from erosion of treated soil. A cknowledgments The authors wish to make the following acknowledg- ments: ( 1 ) GLC analyses, Mrs. Patricia Moy; (2) collection of Muskoka samples, personnel of the Ontario Water Resources Commission; (3) collection of fish samples, the Ontario Depart- ment of Lands and Forests; and (4) stream flow data, the Water Survey of Canada, Division of Environment, Canada. See Appendi) paper. for chemical names of compounds discussed in this TABLE 2. — Insecticide concentrations in bottom mud from three streams in Ontario, Canada — 1971 D*TE (1971) Residues in Parts per 10' (American billion). Dry-Weight Basis' Total DDT p.p'-DDE DiELDRIN 7-CHLORDANE BIG CREEK (AGRICULTURAL) Apr. 21.0 4.0 1.5 10.2 0.4 4.9 0.8 0.2 <0.2 May 15.6 3.2 0.7 6.3 0.7 4.7 0.7 0.1 0.2 June 19.2 4.8 0.7 6.1 1.1 6.5 0.8 <0.1 <0.2 July 17.9 4.8 0.6 5.2 1.0 6.4 0.7 <0.1 <0.2 Aug. 15.9 4.2 0.3 3.9 1.1 6.4 0.7 <0.1 <0.2 Sept. 14.2 4.1 <0.3 3.9 0.9 5.3 0.7 <0.1 0.2 Oct. 22.2 5.0 0.9 7.8 1.0 7.5 4.5 3.1 0.3 THAMES RIVER (URBAN-AGRICULTURAL) May 4.3 1.1 3.2 0.4 _ _ June 2.4 0.5 — 0.2 — 1.6 0.5 — — July 2.1 0.5 — 0.4 — 1.3 0.4 — — Aug. 2.5 0.5 — <0.1 — 2.0 0.6 — — Sept. 2.3 0.4 — 0.3 — 1.7 0.6 — — Oct. 2.0 0.4 — 0.7 — 0.9 0.3 — — MUSKOKA RIVER (RESORT) May 19.1 7.5 <0.4 4.1 1.1 6.5 1.4 1.9 0.3 June 21.7 9.3 <0.4 3.9 1.1 7.4 0.9 <0.1 <0.3 July 12.0 7.0 <0.4 1.6 0.4 3.0 0.6 <0.1 <0.3 Aug. 8.7 3.9 <0.4 1.3 0.4 3.1 0.6 <0.1 <0.3 Sept. 12.7 7.0 <0.4 0.8 0.6 4.3 1.0 0.5 <0.3 NOTE: — = not detected; <0.1 indicates qualitative identification of the compound on all three GLC liquid phases, but the amount was less than the lowest level of reporting. Aldrin, endosulfan, heptachlor. heptachlor epoxide, and lindane were not detected in bottom mud samples. ' Because concentrations were very uniform, results for each month have been averaged for presentation in this table. Vol. 6, No. 4, March 1973 367 TABLE 3. — Insecticide concentrations in fish muscle from three streams in Ontario, Canada — 1971 Number OF Fish Residues in PPM Total DDT -Chlor- DANE Hepta- CHLOR Epoxide Percent Fat BIG CREEK (AGRICULTURAL) Brown trout 6 1.27 0.79 0.04 0.31 0.01 0.13 0.03 _ <0.01 <0.01 1.8 Rainbow trout Small 7 0.42 0.37 0.01 _ <0.01 0.04 0.01 0.01 <0.01 1.1 (12-15 cm) Medium 8 0.23 0.17 0.01 0.03 <0.01 0.03 0.01 0.01 <0.01 0.9 (17-22 cm) Rock bass 8 0.49 0.30 0.02 0.10 <0.01 0.06 0.03 - 0.03 <0.01 4.0 Bluegill 8 0.45 0.27 0.01 0.10 <0.01 0.07 0.03 - 0.03 <0.01 4.0 THAMES RIVER (URBAN-AGRICULTURAL) Carp 3 0.03 0.02 — <0.0I — 0.01 <0.01 <0.01 <0.01 _ 0.8 Bass Small (9-14 cm) 3 0.02 0.01 — <0.01 0.01 <0.01 <0.01 <0.01 - 1.8 Medium (16-17 cm) 5 0.04 0.02 <0.01 0.01 <0.01 <0.01 <0.01 1.6 MUSKOKA LAKES (RESORT) White sucker 1.98 0.96 0.04 0.76 0.01 0.21 0.01 <0.01 <0.0I <0.01 2.8 Lake trout 2.47 1.25 0.10 0.90 O.OI 0.21 0.01 <0.01 <0.01 <0.01 1.6 Lake trout 16.57 5.58 0.71 8.92 0.07 1.29 0.04 0.02 0.01 0.02 9.5 Lake trout 5.71 2.32 0.15 2.76 0.02 0.46 0.01 O.OI <0.01 0.01 2.6 Cisco 5.11 0.95 0.21 3.41 O.OI 0.54 0.02 0.02 <0.01 0.01 8.2 Cisco 19.75 3.04 1.00 14.82 0.01 0.88 0.03 0.03 0.01 0.01 9.8 Cisco 1.41 0.41 0.05 0.84 <0.01 0.11 0.01 0.01 <0.01 <0.01 4.6 Cisco 4.05 0.98 0.10 2.78 <0.01 0.19 0.01 0.01 <0.01 <0.01 5.0 Cisco 2.87 0.75 0.06 1.87 0.01 0.18 0.01 0.01 <0.01 <0.01 4.2 NOTE: — = not detected; <0.01 indicates qualitative confirmation on all three GLC columns, but less than the reporting level of 0.01 ppm. Aldrin, endosulfan, heptachlor, and lindane were not detected in fish muscle samples. LITERATURE CITED (1) Castro, T. F., and T. Yoshida. 1971. Degradation of organochlorine insecticides in flooded soils in the Philip- pines. J. Agric. Food Chem. 19(6): 1 168-1170. (2} Ettinger, M. B., and D. I. Mount. 1967. A wild fish should be safe to eat. Environ. Sci. Technol. 1(3): 203-205. {3) Guenzi, W. D., and W. E. Beard. 1967. Anaerobic bio- degradation of DDT to DDD in soil. Science 156(3778): 1116-1117. (4) Miles. J. R. W , and C. R. Harris. 1971. Insecticide residues in a stream and a controlled drainage system in agricultural areas of southwestern Ontario, 1970. Pestic. Monit. J. 5(3):289-294. (5) Miles, J. R. W. 1972. Conversion of DDT and its metab- olites to dichlorobenzophenones for analysis in the pres- ence of polychlorinated biphenyls. J. Assoc. Off. Anal. Chem. 55(5): 1039- 1041. {6) U.S. Department of the Interior. 1968. Techniques of water resources investigations of the United States Geo- logical Sur\'ey 1968. Ch. A6. p. 1-13. 368 Pesticides Monitoring Journal PESTICIDES IN SOIL Organochlorine Pesticide Residues in Soils and Crops of the Corn Belt Region, United States— 1970 A. E. Carey', G. B. WiersmaS H. Tai", and W. G. MitcheU' ABSTRACT In order to determine the levels of organochlorine pesticides in the Corn Belt region of the United Stales, a study was initiated in 1970 to sample 400 sites in 12 States. The sam- pling areas followed the historical boundaries of the Corn Belt and were selected from sites designated for the Na- tional Soils Monitoring Program. At each site a 2-qt soil sample (composite of 50, 2- by 3-inch cores, taken in a grid pattern over each 10-acre site) was collected as well as a composite sample of any available standing crop. In addi- tion, use records were obtained at each site for the kinds and amounts of pesticides used during the 1970 cropping season as well as the names of other pesticides known to have been used in the previous S years. These data indicated that pesticides had been applied to most of the agricultural acreages in the study area (up to 85%). Forty compounds were identified in use records: 20 herbicides, 17 insecticides, and 3 fungicides. Atrazine was most widely used, followed by captan, malathion, 2,4-D, propachlor (Ramrod'^), amiben, and aldrin. Forty-five percent of the soil samples analyzed contained residues; 11 pesticides or metabolites were de- tected. Arsenic, which can occur naturally in soil, was detected in nearly all soil samples. The most commonly delected residues were those of aldrin, chlordane, and diel- drin. Seven compounds, including four DDT metabolites, were detected in cornstalks, soybeans, sorghum grain, sor- ghum fodder, and hay. ' Technical Services Division. OfBcc of Pesticide Programs. Environ- mental Protection Agency. Beltsville. Md. 20705. - Technical Services Division, Office of Pesticide Programs. Environ- mental Protection Agency. Mississippi Test Facility. Bay St. Louis. Miss. 39520. Vol. 6, No. 4, March 197.'' Introduction Historically, the Corn Belt of the United States has been defined as that area stretching from central Ohio to Nebraska and Kansas where agricultural acreage has been devoted almost exclusively to the growing of corn and silage. Although corn is still the main crop, modem agricultural trends have diversified the production in this particular region to include a variety of other food and feed grains. In 1969 the 12 states outlined in Fig. I produced 79% of the total national corn crop, and at the same time, produced 73% of the total soybean crop and 44% of the total sorghum grain (/). Between 1954 and 1959 there was a 22% decrease in the acreage planted to corn; however, the decrease was offset by a 115% increase in yield per harvested acre during the same time period, amounting to a 75% increase in total production. These increases were partly due to more extensive use of fertilizers and pesticides. The production and sales of synthetic organic pesticides have followed a generally upward trend which began in the I940's when many of the chemicals were first intro- duced; however, in 1969, both production and sales declined for the first time since 1957 (2). The main objective of this study was to determine the levels in 1970 of organochlorine pesticide residues in soils and crops of the Corn Belt region as shown in Fig. 1. In addition, pesticide use records were obtained for sampling sites, indicating the kinds and amounts of pesticides used for the 1970 cropping season as well as the names of any other pesticides known to have been used on the sites in the previous 5 years. 369 FIGURE 1. — Com Bell region of the United States with area studied — 1970 IT ^ --__ /^^^\ n ■ V ■^'•^■v-y/^^ ■Sri ) / *\l J ^^^*Lr~~~^ jL lETl -TO ?7 ^ / .^ ^ L rsW^ ^ ^V T ' <», "— *s?t: m%/-^ / "^ ]7^ ""^T^x "^ . L J— ^ U>--^^ \i R^^ Cora Belt Study Area K } 1 1 Com Belt Slates Sampling Procedures During the late summfir of 1970, a total of 400 sites were sampled in the Corn Belt region. These were selected from the 13,300 cropland and noncropland sam- ple sites already designated for the National Soils Monitoring Program, one-fourth of which are sampled each year. The complete sampling scheme for the Na- tional Soils Monitoring Program has been reported by Wiersma, Sand, and Cox (i). Fifty soil cores, each 2 inches in diameter by 3 inches in depth, were collected in a grid pattern over each 10- acre sampling site, composited, and passed through a V4-inch sieve. A 2-qt metal container was filled from each composite sample, sealed, and shipped to the monitoring laboratory at Gulfport. Miss., for residue analyses. Crops growing on sites at the time of sampling were collected simutaneously with the soil, i.e.. as each soil core was taken, a nearby sample of the standing crop was also taken. The crop samples from each site were composited, air-dried, and packed for shipment to the laboratory. Hay and forage were packed in plastic bags, while corn grain, sorghum grain, and soybeans were packed in 2-qt metal containers. 370 Analytical Procedures PREPARATION OF SAMPLES Soil A 300-g sample of soil plus 80 ml of water used to wet the soil was extracted with 600 ml of 3:1 hexane isopropanol by concentric rotation for 4 hours. The alcohol was removed by three water washes, and the hexane extract was dried through anhydrous sodium sulfate. The sample extract was then stored at low temperature for subsequent gas-liquid chromatographic analysis. Crops For crop samples containing less than 2% fat (corn- stalks, sorghum fodder, and mixed hay), a 100-g sam- ple plus 25 ml of distilled water was blended for 3 minutes in 800 ml of acetonitrile. One-half the sample extract, representing 50 g of original sample, was de- canted into a 500-ml graduated cylinder and then transferred to a 500-ml Erlenmeyer flask. After concen- tration under a three-ball Snyder column to approxi- mately 10 ml, 100 ml of hexane was added, and the hexane-acetonitrile azeotrope was again concentrated to 10 mi. Addition of hexane and concentration to 10 ml were carried out three times to remove essentially all the Pesticides Monitoring Journal acetonitrile. The hexane extract was dried through anhydrous sodium sulfate, the volume adjusted to 100 ml, and the extract stored at low temperature until ready for partitioning. For crop samples containing more than 2% fat (corn, sorghum grain, and soybeans), a 100-g sample was prewashed with 100 ml of isopropanol and 100 ml of hexane, in that order, and the prewashes discarded. The sample was dried and then dry-blended; 100 ml of isopropanol was added, and the sample was blended again. After the addition of 300 ml of hexane, the isopropanol was removed by two washes with aqueous NaCl solution and one wash with distilled water. The water-alcohol layers were discarded, and the hexane layer was concentrated, adjusted to 100 ml, and held at low temperature for partitioning. After the above extraction procedure, all crop samples were partitioned with hexane-acetonitrile as follows: a 50-ml portion of the hexane sample extract was shaken with 100 ml of acetonitrile in a 500-ml separatory fun- nel. The bottom acetonitrile layer was saved. Nanograde acetonitrile (100 ml) was added to the hexane extract, and the separation step above was repeated twice more; then, the hexane was discarded and the three acetonitrile layers combined. The 300-m] acetonitrile extract, which contained essentially all the pesticides in the original hex- ane extract, was backwashed with 25 ml of acetonitrile- saturated hexane and the hexane layer discarded. The acetonitrile sample extract was concentrated to approxi- mately 10 ml under a three-ball Snyder column, and 100 ml of hexane was added. The addition of hexane and concentration to approximately 10 ml were carried out three times after which the sample was essentially in hexane. The hexane extract was diluted to appropriate volume and held at low temperature for subsequent Florisil column cleanup and fractionation. GAS-LIQUID CHROMATOGRAPHY Analyses were performed on gas chromatographs equipped with tritium foil electron affinity detectors for organochlorine compounds and thermionic or flame photometric detectors for organophosphorous com- pounds. A multiple-column system employing polar and nonpoplar columns was utilized to identify and confirm pesticides. Instrument parameters were as follows: Columns: Glass, 6 mm o.d. x 4 mm i.d., 183 cm long, packed with one of the following: 9% QF-1 on 100/120 mesh Gas-Chrom Q; 3% DC-200 on 100/120 mesh Gas-Chrom Q. or 1.5% OV-I7/1.95% QF-1 on 100/120 mesh Supelcoport Carrier gases: S% melhane-argon al a flow rate of 80 ml/min; prepurified nitrogen at a flow rate of 80 ml/min Temperatures: Detector 200° C Injection port 250° C Column QF-1 166° C Column DC-200 170°-175° C Mixed column 185°-190° C Vol. 6, No. 4, March 1973 Sensitivity (minimum detectable levels) for organo- chlorine compounds ranged from 0.002 ppm to 0.03 ppm except for mixtures of poly chlorinated biphenyls (PCB's), chlordane, toxaphene, etc. whose minimum detectable levels were 0.05 to 0.1 ppm. Minimum de- tectable levels for organophosphorous compounds were approximately 0.01 to 0.03 ppm. When necessary, con- firmation of residues was made by thin layer chroma- tography or p-values. Arsenic Arsenic was determined by atomic absorption spectro- photometry. The soil sample was first extracted with 9.6n hydrochloric acid (HCl) and reduced to trivalent arsenic with stannous chloride. The trivalent arsenic was partitioned from HCl solution to benzene, then further partitioned into water for the absorption measure- ment. A Perkin-Elmer Model 303 instrument was used and absorbance measured with an arsenic lamp at 1972 A with argon as an aspirant to an air-hydrogen flame. The minimum detection limit was 0.10 ppm. RECOVERY STUDIES For organochlorine pesticides, the average recovery rate in soil was 90% to 110%. Recovery values for stalks and hay ranged from 80% to 95% with an average of 89%; corresponding values for grains were 90% to 100% with a 95% average. For organophosphate pesti- cides, the average recovery values were 67.1% for soy- beans, 86% for sorghum grain, and 60% for corn stalks. Recovery values for arsenic ranged from 70% to 80%. All residue levels were corrected for percent recovery. Results PESTICIDE USE RECORDS The pesticide-use information, as reported by the farmers, was divided into five categories: Percent of Sftes 15.5 15.5 53.2 (1) No pesticides used in 1970, or in the 5 years prior to 1970 (2) No pesticides used in 1970, but used in the 5 years prior to 1970 (3) Pesticides used in 1970 and in the 5 5 years prior to 1970 t4) Pesticides used in 1970 only, none in the 5 years prior to 1970 (5) No use records available These data indicate that pesticides had been applied to most of the agricultural acreages sampled in the Corn Belt (up to 85%). Although pesticides reportedly had not been applied in 1970 or the past 5 years on 15.5% of the sites, many of the samples taken from these sites contained pesticide residues; however, this is not unusual. Probable explanations include inaccurate record keeping, spray drift, and the persistent nature of many of the compounds. 371 Table 1 lists the pesticides used in 1970 on the sample sites, the average application rate, and the number of sites where applied. Table 1 should be considered a conservative estimate of the amounts of pesticides ap- plied to the study areas. In most cases, farmers were most certain of the kinds and amounts of pesticides they had used for the current cropping season. How- ever, in a few cases, farmers knew neither the names nor the amounts of pesticides used on their crops. TTie use of unknown seed dressings was common, par- ticularly in Nebraska. Since captan and malathion were indicated as being used almost exclusively as seed dress- ings, it is likely that they were the "unknown" seed dressings in many cases. Hence their estimates in Table 1 may be particularly low. TABLE 1. — Pesticides used on sampling sites in the Corn Belt region of the United States during J970 growing season, average application rate, and number of sites where applied Average Number of Compounds Applied Application Sites Where Rate (lb/acre) Applied Alachlor 1.22 15 *AIdrin 1.30 27 Amiben 1.08 29 Atrazine 1.51 78 Borax 1.50 1 Butylate (Sutan) 1.10 3 Buxten 1.88 15 *Captan .03 68 Caibaryl 1.93 6 CDAA .80 1 Ceresan .01 1 Chloropropham (CIPC) .25 2 2,4-D .55 55 2,4-DB .50 1 »DDT 2.00 1 *Dlazinon 1.34 5 *DIcamba .94 5 •Dieldrin .01 2 "Disnlfolon .74 5 "Dyfonate 1.00 I •FensiiUotUon .80 I "Fenthion 2.50 2 Furadan .85 2 •HeptacUor .19 8 Knoxweed .35 2 •Lindane .10 4 Linuron 2.22 5 « Malathion .02 58 MCPB 2.00 1 *MelhoxychIor .01 5 •Nilralin .50 1 Norea .67 .1 NPA .40 2 Panogen .01 1 *Paralliion .40 4 *Pliorate 2.04 13 •Propachlor (Ramrod®) 2.10 31 Propazinc 1.60 I 2,4,5-T .50 1 *TriiloraIin .64 15 * Compounds detectable by described methodology. .^72 In all, 40 different compounds were used : 20 herbicides, 17 insecticides, and 3 fungicides. Atrazine was most widely used, followed by captan, malathion, 2,4,-D, propachlor (Ramrod®), amiben, and aldrin. Fenthion was applied most heavily, with an average application rate of 2.5 lb/acre. Although the list of compounds in Table 1 is lengthy, approximately 68% of all the com- pounds listed were used on five or less sites; 30% of the compounds on the list were used on only one site. RESIDUES DETECTED IN SOIL Pesticide residues were detected in 45% of the soil samples analyzed, and 1 1 pesticides or metabolites were identified. Arsenic, which can occur naturally in soil, was detected in nearly all soil samples. The analytical methods employed were able to detect only 45% of the compounds listed in Table 1 and these are indicated in the table; however, most of the widely used pesticides were included in this group. Table 2 shows the arithmetic means and ranges of resi- due levels in soil from each State as well as the percent of positive samples for each compound. The most com- monly detected residues were those of dieldrin, aldrin, and chlordane. Since very little dieldrin was used in the study area and the use records indicated that aldrin had been used frequently in the past, most of the dieldrin detected has undoubtedly metabolized from aldrin. Although chlordane residues were found in soil samples from 7 of the 12 States sampled (approximately 17% of the samples analyzed), no chlordane applications were indicated on any of the use records for 1970 or for the 5 years prior to 1970. Four DDT metabolites (p,p'- DDE, o,p'-DDT, p,p'-DDT, and p,p'-TDE) were inden- tified and are listed together as DDTR in Table 2. Both endrin and isodrin were detected in about 1% of the samples analyzed, but the use records do not indicate that these compounds were applied in 1970 or in pre- vious years. Endrin is currently registered for use on corn and sorghum grain. Since endrin and isodrin are chemically similar to aldrin and dieldrin, it is likely that the small amounts detected have come from the parent compounds. Also, since endrin, isodrin, and chlordane are persistent compounds (4), the amounts detected could have been present from application prior to 1965 or may represent unreported usage. RESIDUES DETECTED IN CROPS The crops sampled in the study and the residues detected are listed in Table 3. Seven compounds, including the four DDT metabolites listed above, were detected. The greatest number of residues were detected in cornstalk samples. Approximately 20% of all the cornstalk sam- ples contained pesticide residues; however, no residues were detected in corn grain samples from the same sites. Pesticides Monitoring Journal 1 0.10-3.60 1.15 63 91.3 0.20-14.00 4.15 36 100.0 0.10-6.10 1.36 52 68.4 0.20-6.40 1.55 28 100.0 5.50 5.50 1 100.0 0.20-11.40 4.42 14 100.0 a 9 S N »: g d -^ d V S s _ » 0 d <^ V Q Z 0 Z 0 0 _ t 0 d "^ V z < 1 ■=? 5 ,„ -^ So >- d V Q Z s ^ - * go " d V a z Q z ^ z S 5 „ •» o d — V 0 0 _ •» d d " V 9 S N ■« a z ^ Q Z X 9 S f ^ d 9 0 p.1 **; S 0 d i i = ? s s _ * 0 d '^ V 0 z a z i i X i 1 2 5 d MO-*; CO "^ 9 S « »: 5 <= 0 s _ «. do "^ V Q z 0 z z i z u 0 Z S 0 _ - 0 d " V 0 5 _ -^ do — V Q Z 0 z a z z Q 0 - 2 .a "^ 5 2 ' « d s N 2 , 2 S 0 ~ -1 d S — 0 m i ^ - 2 go d a z 0 0 _ -: do t^ V z i i u d 0 en 'f s „ - So "= d S s = 2 d 9 S N - d 0 z Q z z 1 i s s 5 s <= -^ d d d = 0 _ « d d " a z 0 z ft i <« 1 s <£ !S fi - 2 i -s It E ri . I'i 1 d i 0 « < z 0: 1 -s if ? ri ^- £ 1 1 oi : £ ! i B! " < 1 a 1 "5. S It J ■! ^f 1 1 1 |1 1 ° 1 „ 66 < Z a. 1 is ■a 1 -a It E S 1 »! S »• > 0 S S « < Z a. J 0. S 2 1 ? S! 1 'f 1 1 1 ° = a 5 - 5' c 3 g ^ u 2 « < z £ II I 1 1 Z3 - 1 1 ° = a °- - al « 0 S a i " > 0 s 2 a! < Z 0, Vol. 6, No. 4, March 1973 373 _^ o o ^ 00 o\ ri 0 i 1 © i " s 12 3 I s s i P m d S ' a s ^ «; " 2 ^ s 0 S -: 0 0 5 ^ ■* 0 o d d d d " 2 1 Q g s d S N <*» P 0 0 ^ r- Q 0 a Z ^ d ^ d d V r^ Z z i ? O m 1 O s N Q si-'. Q Z Q ^ S d <» d d m ^ o = - ^ 1 o V z fid Q O Q p Q Q i 2 Z z z Z Z M O = 1 s S JI; S _. >": d o •* 9 O (^ ^ 0 a a ll d d ''^ V d d V S d d V ^ ^ z z X u X O JC S N o s „ -- 0 Q Q ff d d d d z Z 0. V X z z 0 z g s d d ^ Q Z S d 0 — d ^ 0 z lU V V z o s rJ S VO M Tf o 9 S « S 9 s o <^ 9 o o ^ 9 5^5 9 0 rs r; fi s - § H § d cs o d "" m S d -* 50 rJ z •* Tt i 9 o d o m ^. d "^ d s d in s o z d 0 z 0 5 „ § V B. Z . ^1 r- K t 0* S ■n ^ ^ ^ ^ „ „ ex S a a a u a a S E i 1 ■o E 1 > > 1 > 1 -^ it E i 1 •0 II 1 1 -S || 1 i 1 •u a a — -^ V a u a T3 "^ a 1 1 a "S a ■^■^ a -a 1 oS : a ^ 13 '^ a '3 a "I a 5 s Pi is a^ 2=1 a^ QA o C u 3 2 o g al s = 1 1 a^ 2 0 S c a's 2 ° 1 f s is > d S i §a » o u 1 ss > 6 b §£ S 6 g Q §s; > d 0 S §a s 0 S W) c ii < z o; < Z 0. 1" z < z £ .2 * < 2; 0. 0 ■5 * 0 < Z 0. 0 a! < z 0. 374 Pesticides Monitoring Journal TABLE 3. — Residues in crops from the 12 States in the Corn Belt region of the United States — 1970 [ND = not detected] Hepta- Ethyl Crop No. OP Samples » DiELDRIN CHLOR EPOXDE P.P- DDE P.P'- DDT o,p'- DDT P,P'- TDE DDTR PARA- THION PCB's 147 145 Cornstalks Range of detected residues (ppm) 0.01-0.04 ND 0.01-0.13 0.01-7.04 0.01-0.51 0.01-0.16 0.01-7.84 0.25 0.53-6.25 Average (ppm) <0.0I <0.01 0.05 <0.01 <0.01 0.06 <0.01 2.80 No. of positive samples 14 2 3 2 2 3 1 10 Percent positive samples* 9.7 1.4 3.4 1.4 1.4 3.4 0.7 6.9 Soybeans 75 Range of detected residues (ppm) 0.01-0.08 0.02-0.03 ND ND ND ND ND ND ND Average (ppm) 0.01 <0.01 No. of positive samples 42 2 Percent positive samples' 56.0 2.7 24 h lot detected Sorghum fodder 21 Range of detected residues (ppm) 0.01 ND ND ND ND ND ND ND ND Average (ppm) <0.01 No. of positive samples 1 Percent positive samples' 4.8 Mixed hay 11 Range of detected residues (ppm) ND ND ND ND ND ND ND ND 0.80-2.94 Average (ppm) 0.57 No. of positive samples 3 Percent positive samples ' 27.3 Represents composite samples of available standing crops collected simultaneously with soil samples. Percent based on number of samples with residues greater than or equal to the sensitivity limits. This selective translocation of residues has been ob- served in other studies (5). The DDTR residues were found in stalk samples from Indiana, Iowa, and Mis- souri. Only residues of dieldrin and heptachlor epoxide were found in soybean samples, with 56.0% and 2.7%, resi>ectively, of the samples containing residues. At this time, the tolerance for dieldrin residues in soybeans is zero (6), and the tolerance for combined heptachlor and heptachlor epoxide residues in soybeans has not been established. The sampling may have occurred shortly after an application, and the residues might have been zero if the proper time interval had been observed. Low levels (<0.01 ppm) of dieldrin residues also were detected in sorghum fodder. Crop samples from sites for which records showed usage of organophosphate pesticides in 1970 were analyzed for these compounds; however, only one sample was positive (0.25 ppm ethyl parathion). In addition to pesticide residues in the crops, two PCB compounds, identified as Aroclor 1232® and 1242®, were also detected. The PCB's were identified by com- VoL. 6, No. 4, March 1973 paring retention times of multiple peaks from sample chromatograms to the corresponding multiple peaks from standard chromatograms of the various PCB's. This type of comparison was made on at least two columns of different polarities. Quantitation was based on comparison of the summation of peak height units from the sample chromatogram. At least three peaks were used for quantitation. Standard PCB's were run at least once daily and usually twice or more. The PCB's were found in cornstalk and hay samples from 6 of the 12 States (Ohio, Indiana, Michigan, Illinois, Iowa, and Missouri) but v/ere not detected in corn grain, soy- beans, or sorghum. The source of the PCB's has not yet been positively identified but is still under investigation. Discussion The presence of residues in crop samples is probably a result of their absorption and translocation to various plant parts. Evidence of translocation of residues has been found in corn (5), soybeans (8-10), alfalfa (10), carrots (14), potatoes (14,15), turnips (8), and pea- 375 nuts (8). Corn plants have been shown to accumulate dieldrin residues largely in the leaves (5). Crops grown in aldrin-treated soils have been found to contain both aldrin and dieldrin (7). No trends concerning the pesticide residue levels in agri- cultural soils of the Corn Belt region can be clearly identified from these data. Pesticides have been widely used throughout the region (on 75% to 85% of the sites sampled), but organochlorine residues in soil were found in less than half of the areas. The ability of a particular soil to retain and/or release pesticide residues is greatly influenced by the interaction between the physical and chemical properties of both the soil and the pesticides applied as well as the microfloral and micro- faunal components of the soil system. In general, soils high in organic matter or clay content tend to retain pesticide residues longer than sandy soils or soils low in organic matter (7,10-13,16); this retention ability ap- pears to be most positively correlated with organic matter content. Initial concentration and the formula- tion of the pesticide are also important. The degrada- tion rate does not remain constant but decreases logarithmically as dosage increases. Sprays tend to dis- appear sooner than dusts because of a faster initial volatilization, although loss from drift is significant for dusts. In addition, different crops absorb pesticide residues from the soil at varying rates (5,7,8,14). In this study almost 20% of all crop samples contained detectable residue levels. Future studies should aim for a more comprehensive correlation among soil properties, soil residue levels, and translocation potentials of particular crops. A cknowledgment The authors wish to thank the staflF of the Monitoring Laboratory at the Mississippi Test Facility, Bay St. Louis, Miss., who did the entire work of processing and analyzing the samples, particularly, T. J. Forehand, L. N. Oloresisima, R. E. Vest, J. L. Landry, and D. A. Cook. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) U.S. Department of Agriculture. 1970. Agricultural Statistics 1970. Government Printing Office, Washing- ton, D.C. 627 p. (2) Fowler, D. L., J. N. Mahan, and H. H. Shepard. 1971. The pesticide review 1970. USD A Agric. Stab. Con- serv. Serv. Washington, D.C. 46 p. {3} Wiersma, G. B., P. F. Sand, and E. L. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(l):63-66. (4) Nash, R. C. and E. A. Woolson. 1967. Persistence of chlorinated hydrocarbon insecticides in soils. Science 157(3791): 924-927. (5) Caro, J. H., and A. W. Taylor. 1971. Pathways of loss of dieldrin from soils under field conditions. J. Agric. Food Chem. 19 (2):379-384. (6) Pesticides Regulation Division, Office of Pesticide Pro- grams, Environmental Protection Agency. 1972. EPA Compendium of Registered Pesticides, Vol. Ill, In- secticides, acaricides, moUuscicides, and antifouling compounds. Government Printing Office, Washington, D.C. (7) Lichtenstein, E. P. 1959. Absorption of some chlori- nated hydrocarbon insecticides from soils into various crops. J. Agric. Food Chem, 7(6): 430-433. (8) Van Middlelem, C. H. 1969. General summary and conclusions. Co-operative study on uptake of DDT. dieldrin, and endrin by peanuts, soybeans, tobacco, turnip greens, and turnip roots. Pestic. Monit. I. 3(2): 70-101. (9) Bruce, W. N., G. C. Decker, and J. G. Wilson. 1966. The relationship of the levels of insecticide contamina- tion of crop seeds to their fat content and soil concen- tration of aldrin, heptachlor, and their epoxides. J. Econ. Entomol. 59(1):179-181. (10) Beall, M. L., Jr., and R. G. Nash. 1969. Crops seedling uptake of DDT, dieldrin, endrin and heptachlor from soils. Agron. J. 61(4):571-575. (11) Edwards, C. A. 1964. Factors affecting the persistence of insecticides in soil. Soils and Fert. 27(6):45 1-454. (12) Lichtenstein, E. P. 1969. Pesticide residues in soils, water and crops. Ann. N.Y. Acad. Sci. 160{1):155-161. (13) Burns. R. G. 1971. The loss of phosdrin and phorate insecticides from a range of soil types. Bull. Environ. Contam. Toxicol. 6(4):3 16-321. (14) Lichenstein, E. P., and K. R. Schulz. 1965. Residues of aldrin and heptachlor in soils and their translocation into various crops. J. Agric. Food Chem. 13(l):57-63. (15) Terriere, L. C, and D. W. Ingalsbe. 1953. Transloca- tion and residual action of soil insecticides. J. Econ. Entomol. 46:751-753. (16) Lichtenstein, E. P., L. J. De Pew, E. L. Eshbaugh, and J. P. Sleesman. I960. Persistence of DDT, aldrin and lindane in some midwestem soils. J. Econ. Entomol. 53:136-142. 376 PESTicroEs Monitoring Journal GENERAL Decay of Parathion Residues on Field-Treated Tobacco, South Carolina — 7972 (11) Julian E. Keil", C. Boyd Loadholt', Samuel H. Sandifer", Wayne R. Sitterly', and Bob L. Brown' ABSTRACT In an effort to confirm the results of a study in 1971 to determine the length of time required for parathion to de- grade to "zero" levels, parathion was applied twice at a rate of .375 lb/acre to field tobacco in South Carolina. After each application, parathion degraded to "zero" levels in 5 days. These results tended to confirm the findings of the original study in which the maximum time required for parathion to degrade to zero levels was estimated to be 7 days and the minimum time 2 days. Weather was charac- terized by scanty rainfall and temperatures averaging 76° F. During the original study, rainfall was heavy and daily temperatures averaged 80.9° F. Introduction A study reported by Keil et al. (1) was carried out in June-July 1971 to observe the decline with time of levels of parathion normally applied to field tobacco. This paper reports the results of a second study conducted in June-July 1972 to confirm the findings of the 1971 study. Methods and Procedures All growing, application, sampling, and analytical tech- niques were identical to those of the earlier study (/). Cokers 319 variety tobacco was planted on April 17, 1972. Plots consisting of three 12-foot rows were randomly selected for treatment with parathion, endo- sulfan, parathion in combination with endosulfan, or as ersity South ' Section of Preventive Medicine, Medical Carolina, Charleston, S.C. 29401. = Department of Biometry, Medical University of South Carolina, Charleston, S.C. 29401. ' Clemson University Truck Experiment Station, St. Andrews Branch, Charleston, S.C. 29407. * South Carolina State Board of Health, Sullivan's Island, S.C. 29482. Vol. 6, No. 4, March 1973 appropriate controls. Each treatment or control plot was replicated four times in a completely randomized design for a total of 16 plots. Guard rows were used to reduce pesticide drift. In the earlier study, parathion and endosulfan were applied as sprays at rates of .375 and .125 lb active ingredient (A.I.) per acre, respec- tively, on June 8, 21, and July 8, 1971. In the present study, parathion and endosulfan were sprayed at these same rates on both June 12 and 28, 1972. Results and Discussion Results of analyses for parathion residues are given in Table I and indicate that parathion residues decayed to "zero" levels in 5 days after each application. Practical "zero" was assumed when statistical differences be- tween actual zero (none detected) and observed values did not exceed the calculated LSD (least significant difference at the .05 level). The results tended to con- firm the findings of the original study in 1971 in which the maximum time required for parathion to degrade to zero levels was estimated to be 7 days and the mini- mum time 2 days. Endosulfan residues were not measured, but tobacco from the endosulfan-treated plots was analyzed for parathion to determine if there was a measurable amount of drift between plots. The parathion-endosulfan treat- ment was included to determine if any decay interac- tion existed between the two chemicals. TTiis was noted at one sampling period, 1 day after application, i.e., more parathion residue was present when parathion-endo- sulfan was applied. This effect was noted in the previous study up to and including the third day after applica- tion. 377 Weather during the 1972 study was characterized by scanty rainfall and temperatures averaging 76° F (Table 2). In the 1971 study, rain had been in excess of 12 inches and daily temperatures averaged 80.9° F. Results of both studies support the findings of Maier-Bode (2) who concluded that rainfall does not significantly affect residue levels of parathion. See Appendi: this paper. for the chemical names of compounds discussed in This work was supported by Environmental Protection Agency Con- tract No. 68-03-0045. LITERATURE CITED (1) Keil, J. £., C. B. LoadhoU, B. L. Brown, S. H. Sandifer, and W. R. Silterly. 1972. Decay of parathion and endo- sulfan residues on field-treated tobacco. South Caro- lina—1971. Pestic. Monit. J. 6(l):73-75, Erratum (This issue). (2) Maier-Bode. H. 1970. Parathion residues. Dtsch. Med. Wochenschr. 95(48):2457. TABLE 1. — Parathion residues on field-treated tobacco by treatment plots, South Carolina — 1972 Sampling Time IN Days FROM Last Application Mean Parathion Residue Level in PPM ON Four Replicate Treatment Plots Application Date Parathion— Treated Plot (.375 A.L lb/acre) Endosulfan — Treated Plot (.125 A.L LB/ACRE) Parathion (.375 A.L lb/acre)/ Endosulfan (.125 A.L lb/acre) — Treated Plot Control Plot June 12 0 0 0 0 0 1 1.30 .21 3.37 .05 3 .46 .05 .26 .03 5 .03 .01 .09 0 10 0 0 0 0 15 0 0 0 0 June 28 1 1.98 .29 1.54 .05 3 .48 .02 .13 .02 5 .07 0 0 0 9 0 0 0 0 15 0 0 0 0 NOTE: LSDoB = lease significant difference at 95% probability level = .50 and may be applied across time or residues. TABLE 2. — Temperature and rainfall during parathion residue degradation Period Time to "Zero" Residue i TEMPERATtniE (°F) Lows Highs Avg.= Rainfall (inches) June 12-17 June 28-July 3 5 days 5 days 50-67 80-87 72 68-70 87-93 80 0 (July 1) 1.08 "Zero" residue level was assumed when statistical differences between actual zero (none detected) and observed values did not exceed the calculated LSD (least significant difference at the .05 level). Overall average temperature, 76° F. 378 Pesticides Monitoring Journal Pesticide Sales and Usage in Kentucky — 1968' E. Edsel Moore ABSTRACT In Kentucky during 1968, 135 pesticide compounds were applied for agricultural and nonagricultural use in a volume of approximately 3.9 million pounds technical material (excluding most pesticides formulated for home, lawn, and garden use). This amounted to about 0.5% of the Nation's total consumption of pesticides. The pesticide poundage used in Kentucky, of which 67% was herbicides, was applied to an estimated I million acres, 4% of the State's land. This included over 900,000 lb of herbicides applied to rights-of-way throughout the State by various utility com- panies. Fourteen of the 135 base compounds sold consti- tuted 73.3% of the total poundage used. These included, in order of volume, methyl bromide, maleic hydrazide, atra- zine, DDT, 2,4-D, chlordane, sulfur, copper sulfate, aldrin. sodium chlorate, TDE, carbaryl. malathion, and methoxy- chtor. Introduction In the United States, the manufacture of pesticides is now a billion dollar industry which began its expansion with the introduction of synthetic organic pesticides during the mid-1940's. Modern public health programs and farm production practices are dependent on pesti- cides. Countless lives have been saved in this country and abroad by the use of pesticides for control of vector-borne diseases. In the United States, the use of pesticides has been an important factor in improving the quality and yield of farm products and has con- tributed significantly to the annual increase in farm income. ' From the Pesticides Program, Division of Environmental Services State Department of Health, Frankfort, Ky. 40601. Vol. 6, No. 4, March 1973 At present, some 60,000 pesticide formulations, con- taining 1 or more of 900 active pesticide chemicals (/), are available for use as insecticides, herbicides, fungi- cides, rodenticides, and plant growth regulators. These are packaged in numerous forms and may be pur- chased at a variety of retail outlets. The usage patterns of pesticides — past, present, and future — have the potential for profoundly influencing the environment and, consequently existing as well as future pesticide monitoring programs. The purpose of the survey reported in this paper was to outline the patterns of pesticide sales and usage in Kentucky during 1968. To compile the principal pesticide sales and usage data for Kentucky, the following sources were contacted: ( 1 ) in-State sales outlets for the pounds of technical materials sold in the State and (2) aerial applicators, utility companies, and State agencies for types and amounts of pesticides used, number of acres treated, and sources of pesticides purchased. Background Information Although Kentucky is developing industrially, it is still a rural State. In 1960, Kentucky had a population of 3,038,156, of whom 55% resided in rural areas (2). The boundaries of the State encompass an area of 40,395 square miles or 25,852,800 acres. Nationally, Kentucky ranked 22d and 37th in population and land area, respectively. In 1964, acreage classified as farm- land totalled 16,265,180 acres, of which 9,364,980 acres were considered cropland (i); there were approxi- mately 133,000 farms averaging 123 acres in size. Kentucky's economy depends heavily on agriculture. Economically, tobacco is Kentucky's most important 379 □ :::z'Z""' dominating Boundary iif eastern Kentucj^y toa! field- in dollars and i . based on 1964 US Census of Agri- raj area with subsistence farming pre- FIGURE 1. — Agricultural activity by county, Kentucky — 1964 farm commodity, providing one-third of the agricul- tural income, followed by the sale of livestock and the dairy industry. Most of this farm income is derived from central, northern, and western areas. The Eastern Kentucky Coal Field area includes 38 counties, with 16 counties comprising the active coal mining area (Fig. 1) (Div. of Strip Mining and Reclamation, Kentucky State Dep. of Natural Resources, Frankfort 1969, per- sonal communication). Due to its topography, this entire area, with the exception of two counties, is a nonproductive agricultural region, with subsistence farm- ing predominating. In Kentucky, since 1961, approximately 3.7 million acres of crops have been harvested each year; principal crops have included corn, hay, soybeans, small grains, and tobacco (Table I) (3). Since 1960, the total crop acreage has not fluctuated more than 1%; there have been, however, changes in the acreages planted to specific crops. During an 8-year period from 1960-1968, the overall agricultural gross product increased from 560 million dollars to well over 910 million dollars (U.S. Dep. of Agric. Statistical Reporting Service, Louisville Branch Off., 1969, personal communication) , an amount ap- proaching one-third of the State's total gross product. This can be attributed, in part, to a greater shift towards beef cattle, swine, and grain production, particularly 380 TABLE I. — Crops harvested in Kentucky, 1967 Approximate Crops Acreage Harvested Com 1,218,000 Popcorn 19,000 Hay Clover and Timothy 616,000 Lespedeza 415,000 Alfalfa 383,000 Other 275,000 Soybeans 310.000 Small grains (wheat, barley, oats, and rye) 247,000 Tobacco 177,000 Fruits and Vegetables 11,000 Miscellaneous 30,000 Total 3,701,000 west of a line extending north and south from Jefferson County to Monroe County and west to the Mississippi River. This area encompasses some 45 to 50 counties. Secondly, Kentucky is a major producer of milk and dairy products, and this industry is increasing. In 1968, nationally, Kentucky ranked 1 3th in milk production and 2d and 7th in production of evaporated milk and cheese, respectively. In addition, pesticide usage is responsible for a significant portion of this increase. Pesticides Monitoring Journal PESTICIDE LEGISLATION In 1968, Kentucky was one of 47 States that had a pesticide registration law; currently all 50 States have registration laws. Kentucky does not, however, have a law that specifies the reporting of pesticide sales or usage. The State laws and regulations that apply to pesticides are presented in Table 2. In 1968, results of a question- naire survey (conducted by mail by the Kentucky State Department of Health) showed that the 40 largest cities in Kentucky (4,000 population and above, based on 1960 census figures) had no laws, codes, or ordinances applicable to pesticides on the local level. METHODS OF APPLICATION In Kentucky, ground application is the most common method of applying pesticides. Several different types of equipment are used, the most common being the self- prof)elled "highboy" (a tri-wheeled vehicle with 5-6 ft clearance, the principal application equipment used in the tobacco-growing areas) and the tractor-drawn trailer rig or tractor-mounted spray boom. An estimated 1,500 highboys were in use in 1968 (Kentucky Distributors of Highboys, personal communication). In the princi- pal fruit- and vegetable-growing areas, powered speed and row-crop sprayers are the most widely used methods of application. Dust application is diminishing and con- stitutes only a small portion of the total pesticide usage for all commercial agricultural crops. Aerial application of pesticides is not a thriving enter- prise in Kentucky as it is in the Great Plains States be- cause of the small size and inaccessibility of fields to be treated; this is evidenced by the small number of ojjera- tors licensed in 1968, 8 compared with 12 in 1960 (Kentucky Dep. of Aeronautics, personal communica- tion). In 1968, application by two operators was con- fined to weed and brush control on rights-of-way of various utility companies, principally in 12 southeastern Kentucky counties (Fig. 2). The total acreage in Ken- tucky treated for all purposes by aerial application was approximately 14,000 acres. Pesticide Use Patterns AGRICULTURAL USAGE In Kentucky, pesticide usage generally begins in March with application to peaches, apples, and alfalfa and continues until late August or early September, depend- ing on the growing season within the State. The peak periods are usually in April, May, and June (Table 3), with an estimated 857c-9Q'7c of the pesticide applica- tions occurring from April through August. Data abstracted from 1964 U.S. Census of Agriculture (4) indicated that 1.21% of the farmland in Kentucky or 196,808 acres were treated for insect and disease control, and 2.69% or 437,533 acres were treated for TABLE 2. — Slate laws and regulations applicable to pesticides, Kentucky — 1968 State Laws and Regulations Agency Responsible for Administration and Enforcement Explanation of Law or Regulation REGISTRATION AND LABELING LAWS Eonomic Poison Law — 1956 Kentucky Revised Statutes Chapters 217.540 to 217.640 Food, Drug and Cosmetic Act — Revised 1960 Kentucky Revised Statutes Chapters 217.005 to 217.215. 217.992 Division of Regulatory Services University of Kentucky of Environmental Services State Department of Health Requires the registration of all substances or mixtures of substances intended for preventing, destroying, repelling, or mitigating any insects, rodents, fungi, bacteria, weeds, or other forms of plant or animal life or virus (except viruses on or in living ir.an or other animals) which are declared to be a pest. A section of this act requires that pesticide residues on or in raw agricultural products must comply with tolerances established by the U.S. Food and Drug Administration provided a tolerance has been established. USE AND APPLICATION LAW Termite and Pest Control Industry Law — 1954. Revised 1960 as the Kentucky Structural Pest Control Act Kentucky Revised Statutes Chapters 249.250 to 249.340, 249.990 Division of Noxious Weed and Pest Control State Department of Agriculture Basically, requires the licensing of all pest con- trol operators by the State Department of Agri- culture. Applicants must pass an examination to secure a license. REGULATIONS Aerial Applicators Regulation — 1952 KAV-5-2 to KAV-5-10 Kentucky Revised Statutes Chapter 183 Occupational Health Regulations — 1963. Revised 1966 Kentucky Revised Statutes Sections 211.080. 211.180 State Department of Aeronautics Division of Occupational Health State Department of Health Requires the licensing of all aircraft engaged in commercial aerial application. Requires compliance with threshold limit values established for pesticides in the atmosphere in pesticide and chemical manufacturing and formulating plants. NOTE: In 1972. Kentucky enacted a pesticide use and application act— "Kentucky Pesticide Use and Application Act of 1972" (Ky. Rev. St. 1972 S217B.010 to s217B.099). Vol. 6, No. 4, March 1973 381 i»w ©^ \^Q3C"^"^^\\ V^' <«. V"^ J>yL*o» '/~V'''^ ^~7v / ^^~^ i:^^ ^2^w^\ ^ J^^PS vw^ r^'-'^^^^^^^ jT^ ^""~~V' „.^ JL^ [32^-"- h/^ __^^^^^«=~^^^^ >-^ ^< f U"<*. /_. r^ V ^'^"^ ^''''~~-V'^--v T«lO0 ^^"^ V^"*°^ i=^//\ jACKSO-V'^^'^ ) ^^.^'^ KNOn \ / >/ /...^ .y.-v ^it^ gpOM. ■""t^^ ^^^C^^^^ / \ »«. j^ — ^^''^^0/0m ^'^^!y///X ^^^^^ \ . /"^^.o. ^ "^~' 'P' □ ' — rcjced hv l.ccrscd len.il .ipplicaiop. 05 toiin ^ Uulily compa V righK-ol way Ire led for xcpcl.ilnc prowlh h> .iifcr^ifl licensed by ihe Kcnii.tky Dcp.irinienl of Aeronautics (U NOTF :<, w. sl.n, K,nn,ck. c„ niies .n which ihe Sla.e )cparimeni i)( Apnciilliirc mamlamcd ninsqiiilo ciinir*i| prugrams are not included FIGURE 2. — Aerial application of pesticides by county, Kentucky — 1968 TABLE Ti.— General agricultural and nonagricultural pesticide usage by months, Kentucky Pesticide Usage Application Period Jan. 1 Feb. | Mar. 1 Apr. 1 May 1 June 1 July Aug. Sept. Oct. Nov. Dec. AGRICULTURAL CROPS AND FIELDS Fruits (excluding dormant) X X X X X X X Vegetables (excluding greenhouse-grown) X X X X X Com Soil Crop X X X X X Alfalfa '^ X X X Tobacco Soil (excluding tobacco beds) Crop X X X X X X Small grains X X Soybeans X X X Pasture (Thistle control) X X X NONAGRICULTURAL USAGE Mosquitoes X X X X X X Rights-of-way X X X X Johnson grass X X X .182 Pesticides Monitoring Journal ^0 coiinlic% in which herhicidc ii^^c |\ fttiltr than t NOTE 9 counties did mil rcvpind lo the survey Kined hy CiiuRly Asncultural Fxleniion Agents in ^ FIGURE 3. — Counties in which herbicide usage is greater than insecticide usage, Kentucky — 1968 weed control. Nationally, Kentucky ranked 40th and 35th, respectively, in each category of treatment. By comparison, although the total acreage is small. New Jersey ranked first in the Nation with 13.9% of its farmlands being treated for insect and disease control, and Delaware ranked first in weed control, treating 21.42% of its farmland. Responses from 1 1 1 of Kentucky's 1 20 County Agents to a questionnaire survey indicated that an estimated 89% of the farmers in Kentucky used some type of pesticide material in 1968. Fifty agents estimated that farmers in their counties used more herbicides than insecticides; these were primarily in the western and cen- tral areas of the State (Fig. 3). A decrease in pesticide usage was not reported by any responding agent. TYPES AND POUNDAGE OF PESTICIDES SOLD BY IN-STATE OUTLETS In 1968, approximately 3,800 pesticide formulations, involving an estimated 150 base chemicals, were regis- tered for sale in Kentucky (Economic Poison Registra- tion Section, Div. of Regulatory Services, Univ. of Kentucky, Lexington, Ky., personal comnmnication) . Registrations represented some 480 manufacturers and formulators. Some firms register all their products, although they may not necessarily be sold in the State (there is no additional charge after the first 10 registra- tions). Registration of pesticides incorporated with Vol. 6, No. 4, March 1973 commercial fertilizers for agricultural use and special lawn preparations totaled approximately 200. Data from in-State sales outlets (distribution outlets, manufacturers or their representatives, dealers buying direct, etc.) reflected the sale of 2,850,734 lb of pesti- cides in Kentucky during 1968 (Table 4). Some 135 base pesticide chemicals were named; in all probability, additional base chemicals were sold but were not reported by these sources because they were overlooked or the poundage was considered unworthy of mention. These sources estimated that the bulk of the poundage was used to treat farmland, although about 5% of this total may have been formulated and packaged in small containers for the home and garden use market. The total poundage of pesticides sold by in-State outlets is listed in Table 4 as herbicides (growth regulators, soil sterilants, defoliants, and fumigants are grouped with herbicides), insecticides, fungicides, and rodenticides, in order of pounds sold. It was reported that herbicide usage is increasing more rapidly than any of the other groups of pesticides. Three of the 62 herbicides — methyl bromide, maleic hydrazide (MH-30), and atrazine — constituted 67.5% of the pounds of herbicides sold. The first two were used primarily for tobacco, although an undetermined quan- tity of methyl bromide was used to fumigate hay and 383 TABLE 4. — Pesticides sold by in-State outlets, Kentucky- 1968 (agricultural usage) TABLE 4. — Pesticides sold by in-State outlets, Kentucky- 1968 (agricultural usage) — Continued Pounds of Technical Material Sold Pounds of Technical Material Sold HERBICIDES— 56.1% OF SALES Methyl bromide MH-30 (maleic hydrazide) Atrazine 2,4-D (all forms) Sodium chlorate Diphenamid (Enide®) 2,4,5-T (all forms) Dalapon NPA (Alanap®) TrifJuralin (Treflan®) EPTC (Eptam®) Amiben Calcium hydrogen methanearsonate Vemolate (Vemam) Sodium arsenite Linuron (Lorox®) DCPA (Dacthal®) Simazine CIPC (Chloro-IPC) Solan DSMA (disodium methanearsonate) Paraquat Sutan Picloram (Tordon®) DNOC, sodium salt Chloroxuron (Tenoran®) Planavin Dichlobenil (Casoron®) Vorlex® Isocil (Hyvar®) Metham (Vapam®) Benefin (Balan®) Dicamba (Banvel-D®) Silvex Diuron (Karmex®) Monuron (Telvar®) Amitrole CDAA (Randox®) Endothall Misc. herbicides (23) Total 431,788 352,956 200,679 142,248 99,047 49,359 38,356 30,079 22,794 22,001 19,373 18,224 16,670 15,845 14,580 14,376 13,513 11,498 10,420 9,090 8,294 7,184 6,387 4,030 3,532 3,369 2,500 2,454 2,440 2,400 2,118 1,614 1,600 1,240 1,200 1,200 1,006 890 600 13.456 1,600,410 INSECTICIDES— 31.4% OF SALES Chlorinated hydrocarbons (21,8%) DDT Chlordane Aldrin TDE (Rhothane®) Methoxychlor Toxaphene Dieldrin Endosulfan (Thiodan®) Dicofol (Kelthane®) Lindane BHC Heptachlor Tetradifon (Tedioi. ) Endrin Subtotal 151,015 127,778 101,079 94,449 46,967 29,881 26,979 21,393 8,898 4,025 3,456 2,347 1,407 500 620.174 INSECTICIDES— 31.4% OF SALES— Continued Organophosphates (5.3%) Malathon Diazinon Parathion Disulfoton (Di-Syston®) Naled (Dibrom®) Azinphosmethyl (Guthion®) Demeton (Systox®) Ethion Ciodrin® Ronnel (Korlan®) Dimethoate (Cygon®) Mevinphos (Phosdrin®) DDVP (Dichlorvos) Misc. organophosphates (5) Subtotal Carbamates (2.8%) Carbaryl (Sevin®) Subtotal Miscellaneous (1.5%) Lead arsenate Pyrethrins Piperonyl butoxide Rotenone Other misc. (9) Subtotal Total 51,467 20,728 19,799 18,858 14,800 11,899 6,000 1,975 1,347 984 871 720 536 394 150,378 31,467 3,076 3,025 2,254 1,952 41,774 FUNGICIDES— 12.0% OF SALES Sulfur Copper sulfate Captan Zineb Maneb Ferbam Lime sulfur Phaltan® Cyprex® Nabam (Dithane®) Polyram® (Metiram) Botran® Thiram Misc. fungicides (4) Total 126,180 107,772 38,590 20,620 20,527 8,010 6,062 5,905 3,210 1,168 1,168 1,200 760 1,523 342,695 RODENTICIDES— 0.5% OF SALES Warfarin Arsenic trioxide Zinc phosphide Prolan® Misc. rodenticides (4) Total 9,482 2,916 1,270 699 232 14,599 GRAND TOTAL 2,850,734 For simplicity in reporting, products containing a combina- tion of chemicals, different brand or trade names with the same pesticide(s) were convened to basic chemicals. Salts, acids, etc., of the same basic component are reflected as one compound, such as the salts and acids of 2.4-D. Pesticides of less than 500 pounds are grouped under miscellaneous. 384 Pesticides Monitoring Journal straw for the control of cereal leaf beetle transported into Kentucky from a contaminated out-of-State zone. The remaining 59 herbicides were used to control broad- leaf weeds and grasses. The persistent chlorinated hydrocarbon insecticides were used more extensively in 1968 than any other insecticide group; their sales constituted 69.4% of the total pounds of insecticides sold. Approximately 4V4 lb were sold for every pound of organophosphate com- pounds. The chlorinated hydrocarbon compounds were applied as soil insecticides for field crops; foliar sprays on selec- tive food and feed crops and nonfood crops, such as tobacco and seed crops; for selective control of live- stock insects; and for household and industrial pest con- trol. As a soil insecticide for field crops, aldrin was the most widely used. An undetermined amount was in- corporated into various commercial fertilizer prepara- tions (168 different preparations containing aldrin were registered in 1968). If the amount used in this form were known, aldrin rather than DDT, would probably be the most widely applied persistent pesticide in 1968. Most of the DDT used in Kentucky in 1968 was applied to tobacco. The 18 organophosphate compounds listed (Table 4) accounted for only 5.3% of the total pounds of p)esti- cides, almost twice the poundage for the carbamates (excusively carbaryl). Malathion was the most widely used followed by diazinon, parathion, and disulfoton. The organophosphates were applied as soil insecticides and as foliar sprays on grain, tobacco, fruit, vegetable, and forage crops. A few of these compounds, including co-ral, malathion, and ciodrin, were used to control live- stock insects. Carbaryl was used primarily as a foliar spray on grain, forage, fruit, and vegetable crops. The most widely used fungicides were sulfur, captan, zineb, and maneb, constituting 60% of the total in this group. Warfarin was the most prevalent rodenticide. It is estimated that the total poundage in Table 4 reflects 85% of the actual total pounds of pesticides sold in Kentucky in 1968. The ratio for category of pesticides would probably be the same if the total quantity sold by State outlets were known. Fourteen of the 135 base compounds sold constituted 73.3% of the total pesticide pounds. These included, in order of volume, methyl bromide, MH-30, atrazine, DDT. 2,4-D, chlordane, sulfur, copper sulfate, aldrin, sodium chlorate, TDE, carbaryl, malathion, and methoxychlor. From a questionnaire survey of aerial applicators lic- ensed in Kentucky, it was determined that commercial Vol. 6, No. 4, March 1973 aerial application of pesticides to agricultural crops in 1968 involved less than 10,000 acres, primarily tobacco, small grains, and alfalfa in some 25 counties (Fig. 2). Tobacco accounted for 40% of the total. Approximately 20,500 lb of pesticides (technical material), half of which was MH-30, followed by DDT, toxaphene, and TDE (Rhothane®) were applied by winged aircraft. These four materials constituted 87% of the total. Most of the aerial application to agricultural crops involved application of MH-30 to small plots of less than 10 acres. Pesticides applied by aerial applicators for agri- cultural purp>oses were purchased from in-State outlets and are reflected in the data in Table 4. State agencies, such as the institutional farm system, State universities, the Department of Fish and Wildlife, etc., purchased 38,513 lb of technical materials which included all four groups of pesticides, principally in- secticides and herbicides (Division of Purchasing, Ken- tucky State Department of Finance, Frankfort, Ky., personal communication). This poundage was included in 1968 sales data; it was purchased on competitive bids from in-State vendors. NONAGRICULTURAL USAGE, PURCHASED DIRECTLY FROM OUT-OF-STATE SOURCES A total of 54 utility companies were surveyed by mail questionnaire concerning the i>esticides applied to rights-of-way in Kentucky in 1968. The companies surveyed included railroads; gas transmission, communi- cations, and power companies; and selected rural water districts. All are licensed by the Kentucky Public Serv- ice Commission. The rural water districts contacted did not apply any pesticides. The utility companies applied 920,820 lb of materials (exclusively herbicides for weed and brush control) to company-owned prop- erty and rights-of-way in numerous areas of the State (Table 5). The principal basic materials used included sodium chlorate-calcium chloride and diuron (Kar- mex®) mixture; 2,4-D, 2,4,5-T, and various combina- tions; isocil (Hyvar-X®); and fenuron (Dyhar®). These constituted 95% of the total materials used. The State Department of Agriculture maintains a mos- quito control program in approximately 28 western Kentucky counties and reported spraying 161,500 acres in 1968 (Division of Noxious Weed and Pest Control, Kentucky State Department of Agriculture, Frankfort, Ky., personal communication). Officials estimate that about one-half of the acreage was sprayed by winged aircraft either owned by or under contract to the Department. The four materials used in the program included DDT (which is no longer used), Lethane®, malathion, and naled. The 16,800 lb of technical mate- rial applied in 1968 were purchased in 1967 directly from the manufacturer and are not part of the sales data. 385 TABLE 5. — Pesticides purchased directly from oul-of-State sources, 1968 (nonagriculturat usage) Pounds of Technical Users Materials Used Utility Companies Railroads (8,647 acres treated) 680,010 Power Companies (7,782 acres treated) 191,070 Gas Transmission Companies (1,511 acres treated) 47,400 Rural Water Districts — Commnication (75 acres treated) 2,340 Total (18,015 acres treated) 920,820 Department of Agriculture Mosquito Control Program (161,500 acres treated) 16,800 State Highway Department (39,400 acres treated) 122,955 The State Highway Department applied 122,955 lb of technical material (herbicides only) in 1968 on an esti- mated 39,400 acres of State rights-of-way (Division of Roadside Development, Kentucky State Department of Highways, Frankfort, Ky., personal communication). Application was primarily by truck, and principal mate- rials (about 90% of the total), included 2,4,-D, 2,4,5-T, MH-30, picloram, and dalapon. These materials were purchased from out-of-State firms. Railroads used 73.8% of the total poundage, followed by power companies (20.7%), gas transmission com- panies (5.1%), and communications companies (0.4% ) . The utility firms reported treating approximately 18,000 acres of which 4,000 were treated by out-of-State based helicopters under contract: The remaining 14,000 acres were treated by surface spray rigs particularly designed for trucks and railcars. A small amount of herbicides in pellet and granular form was applied by cyclone dis- tributors. Small quantities of liquid mix were cilso ap- plied by knapsack and hand sprayers. Approximately 95% of the herbicides applied by contractors or com- pany employees were purchased from out-of-State firms. These were located generally in Pennsylvania. Indiana, and Georgia. Hence, the volume used in utility opera- tions is not reflected in the pounds of pesticides sold by in-State outlets. Discitssion In Kentucky in 1968, pesticide usage for all purposes totaled more than 3.9 million pounds of technical mate- rial purchased from in-State and out-of-State outlets. This represents about 0.5% of the Nation's estimated total of 800 million pounds used domestically (5). The poundage for herbicides constituted approximately 67% 386 of the total. Approximately 1,060,575 lb (27% of the total poundage) were purchased from out-of-State sources. Herbicides applied to utility company and State Highway Department rights-of-way constituted all but 16,800 lb (used for mosquito control) of this total. The total dollar value of pesticides purchased in 1968 for use in Kentucky was estimated at 18 to 20 million dollars. Exact figures cannot be determined because re- tailers are not required to report sales to any State regulatory agency. The estimate includes small pack- age sales (dusts, liquids, etc.) and specialty pesticides such as aerosols, plunger dispenser devices, pastes, and tablets (all for home or garden use). It is hypothesized that the value would be significantly greater had there been a practical method of estimating dollar sales for sp>ecial lawn fertilizer preparations containing various pesticides and for pesticides used on Federal Govern- ment installations such as military bases or depots, by municipalities, by pest control operators, or by others that may have been excluded in the study who purchase directly from out-of-State sources. It is likely that millions of dollars are spent on specialty pesticides in various forms for use in and about the home. Most formulations for this market such as aero- sols, dusts, and granules are purchased in a form suitable for application without the addition of diluents. Con- sequently, in terms of pounds of technical material, they constitute only a small segment of the total quantities of pesticides sold and used in 1968, but are much more important in terms of dollar sales. Although pesticide usage is increasing annually (about 13%-15%), Kentucky ranked very low nationally in 1964 in the percentage of farmland treated, with less than 4% of Kentucky's farmland receiving some type of pesticide treatment (634,341 acres). This may be attributable, in part, to the types of crops grown in Kentucky. In the middle southern and southeastern States few pesticides are applied to soybeans and corn, major crops in Kentucky (Table 1). In addition, tobacco, another major crop in the State, is normally grown on the same soil only once every 2 or 3 years; therefore, the total acreage that receives pesticides in tobacco production is greater than the acreage for a given year (6). Hypothetically, if the total poundage had been confined entirely to agricultural use and evenly distributed over all of the State's farmland (16,265,180 acres), it would total less than 0.25 lb (4 oz) of tech- nical material per acre, or use confined to cropland (9,364,980 acres), would amount to less than 0.5 lb/ acre. The bulk of pesticides for agricultural purposes are used on grain, tobacco, and hay crops principally grown in 29 central (north, south) and 16 western Kentucky counties (Hardin, Hart, Barren, and those west) (Fig. 1). Pesticides Monitoring Journal From a monetary standpoint (retail), MH-30 was the most important pesticide in 1968, with sales of about 1.5 million dollars. Furthermore, it appeared that more dollars were expended for pesticide use on tobacco than any other crop. Perhaps the two most signiicant pesticides to be introduced in recent years in Kentucky are methyl bromide and MH-30. Both are used exten- sively in the production of tobacco and have been responsible for revolutionizing this particular industry. MH-30, a growth regulator, has all but eliminated the hand control of sucker growth. Methyl bromide, a fumigant, is very effective against soil insects in prepara- tion of tobacco plant beds. Conclusions In Kentucky the continued increase in pesticide usage will be an important factor in the growth of the agri- cultural gross product. It is anticipated that [pesticide usage, especially herbicides, will continue to accelerate. Data on the principal uses, types, and volume of pesti- cides are important in this era of national concern for the environment, particularly with respect to the per- sistent pesticides. Such information will provide a basis for projecting future usage trends. The work reported in this paper was supported under Contract No. PH 21-68-2039 by the Division of Pesticide Community Studies, Office of Pesticide Programs, U.S. Environmental Protection Agency, Chamblee, Ga. LITERATURE CITED (1) U.S. Department of Health, Education, and Welfare. 1969. Report of the Secretary's Commission on pesti- cides and their relationship to environmental health. Government Printing Office, Washington, D.C. p. 46. (2) U.S. Bureau of the Census. 1963. U.S. census of popula- tion: Vol. 1. Characteristics of the population, Part 19, Kentucky. Government Printing Office, Washington, D.C. p. 19-9. (3) Kentucky Department of Agriculture and Statistical Reporting Service. U.S. Department of Agriculture. 1967. Kentucky agriculture statistics, 1966 and 1967. Ken- tucky State Dep. Agric, Frankfort, Ky. 178 p. (4) U.S. Bureau of the Census. 1967. Census of agriculture, 1964. Vol. I. Government Printing Office, Washington, DC. (5) U.S. Department of Agriculture, Agricultural Stabiliza- tion and Conservation Service. 1969. The pesticide re- view 1969. Washington, D.C. p. 8, 14. (6) Sheets, T. J. 1966. The extent and seriousness of pesti- cide buildup in soils, p. 311-330 in N. C. Brady [ed.] Agriculture and the quality of our environment. The Plimpton Press, Norwood, Mass. Vol. 6, No. 4, March 1973 387 APPENDIX Chemical Names of Compounds Discussed in This Issue* ALDRIN ARSENIC BHC CHLORDANE DDE DDT (including its isomers and dehydrochlorination products) ENDOSULFAN (THIODAN®) ENDRIN HEPTACHLOR HEPTACHLOR EPOXIDE ISODRIN LINDANE MIREX PARATHION POLYCHLORINATED BIPHENYLS (PCB's) TDE (DDD) (including its isomers and dehydrocWorina- tion products) TOXAPHENE TRIFLURALIN Not less than 95% of l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-endo-c3ro-5,8-dimethanonaphthaIene AS2O3 1,2,3,4,5,6-hexachlorocycIohexane, mixed isomers 1,2,4,5,6,7 ,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-methanoindane l,l-dichloro-2,2-bis(p-chlorophenyl) ethylene l,l,l-trichloro-2,2-bis(p-chlorophenyI)ethane; technical DDT consists of a mixture of the p,p'-isomer and the o,p'-isomer (in a ratio of about 3 or 4 to 1 ) Not less than 85% of 1,2,3,4, 10,10-hexachloro-6,7-epoxy-!,4,4a,5,6,7,8a-octahydro-l,4-i?ndo-exo-5,8-dimethano= naphthalene 6,7,8.9,10,I0-hexachloro-I,5.5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide 1,2,3, 4, 10, 10-hexachloro-6,7-epoxy-l, 4,4a, 5,6,7, 8,8a-octahydro-l,4-ffndo-cndo-5,8-dimethanonaphthalene l,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4.7,7a-tetrahydro-4,7-methanoindan l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-CMdo, fndo-5,8-dimethanonaphthalene 1,2,3,4,5,6-hexachIorocycIohexane, 99% or more gamma isomer dodecachlorooctahydro-l,3,4-metheno-l//-cyclobuta[cd]pentalene 0, 0-diethyl 0-p-nitrophenyI phosphorothioate Mixtures of chlorinated biphenyl compounds having various percentages of chlorination I,l-dichloro-2,2-bis(p-chlorophenyl)ethane; technical TDE contains '. chlorinated camphene containing 67% to 69% chlorine a,a,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine ; o,p- er also •Chemical names of compounds discussed in the paper "Pesticide Sales and Usage in Kentucky — 1968" are not included in this Appendix. 388 Pesticides Monitoring Journal ERRATA PESTICIDES MONITORING JOURNAL, Volume 6, Number 1, p. 31. In the paper "Mercury and lead resi- dues in starlings — 1970," a number of values included in TABLE 2 — Mercury' residues in starlings, 1970 were in error. The corrected table is shown below: TABLE 2. — Mercury residues in starlings, 1970 Mercury Residue 1 (PPM) Sampling Site Number Mercury Residue ' (PPM) Sampling Site Number Mercury Residue 1 (PPM) Sampling Srre Number 0.05 0.06 1.50 1.90 0.878 0.417 0.47 <0.05 0.07 0.11 <0.175 <0.05 0.07 <0.0S <0.057 0.05 0.07 0.06 0.14 0.080 0.023 <0.05 0.10 0.11 0.06 <0.080 0.08 0.09 0.06 0.08 0.078 0.055 0.09 <0.05 <0.055 <0.05 0.06 < 0.067 <0.05 <0.05 < 0.060 4-C-l 2 Mean l-D-1 » 2 3 4 Mean SB Mean SE 3-D-l 2 3 4-D-l 2 <0.05 <0.05 0.08 0.05 <0.05 <0.05 <0.058 <0.05 0.06 <0.05 <0.060 0.05 <0.05 <0.05 <0.05 <0.050 <0.05 < 0.065 0.05 <0.05 < 0.050 0.10 0.07 0.05 <0.05 < 0.068 0.15 <0.05 <0.05 0.08 <0.083 0.11 <0.05 0.05 <0.05 < 0.065 2-F-l 2 3 4 Mean SE 3-F-l 2 3 1-G-l 2 3 4 Mean SE 2-G-l 2 3 4-G-l 2 3 2-H-l 2 <0.05 <0.05 <0.05 0.18 < 0.083 0.13 0.15 0.13 0.09 0.125 0.010 0.08 <0.05 <0.065 <0.05 0.05 <0.05 0.05 <0.050 <0.05 <0.05 <0.05 <0.05 0.05 <0.05 <0.05 <0.05 < 0.050 <0.05 <0.05 <0.05 0.10 < 0.062 0.05 0.06 0.055 0.067 0.05 0.07 0.19 <0.05 <0.090 3-H-l 2 3 4-H-I 2 3-1-1 2 3 Mean SE Mean SE NOTE: — = no sample taken. ' Parts per million whole body. ' wet-weight basis. ' Vol. 6, No. 4, March 1973 389 ERRATA — Continued PESTICIDES MONITORING JOURNAL, Volume 6, Number 1, p. 73-75. In the paper "Decay of parathion and endosulfan residues on field-treated tobacco, South Carolina — 1971," the values reported for parathion and endosulfan as pounds of active ingredient applied per acre were in error. Parathion was applied at a rate of .375 lb A.I. per acre rather than the 1 .5 lb A.I. per acre as stated, and endosulfan was applied at a rate of .125 lb A.I. per acre rather than .5 lb A.I. per acre. These corrected values should be inserted in the Abstract, in the first paragraph under the Methods and Procedures section, and in Table 1 and Figs. 1 and 2. PESTICIDES MONITORING JOURNAL. Volume 6, Number 3. In the paper "Residues of organochlorine pesticides, polychlorinated biphenyls, and mercury and autopsy data for bald eagles, 1969, 1970," on page 138, the word cholera was misspelled as "chlorea" in the first and second sentences of the third paragraph. PESTICIDES MONITORING JOURNAL, Volume 6, Number 3, p. 198 and 199. In the paper "Pesticide resi- due levels in soils. FY 1969 — National Soils Monitoring Program," the maps in Figs. 1 and 3 were reversed. The map shown in Fig. 3 belongs with the caption "FIGURE 1. — Arsenic residues in cropland soil"; the map shown in Fig. 1 belongs with the caption "FIGURE 3. — Dieldrin residues in cropland soil." Acknowledgment The Editorial Advisory Board wishes to acknowledge with sincere appreciation the efforts of the following persons who assisted in reviewing papers submitted for publication in Volume 6, Nos. 1-4, of the Pesticides Monitoring Journal: J. H. Caro Austin S. Fox Kenneth R. Hill Henry Johnson L. R. Kamps Thair G. Lament James J. Lichtenberg Bernadette McMahon Mildred L. Porter Susan J. Young Agricultural Research Service USDA Economic Research Service Agricultural Research Service Environmental Protection Agency Food and Drug Administration Fish and Wildlife Service Environmental Protection Agency Food and Drug Administration Food and Drug Administration Food and Drug Administration 390 Pesticides Monitoring Journal SUBJECT AND AUTHOR INDEXES Volume 6, June 1972-March 1973 Primary headings in the subject index consist of pesti- cide compounds, the media in which residues are moni- tored, and several concept headings, as follows: Pesticide Compounds (listed alphabetically by common name or trade name where there is no common name) Media and Concept Headings Degradation Experimental Design Factors Influencing Residues Food and Feed Humans Pesticide Sales and Usage Plants (other than those used for food and feed) Sediment SoU Water Wildlife Comp)ound headings are also used as secondary head- ings under the primary media and concept headings and vice versa. When a particular paper discusses five or more organochlorines or three or more organophos- phates or herbicides, the compounds are grouped by class under the media or concept headings; in the pri- mary headings, however, all compounds are listed individually. The specific compounds or elements which Vol. 6, No. 4, March 1973 have been grouped in various combinations by class for certain papers are as follows: Organochlorines Organophosphates aldrin BHC /lindane chlordane DCBP carbophenothion DEF diazinon DDE ethion DDT malathion dicofol dieldrin endosulfan methyl parathion parathion endrin heptachlor/heptachlor Herbicides epoxide isodrin atrazine methoxychlor 2,4-D mirex DCPA TDE toxaphene In the author index, the names of both senior and junior authors appear alphabetically. Full citation is given, however, only under the senior author, with a reference to the senior author appearing under junior authors. 391 SUBJECT INDEX DDE (confd) Aldrin Sedimem 6(2) 6(4) SoU 6(3) 6(4) 6(4) Water 6(2) 6(3) 6(4) Wildlife 6(1): 6(2) 6(2) 6(3): 6(4) 97-102 :363-368 194-228 233-237 369-376 97-102 166-170 363-368 43-49 97-102 115-121 166-170 363-368 CarbophenothioD Soil 6(3): 194-228 Chlordane Plants (other than those used for food and feed) 6(l):56-64 Sediment 6(l):56-64 6(4) :363-368 Soil Aroclor 1254®, see PCB's Arsenic Food and Feed 6(2):89-90 Soil 6(2):89-90 6(2):126-129 6(3): 194-228 6(4):369-376 Atrazine Sou B BHC/Lindane Factors Influencing Residues 6(2):84-88 Humans 6(2):84-88 Plants (other than those used for food and feed) 6(l):56-64 Sediment 6(l):56-64 6(2):97-102 6(3):179-187 6(4) :363-368 SoU 6(3): 194-228 6(l):56-64 6(2):97-102 6(3):I66-170 6(3): 179-187 6(4) :363-368 fe 6(I):33-40 6(l):43-49 6(l):56-64 6(2):97-102 6(3): 166-170 6(4) :363-368 6(2): 126-129 6(3): 194-228 6(4) :369-376 6(I):56-64 6(4) :363-368 Fe 6(l):43-49 6(l):56-64 6(4):363-368 2,4-D Soil 6(3): 194-228 Dacthal®, see DCPA DCBP (4,4'-dichlorobenzophenone ) Wildlife 6(3):133-138 DCPA Soil 6(3): 194-228 DDD, see TDE DDE, see also DDT Factors Influencing Residues 6(l):l-3 6(1):9-13 6(2):84-88 Food and Feed 6(1): 14-22 Humans 6(l):l-3 6(l):4-8 6(1):9-13 6(2) :84-88 Plants (other than those used for food and feed) 6(l):56-64 Sediment 6(l):56-64 6(2):97-102 6(3):179-187 6(3): 188-193 6(4) :363-368 6(1) 6(1) 6(2) 6(3) 6(3) 6(3) 6(4) fe 6(1) 6(1): 6(1) 6(1); 6(1); 6(1): 6(2); 6(3); 6(3): 6(3); 6(4) 6(4) 56-64 65-72 97-102 166-170 179-187 188-193 363-368 14-22 23-26 33-40 43-49 50-55 56-64 97-102 133-138 139-143 166-170 238-362 363-368 DDT, see also DDE, TDE Factors Influencing Residues 6(l):l-3 6(1):9-13 6(2):84-88 6(4):238-362 Food and Feed 6(l):14-22 Humans 6(l):l-3 6(l):4-8 6(1);9-13 6(2):84-88 Sediment 6(2):97-102 6(3):179-187 6(3):188-193 6(4):363-368 Soil SoU 6(l):65-72 6(2):126-129 6(3): 194-228 6(4):369-376 DEF Soil 6(l):65-72 6(2): 126-129 6(3): 194-228 6(4) :369-376 6(l):56-64 6(l):65-72 6(2):97-102 6(3):166-170 6(3): 179-187 6(3):188-193 6(4):363-368 fe 6(l):14-22 6(l):23-26 6(l):33-40 6(l):43-49 6(l):50-55 6(2):97-102 6(3):133-138 6(3): 139-143 6(3):166-170 6(4) : 23 8-362 6(4):363-368 6(3): 194-228 392 Pesticides Monitoring Journal Degradation Plants (other than those used for food and feed) endosulfan 6(l):73-75 parathion 6(l):73-75 6(4):377-378 Diazinon Soil 6(3): 194-228 Wildlife 6(2):115-121 6(3):160-165 Dicofol Sou 6(3): 194-228 Dieldrin Factors Influencing Residues 6(1);9-13 6(2): 84-88 6(4):238-362 Food and Feed 6(4): 233-237 Humans 6(l):4-8 60:9-13 6(2):84-88 Plants (other than those used for food and feed) 6(I):56-64 Sediment 6(l):56-64 6(2):97-102 6(3):179-187 6(3): 188-193 6(4) :363-368 Sou 6(2): 126-129 6(3): 194-228 6(4):233-237 6(4) : 369-376 Water 6(l):56-64 6(2):97-102 6(3):179-187 6(3): 188-193 6(4) :363-368 Wildlife 6(I):23-26 60:33-40 6(l):43-49 6(l):50-55 6(l):56-64 6(2) :97-102 6(2):115-121 6(3):133-138 6(3): 166-170 6(3):229-230 6(4) :23 8-362 6(4):363-368 Dursban® Wildlife 6(3): 160-165 Endosulfan Degradation 6(l):73-75 Factors Influencing Residues 6(l):73-75 Plants (other than those used for food and feed) 6(l):73-75 Sediment 6(3): 179-187 6(4):363-368 Sou 6(3): 194-228 Water 6(3): 179-187 6(4):363-368 Wildlife 6(4) :363-368 Vol. 6, No. 4, March 1973 Endrin Factors Influencing Residues 6(4) :238-362 Sediment 6(2):97-102 6(4) :363-368 Sou 6(2): 126-129 6(3); 194-228 6(4) :369-376 Water 6(2):97-102 6(4):363-368 Wildlife 6(l):43-49 6(2):97-102 6(2):n5-121 6(4) :238-362 6(4):363-368 Ethion Soil 6(3): 194-228 Experimental Design Water Monitoring 6(3):171-178 Factors Influencing Residues Age BHC/Lindane 6(2):84-88 DDE 6(1):9-13 6(2):84-88 DDT 6(1):9-13 6(2):84-88 dieldrin 6(1):9-13 6(2):84-88 mercury 6(2):80-83 selenium 6(2);107-1I4 Climatological Conditions endosulfan 6(l):73-75 parathion 6(1):73-7S 6(4) :377-378 Geographical Location organochlorines 6(4):238-362 PCB's 6(4): 238-362 Interaction endosulfan 6(l):73-75 parathion 6(I):73-75 parathion-endosulfan 6(4):377-378 Sex BHC/Lindane 6(2):84-88 DDE 6(l):l-3 6(1):9-13 6(2):84-88 DDT 6(l):l-3 6(1):9-13 6(2):84-88 dieldrin 6(1):9-13 6(2):84-88 mercury 6(2):80-83 Factors Influencing Residues (confd) Species, Strain, or Race DDE 6(l):l-3 6(1):9-13 DDT 6(l):l-3 6(1):9-13 dieldrin 6(1):9-13 organochlorines 6(4):238-362 Storage of Samples organochlorines 6(4) :238-362 Food and Feed Corn organochlorines 6(4) :369-376 parathion 6(4) :369-376 PCB's 6(4) :369-376 Dairy Products DDE 6(l):14-22 DDT 6(l):14-22 dieldrin 6(4): 233-237 mirex 6(1): 14-22 TDE 6(l):14-22 Grain and Forage (for use as animal feed) DDE 6(1): 14-22 DDT 6(l):14-22 dieldrin 6(4):233-237 mirex 6(1): 14-22 organochlorines 6(4):369-376 parathion 6(4) :369-376 PCBs 6(4):369-376 TDE 6(l):14-22 Meat, Fish, and Poultry DDE 6(1): 14-22 DDT 6(1): 14-22 mirex 6(1): 14-22 TDE 6(1): 14-22 Potatoes arsenic 6(2):89-90 Tobacco, see Plants (other than those used for food and feed) H HCB Humans 6(l):4-8 Sediment 6(3):I79-187 Heptachlor/Heptachlor Epoxide Humans 6(2) :84-88 Sediment 6(2) :97-102 6(3): 179-187 6(4) :363-368 393 Heptachlor/Heptachlor Epoxide (cont'd) Sou 6(2):126-129 6(3): 194-228 6(4):369-376 Water 6(2) :97-102 6(3): 166-170 6(3): 179-187 6(4):363-368 WUdUfe 6(l):33-40 6(l):43-49 6(l):50-55 6(2) :97-102 6(2):115-121 6(3):133-138 6(4):363-368 Hesachlorobenzene, see HCB Humans Adipose DDE 6(1):9-13 DDT 6(1):9-13 dieldrin 6(I):9-13 organochlorines 6(2): 84-88 Blood DDE 6(1):9-13 DDT 6(1):9-13 dieldrin 6(1):9-13 Hair mercury 6(2) :80-83 Milk DDE 6(l):4-8 DDT 6(l):4-8 dieldrin 6(l):4-8 HCB 6(l):4-8 TDE 6(l):4-8 Serum DDE 6(l):l-3 DDT 6(1): 1-3 organochlorines 6(2):84-88 Isodrin Sou 6(3): 194-228 6(4) :369-376 Lead Wildlife 6(1):27.32 Lindane, see BHC/Lindane M Malathion Sediment 6(3):188-193 Soil 6(3):194-228 Water 6(3): 188-193 394 Mercury Factors Influencing Residues 6(2) :80-83 Humans 6(2):80-83 Wildlife 6(l):23-26 6(l):27-32 6(l):50-55 6(2):91-93 6(2): 103-106 6(2): 122-125 6(3):133-138 6(3): 144-159 Methoxychlor Sou 6(3): 194-228 Water 6(3): 166-170 Wildlife 6(3):166-170 Methyl Parathion, see also Parathion WildUfe 6(2):115-I21 Mirex Factors Influencing Residues 6(4) :238-362 Food and Feed 6(l):14-22 Wildlife 6(l):14-22 6(l):41-42 6(4) :23 8-362 Parathion, see also Methyl Parathion Degradation 6(l):73-75 6(41:377-378 Factors Influencing Residues 6(I):73-75 6(4):377-378 Food and Feed 6(4):369-376 Plants (other than those used for food and feed) 6(l):73-75 6(4):377-378 Sediment 6(3): 179-187 Soil 6(3): 194-228 Water 6(3): 179-187 Wildlife 6(2):115-121 PCB's Factors Influencing Residues 6(4) :238-362 Food and Feed 6(41:369-376 Wildlife 6(l):23-26 6(l):33-40 6(l):43-49 6(l):50-55 6(3): 133-138 6(3):I39-143 6(4) :238-362 PCNB Soil 6(3): 194-228 PCS (Pentachlorophenol) Water 6(l):56-64 Pentachlorophenol, see PCB Pesticide Sales and Usage Kentucky 6(4) :379-387 Plants (other than those used for food and feed) Algae organochlorines 6(l):56-64 Tobacco endosulfan 6(l):73-75 parathion 6(l):73-75 6(4):377-378 Polychlorinated Biphenyls, see PCB's Sediment HCB 6(3): 179-187 organochlorines 6(l):56-64 6(2):97-102 6(3):179-187 6(4):363-368 parathion 6(3): 179-187 toxaphene 6(2) :94-96 Cisterns DDE 6(3):188-193 DDT 6(3): 188-193 dieldrin 6(3): 188-193 malathion 6(3):188-193 TDE 6(3): 188-193 Selenium Factors Influencing Residues 6(2):107-114 Wildlife 6(2):I07-114 Soil, see also Sediment arsenic 6(3): 194-228 herbicides 6(3): 194-228 organochlorines 6(3): 194-228 organophosphates 6(3): 194-228 PCNB 6(3):194-228 trifluralin 6(3):194-228 Corn Belt Region arsenic 6(4):369-376 organochlorines 6(4):369-376 Feed Crop dieldrin 6(4):233-237 Forest DDE 6(l):65-72 DDT 6(l):65-72 TDE 6(l):65-72 Pasture dieldrin 6(4):233-237 Potato Fields arsenic 6(2) :89-90 Pesticides Monitoring Journal Soil, see also Sediment (cont'd) Urban arsenic 6(2): 126-129 organochlorines 6(2): 126-129 TDE (DDD) Food and Feed 6(1): 14-22 Humans 6(l):4-8 6(2) :84-88 Plants (other than those used for food and feed) 6(l):56-64 Sediment 6(l):56-64 6(2):97-102 6(3):179-187 6(3): 188-193 6(4) :363-368 Sou 6(l):65-72 6(2): 126-129 6(3): 194-228 6(4) :369-376 Water 6(l):56-64 6(l):65-72 6(2):97-102 6(3): 179-187 6(3): 188-193 6(4) :363-368 Wildlife 6(1): 14-22 6(I):23-26 6(I):33-40 6(l):43-49 6(l):50-55 6(l):56-64 6(2):97-102 6(3):133-138 6(3):229-230 6(4) :238-362 6(4): 363-368 Thiodan®, see Endosulfan Toxaphene Factors Influencing Residues 6(4):238-362 Sediment 6(2):94-96 Soil 6(2): 126-129 6(3): 194-228 WUdlife 6(2) :94-96 6(4):238-362 Trifluralin Soil 6(3): 194-228 6(4):369-376 Trithion®, see Carbophenothion W Water, see also Sediment organochlorines 6(l):56-64 PCP 6(l):56-64 Water, see also Sediment (cont'd) Cisterns DDE 6(3): 188-193 DDT 6(3): 188-193 dieldrin 6(3): 188-193 malathion 6(3):188-193 TDE 6(3): 188-193 Estuarine Waters organochlorines 6(2):97-102 Experimental Design 6(3):171-178 Rivers and Streams DDE 6(I):65-72 DDT 6(l):65-72 organochlorines 6(3): 166-170 6(3):179-187 6(4):363-368 parathion 6(3): 179-187 TDE 6(l):65-72 Wildlife Birds DDE 6(I):14-22 DDT 6(1): 14-22 lead 6(l):27-32 mercury 6(1): 27-32 6(2):91-93 6(3):133-138 miren 6(1): 14-22 6(l):41-42 organochlorines 6(l):33-40 6(3):133-I38 PCB's 6(l):33-40 6(3):133-I38 TDE 6(l):14-22 Birds' Eggs DDE 6(1): 14-22 DDT 6(l):l4-22 mercury 6(l):50-55 mirex 6(1): 14-22 organochlorines 6(l):50-55 PCBs 6(l):50-55 TDE 6(1): 14-22 Deer and Elk DDE 6(l):14-22 DDT 6(1): 14-22 mirex 6(1): 14-22 TDE 6(1): 14-22 Wildlife (cont'd) Fish DDE 6(l):14-22 6(l):23-26 6(3): 139-143 DDT 6(1): 14-22 6(l):23-26 6(3):139-143 dieldrin 6(l);23-26 mercury 6(l):23-26 6(2): 103-106 6(2): 122-125 6(3): 144-159 mirex 6(1): 14-22 organochlorines 6(l):43-49 6(l):56-64 6(2):97-102 6(3):166-170 6(4):363-368 PCBs 6(l):23-26 6(l):43-49 6(3): 139-143 selenium 6(21:107-114 TDE 6(1): 14-22 6(l):23-26 Invertebrates (other than shellfish) DDE 6(1): 14-22 6(3): 139-143 DDT 6(1): 14-22 6(3): 139-143 diazinon 6(3):160-165 Dursban® 6(3):160-165 mirex 6(l):14-22 PCB's 6(3):139-143 TDE 6(1): 14-22 Rodents dieldrin 6(2):115-121 heptachlor epoxide 6(2):115-121 organophosphates 6(2):115-I21 Shellfish DDE 6(3): 139-143 DDT 6(3): 139-143 diazinon 6(3): 160-165 dieldrin 6(3): 229-230 Dursban® 6(3):160-165 organochlorines 6(2):97-102 6(4):238-362 PCB's 6(3): 139-143 6(4);238-362 Vol. 6, No. 4, March 1973 395 AUTHOR INDEX Adley, F. E., and Brown, D. W. Mercury concentrations in game birds, State of Washington— 1970 and 1971. 6(2) :91-93 B Baetcke, K. p., Cain, J. D., and PoE, W. E. Mirex and DDTR resi- dues in wildlife and miscellaneous samples in Mississippi — 1970. 6(l):14-22 Barton, J. R., see Bradshaw, J. S. Belisle, a. a., Reichel, W. L., Locke, L. N., Lamont, T. G., Mui- hern. B. M., Prouty, R. M., DeWolf, R. B., and Cromartie, E. Residues of organochlorine pesticides, polychlorinated biphen- yls, and mercury and autopsy data for bald eagles, 1969 and 1970. 6(3):133-138; Erratum 6(4):390 Benson, W. W,, and Gabica. J. Total mercury in hair from 1,000 Idaho residents— 1971. 6(2):80-83 Benson, W. W., see Wyllie, J. Bevenue, a., Hylin, J. W., Kawano, Y., and Kelley, T. W. Organo- chlorine pesticide residues in water, sediment, algae, and fish, Hawaii— 1970-71. 6(l):56-64 Bollen, W. B., see Tarrant, R. F. Bradshaw, J. S., Loveridge, E. L., Rippee, K. P., Peterson, J. L., White, D. A., Barton, J. R., and Fuhriman, D. K. Seasonal variations in residues of chlorinated hydrocarbon pesticides in the water of the Utah Lake drainage system — 1970 and 1971. 6(3): 166-170 Brown, B. L., see Keil, J. E. Brown, D. W., see Adley, F. E. Bruce, W. N.. see Moore, S., Ill BuRDiCK, G. E., see Pakkala, I. S. Butler, P. A. Organochlorine residues in estuarine mollusks. 1965-72 — National Pesticide Monitoring Program. 6(4) :238-362 Cain, J. D., see Baetcke, K. P. Canario, M. T., Jr., see Check, R. M. Carey, A. E., Wiersma, G. B., Tai, H., and Mitchell, W. G. Organo- chlorine pesticide residues in soils and crops of the Com Belt region. United States— 1970. 6(4):369-376 Carr, R. L., Finsterwalder, C. E., and Schibi, M. J. Chemical resi- dues in Lake Erie fish— 1970-71. 6(l):23-26 Check, R. M., and Canario, M. T., Jr. Residues of chlorinated hydro- carbon pesticides in the northern quahog (hard-shell clam), Mercenaria mercenaria— 1968 and 1969. 6(3);229-230 Colcolough, J. J., see Keil, J. E. Cromartie, E., see Belisle, A. A. Culbertson, J. K., see Feltz, H. R. Curry, L., see Lenon, H. D DeWolf, R. B., see Belisle, A. A. DuRANT, C. J., and Reimold, R, J. Effects of estuarine dredging of toxaphene-contaminated sediments in Terry Creek, Brunswick, Ga— 1971. 6(2):94-96 Hanks, A. R., see Giam, C. S. Harris, C. R., see Miles, J. R. W. Harris, E. J., see Pakkala, I. S. Henderson, C, Inglis, A., and Johnson, W. L. Mercury resi- dues in fish, 1969-1970 — National Pesticide Monitoring Program. 6(3):144-159 Hensel, R. J., see Wiemeyer, S. N. Herring, J. see Knight, L. A., Jr. Herzel. F. Organochlorine insecticides in surface waters in Germany — 1970 and 1971. 6(3):179-187 Hylin, J. W., see Bevenue, A. Inglis, A., see Henderson, C. Jamieson, D., see Reinke, J. Johnson, W. L., see Henderson, C. Kadoum, a. M., see Robel, R. J. Kawano, Y., see Revenue, A. Keenly, D. R., see Steevens. D. R. Keil, J. E., Weston, W., Ill, Loadholt, C. B., Sandiper, S. H., and Colcolough, J. J. DDT and DDE residues in blood from children South Carolina— 1970. 6(1); 1-3 Keil, J. E., Loadholt, C. B., Brown, B. L., Sandiper, S. H., and Sitterly, W. R. Decay of parathion and endosulfan residues on field-treated tobacco. South Carolina— 1971. 6(l):73-75; Erratiun 6(4):390 Keil, J, E., Loadholt, C. B., Sandiper, S. H., Sitterly. W. R., and Brown, B. L. Decay of parathion residues on field-treated tobacco. South Carolina— 1972 (II). 6(4) :377-378 Kelley, T. W., see Bevenue, A. Knight, L. A., Jr., and Herring, J. Total mercury in largemouth bass {Micropterus salmoides) in Ross Barnett Reservoir, Mississippi — 1970 and 1971. 6(2):103-106 KuHLMAN, D. E., see Moore, S., Ill Lamont, T. G., see Belisle, A. A. Lee, Y. W., see Sumner, A. K. Lenon, H., Curry, L., Miller, A., and Patulski, D. Insecticide residues in water and sediment from cisterns on the U. S. and British Virgin Islands— 1970. 6(3):188-193 LiGAS, F. J., see Wiemeyer, S. N. Lisk, D. J., see Pakkala, I. S. Loadholt, C. B., see Keil, J. E. Locke, L. N., see Belisle, A. A. LoPER, B. R., see Tarrant, R. F. Loveridge, E. L., see Bradshaw, J. S. Fay, R. R., and Newland, L. W. Organochlorine insecticide residues in water, sediment, and organisms, Aransas Bay, Texas — Septem- ber 1969-June 1970. 6(2) :97-102 Feltz, H. R. Editorial: These changing times. 6(2) :79 Feltz, H. R., and Culbertson, J. K. Sampling procedures and prob- lems in determining pesticide residues in the hydrologic ment. 6(3):171-178 Finsterwalder, C. E., see Carr, R. L. Fuhriman, D. K., see Bradshaw, J. S. Gabica, J., see Benson, W. W. Gabica, J., see Wyllie, J. Giam, C. S., Hanks, A. R., Richardson, R. L., Sackett, W. M., and Wong, M. K. DDT, DDE, and polychlorinated biphenyls in biota from the Gulf of Mexico and Caribbean Sea— 1971. 6(3):139-143 Greene, N. C, see Newton, K. G. Gutenmann, W. H., see Pakkala, I. S. 396 M Marganian, v. M., and Wall, W. J., Jr. Dursban® and diazinon residues in biota following treatment of intertidal plots on Cape Cod— 1967-69. 6(3): 160-165 Martin, W. E. Mercury and lead residues in starlings — 1970. 6(l):27-32; Erratum 6(4) :389 Martin, W. E., and Nickerson, P. R. Organochlorine residues in starlings— 1970. 6(l):33-40 Mathisen, J. E., see Wiemeyer, S. N. Miles. J. R. W., and Harris, C. R. Organochlorine insecticide resi- dues in streams draining agricultural, urban-agricultural, and resort areas of Ontario, Canada — 1971. 6(4):363-368 Miller. A., see Lenon. H. Mitchell, W. G.. see Carey. A. E. Moore, D. G.. see Tarrant, R. F. Moore, E. E. Pesticide sales and usage in Kentucky — 1968. 6(4):379- 387 Pesticides Monitoring Journal NfooKE, S., in, Bruce, W. N„ Kuhlman, D. E., and Randell, R, A study of the sources of insecticide residues in milk on dairy farms in lUinois— 1971. 6(4):233-237 MULHERN, B. M., see Belisle, A. A. MlTLHERN, B. M., see WiEMEYER, S. N. N Newland, L. W., see Fay, R. R. Newton, K. G., and Greene. N. C. Organochlorine pesticide resi- due levels in human miUc — Victoria, Australia — 1970. 6(l):4-8 NiCKERSON, P. R., see Martin, W. E. o Oberheu, J. C. The occurrence of mirex in starlings collected in seven southeastern States— 1970. 6(l):41-42 Sand, P. F., see Wiersma, G. B. Sandifer, S. H., see Keil, J. E. ScHiBi, M. J., see Carr, R. L. SiTTERLY, W. R., see Keil, J. E. Stalling. C. D., see Robel, R. J. Steevens, D. R., Walsh, L. M., and Keeney, D. R. Arsenic residues in soil and potatoes from Wisconsin potato fields — 1970. 6{2):89-90 Sumner, A. K., Saha, J. G., and Lee, Y. W. Mercury residues in fish from Saskatchewan waters with and without known sources of pollution— 1970. 6(2):122-I25 Tai, H., see Carey, A. E. Tai, H., see Wiersma, G. B. Tarrant. R. F., Moore, D. G., Bollen, W. B., and Loper, B. R. DDT residues in forest floor and soil after aerial spraying, Oregon— 1965-68. 6(l):65-72 PaKKALA, I. S., GUTENMANN, W. H., LiSK, D. J., BUKDICK, G. E., and Harris, E. J. A survey of the selenium content of fish from 49 New York State waters. 6(2):107-114 Patulski, D., see Lenon, H. Peterson, J. L., see Bradshaw, J. S. PoE, W. E., see Baetcke, K. P. Postupalsky, S., see Wiemeyer. S. N. Prouty, R. M., see Belisle, A. A. R Randell, R., see Moore, S., Ill Reichel, W. L.. see Belisle, A. A. Reimold, R. J., see Durant. C. J. Reinke, J., Uthe, J. F., and Jamieson, D. Organochlorine pesticide residues in commercially cought fish in Canada — 1970. 6(l):43-49 Richardson, R. L., see Giam, C. S. Rippee, K. p., see Bradshaw, J. S. RoBARDS, F. C, see Wiemeyer, S. N. Robel, R. ]., Stalling, C. D., Westfahl. M. E., and Kadoum, A. M. Effects of insecticides on populations of rodents in Kansas — 1965-69. 6(2): 115-121 Sackett, W. M., see Giam, C. S. Saha, J. G., see Sumner, A. K. Uthe, J. F., see Reinke, J. u w Wall, W. J.. Jr., see Marganlan, V. M. Walsh, L. M., see Steevens, D. R. Warnick, S. L. Organochlorine pesticide levels in human serum and adipose tissue, Utah— fiscal years 1967-71. 6(1):9-13 Westfahl, M. E., see Robel, R. J. Weston, W., Ill, see Keil, J. E. White, D. A., see Bradshaw, J. S. Wiemeyer, S. N.. Mulhern, B. M., Ligas, F. J.. Hensel. R. J., Mathisen, J. E., RoBARDS, F. C, and Postupalsky, S. Residues of organochlorine pesticides, polychlorinated biphenyls, and mer- cury in bald eagle eggs and changes in shell thickness — 1969 and 1970. 6(l):50-55 Wiersma, G. B., Tai. H., and Sand, P. F. Pesticide residues in soil from eight cities— 1969. 6(2): 126-129 Wiersma. G. B., Tai. H., and Sand, P. F. Pesticide residue levels in soils, FY 1969— National Soils Monitoring Program. 6(3) :I94-228; Erratum 6(4): 390 Wiersma, G. B., see Carey, A. E. Wong, M. K., see Giam, C. S. Wyllie, J., Gabica, J., and Benson, W. W. Comparative organo- chlorine pesticide residues in serum and biopsied lipoid tissue: a survey of 200 persons in Southern Idaho — 1970. 6(2) :84-88 Vol. 6, No. 4, March 1973 397 Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretive information which contribute to the understanding and evaluation of pesticides and their residues in relation to man and his environment. TTie publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries; medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. Accuracy, reliability, and limitations of the sam- pling and analytical methods employed must be clearly demonstrated through the use of appropriate procedures, such as recovery experiments at appropriate levels, confirmatory tests, internal standards, and inter-labora- tory checks. The procedure employed should be ref- erenced or outlined in brief form, and crucial points or modifications should be noted. Check or control samples should be employed where possible, and the sensitivity of the method should be given, particularly when very low levels of pesticides are being reported. Specific note should be made regarding correction of data for percent recoveries. Preparation of manuscripts should be in con- formance to the CBE Style Manual, 3d ed. Coun- cil of Biological Editors, Committee on Form and Style, American Institute of Biological Sciences, Washington, D. C. and/or the Style Manual of The United States Government Printing Office. An abstract (not to exceed 200 words) should accompany each manuscript submitted. All material should be submitted in duplicate (original and one carbon) and sent by first-class mail in flat form — not folded or rolled. -Manuscripts should be typed on 8V2 x 11 inch paper with generous margins on all sides, and each page should end with a completed para- graph. All copy, including tables and references, should be double spaced, and all pages should be num- bered. The first page of the manuscript must contain authors' full names listed under the title, with affiliations, and addresses footnoted below. Charts, illustrations, and tables, properly titled, should be appended at the end of the article with a notation in text to show where they should be inserted. 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Pesticides ordinarily should be identified by common or generic names approved by national scientific so- cieties. The first reference to a particular pesticide should be followed by the chemical or scientific name in parentheses — assigned in accordance with Chemical Abstracts nomenclature. Structural chemical formulas should be used when appropriate. Published data and information require prior approval by the Editorial Advisory Board; however, endorsement of published in- formation by any specific Federal agency is not intended or to be implied. Authors of accepted manuscripts will receive edited typescripts for approval before type is set. After publication, senior authors will be provided with 100 reprints. Manuscripts are received and reviewed with the under- standing that they previously have not been accepted for technical publication elsewhere. 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