The Pesticides Monitoring Journal is published quarterly under the auspices of the WORKING GROUP, Subcommittee on Pesticides, President's Cabinet Committee on the Environment, 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; Defense; the Interior; Health, Education, and Welfare; State; and Transportation. The Pesticide Monitoring Panel consists of representatives of the Agricultural Research Service, Consumer and Marketing Service, Federal Extension Service, Forest Service, Department of Defense, Fish and Wildlife Service, Geological Survey, Federal Water Quality Administration, Food and Drug Administration, Environmental Health 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 pesticides monitoring network, are expected to be principal sources of data and interpretive articles. How- ever, 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 institutions, 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 Andrew W. Briedenbach, Environmental Health Service 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 5 June 1971 Number 1 Page RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Organochlorine insecticide residues in fish — jail 1969 (National Pesticide Monitoring Program) 1 Croswell Henderson, Anthony Inglis, and Wendell L. Johnson Dieldrin levels in fish from Iowa streams 12 Robert L. Morris and Lauren G. Johnson PESTICIDES IN SOIL Insecticide usage and residues in a newly developed great plains irrigation district 17 Herbert Knutson, A. M. Kadoum, T. L. Hopkins, Glen F. Swoyer, and T. L. Harvey Organochlorine insecticide residues in soil from vegetable farms in Saskatchewan 28 Jadu G. Saha and Arthur K. Sumner BRIEFS Preliminary study of mercury residues in soils where mercury seed treatments have been used 32 P. F. Sand, G. B. Wiersma, H. Tai, and L. J. Stevens APPENDIX Chemical names of compounds mentioned in preceding papers 34 lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll^ NATIONAL PESTICIDE MONITORING PROGRAM (Revised) Introduction 35 R. E. Duggan Criteria for defining pesticide levels to be considered an alert to potential problems 36 Panel on Pesticide Monitoring, Working Group on Pesticides (W. S. Murray, Executive Secretary) National food and feed monitoring program 37 R. E. Duggan and H. R. Cook The national human monitoring program for pesticides 44 Anne R. Yobs Expanded program for pesticide monitoring of fish 47 Anthony Inglis, Croswell Henderson, and Wendell L. Johnson Monitoring pesticides in wildlife 50 E. H. Dustman, W. E. Martin, R. G. Heath, and W. L. Reichel Estuarine monitoring program 53 Thomas C. Carver National monitoring program for the assessment of pesticide residues in water 54 H. R. Feltz, William T. Sayers, and H. P. Nicholson A sampling design to determine pesticide residue levels in soils of the conterminous United States 63 G. B. Wiersma and P. F. Sand National monitoring program for air 67 Anne R. Yobs Revised chemicals monitoring guide for the National Pesticide Monitoring Program 68 Milton S. Schechter RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Organochlorine Insecticide Residues in Fish — Fall 1969 Naitonal Pesticide Monitoring Program' Croswell Henderson, Anthony Inglis, and Wendell L. Johnson ABSTRACT The fish monitoring program conducted by the Bureau of Sport Fisheries and Wildlife since 1967 was continued in 1969. A total of 147 composite fish samples were collected at 50 nationwide monitoring stations during the fall of 1969. Each sample was analyzed by a commercial laboratory for residues of 1 1 organochlorine insecticides, lipids, and poly- chlorinated biphenyls (PCB's). DDT and/or metabolites were found in all samples with residue levels of total DDT (DDE + TDE + DDT) ranging from 0.03 to 57.8 ppm (mg/kg, wet weight, whole fish). Dieldrin residues ranging from 0.01 to 1.59 ppm were found in all but 10 of the 147 samples. Other organochlorine insecticides were found less frequently. Confirmatory analyses were conducted on some samples, and studies were made to determine effects of PCB's on insecti- cide residue analyses. Introduction A nationwide monitoring program to determine residue levels of organochlorine insecticides in fish was initiated by the Bureau of Sport Fisheries and Wildlife in the spring of 1967 and was continued during 1968 and 1969. Residue data for 1967 and 1968 fish collections were reported in a previous issue of this Journal (5). This report contains data on organochlorine insecticide residues in fish collected at 50 nationwide monitoring stations during the fall (September, October, November) of 1969. Data on polychlorinated biphenyls (PCB's) and lipid content are included. Common names of fishes as designated by the American Fisheries Society (/) are used throughout this report. Methods FISH COLLECTIONS Fish were collected from the same 50 sampling stations used in 1967 and 1968 (5). The specific locations are shown in Fig. 1 and listed in Table lA. Previous data indicated little difference in residue levels in the spring and fall; thus, collections were made only once during 1969, in the fall (September, October, November) when collecting the desired species was less difficult. FIGURE 1. — Fish sampling stations — National Pesticide Monitoring Program ^ From the Division of Fishery Services, Bureau of Sport Fisheries and Wildlife, U.S. Department of the Interior, Washington, D.C. 20240. Vol. 5. No. 1, June 1971 As in previous collections, three comp>osite samples, each of a different species, were collected at each station. Generally, each composite consisted of five uniform size adult fish of the same species. A special effort was made to collect the three designated species which had pre- dominated in past collections and on which most residue data were available. Fish were collected, frozen, pack- aged, and shipped to the analytical laboratory as described previously (5). LABORATORY ANALYSES A single commercial laboratory analyzed all samples for residues of 1 1 organochlorine insecticides. Methods used by this laboratory (Laboratory C) are described in detail in a previous issue of this Journal (5). PCB's were esti- mated by using Aroclor 1 254 as a standard and measur- ing the peak between TDE and DDT. To determine the lipid content, a separate 20-g sample was weighed into a 150-ml beaker and dried at 40°C in an air oven for 36-48 hours. The sample was removed from the oven and ground with NaoSO^ (approximately 20-50 g). TTie ground sample was placed in a 33-mm x 94-mm Whatman extractor thimble and extracted 8 hours on a Soxhlet extractor using 70 ml of ethyl ether and 170 ml of petroleum ether. The extract was con- centrated to 10-15 ml on a steam bath, then transferred to a tared 50-ml beaker, and the remainder of the solvent evaporated off on a steam bath. The beaker was placed in an oven at 40°C for 4-6 hours, removed, desiccated, weighed, and the amount of fat calculated. Confirmatory analyses were conducted on homogenate subsamples from 1 1 of the original composite samples. Two laboratories participated in this work. Laboratory C and the Bureau of Sport Fisheries and Wildlife Fish- Pesticide Research Laboratory (Laboratory F) (5). Laboratory C conducted a repeat analysis for DDT and metabolites on a fresh sample of each of the 1 1 homo- genates by its conventional methodology. An alkaline hydrolysis was then performed on a portion of the extract, thus converting most of the DDT to DDE. The method used is described in the FDA Pesticide An- alytical Manual, Section 211.16 D {14). PCB's were measured by using Aroclor 1254 as a standard and measuring the pieak at DDT on the hydrolyzed sample. Average recovery rates for analyses carried out by Laboratory C are as follows: DDE-85%, DDD-83%, DDT-82%, dieldrin-84%, aldrin-60%, endrin-68%, heptachlor and heptachlor epoxide-75%, lindane and BHC-80% . No corrections for recovery have been made in the residue values from this laboratory. Sensitivity for all organochlorine insecticides was 0.005 ppm. Subsamples and extracts of the 11 composites were shipped to Laboratory F, which analyzed samples for DDE, TDE, and DDT by their conventional procedure which is described in detail in the Pesticides Monitoring Journal (5). A more elaborate analysis was conducted on some of the samples (12). The method employed in these analyses did not utilize Florisil or partition to separate the fat from the pesticides. A one-step cleanup was accomplished by using gel permeation. The gel was BIO RAD SX-2 with cyclohexane as a solvent. The gel column was 2.2 cm i.d. x 24 cm. By using a pump, a flow rate of 3 ml/min was maintained. The extraction method and gel permeation yielded quantitative recovery for the pesticides of interest. Only BHC required a slight correction factor due to evaporation losses. For gas chromatographic analysis a 0.3% OV-7 (Supelco Inc.) coating on 80/90 mesh glass beads was used in a 2-mm X 6' column at a temperature of 170°C and nitrogen carrier gas flow of 15 cc/min. Only those samples in which the PCB's did not interfere were quantitated. Laboratory F also conducted confirmatory analyses for organochlorine insecticides and PCB's on some of the extracts with a mass spectrometer. Extracts of 5 g of fish homogenate which had been subjected to the Florisil cleanup procedure were concentrated to approximately 30 jx\, and 2 jj\ of the extract was examined with a Perkin-Elmer Model 270 gas chromatograph-mass spectrometer. Spectra obtained from the samples were compared to those obtained from reference standard compounds. Laboratory F also conducted additional analyses in order to confirm PCB and pesticide residues in some samples with relatively high PCB levels. The extracts obtained from the Florisil cleanup were separated into PCB and pesticide fractions using silicic acid column chromatog- raphy as described by Armour and Burke (2). This procedure apparently does an excellent job in separating PCB's and pesticides and will minimize PCB interfer- ences if employed as a cleanup method. Recovery rates for Laboratory F's conventional pro- cedure were as reported previously (5), while the gel permeation method produced recoveries of 97 ± 3% for organochlorine insecticides and 99% for PCB's. Sensitivity for both types of residues was 0.01 PPM. No correction for recovery was made with the gel permea- tion method. Results FISH COLLECTIONS A total of 147 composite fish samples were collected from the 50 stations in the fall of 1969. At only three stations were collectors unable to obtain the full com- plement of three samples, but at least one sample was obtained at all stations. Most of the composites con- sisted of five fish; however, a few were less, and three samples consisted of only one large fish. At most of the stations, collectors were successful in obtaining the designated three species of fish. In 1969, at all stations, at least one species was collected for which Pesticides Monitoring Journal previous residue data are available. Forty-four different species of fish are represented in the 1969 collections. However, of the 147 samples collected, 16 species were collected only once, and 13 were collected twice. On the other hand, carp were collected 22 times; largemouth bass 16 times; and channel catfish 13 times. Various sjjecies of suckers were collected 26 times. RESIDUE LEVELS IN FISH Results of residue analyses for the 1969 samples are shown in Tables lA and IB. In addition to the organo- chlorine insecticides, estimated values for PCB's are given. AH values are reported as ppm (milligram per kilogram), wet weight, whole fish. Lipid content is re- ported as percentage by weight of the whole fish. Also shown in Table lA are station locations, species of fish, number of fish, and average length and weight of all fish in the composite. DDT and metabolites were found in all of the 147 composite samples collected in 1969. Residue levels of total DDT (DDT + TDE + DDE) in the samples ranged from a low of .03 ppm at Station 50 to a high of 57.8 ppm at Station 12. The high value was from a single large (10 lb) channel catfish and may not represent the true picture at this station. Only 1 of 14 other composite samples from this station collected during 1967, 1968, and 1969 has exceeded 5 ppm. and most samples were well below this value. Some of the highest values for samples from other stations ranged from 5 to 20 ppm total DDT. Mean levels (three composite samples) were above 5 ppm total DDT at Stations 4, 12. 14, and 21 and between 2 and 5 ppm at Stations 3, 16. 18, and 24. The median level at the 50 stations was about 1 ppm. Dieldrin was present in all but 10 of the 147 samples. Residue levels ranged from .01 ppm in a number of samples to a maximum of 1.59 ppm in a sample from Station 13. Mean levels were above 0.3 ppm at Stations 2, 4, 10, 13, and 26 and exceeded 0.1 ppm at five other stations. Mean levels were .01 ppm or below at 10 sta- tions, and residues were not found in any samples from 2 stations. The median level for the 50 stations was approximately 0.03 ppm. BHC was the next most frequently found insecticide. Residues were reported in all but 15 of the 147 samples and in some samples at all but one of the 50 stations. Residue levels in composite samples ranged from 0.01 ppm to a maximum of 4.37 ppm. Mean levels exceeded 0.3 ppm at Stations 15, 23, and 24 and exceeded 0.1 ppm at an additional nine stations. On the other hand, mean levels were 0.01 ppm or less at 20 stations. TTie median level was approximately 0.02 ppm. Lindane, the gamma isomer of BHC, was not reported as such in any Vol. 5, No. I.June 1971 samples; however, it was included in the results reported for BHC. Heptachlor residues were reported in only three samples, all of these from Station 16. Values ranged from .07 ppm to .45 ppm with a mean value at this station of .25 ppm. Heptachlor epoxide was reported in only six samples at three stations. Values ranged from .03 to .34 ppm in composite samples. Chlordane was found at 6 stations and in 16 of the 147 composite samples. Residue levels ranged from 0.09 ppm to a maximum of 13.5 ppm in one sample at Station 16. Mean levels at Stations 4, 16, and 24 ranged from .70 to 5.27 ppm. Levels at the other three stations were below .10 ppm. No residues of aldrin, endrin. or toxaphene were re- ported in any of the 1969 samples. CONFIRMATORY ANALYSES Results of the initial analyses by Laboratory C of 11 composites for DDE, TDE, DDT, and PCB's, and repeat analyses before and after alkaline hydrolysis are shown in Table 2. As can be noted, total DDT (DDT + TDE + DDE) residues are reasonably comparable for repeat analyses both before and after alkaline hydrolysis. In a few samples with high PCB's (Station 3-goldfish, Station 4-white perch, and Station 24-channeI catfish), total DDT residues after hydrolysis appear lower than those initially reported. No corrections have been made in the values reported in Table 2. However, where high PCB's are reported, the reported TDE and DDT levels may also be high. The results of the analyses by Laboratory F of sub- samples of some of the composites by both their regular and gel permeation methods are also shown in Table 2. The DDT and PCB results reported by the two labora- tories and by different methods appear to be in fair agreement. The results reported for residues of other organochlorine insecticides by the two laboratories are shown in Table 3. While the results are in fair agreement, the greatest differences between the data are found in the residue levels of BHC. No clear explanation is available for these differences. Laboratory F reported that with its chro- matographic column, the potential for interference with BHC is great; however, cross-column analyses tended to confirm the initially reported levels of BHC. They did not confirm the presence of heptachlor epoxide in the three samples in which it was reported by Laboratory C. There were no peaks which could be made to correspond to heptachlor epoxide. Discussion and Conclusions The 1969 residue data for total DDT (DDE + TDE + DDT) and dieldrin follow a pattern consistent with that reported in 1967 and 1968 (5). While residue values are somewhat different, stations from which the higher levels are reported in 1969 are generally the same as those from which high levels were reported previ- ously. The 1969 residue data for other organochlorine insecti- cides was less consistent with earlier results. BHC was reported in a far greater percentage of samples in 1969 than during any previous sampling period. The reason may be that in the past, laboratories had been requested to report lindane (the gamma isomer of BHC) but not BHC as such. The 1969 results probably include other isomers. Chlordane and heptachlor epoxide were not re- ported in 1969 from some stations at which these resi- dues were reported consistently in earlier data. Also, residues were repwrted from a few stations in 1969 at which residues had not been reported previously. Endrin residues had been reported in a few previous samples but were not reported in any samples in 1969. The rea- sons for these dissimilarities are not known but may be due to refinements in laboratory techniques, differences in deciphering chromatograms, or real differences in samples. The results of confirmatory analyses (Tables 2 and 3) indicate that DDT and dieldrin values are reliable. In a few samples where high PCB's were found, there is some indication that the 1969 total DDT values may also be high. The presence of BHC, heptachlor, and chlordane in some samples was confirmed by both participating lab- oratories, although the values were somewhat different. The presence of heptachlor epoxide in several samples was not confirmed by Laboratory F. A re-examination of chromatograms for the fall 1968 samples of Labora- tory C indicate that the values reported for heptachlor epoxide may have been PCB's or something else. There- fore, we would be reluctant to place much significance on the results of heptachlor and heptachlor epoxide. Other investigators, including Reynolds (70) and Rise- brough (11), have shown PCB's to cause some inter- ference with p)esticide residue analyses. The 1969 residue results reported here (Tables lA and IB) for DDT and dieldrin are in reasonable agreement with results reported from other recent fish monitoring studies in Nebraska (5), Louisiana {4). New York (5), Lake Michigan (9), and Connecticut (13). Also, there is a striking correlation between organo- chlorine insecticide residues in water reported by Lichtenberg, et al. (7) and our residues in fish. The sta- tions reported to have the most frequent occurrence of insecticide residues in water during 1967 and 1968 in- clude some of our stations with consistently high residues in fish. Likewise the stations reported to have less fre- quently occurring water residue levels correspond closely to our stations with the lowest levels in fish. Again, as in previous data, there was no definite correla- tion between residue levels in different species of fish. Examination of the data indicates that some species such as channel catfish, white perch, and largemouth bass are consistently among those having the highest residue levels, while bluegills and bullheads are usually among those having the lowest. Also, no definite correlation could be established between lipid content and insecticide residue levels. To date, samples collected at the same station are too few in number to establish definite size, species, or lipid correlations with insecticide residue levels. Perhaps as more data are obtained, statistical evaluation may help in establishing such relationships, or it may be necessary to conduct more intensive studies, such as that conducted in Lake Michigan by Reinert (9) in some areas. A comparison of the 1968 and 1969 residue data for total DDT (DDE + TDE + DDT) and dieldrin are shown in Table 4. Each value represents the station mean of three composite samples. The 1967 data are not included in this table for several reasons. The fall 1967 laboratory cross-checks (5) cast some doubt as to the validity of some of the 1967 data. Also, the species collected at each station in 1968 and 1969 were generally the same, while 1967 collections were more diversified and the species at some stations considerably different from those in the later collections. As can be noted in Table 4. there appears to be a de- crease in total DDT values at some stations between the fall of 1968 and the fall of 1969. In the fall of 1968 mean values for total DDT exceeded 5 ppm. the Food and Drug Administration interim guideline for residues in fish shipped in interstate commerce (15), at eight stations, while in 1969 this value was exceeded at only four stations. Dieldrin residue levels continued to remain high in 1969 at the same stations where high levels were found in 1968. In fact, the proposed FDA action level of 0.3 ppm for Lake Michigan (8) was exceeded at three sta- tions in the fall of 1968 and at five stations in 1969. TTie major conclusions that can be drawn from this study to date are that DDT and dieldrin occurred in almost aU fish samples examined. Residue levels of these insecti- cides remained high at some stations in 1969. Other Pesticides Monitoring Journal organochlorine insecticides were present in fewer samples and at generally lower levels than in previous years. The fish monitoring program has been expanded in 1970 to include an additional 50 stations, located on major waters throughout the United States. It is interesting to note that many States are now participating in our monitoring program and that a number of States have established their own program to monitor fish from additional waters within their State. A cknowledgments Again, we greatly appreciate the assistance of Bureau of Sport Fisheries and Wildlife and State fishery personnel for assisting in fish collections. We also wish to thank the Fish-Pesticide Research Laboratory, Bureau of Sport Fisheries and Wildlife, Columbia, Mo. for its participation in the confirmatory analyses. See Append!] paper. of compounds mentioned in this LITERATURE CITED (1) American Fisheries Society. I960. A list of common and scientific names of fishes from the United States and Canada. Waverly Press, Inc., Baltimore, Md., 102 P- (2) Armour, J. A. and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Ass. Offic. Anal. Chem. 53(4):76 1-768. (3) Dappen, Glen E. 1969. Pattern of usage of chlorinated hydrocarbons and residuals in channel catfish. D. J. Report Project No. F-4-R-14. Job 22, Nebraska Game and Parks Commission, Lincoln, Nebr. (4) Epps, E. A., Frances L. Bonner, L. D. Newsorrt, Richard Carlson and R. O. Smitherman. 1967. Pre- liminary report on a pesticide monitoring study in Louisiana. Bull. Environ. Contamination Toxicol. 2(6):333-339. (5) Henderson, C, W. L. Johnson, and A. Inglis. 1969. Organochlorine insecticide residues in fish. Pesticides Monit. J. 3(3):145-171. (6) Kilborne, R. Stewart. 1970. First results: DDT residues. The Conservationist, Feb.-Mar. New York Conserv. Dep. Albany, N.Y. p. 38. (7) Lichtenberg, James J., James W. Eichelberger, Ronald C. Dressman, and James E. Longbottom. 1969. Pesti- cides in surface waters of the United States — a 5-year summary, 1964-68. Pesticides Monit. J. 4(2):71-86. (8) Mount, D. I. 1968. Report on insecticides in Lake Michigan. Comm. of the Lake Michigan Enforcement Conf., Fed. Water PoUut. Contr. Admin., Duluth, Minn. Mimeogr. rep. 44 p. (9) Reinert, Robert E. 1970. Pesticide concentrations in Great Lakes fish. Pesticides Monit. J. 3(4):233-240. (10) Reynolds, Lincoln M. 1969. Polychlorobiphenyls (PCB's) and their interference with pesticide residue analyses. Bull. Environ Contamination Toxicol. 4(3) 128-143. (;/) Risebrough, R. W., P. Rieche, D. B. Peakall, S. G Herman, and M. N. Kirven. 1968. Polychlorinated biphenyls in the global ecosystem. Nature 220:1098 1102. (12) Stalling, D. L., R. C. Tindle, and J. L. Johnson. Pesti cide cleanup by gel permeation chromatography. Pre sented at 161st national ACS meeting, Los Angeles, Calif. March 29-April 2, 1971. (13) Turner, Neely. 1970. DDT in fish: second report. Circ, Conn. Agri. Expt. Sta. No. 232. 8 p. (14) U.S. Department of Health, Education and Welfare. Food and Drug Administration. 1968. Alkaline hydro lysis. Pesticide Analytical Manual Vol. 1 Section 211 16 D. (15) U.S. Department of Health, Education and Welfare 1969. Food and Drug Administration OflBcial News Release, April 22. TABLE lA. — Organochlorine insecticide residues in fish, fall 1969 ON Number Location Collection Data Organochlorine Insecticides (PPM)» STA-n Species No. OF Fish Average a Q Q g a i pa u Length (Inches) Wt. (Lb.) Lipids (Percent) #1 Stillwater River Old Town, Maine White sucker Yellow perch Chain pickerel 5 5 5 15.0 7.7 13.7 1.5 0.2 0.5 4.22 4.35 1.30 .05 .10 .06 .05 .06 .09 .05 .06 .08 .15 .22 .23 .01 .02 .02 .22 .25 .07 .27 .31 .45 #2 Connecticut River Windsor Locks, Conn. White catfish Yellow perch » White perch 5 3 5 12.0 8.8 10.0 0.9 0.4 0.6 5.94 5.96 5.13 .38 .49 .64 .43 .51 .65 .31 .60 .63 1.12 1.60 1.92 .50 .20 .26 .23 .20 .25 2.16 3.40 5.34 #3 Hudson River Poughkeepsie, N.Y. Goldfish 3 Pumpkinseed Largemouth bass 2 5 5 11.7 6.2 9.2 1.5 0.2 0.5 12.1 3.03 2.93 1.24 .23 1.34 1.91 .39 1.22 .65 .23 .74 3.80 .85 3.30 .04 .05 .16 .51 .09 .27 9.50 2.68 4.82 #4 Delaware River Camden, N.J. White sucker Brown bullhead White perch • 5 5 5 14.7 11.7 9.4 1.4 0.9 0.5 1.85 8.54 6.84 4.82 1.65 10.90 3.45 1.76 8.07 .59 .30 1.30 8.86 3.71 20.27 .35 .25 .56 .20 .18 .18 2.02 4.00 <.10 #5 Susquehanna River Conowingo Dam, Md. Carp Channel catfish Yellow perch 4 5 5 20.0 13.6 9.1 3.5 0.9 0.4 2.38 9.65 3,08 .24 .30 Jl .18 .30 .24 .09 .18 .20 .51 .78 .75 .06 .16 .13 .01 .16 .02 .69 1.21 1.31 Vol. 5, No. 1, Jiwe 1971 TABLE 1 A. — Organochlorine insecticide residues in fish, fall 1969 — Continued DN Number Location Collection Data Organochlorine iNSEcncmEs (PPM)^ Stati Species No. OF Fish Average Q Q 1 a 1 i 5 AND Length (Inches) Wt. (Lb.) Lipids (Percent) i #6 Potomac River Little FaUs, Md. Carp White sucker Largemouth bass 5 S 5 15.1 12.7 10.5 1.9 0.8 0.5 3.76 5.27 0.44 .38 .10 .17 .43 .12 .17 .18 .11 .14 .99 .33 .48 .05 .04 .03 .01 .01 .01 1.04 .56 1.04 #7 Roanoke River Roanoke Rapids, N. C. Redhorse (sucker) Brown bullhead Largemouth bass 5 5 4 19.0 9.6 9.7 2.8 0.4 0.6 5.63 2.34 2.60 .36 .26 .72 .44 .16 .35 .25 .08 .31 1.05 .50 1.38 .12 .03 .10 .02 .01 .01 <.10 .34 <.10 #8 Cape Fear River Elizabethtown, N. C. Gizzard shad Channel catfish Brown bullhead 5 2 5 12.0 21.5 10.8 0.6 3.9 0.6 2.31 8.39 2.09 .27 1.03 .23 .37 1.28 .28 .15 .45 .14 .79 2.76 .65 .05 .07 .02 .10 .20 .05 .86 3.26 .64 #9 Cooper River Summerton, S. C. Spotted sucker Bluegill Largemouth bass 5 5 5 12.6 6.8 13.4 1.2 0.2 1.3 3.49 0.70 5.49 .29 .36 1.63 .19 .14 .68 .14 .24 1.56 .62 .74 3.87 .01 .01 .01 .02 <.10 .73 <.10 #10 Savannah River Savannah, Ga. Carp BluegUl Largemouth bass 4 3 4 15.8 7.3 10.5 1.8 0.3 0.8 3.15 4.39 2.45 .30 .22 .37 .21 .15 .20 .14 .11 .19 .65 .48 .76 .54 .55 .34 .02 .02 .02 .58 .52 1.18 #11 St. Johns River Welaka, Fla. Channel catfish Redbreast sunfish Largemouth bass 5 4 3 11.0 5.8 17.3 0.9 0.2 3.2 7.52 2.38 9.26 .04 .02 .12 .04 .02 .11 .02 .03 .06 .10 .07 .29 .01 .01 .01 .01 .01 .14 .15 .31 #12 St. Lucie Canal Indian town, Fla. Channel catfish ' Bluegill Largemouth bass 1 5 5 27.0 7.6 13.4 10.0 0.4 1.6 10.4 3.45 2.88 42.3 .81 .20 10.40 .45 .21 5.07 .24 .10 57.77 1.50 .51 .06 .01 .02 .03 1.25 .35 .56 #13 Apalachicola River Jim Woodruff Dam, Fla. Spotted sucker Channel catfish Largemouth bass * 5 5 5 17.4 11.6 15.6 2.3 0.9 2.7 4.94 6.18 9.86 .45 .56 1.26 .32 .65 .99 .14 .16 .44 .91 1.37 2.69 .30 .36 1.59 .03 .04 .07 <.10 .69 <.10 #14 Tombigbee River Mcintosh, Ala. Carp Striped mullet Largemouth bass ^ 5 5 5 20.8 16.0 14.0 4.6 1.8 1.5 6.15 8.07 4.53 2.93 4.55 5.85 .74 2.26 2.73 .14 1.12 1.57 3.81 7.93 10.15 .01 .02 .03 .08 .28 .12 <.10 <.10 <.10 #15 Mississippi River Luling, La. Carp Striped mullet Channel catfish « 5 4 5 13.4 14.3 13.0 1.7 1.1 0.9 15.5 7.64 20.1 .06 .08 .09 .16 .20 .22 .07 .30 .15 .29 .58 .46 .13 .39 .12 .99 1.14 1.50 .46 1.39 .66 #16 Rio Grande Brownsville, Tex. Gizzard shad ^ Channel catfish Blue catfish 5 5 5 11.4 15.2 13.5 0.6 0.9 0.7 4.40 4.95 1.64 1.54 2.93 1.87 .73 .11 .08 .13 .07 .04 2.40 3.11 1.99 .50 .01 .06 .06 .14 .22 <.10 <.10 #17 Genessee River Scottsville, N. Y. White sucker Rock bass Walleye 5 5 2 15.1 7.2 17.2 1.5 0.3 1.6 2.95 2.33 4.70 .22 .08 .42 .34 .05 .29 .19 .06 .20 .75 .19 .91 .02 .03 .20 .01 1.54 .39 1.25 #18 Lake Ontario Port Ontario, N. Y. Yellow perch White perch ' Rock bass 4 5 3 10.4 9.5 8.6 0.6 0.5 0.6 7.21 9.68 5.77 .75 1.95 .60 .71 1.47 .59 .67 1.11 .49 2.13 4.53 1.68 .10 .06 .07 Jl .26 .14 7.08 7.68 4.10 #19 Lake Erie Erie, Pa. White sucker Freshwater drum Yellow perch 3 5 5 14.8 13.5 9.4 1.5 1.1 0.4 5.07 6.21 4.64 .43 .26 .35 .51 .28 .31 .42 .31 .42 1.36 .85 1.08 .04 .04 .04 .01 .02 .01 2.48 1.94 233 #20 Lake Huron Bayport, Mich. Carp Channel catfish Yellow perch 5 5 5 16.3 15.9 9.9 2.1 1.5 0.5 11.7 14.8 3.58 .30 .70 .48 .43 .77 .68 .14 .41 .36 .87 1.88 1.52 .02 .04 .02 .04 .29 .02 11.7 4.00 4.02 #21 Lake Michigan Sheboygan, Wis. Bloater a White sucker ^ Yellow perch 5 5 5 12.0 12.1 10.3 0.8 0.7 0.6 26.5 4.36 6.69 3.52 2.30 2.41 .74 3.81 1.47 1.80 2.50 2.56 6.06 8.61 6.44 .37 .03 .06 .08 .20 .05 1.24 14.8 12.6 #22 Lake Superior Bayfield, Wis. Bloater Lake whitefish Lake trout 5 5 4 11.2 16.1 22.0 0.4 1.2 3.0 12.1 13.2 12.0 1.07 .34 .98 .15 .12 .15 .59 .28 .45 1.81 .74 1.58 .02 .03 .02 .03 .05 .02 3.47 1.96 2.84 #23 Kanawha River Winfield, W. Va. Carp Brown bullhead « White crappie " 4 4 5 8.6 11.9 7.6 0.4 0.8 0.2 6.44 5.90 2.08 .08 .17 .03 .19 .40 .25 .09 .09 .27 .66 .37 .02 .02 .02 .31 4.37 2.19 .31 1.20 .83 #24 Ohio River Marietta, Ohio Carp Redhorse (sucker) Channel catfish ' Largemouth bass 4 10 1 5 10.1 7.9 15.7 11.3 1.6 0.04 1.3 0.7 9.92 2.25 8.74 7.11 .39 .17 .75 1.69 .36 .30 1.65 1.76 .21 .19 .80 .74 .96 .66 3.20 4.19 .04 .02 .05 .07 .22 .18 .63 .47 1.73 <.10 6.77 8.07 Pesticides Monitpring Jolirnal TABLE lA. — Organochlorine insecticide residues in fish, fall 1969 — Continued N Number Location Collection Data 1 Organochlorine iNSEcricmES (PPM)i Static Species No. OP Fish Average a a D < (J U 5 AND Length (Inches) Wt. (Ls.) Ln>ros (Percent) 0. 1 #25 Cumberland River QarksviUe, Teiin. Carp Bluegill Largemouth bass 5 5 5 11.8 6.2 11.8 0.8 0.1 0.8 2.59 1.21 1.40 .29 .21 .59 .26 .22 .58 .11 .16 .37 .66 .59 1.54 .02 .03 .02 .03 .02 .02 .89 1.19 3.15 #26 Illinois River Beardstown, m. Carp' Bigmouth buffalo White crappie 5 5 5 15.3 16.7 8.9 1.9 2.7 0.4 5.76 6.22 3.55 1.74 .15 .23 1.86 .17 .27 .96 .11 .15 4.56 .43 .65 .49 .42 .27 .06 .07 .09 11.3 1.21 1.79 #27 Mississippi River Guttenberg, Iowa Carp Bluegill Largemouth bass 5 5 5 13.9 7.1 12.0 1.4 0.4 1.0 3.61 4.51 1.03 .06 .04 .10 .09 .03 .17 .05 .04 .14 .20 .11 .41 .01 .01 .01 .01 .01 .54 .35 1.41 #28 Arkansas River Pine Bluff, Ark. Carp Smallmouth buffalo Flathead catfish 3 4 2 21.0 16.3 21.0 3.8 2.5 4.6 3.60 8.54 6.68 1.20 .46 .82 .41 .46 .80 .30 .50 .60 1.91 1.42 2.22 .01 .12 .03 .19 .08 .02 1.69 2.66 3.88 #29 Arkansas River Keystone Reservoir, Oklahoma Carp Bluegill Largemouth bass 5 5 5 14.5 6.2 15.0 1.5 0.2 2.5 1.59 1.65 3.77 .07 .15 .12 .04 .09 .12 .03 .11 .10 .14 .35 .34 .01 .02 .03 .01 .03 .09 .24 .46 .66 #30 White River DeValls Bluff, Ark. Carp Bigmouth buffalo Chaimel catfish 1 3 4 24.0 15.7 14.5 7.5 2.0 0.8 13.4 10.9 5.83 .75 .62 .49 .58 .60 .23 .08 .51 .19 1.41 1.73 .91 .05 .04 .02 .07 .03 .01 <.10 <.10 <.10 #31 Missouri River Nebraska City, Nebr. Carp Chann'^I catfish Goldeye • White crappie « 5 5 5 5 13.6 13.0 12.5 8.7 1.2 0.8 0.8 0.2 5.46 8.88 13.8 .25 .06 .23 .57 .08 .22 .40 .06 .20 1.22 .20 .65 .02 .03 .08 .02 .01 .05 4.58 .47 1.33 #32 Missouri River Garrison Dam, N. Dak. Carp Goldeye WaUeye 2 5 4 15.2 10.8 17.6 1.6 0.3 1.4 7.05 14.0 5.03 .03 .03 .05 .02 .02 .03 .01 .02 .04 .06 .07 .12 .01 .01 .01 .01 .02 .01 <.10 .18 .22 #33 Missouri River Great Falls, Mont. Redhorse (sucker) Goldeye 5 5 16.9 12.9 2.0 0.5 7.88 12.5 .03 .29 .03 .28 .02 .34 .08 .91 .01 .02 .02 .08 .25 2.35 #34 Red River (North) Noyes, Minn. White sucker Sanger 2 3 16.4 13.7 2.1 0.9 4.23 4.93 .08 .38 .07 .10 .07 .18 .22 .66 .01 .01 .01 .01 .44 1.09 #35 Green River Vernal, Utah Carp Flannelmouth sucker Black bullhead 5 3 3 11.0 19.2 5.4 0.9 2.6 0.2 2.50 8.97 1.51 .04 .13 .03 .08 .28 .02 .07 .19 .01 .19 .60 .06 .01 .01 .01 .02 .83 2.14 .15 #36 Colorado River Imperial Reservoir, Ariz. Carp Channel catfish Largemouth bass 5 3 5 16.9 9.2 10.3 2.5 0.2 0.5 5.30 4.20 1.66 .26 .61 .12 .05 .09 .04 .03 .10 .06 .34 .80 .22 .01 .01 .01 .01 .01 .01 .25 .64 .40 #37 Truckee River Femley, Nev. Carp Brown bullhead Largemouth bass 5 5 5 14.6 10.2 12.3 1.5 0.7 1.1 4.98 4.47 4.77 .13 .08 .19 .06 .07 .18 .05 .06 .10 .24 .21 .47 .01 .02 .01 .02 .03 .54 .71 .98 #38 Utah Lake Provo, Utah Carp Black bullhead White bass 5 5 5 17.0 9.8 10.2 2.1 0.5 0.5 8.51 6.15 2.87 .10 .04 .13 .08 .05 .09 .04 .03 .21 .22 .12 .43 .02 .03 .02 .01 .01 .01 .29 .21 1.04 #39 Sacramento River Sacramento, Calif. Carp White catfish Largemouth bass 5 5 3 12.9 14.1 10.8 0.9 1.3 0.6 4.14 5.56 1.83 .94 .86 .30 .32 .32 .18 .08 .21 .16 1.34 1.39 .64 .01 .01 .01 .01 <.1C <.1C <.1C #40 San Joaquin River Los Banos, Calif. Carp Channel catfish Black crappie 5 5 5 14.7 16.1 10.4 1.3 1.2 0.6 1.99 5.65 6.07 .86 .78 .62 .40 .58 .49 .14 .21 .25 1.40 1.57 1.36 .01 .20 .36 .01 .02 <.1C <.1C <.1C #41 Snake River Hagerman, Idaho Largescale sucker Northern squawfish Rainbow trout 5 5 5 15.0 15.5 13.2 1.4 1.3 1.0 4.77 3.06 6.42 .33 .94 .50 .12 .11 .16 .05 .08 .07 .50 1.13 .73 .05 .01 .04 .01 .01 .34 .7« .55 #42 Snake River Lewiston, Idaho Largescale sucker Smallmouth bass Northern squawfish 5 3 2 15.9 7.0 13.0 2.0 0.3 0.8 11.1 5.35 1.68 .12 .30 .48 .08 .14 .03 .07 .16 .05 .27 .60 .56 .05 .04 .02 .02 .01 .48 <.1C .58 #43 Salmon River Riggins, Idaho Largescale sucker 5 15.2 1.6 4.75 .14 .06 .09 .29 - - .4C Vol. 5, No. 1, June 1971 TABLE lA. — Organochlorine insecticide residues in fish, fall 1969 — Continued DN Number Location Collection Data Organochlorine Insecticides (PPM)i Stati Species No. OF Fish Average Q i 0 0 05 f\ AND Length (Inches) WT. (Lb.) Lipids (Percent) P. 11) #44 Yakima River Granger, Wash. Largescale sucker Black crappie Smallmouth bass 5 S 2 13.3 7.4 10.0 0.9 0.3 0.9 4.60 1,88 4.58 .47 .94 .94 .29 .22 .23 .45 .25 .20 1.21 1.41 1.37 .03 .04 .03 .01 .01 .01 <.10 .88 <.10 #45 Willamette River Oregon City, Oreg. Largescale sucker Chiselmouth White crappie 5 4 5 13.9 10.2 6.9 1.2 0.5 0.2 10.8 2.98 1.76 .15 .14 .22 .25 .09 .22 .14 .07 .10 .54 .30 .54 .09 .01 .08 .12 .03 .07 1.16 .71 1.11 #46 Columbia River Bonneville Dam, Oreg. Largescale sucker Chiselmouth Northern squawfish 5 4 5 16.5 7.9 13.1 2.0 0.3 1.0 5.25 7.67 4.91 .36 .70 1.87 .17 .41 .45 .11 .09 .10 .64 1.20 2.42 .01 .03 .01 .01 .02 .01 1.04 .98 1.19 #47 Klamath River Hombrook, Calif. Klamath sucker Yellow perch Rainbow trout 5 5 5 13.5 8.9 11.6 1.2 0.4 0.8 3.99 3.69 6.09 .02 .03 .08 .01 .03 .03 .02 .03 .03 .05 .09 .14 .01 .01 .01 .13 .28 .27 #48 Rogue River Gold Ray Dam, Oreg. Bridgelip sucker Brown bullhead Black crappie 5 5 4 14.0 9.5 7.0 1.5 0.5 0.3 6.96 3.72 3.90 .35 .86 .40 .38 1.01 .35 .38 .42 .22 1.11 2.29 .97 .02 .02 .02 .02 .02 .03 2.75 3.62 1.83 #49 Chena River Fairbanks, Alaska Longnose sucker Arctic grayling Round whitefish 5 5 5 15.0 11.7 10.0 1.2 0.5 0.2 3.02 4.44 3.72 .54 .25 .27 .52 .16 .31 .10 .21 .34 1.16 .62 .92 .01 .01 .01 .03 .12 .04 3.87 . 1.42 2.62 #50 Kenai River Soldatna, Alaska Longnose sucker Lake trout Rainbow trout 5 5 5 15.5 14.6 13.2 1.5 0.9 0.9 1.53 2.64 5.48 .01 .04 .08 .01 .02 .03 .01 .03 .03 .03 .09 .14 - .01 .01 .01 1.53 2.64 5.48 ' Milligram per kilogram, wet weight — whole fish. ' Lindane residues included with BHC. " Confirmatory analysis performed on this sample. * These species combined into one composite sample for analysis. TABLE IB. — Organochlorine insecticide residues in fish — jail 1969 AND Location Species Organochlorine Insecticides (PPM)!-^ Station Nin^BER Heptachlor Heptachlor Epoxide Chlordane #4 Delaware River Burlington, N.J. White sucker Brown bullhead White perch » 3 - .44 .31 1.75 #6 Potomac River LitUe FaUs, Md. Carp — — .14 #15 Mississippi River Luling, La. Carp Striped mullet Channel catfish ^ — .04 .03 .09 .09 .09 #16 Rio Grande McAllen, Tex. Gizzard shad » Channel catfish Blue catfish .45 .07 .22 ~ 13.5 1.01 1.30 #17 Genessee River ScottsviUe, N.Y. White sucker WaUeye - — .12 .10 #23 Kanawha River Winfield, W.Va. Brown bullhead " White crappie ' — .34 .17 — #24 Ohio River Marietta, Ohio Carp Redhorse sucker Channel catfish * Largemouth bass - - .68 .20 .98 .95 #28 Arkansas River Pine Bluff, Ark. Smallmouth buffalo — .16 — Additional residue values not included in Table 1 . Milligram per kilogram, wet weight — whole fish. Confirmatory analysis performed on this sample by Laboratory F. Pesticides Monitoring Journal TABLE 2. — Results of confirmatory analyses (DDT and PCB residues) Insecticide DDT AND PCB Residues (PPM)' Station Number AND Species Laboratory C Laboratory F 1st 2nd After Gel Run Run Hydrolysis Regular Permeation #2 DDE .64 .62 1.09 White perch TDE .65 .67 .57 DDT .63 .83 .73 PCB 5.34 4.58 #3 DDE 1.24 .98 .87 Goldfish TDE 1.91 1.52 .83 DDT .65 .78 .75 PCB 9.50 4.80 #4 DDE 10.9 6.93 6.77 4.9 6.4 White perch TDE 8.07 4.79 .39 3.2 6.0 DDT 1.30 .94 .73 0.5 .71 PCB <0.10 4.17 •10.0 #12 DDE 42.3 49.3 59.0 •25.4 Channel catfish TDE 10.4 8.14 <0.01 » 11.0 DDT 5.07 4.56 <0.01 »7.1 PCB 1.25 <0.50 .50 #13 DDE 1.26 .82 .96 1.9 1.50 Largemouth bass TDE .99 .65 .05 0.9 .77 DDT .44 .40 .11 0.5 .40 PCB <0.10 .68 — #14 DDE 5.85 5.05 5.99 4.9 Largemouth bass TDE 2.73 2.34 .03 3.2 DDT 1.57 1.98 .24 0.5 PCB <0.10 1.04 M.O #16 DDE 1.54 1.04 1.21 1.0 «.47 Gizzard shad TDE .73 .79 .05 0.9 ».28 DDT .13 .21 .31 .01 .01 PCB .22 3.12 .10 — #18 DDE 1.95 2.29 2.81 White perch TDE 1.47 1.35 .94 DDT 1.11 1.43 .89 PCB 7.68 5.47 #21 DDE 3.52 3.39 3.85 2.2 ».33 Bloater TDE .74 .66 .16 1.8 1.99 DDT 1.80 1.56 .29 1.0 ».38 PCB 1.24 1.67 1.0 «»3.0 White sucker PCB 14.8 ».' 15.0 #23 DDE .17 .27 .26 ».10 Brown bullhead TDE .40 .45 ^9 ' — DDT .09 .18 .13 ».05 PCB 1.20 1.67 s.' 2.25 #24 DDE .75 .62 .66 Channel catfish TDE 1.65 .94 .81 DDT .80 .66 .62 PCB 8.07 5.21 #26 DDE 1.74 •.07 Carp TDE DDT PCB 1.86 .96 IIJ •.12 ».10 •■• 3.8 ^ Milligram per kilogram, wet weight — whole fish. ^ Composed of 1:1 (w/w) mixture of Aroclor 1248 and 1254; confirmed by mass spectrometry. 8 Residue composition confirmed by mass spectrometry. * Confirmed by mass spectrometery to be Aroclor 1254. ^ Separation by method of Armour and Burke (2). " Aroclor 1254. ' Aroclor 1248. NOTE; — = not detected; blank space = not determined. Vol. 5, No. 1, June 1971 TABLE 3. — Results of confirmatory analyses (organochlorine insecticides other than DDT and PCB's) Laboratory Residues in PPM ^ AND Species DiELDRIN BHC Heptachlor Heptachlor Epoxide Chlordane #4 White perch C pa .56 .08 .18 2.5 - - 1.75 1.2 #12 Channel catfish C ps .06 S.04 .03 - — — #13 Largemouth bass C pa 1.59 1.22 .07 .33 — — — #15 Channel catfish C pa .12 1.50 6.0 — .03 .09 .37 #16 Gizzard shad C pa .50 .06 .01 .45 .33 — 13.5 «7.6 #23 White crappie C pa .02 2.19 .06 - .17 - Brown bullhead C .02 4.37 - .34 - #26 Carp C F« .49 .06 - - .48 1 Milligram per kilogram, wet weight — whole fish, a Analysis by Laboratory F, gel permeation method. * Residue composition confirmed by mass spectrometry. * Analysis by regular method and separation by method of Armour and Burke (2). NOTE: — = not detected; blank space = not determined. TABLE 4. — Organochlorine insecticide residues in fish — mean values 1968 and 1969 samples DDT and Metabolites (PPM)' Dieldrin (PPM)i Station Number and Location Fall 1969 Fall 1968 a Spring 1968 = Fall 1969 Fall 1968 = Spring 1968 2 ATLANTIC COAST STREAMS #1 Stillwater River .20 .14 .30 .00 .02 .07 #2 Connecticut River 1.55 3 27 .85 .32 .34 .20 #3 Hudson River 2.65 10.10 2.33 .08 .15 .20 #4 Delaware River 10.95 15.66 16.85 .39 .17 .10 #5 Susquehanna River .68 .98 .92 .12 .10 .03 #6 Potomac River .60 1.38 .32 .04 .04 .07 #7 Roanoke River .98 .90 .42 .08 .05 .11 #8 Cape Fear River 1.40 1.23 .49 .05 .05 .13 #9 Cooper River 1.74 2.59 2.91 .01 .01 .15 #10 Savannah River .63 .59 .40 .48 .68 .38 #11 St. Johns River .15 .26 .21 .01 .00 .01 #12 St. Lucie Canal 3 19.93 3(1.01) 3.69 2.52 .03 .01 .00 GULF COAST STREAMS #13 Apalachicola River 1.66 4.26 .37 .75 .20 .16 #14 Tombigbee River 7.30 11.91 9.03 .02 .04 .58 #15 Mississippi River (La.) .44 1.02 .51 .21 .15 .04 #16 Rio Grande 2.50 5.48 2.79 .17 .00 .24 GREAT LAKES DRAINAGE #17 Gennessee River .62 .91 .70 .02 .05 .01 #18 Lake Ontario 2.78 8.97 2.81 .05 .06 .18 #19 Lake Erie 1.10 1.05 .32 .04 .05 .01 #20 Lake Huron 1.42 1.96 1.52 .03 .01 .02 #21 Lake Michigan 7.04 5.02 4.83 .15 .13 .05 #22 Lake Superior 1.38 .91 .96 .02 .02 .03 10 Pesticides Monitoring Joltrnal TABLE 4. — Organochlorine insecticide residues in fish — mean values 1968 and 1969 samples — Continued Station Number and Location #23 #24 #25 #26 #27 #28 #29 #30 #31 #32 #33 #37 #38 Kanawha River Ohio River Cumberland River lUincis River Mississippi River (Iowa) Arkansas River (Ark.) Arkansas River (Okla.) White River Missouri River (Nebr.) Missouri River (N. Dak.) Missouri River (Mont.) Truckee River Utah Lake DDT and METABOLrTES (PPM)i Fall 1969 Fall 1968 2 Spring 1968 > DIELDRIN (PPM)> Fall 1969 MISSISSIPPI RIVER SYSTEM .43 2.25 1.85 .28 1.35 1.32 1.87 1.23 .83 .72 5.86 HUDSON BAY DRAINAGE INTERIOR BASINS Fall 1968* .02 .03 05 .03 .02 .03 .39 .31 .01 .03 .05 .03 Spring 1968 = #34 Red River (North) .44 1.35 .53 .01 .04 .20 COLORADO RIVER SYSTEM #35 #36 Green River Colorado River .28 .45 .08 .11 .27 .25 .01 .01 .00 .00 .02 .02 CALIFORNIA STREAMS #39 #40 Sacramento River San Joaquin River 2.46 1.58 5.97 1.32 COLUMBIA RIVER SYSTEM #41 Snake River (Hag) #42 Snake River (Lew) #43 Salmon River #44 Yakima River #45 WUlamette River #46 Columbia River .26 1.92 PACIFIC COAST STREAMS #47 #48 Klamath River Rogue River ALASKAN STREAMS #49 #50 Chena River Kenai River 1.15 .06 Milligram per kilogram, wet weight — whole fish. Spring and fall, 1968 data from Henderson et al (5). The fall 1969 mean value (19.93) includes one large (10 lb) channel catfish which contained 57.8 ppm total DDT. The value 1.01 excludes this sample. Vol. 5, No. 1, June 1971 11 Dieldrin Levels in Fish From Iowa Streams^ Robert L. Morris and Lauren G. Johnson ABSTRACT The use of aldrin as an agricultural pest control chemical on Iowa row cropland results in dieldrin levels in the edible portion of adult catfish exceeding FDA action guidelines by up to five times. The elevated dieldrin levels are widespread and appear also in carp and buffalo but not in pan and game fish species such as bass, crappie, bluegill, walleye, and northern pike, probably due in part to different feeding habits. Fish taken from rivers not draining row cropland do not exhibit this phenomenon. Pesticides apparently are adsorbed on soil particles and move into streams during rain or snow-melt runoff on erosion silt. Improved soil conservation practices resulting in reduced sillation must be instigated on a broad scale to keep agri- cultural pesticides on the fields and out of streams. Introduction The State Hygienic Laboratory in conjunction with the State Conservation Commission undertook a study of the concentrations of pesticides in the edible portions of fish in Iowa streams. Locations of streams studied are shown in Fig. L Several species of fish have been analyzed to determine the levels of dieldrin and other durable pesticides in the edible portion of their flesh. Studies show that the per- sistent pesticides used for rowcrop treatment in Iowa have washed off the soil as erosion silt and settled to the bottom in streams across the State (i). Analysis of silt samples taken from river bottoms in Iowa showed that dieldrin is widely distributed in the bottom sediments of rivers draining rowcrop farm land. Concentrations rang- ing up to a maximum of 35 parts per billion (ppb) of dieldrin were measured in these samples (4). FIGURE I. — Locations of streams studied in Iowa From the State Hygienic Laboratory, University of Iowa, Iowa City, Iowa 52240. 12 One study of agricultural runoff water showed that chlorinated hydrocarbon pesticides are reaching Iowa streams both as soluble material and through adsorp- tion on soil particles which make up much of the tur- bidity or silt so prevalent in Iowa rivers (3). In this study approximately half of the chlorinated hydrocarbon pesticide load was carried by the silt which gradually settles to the bottom and remains there for extended periods. A regular program of stream surveillance for chlorinated hydrocarbon pesticides in selected Iowa rivers has been in force for several years and provided a basis for the Pesticides Monitoring Journal selection of many of the sample sites chosen in this study (2). During 1969 and 1970 the Nishnabotna River has consistently had higher dieldrin levels than any other river monitored, with a maximum of 0.068 ppb total (dissolved plus suspended) dieldrin recorded. The Iowa River has had slightly lower levels during this period with a maximum of 0.051 ppb total dieldrin. The other rivers monitored have shown lower dieldrin concentra- tions. The Food and Drug Administration (FDA) action guideline for the maximum permissible concentration of dieldrin in the edible portion of fish is 300 ppb. The Food and Drug Administration has recommended that fish containing dieldrin above this level not be eaten. Sampling and Analytical Methods The fish analyzed in this study were collected by the State Conservation Commission at the sites listed. Fillets were taken from each fish, wrapped in aluminum foil, frozen, and sent to the State Hygienic Laboratory. Composite samples of fillets of fish of the same approxi- mate size from each location were prepared by grinding the fillets in a meat grinder and mixing the ground flesh. Four single fish were analyzed from the Mississippi River, as noted in Table 1, and one composite of 333 Big Mouth Buffalo is listed in Table 2. With the exception of these samples, 90'%' of the com- posites contained from three to six individual fish, with the average being four fish in each composite. The length of the individual fish in any composite did not vary from the average length by more than 1 inch in most cases. A 15-g sample of each composite was analyzed by stand- ard methods (/). Each sample was extracted in a high speed omni mixer with 175 ml of 35% water/ acetoni- trile. The extract was filtered and partitioned into 100 ml of petroleum ether by the addition of 600 ml of water. The petroleum ether was concentrated to 10 ml and placed on a standard Florisil column. The insecticides were eluted from the column in two fractions. The first fraction was eluted from the column with 200 ml of 6% ethyl ether/petroleum ether. The second fraction was eluted with 200 ml of 15% ethyl ether/ petroleum ether. Dieldrin was recovered in the 15% fraction. After concentrating to appropriate volumes the fractions were chromatographed on an F & M Model 400 gas chromatograph equipped with an electron capture de- tector. The temperatures of the injector, oven, and detector, respectively, were 200°C, 175°C and 200°C. The carrier gas flow rate was 50 cc per minute. A polar Vol. 5, No. 1, June 1971 column packed with 6% QF-1:4% OV-1 on 100/120 mesh Gas Chrom Q was used for all quantitation, and a 3% OV-1 on 100/120 mesh Gas-Chrom Q column was used for confirmation. The dieldrin standard used for quantitation was 99 + % HEOD. The dieldrin concentration in Tables 1, 2, 3 and 4 are on a wet-weight basis, and no corrections based on re- covery factors were used. Residts and Discussion Species of fish feeding on the bottom area appear to have aggregated larger amounts of dieldrin, a degrada- tion product of aldrin used for com rootworm treat- ment, than have species whose feeding habits are less directly related to the bottom silts. Catfish have evidenced the highest dieldrin levels (up to 1600 ppb) as shown in Table 1, and other rough fish such as buffalo, carp, and carp suckers have been some- what lower (see Table 2). Pan and game fish, shown in Table 3, have a much lower dieldrin content than catfish and are well below the Food and Drug Administration action guideline. The Coralville Reservoir was chosen as a sampling loca- tion for these fish because of the high level of dieldrin in the catfish and the ready availability of these other species. The Mississippi River was also selected because of the importance of commercial fishing on this river. A definite relationship exists between the dieldrin con- tent of catfish and their age or size. Residues in catfish under 15 inches in length are below maximum accept- able dieldrin concentrations in most locations. This is probably due to increased oil content in older, larger catfish and of course to longer exposure in their con- taminated environment. A distinct relationship also exists between river latitude and dieldrin content in catfish, probably due to accumu- lated siltation as rowcrop draining streams proceed southward. This is particularly well illustrated in the Iowa, Mississippi, and Nishnabotna when the dieldrin concentrations in catfish of comparable size are com- pared at different locations on the rivers. Impounding of a given stream tends to produce conditions conducive to dieldrin buildup in bottom feeders as silt settles out over broader areas of feeding habitat. Streams in northeast Iowa draining non-rowcrop areas and v'hich carry far less silt load apparently are not producing elevated pesticide levels in catfish or other species. 13 Catfish taken from the Mississippi, which receives drainage from the interior streams such as the Iowa- Cedar, Skunk, and Des Moines Rivers, indicate levels slightly above acceptability in its lower Iowa reaches, but catfish caught above the Muscatine-Davenport area are well below the Food and Drug Administration action guideline. Therefore, it seems fair to say that larger catfish over the entire State have accumulated abnormally high dieldrin levels in the edible portion with the exceptions of the upper Mississippi, the northeast Iowa streams, and the northern reaches of the interior streams. Pan and game fish show no evidence of pesticide concentrations approaching significance to date. Catfish caught in the Missouri River also do not appear to have this problem. in Table 4. These split sample values show excellent correlation and validate the analytical data on which the conclusions of this paper are based. FDA was burdened with another analytical problem at the time we requested their assistance and were able to handle only two composites. We chose to submit the two in the action guideline critical concentration range. Since turbidity correlates with pesticide levels in streams, better soil conservation practice, holding the agricultural chemicals on the fields where they belong, would appear to be the most logical method of improving the problem. Reduction of pesticide use to a minimum level consistent with farm product economics should also be immedi- ately instigated. Residues of other chlorinated hydrocarbon insecticides were detected in the samples but at levels significantly below the dieldrin concentrations. Traces of DDT and its metabolites, heptachlor epoxide, aldrin, and gamma and alpha chlordane were detected in many of the samples. One catfish sample from the Coralville Reservoir which contained 1440 ppb dieldrin also had 910 ppb aldrin in it. However the ratio of dieldrin to aldrin was generally closer to 10 to 1 in those samples where aldrin was detected. Replicate samples of actual fish composites were sent to the FDA laboratories in Kansas City and to the Shell Development Company Pesticide Residue Laboratory in Modesto, Calif., for confirmation on a triple blind per- formance evaluation basis, and the results are shown Because there are several pesticide formulating and blending plants and numerous applicators scattered around the State, the contribution of these potential sources of dieldrin directly into the aqueous environment as industrial waste is also being investigated. A cknowledgments The authors gratefully acknowledge the contribution and assistance of Mr. Garland Reed of the FDA Re- gional Laboratories in Kansas City, Dr. Paul Porter of Shell Development Corporation, Modesto, Calif., and Mr. Harry Harrison of the Iowa State Conservation Commission, Des Moines, Iowa. See Appendix for chemical names of compounds mentioned in this paper. TABLE 1 . — Results of analysis for dieldrin residues in edible portion of catfish (composite samples) Date Sample Average River Location Collected Length Dieldrin (1970) (Inches) (PPB) East Nisbnabotna Shenandoah 7/6 15.7 940 Shenandoah 7/6 11.5 400 Nishnabotna Hamburg 7/6 16.5 1600 Hamburg 7/6 11.7 820 Iowa LeGrande 8/20 17.5 360 Marengo 8/17 17.0 680 Marengo 8/17 9.5 195 Coralville Reservoir 8/10 24.0 1440 Coralville Reservoir 7/17 23.0 820 Coralville Reservoir 10/14 21.5 920 Coralville Reservoir 7/13 16.1 720 Coralville Reservoir 7/8 15.5 480 Coralville Reservoir 7/8 10.0 370 14 Pesticides Monitoring Journal TABLE 1. — Results of analysis for dieldrin residues in edible portion of catfish (composite samples) — Continued Date Sample Average RrvEE Location Collected Length Dieldrin (1970) (Inches) (PPB) (^ mile below Coralville Dam) 8/17 20.0 1250 (% mile below Coralville Dam) 8/21 20.2 885 (% mile below Coralville Dam) 8/17 10.0 210 Fredonia 8/17 18 730 Nodaway Clarinda 8/20 16.7 1100 Cedar Mt. Vernon 8/31 18.0 580 Rochester 8/20 19.4 530 Des Moines Red Rock Reservoir 8/24 16.6 570 Keosauqua 8/27 16.6 270 Mississippi Dubuque, Pool 12 8/22 20 73 Sabula, Pool 13 6/15 18 52* Clinton, Pool 14 6/15 14 79* Camanche, Pool 14 6/15 14 360* Camanche, Pool 14 6/15 14 110* Muscatine, Pool 17 8/22 12 230 Burlington, Pool 19 8/22 23 435 Pool 20, Below Keokuk 10/19 14.6 380 Pool 20, Below Keokuk 10/19 12.3 260 Little Sioux Correctionville 8/22 16.9 340 Skunk Oakland Mills 9/9 10.8 325 Wapsipinicon Independence 9/16 15.5 110 WheaUand 8/27 15.7 325 Lake MacBride Lake MacBride 9/18 17.6 240 Lake MacBride 9/18 15.7 230 Big Sioux Sioux City (10 miles above) 8/22 17.5 230 Maquoketa Maquoketa 9/14 19.1 220 East Grande Davis 8/20 16.3 200 Boyer West Leveland 8/22 10.2 170 Chariton Rathbun Reservoir 9/1 13.0 140 Turkey Elkader 9/3 16.2 60 MillviUe 8/27 16.5 78 Lake AHerton Lake AUerton 8/19 15.8 39 Missouri Sioux City 8/22 15.0 34 'Single fish. TABLE 2. — Results of analysis for dieldrin residues in edible portion of rough fish (composite samples) RrvER Location Species Date Sample Collected Average Length (Inches) Dieldrin (PPB) Iowa Coralville Res. Big mouth buffalo 11/7/69 18.0 840 Carp 11/7/69 20.4 214 Carp sucker 11/7/69 14.4 313 Big mouth buffalo 6/24/70 17.5 782* Lake MacBride Lake MacBride Big mouth buffalo 11/7/69 22.2 720 Carp 11/7/69 22.0 135 Des Moines Red Rock Res. Big mouth buffalo 6/10/70 17 520 Carp 6/10/70 18 560 Mississippi Guttenberg, Pool II Big mouth buffalo 11/3/69 18.5 28 Carp 11/3/69 17.5 15 •Composite of 333 fish Vol. 5, No. 1, June 1971 15 TABLE 3. — Results of analysis for dieldrin residues in edible portion of pan and predator game fish (composite samples) River Location Species Date Sample Collected Average Length (Inches) Dieldrin (PPB) Iowa Coralville Res. Largemouth bass 11/7/69 14.6 35 Black crappie 11/7/69 9.2 12 Largemouth bass 9/28/70 15.6 80 White crappie 9/29/70 11.8 59 Black bullhead 9/29/70 12.3 98 Blue gill 9/28/70 6.1 34 Walleye 9/29/70 13.3 24 Northern pike 9/29/70 22.0 54 Lake MacBride Lake MacBride Largemouth bass 11/7/69 10.6 18 Bluegill 11/7/69 9.6 14 Mississippi Guttenberg, Pool II Walleye 11/3/69 25 41 Guttenberg, Pool n Walleye 11/3/69 25.2 20 Guttenberg, Pool n Walleye 11/3/69 27 33 Sabula, Pool 13 Largemouth bass 10/12/70 15.0 11 Montpelier, Pool 16 Largemouth bass 10/13/70 13.4 39 Burlington, Pool 19 Largemouth bass 10/15/70 15,3 41 Sabula, Pool 13 White bass 10/15/70 13.6 91 Montpelier, Pool 16 White bass 10/13/70 13.7 175 Burlington, Pool 19 White bass 10/15/70 9.8 110 Burlington, Pool 19 Walleye 10/15/70 16.5 60 TABLE 4. — Results of analysis of replicate interlaboratory catfish samples Sample Number Date Sample Collected Dieldrin Residues in PPB River FDA Shell SHL* East Nishnabotna Nisbnabotna Nishnabotna Iowa 1 2 3 4 8/6/70 8/6/70 8/10/70 8/10/70 398 592 440 630 1030 1400 470 620 980 1440 •State Hygienic Laboratory TABLE 5. — Identification of fish analyzed Common Name Scientific Name Channel catfish Ictalurus punctatus (Rafinesque) Big mouth bufialo Ictiobus cyprinellus (Valenciennes) Carp Cyprinus carpio Linnaeus Carpsucker Carpiodes sp. Largemouth bass Microplerus salmoides (LacipSde) Black crappie Pomoxis nigromaculatus (LeSueurr) White crappie Pomoxis annularis Rafinesque Black bullhead Iclalurus melas (Rafinesque) BluegiU Lepomis macrochirus Rafinesque WaUeye Stizostedlon vilreum (MitcheU) Northern pike Esox Lucius Liimaeus White bass Roccus chrysops (Rafinesque) 16 LITERATURE CITED (J) U. S. Department of Health, Education, and Welfare, Food and Drug Administration. 1968. Pesticide An- alytical Manual Vol. 1, Sec. 211.13g, 211.15, and 212.13a. (2) Johnson, L. G.. and R. L. Morris. 1971. Chlorinated hydrocarbon pesticides in Iowa rivers. Pesticides Monit. J. 4(4):216-219. (3) Morris, R. L., and L. G. Johnson. 1970. Pollution problems in Iowa. In: Water resources of Iowa, edited by P. J. Horick. Available from the Iowa Acad, of Sci. Univ. of Northern Iowa, Cedar Falls, Iowa, p. 89-109. (4) Morris, R. L. and L. G. Johnson. 1970. Pesticide levels in fish and bottom silts. Rep. No. 71-10, State Hygienic Laboratory, Univ. of Iowa, Iowa City, Iowa. Pesticides Monitoring Journal PESTICIDES IN SOIL Insecticide Usage and Residues in a Newly Developed Great Plains Irrigation District^ Herbert Knutson^ A. M. Kadoum^ T. L. Hopkins', Glen F. Swoyer°, and T. L. Harvey* ABSTRACT Surveys of insecticide use from 1960-69 indicated generally light application of insecticides throughout the District before irrigation started in 1963: after irrigation, use of organophos- phates and carbamates increased greatly. Soil and foliar applications of insecticides were made an- nually from 1965-69 at approximate maximum recommended rates to a 20-acre, irrigated cornfield receiving 30 to 42 inches of moisture per year. Soil applications of diazinon and parathion at planting time in May residted in no detectable soil or foliage residues in samples taken after 1.5 to 2.5 months. Similar applications of heptachlor resulted in total heptachlor-heptachlor epoxide residues from 0.16 to 1.30 ppm at harvest without successive yearly accumulation: about 95% of the combined residue disappeared in a year. Similar applications of aldrin re- sulted in aldrin-dieldrin residues of 0.28 to 1.10 ppm without successive yearly accumulation; about 80 to 90% of the combined residue disappeared in a year. Dieldrin residues at hanest and during winter tended to increase from year to year in relation to aldrin. A single, heavy soil application of aldrin resulted in 10 to 20 times more dieldrin than aldrin during the second year. Aldrin was well below 0.01 ppm. the third year, but dieldrin remained at 0.1 to 0.2 ppm during the 3 remaining years studied. Heptachlor and aldrin residues were not detected in the Contribution No. 1035, Department of Entomology; No. 252, Ft. Hays Branch, Kansas Agricultural Experiment Station; and No. 44, Kansas Water Resources Research Institute, Manhattan, Kans. 66502. Department of Entomology, Kansas Agricultural Experiment Station, Kansas State University, Manhattan, Kans. 66502. ' Ft. Hays Branch Station, Hays, Kans. 67601. Vol. 5, No. 1, June 1971 foliage following soil treatment, but traces of heptachlor epoxide or dieldrin were sometimes detected. Diazinon foliar sprays applied in early August persisted in the foliage at harvest at 0.02 to 0.05 ppm, endrin at 0.06 to 2.43 ppm, and methyl parathion at 0.0 to 0.07 ppm. No residues were detected in the grain following either soil or foliage applications. Capped wells, from 13 to 71 feet deep, contained no residues at the 0.1 ppb level, indicating no vertical penetration from surface applications (penetration did not exceed 12 inches) and no lateral contamination of ground water from adjacent land. Surface water samples from the Smoky Hill River and the Cedar Bluff Reservoir contained no residues at the 0.1 ppb level. Aldrin, dieldrin, endrin, heptachlor, heptachlor epoxide, and DDE were infrequently detected in surface waters at trace levels f< 0.1 ppb). Introduction A unique opportunity to study insecticide usage and resulting residues was provided as the Cedar Bluff Irri- gation District in Central Kansas developed from an area of dry-land farming practices with little insecticide usage to land with intensified crop production and in- secticide usage. Knowing the distribution, magnitude, and persistence in the ecosystem of insecticide residues resulting from normal agricultural practices during such a transition from dry-land farming to irrigation could help to evalu- ate the long range residue potential of these chemicals and to anticipate and possibly prevent negative environ- mental effects. 17 A survey of pesticide usage in the Disirict area was made, both before and after irrigation practices were initiated, to determine the types and quantities of pesti- cides applied. In addition, insecticide residue studies were made on an experimental irrigated field. Annual ap- plications of persistent and nonpersistent insecticides most likely to be used on crops in the District were made at approximate maximum rates recommended for both soil and crop foliage. Insecticide residues were de- termined in soil, corn foliage and grain, and in ground and surface water at intervals throughout the growing season for several consecutive years. Also, river and reservoir waters sampled from stations in the District were analyzed for insecticide residues. The District currently consists of 6600 acres located along the Smoky Hill River from the Cedar Bluff Dam eastward, largely in Ellis County (Fig. 1). Irrigation was begun in June 1963. The District is representative of many areas already irrigated and others to be irrigated in the Central Great Plains. Leonard (13) has published a geohydrologic description of the District. FIGURE 1. — Treated cornfield in Cedar Bluff Irrigation District, Ellis County, Kans. — west boundary of SW 1/4, SE 1/4, Sec. 31, T 14S, R 19W KANSASi \ ^ % ^ ,£22ii fr" '^""^ \^ I 1 Bench 1 Y^ i 1 B,r>5r, J \ -etiKt.la. B.rch 31. Bench 4b 1 L County Road O Sorfaci O Wells Bench 1. Soil treatment — diazinon, foliar treatments — diazinon and endrin. Bench 2. Soil treatment — heptachlor. Bench 3a. Soil treatment — parathion, foliar treatment — methyl para- thion. Bench 3b. Soil treatment — aldrln. Bench 4a. Soil treatment — aldrin, heavy in 1965. Bench 4b. Untreated. Insecticide Use Survey Quantities of insecticides applied in the Cedar Bluff Irrigation District from 1960-69 were estimated from data collected from 48 farmers, or 80% of the farm units, operating within the District. Some operators' land was predominantly outside the District, but because we 18 were concerned with pesticide use in the District, these farm units were eliminated. A local resident, well ac- quainted with the area, interviewed each grower an- nually from 1964-69. In 1964, data were collected for 1960-64. Detailed information was obtained on quanti- ties of all pesticides used, but only insecticides are re- ported here (Table 1). Insecticide use was recorded in four categories — application to field crops, seed treat- ments, use on cattle, and use in and around homesites (including farm buildings, gardens, lawns, trees, etc.). The last category (homesites) was omitted from the total compilation because, unlike the other three, the insec- ticides and amounts used could not be ascertained re- liably. Homesites probably contributed little to total in- secticide use since they occupy considerably less than 1 % of the District area. Insecticides used, reported by acres or cattle treated, were converted to pounds of active ingredient, assuming maximum rates recommended by manufacturers. The total insecticide usage reported from 80% of the irrigation district growers from 1960-69 was 10,635 lb (Table 1). Of the total 99%, or 10,514 lb, was applied to field crops. Applications to cattle and seeds. 78 and 43 lb, respectively, were combined in the table with field applications. However, all DDT and toxaphene, and most of the methoxychlor, were reported for cattle. The 10-year totals for seed treatment insecticides were diel- drin, 35 lb; malathion, 6 lb; and methoxychlor, 2 lb. The organophosphorus and carbamate insecticides were reported at 8,376 and 1,865 lb, respectively, compared with 376 lb for the organochlorine compounds. Most of the organochlorines (70%) were applied during the first 5 years: nearly all of the organophosphates (98%) and carbamates (100%) were reported during the last 5 years of our survey. Increased use of insecticides (organophosphates and carbamates) closely parallels increases in irrigation and corn acreage. Insecticide use averaged 2,905 lb/year during 1967-69 (94% to control corn rootworms). Three insecticides (diazinon, phorate, and carbaryl) accounted for 90% of the total reported. Field Study An irrigated, 28.5-acre cornfield was used for intensive study; the cultivated area was 19.51 acres (Fig. 1). The field consisted of six separate benches each subdivided into approximately 1-acre blocks for replicate samples. Bench 1 had three blocks, because it was narrower and shorter than the remaining five benches, each having four blocks. The soil in the experimental field is a silty clay loam. It is characteristic of the Central Great Plains region, al- though it contains slightly more clay than is typical of the Pesticides Monitoring Journal TABLE 1. — Calculated pounds of insecticides used for field crops, cattle, and seed treatments in the Cedar Bluff Irrigation District for 10 years, 1960-69 iNSEcncroEs Insecticide Use In Pounds • 1960 1961 ORGANOCHLORINES Aldrin 92 125 75 14 306 Dieldrin 4 4 4 7 6 3 1 1 3 2 35 DDT 3 3 3 4 4 17 Methoxychlor 1 1 2 2 3 2 2 13 Toxaphene 2 Total 7 7 8 104 139 5 79 18 5 4 376 ORGANOPHOSPHATES Diazinon 147 545 817 1760 679 14 3962 Phorate 165 1448 2205 3818 Fensulfothion 187 30 217 Parathion 20 45 126 191 Malathion 2 1 2 8 2 156 171 Ronnel 5 4 1 10 Cruf ornate 2 2 4 Dioxathion 1 1 1 3 Total 149 567 824 1938 2364 2534 8376 CARBAMATES Carbaryl Buxten 19 426 947 350 123 1742 123 Total 19 426 947 473 1865 PLANT DERIVATIVES Pyrethrins Rotenone 1 I 1 1 1 1 1 4 1 4 2 10 8 Total 1 1 1 1 2 1 5 6 18 GRAND TOTAL 8 8 9 105 290 573 927 2388 3316 3011 10,635 Values represent 80% of the farm units. Some operators' land was predominantly outside the District; this 20% omitted. immediate area. Samples from each bench had an aver- age pH of 6.4 and ranged from 6.0 in Bench 1 to 6.6 in Bench 3a. Organic matter averaged 1.65% and ranged from 1.0% in Bench 3a to 2.0% in Bench 4a. Overland runoff from higher land north of the experimental field is intercepted by the main irrigation canal. Water is conducted by siphon to the benches from the lateral ditch along the western boundary of the field. Average rainfall is about 23 inches per annum, of which 75% normally occurs in localized convective storms during the growing season, April through September. Measure- ments of rainfall and irrigation water for 1965-69 are given in Table 2. Rainfall measurements in 1965 through March 1966 were taken at the dam; the amounts for October 1967 through March 1968 were recorded from the nearest rain gauge. Other rainfall records were taken at the edge of the experimental field. Water on the field varied from 30 to 42 inches during the years 1965-69. Detailed descriptions of water percolation, soil structure at various depths, and other characteristics of the study area are given by Leonard (72). Vol. 5, No. 1, June 1971 TABLE 2. — Rainfall and applied water on treated experimental field during water years 1965-69 Rainfall Irrigation Year Period (INCHES) (INCHES) Total 1965 4/1-9/30 19.7 18.8 38.5 10/1/64-9/30/65 23.2 18.8 42.0 1966 4/1-9/30 17.2 13.7 30.9 10/1/65-9/30/66 20.2 13.7 33.9 1967 4/1-9/30 23.4 4.3 27.7 10/1/66-9/30/67 26.0 4.3 30.3 1968 4/1-9/30 15.1 21.6 36.7 10/1/67-9/30/68 16.3 21.6 37.9 1969 4/1-9/30 26.3 8.6 34.9 10/1/68-9/30/69 32.8 8.6 41.4 TREATMENT Insecticides were applied to the experimental field to control com rootworms, fall armyworms, and other in- sects. Treatments were made annually to Benches 1, 2, 3a, and 3b, and once in 1965 to 4a at approximately four times the maximum approved rate (Table 3). In- secticides applied to soil were diazinon (Bench 1), heptachlor (Bench 2), parathion (Bench 3a), and aldrin 19 TABLE 3. — Dates of insecticide treatment and sampling of soil, foliage, and grain on an experimental irrigated cornfield Dates of Treatment and Sampling ' Treatment and Samples 1965 1966 1967 1968 1969 1970 Soil, pretreatment AprU 30 AprU 28 April 4 May 1 — April 15 Soil, posttreatment May 10-11 May 12 May 15-16 May 25 May 17 — Foliage, pretreatment — July 29 Aug. 1 Aug, 14 — — Foliage, posttreatment Aug. 19 Aug. 3 Aug. 10 Aug. 15 Aug. 5 — Harvest time — dates that soil. Sept. 29 Sept. 9 Sept. 12 Oct. 4 Oct. 23 — foliage, and grain were Oct. 10 Oct. 25 sampled All benches receiving different insecticide treatments were treated and sampled the same day; untreated control benches were sampled the same dates. (Bench 3b). In addition, both diazinon and endrin were applied on foliage in Bench 1 and methyl parathion on foliage in Bench 3a annually. Benches 4a and 4b were controls on air- and water-borne contamination; how- ever, aldrin was applied on 4a. Soil treatments were de- posited in a 7-inch band in the drill row with a granular applicator attachment to a 4-row, 30-inch planter. Aldrin was sprayed on Bench 4a in 1965 as a diluted emulsifiable concentrate and was disked in immediately. Foliar applications were by plane during early morning at silking time. All insecticides were applied as emulsions in 2 gallons of water per acre. SAMPLING Soil samples (Table 3) generally were taken at the follow- ing times: (1) early in the spring before soil treatment, (2) following planting and accompanying soil treatment, (3) immediately before foliar treatment, (4) after foliar treatment, and (5) at harvest of silage and mature grain. Samples consisted of soil cores % inch in diameter taken to a depth of 6 inches. In 1965 and 1966 duplicate soil cores were taken in planted rows containing granules, and duplicate soil cores were also taken midway between the granule-treated rows. This totaled 100 cores per block taken at 25 approximately equidistant sampling points. For 1967-70 the number of cores was reduced to one core in planted rows and one midway between the granule-treated rows, totaling 50 per block. Core samples were taken along a straight diagonal line across each block, in a zig-zag design across the bench. Cores from each block were composited. Residue data are the averages of six to eight replicate analyses of a composite from each of the three blocks in Bench 1 and averages of similar replications of each comfKKite from each of the four blocks in the remaining benches. Data derived from soil samples taken and composited immediately after planting do not accurately reflect the distribution of soil residues in the bench. At planting, the granules are concentrated in the rows. Irrigation and soil manip- ulation during the growing season tended to disperse the granules, and fall plowing further dispersed them so that the pretreatment data from the following spring are more representative. 20 Additional soU cores, 2 inches in diameter and 47 to 52 inches deep, were taken during November 1968 to de- termine insecticide penetration. Com and sorghum foliage samples were taken on ap- proximately the same diagonal lines as soil samples, with 12 approximately equidistant sampling points per block. One whole plant cut at ground level was taken in 1965, 1966, and 1967 at each sampling point. Sub- sequently, plants were divided into four equal parts with V4 of a plant retained from each sampling point. Com- posited samples of plant quarters represented 1 2 different plants and approximated the mass of 3 plants per block. Composite foliage samples from each block were bagged individually with dry ice for transit to the laboratory. To obtain samples of ground water, small-bore wells were drilled in the berms separating the graded benches prior to irrigation (Fig. 1) by the U. S. Geological Survey in cooperation with the Kansas State Department of Health and the Kansas State Geological Survey. Depths of the wells ranged from 1 3 feet in the northwest comer to 71 feet in the southern row. They were drilled to bedrock and remained capped except when being sampled. Asphalt cones were installed around well pipes at ground level to seal out rain water. During the first 2 years, each well was equipp>ed with an individual sampling hose, and water was removed with an attached suction hand pump. Initially, the samples were collected in glass carboys and later in 1 -gallon brown glass bottles, both with aluminum foil-covered stoppers. The pump and exp»osed hose were cleaned with 1 gallon of distilled water between each sampling to minimize cross con- tamination. During the last 2 years, samples were generally obtained by a 1 -gallon bail made with 10 feet of 1%-inch o.d. plastic pipe fitted with a l'/2-inch diameter brass check valve on the leading end. TTie opposite end was fitted with a bracket and 70 feet of light chain for lowering and raising the bail. Water was released through the check valve into a collecting can and poured into sample bottles. After each sampling, the bail was thoroughly Pesticides Monitoring Journal rinsed in a 12-foot long, 2-inch i.d. plastic tube of distilled water. The chain and collecting can were thoroughly washed with acetone. Buckets sunk to ground level in the lowest portion of the exi>erimental field served to collect runoff samples after field application of insecticides (Fig. 1). Water and silt samples were also taken on the Slmoky Hill River just above and below where drainage from the experimental field occurred; in the Cedar Bluff reservoir in a cove near the dam; and, when feasible, where water entered the test field from the irrigation canal. Water samplings of both well and surface water were taken 18 times during 4 years: May 12, June 14, July 16, August 16, September 14, and October 19 in 1966; April 14, May 16, June 30, August 22, September 12, and October 25 in 1967; May 1, August 14, October 14, and November 24 in 1968; and May 17 and August 5 in 1969. ANALYTICAL PROCEDURES TTie soil composites from each block were processed by screening through a "4 -inch mesh sieve and then mixed thoroughly. Extreme care was used to prevent contami- nation. All equipment was thoroughly washed with de- tergent and water and rinsed with acetone after proces- sing replicates from each bench. A subsample of ap- proximately 400 g was taken from each composite for analysis. The 400-g subsamples were divided into six to eight duplicate moist soil samples, weighing 50 g each. These were placed in quart mason jars to which 100 ml of isopropyl alcohol and 1 00 ml of benzene were added. The mixture was shaken vigorously for 20-30 minutes on a mechanical shaker, decanted into a separatory funnel, and the two layers allowed to separate. The lower aqueous layer was drained off and discarded. The benzene extract was dried with anhydrous sodium sulfate and then concentrated under vacuum at 35°-40°C just to dryness. The residue was then taken up in hexane for cleanup and gas chromatographic analysis. All solvents were glass-distilled and purified for gas chromatographic analysis. The plant samples from each block were cut into Vi- to %-inch lengths, subsequently mixed, and an approxi- mate 400-g subsample taken from each composite for analysis. Duplicate samples of foliage or grain, each weighing 40 g, were blended in an explosion-proof Waring blendor or Omnimixer with 200 ml of acetoni- trile at high speed for 1-2 minutes. The extract was con- centrated to about 20 ml under vacuum at 35-4(j'C and then transferred to a 500-ml separatory funnel, using small rinses of hexane totaling 20 ml. The mixture was shaken thoroughly with an additional 200 ml of water Vol. 5, No. 1, June 1971 for 1-2 minutes. After the two phases separated, the lower aqueous layer was discarded and the upper hexane layer collected in a 50-ml centrifuge tube for cleanup and gas chromatographic analysis. Water samples were stored at 40°F until analyzed for diazinon, parathion, methyl parathion, malathion, en- drin, aldrin, dieldrin, heptachlor, heptachlor epoxide, p,p'-DDE, o,p'-DDT, and p,p'-DDT. Two-liter samples of water in 3-gallon glass bottles were extracted with 200 ml of 50% benzene in hexane, shaken vigorously for 20 minutes on a mechanical shaker. The liquid phases were separated and the lower aqueous layer dis- carded. The solvent extract was concentrated under vacuum at 35°-40°C just to dryness and the residue dis- solved in hexane for cleanup and gas chromatographic analysis. Cleanup methods for all extracts, recoveries of insecti- cides from fortified samples, and sensitivities by gas chromatographic analysis are reported by Kadoum (9,10). Insecticide residues were not corrected for re- covery with the exception of methyl parathion, since re- covery from fortified samples was essentially 100%. The insecticides were separated and detected by electron- capture gas chromatography using a 6-foot glass column, packed with 3% DC-1 1 on 60/80 mesh silanized Gas Chrom P (Applied Science Labs, State College, Penn.). Operating conditions were as follows: nitrogen carrier gas flow rate, 36 ml /minute; column temperature, 200° C; injection temperature 240°C; detector cell, 220°C; volume of extract injected, 4 yul. Diazinon and parathion soil treatments Table 4 contains the results of analyses of soil samples taken immediately after annual applications of diazinon and parathion to Benches 1 and 3a, respectively. No detectable residues of either compound were found in samples obtained 1.5 and 2.5 months after treatment. TABLE 4. — Residues of diazinon and parathion in soil of an irrigated cornfield (Bench 1 and 3a, respectively) receiving annual applications at approximate maximum recommended rates Diazinon (Bench 1) Parathion (Bench 3a) Year Treatment Rate (lb/acre) Average Residues IN PPM ' Treatment Rate (lb/acre) Average Residues in PPM ' 1966 1967 1968 1969 0.89 0.93 2.05 1.03 0.69 3.34 0.85 0.90 1.40 0.79 1.01 0.80 0.89 4.07 0.50 133 Residues in samples taken immediately after application. Samples obtained 1.5 to 2.5 montlis after treatment contained no detectable residues. 21 The only explanation we have for high residues in 1967 samples taken immediately after planting (3.34 ppm, diazinon and 4.07 ppm, parathion) is the possible ir- regular release of granules at sampling points in the drill row. Organophosphorus and carbamate insecticides are re- placing the more persistent organochlorine compounds as soil insecticides for corn rootworm control. Diazinon and parathion may be generally considered typical in behavior of the newer organophosphorus soil insecti- cides. Both are essentially degraded within 2 months following application to irrigated soil. Getzin (4) ob- served that about 50% of the diazinon present in moist soil stored in sealed containers disappeared in 4 weeks but 10 to 15% remained at 20 weeks. Some studies have shown that microbial metabolism can be important in soil degradation of diazinon particularly in submerged soils (20,21) as would occur periodically during the ir- rigation season. Other studies did not find microbial de- gradation to be important in diazinon breakdown (5.6). although diazinon degradation increased with both in- creased temperature and moisture levels, with tempera- ture considered more effective (5). Bioassays of soils treated with diazinon and parathion also have indicated rapid degradation. Harris (7) found that diazinon and parathion both disappeared in 2 to 4 weeks in sandy loam soil but jjersisted slightly longer in muck soils with high organic matter content. Diazinon soil treatments at 3 ppm showed little or no toxicity after 30 days (19). This degradation rate compares closest to soil concentrations from maximum recom- mended rates used in the study reported here. Laboratory studies (15) showed that parathion is most persistent in dry soil and least persistent in high moisture soils and that microorganisms rapidly degrade parathion to nontoxic products. Getzin and Rosefield (6) also ob- served that parathion, unlike diazinon, was degraded more rapidly in nonsterile soil than in autoclaved soil. High moisture favoring chemical hydrolysis and mi- crobial degradative metabolism should cause minimal persistence of the organophosphorus insecticides ap- plied to irrigated fields. Also, soil temperatures, solar irradiation, and organic matter content of soil influence disappearance rates. Heptachlor soil treatments Heptachlor soil treatments at planting time were made annually to Bench 2 at approximately 0.5 lb per acre except for 1.2 lb per acre in 1969. Initial soil concentra- tions of heptachlor varied from 0.25 to 1.68 ppm while those of heptachlor epoxide varied from 0.10 to 1.25 ppm. Total heptachlor-heptachlor epoxide soil residues at harvest varied from 0.16 to 1.30 ppm with no cumu- lative trend (Table 5). Approximately 40% of the total spring posttreatment residue (average 4-year data) re- mained in the soil at harvest after 4 months. Heptachlor epoxide varied from 16 to 81% of the total residue at harvest with no trend to accumulate. Data from one year to the next indicated that more than 95% of spring posttreatment residues disappeared by the following spring. Young and Rawlins (24) applied heptachlor to four soil types at 2-4 lb/acre and found approximately 26% re- maining after 21 months. Lichtenstein et ah (16). report- ing on 5 years of applying aldrin and heptachlor to soil at 5 lb/ acre, found total residue steadily increasing, with slow declines over the next 5 years of no treatment. The much lower application rates for corn rootworm control gave no yearly increase in total residue in our study. In soils, microbial degradation of heptachlor and hep- tachlor epoxide to less toxic metabolites appears to be important in reducing residues (17). Aldrin soil treatments Aldrin soil treatments at planting time were made annu- allv to Bench 3b at approximately 1.0 lb/ acre except in 1968 when the recommended rate was reduced. Post- treatment soil concentrations of 0.91 to 2.06 ppm of TABLE 5. — Heptachlor-heptachlor epoxide residues in soil of an irrigated cornfield (Bench 2) receiving annual applications of heptachlor at approximate maximum recommended rates Treatment Average Residues in PPM Pretreatment 1 Posttreatment i Harvest ^ Year Rate lb/acre (Spring) (Spring) (Fall) Heptachlor Heptachlor Heptachlor Heptachlor epoxide Total Heptachlor EPOXIDE Total Heptachlor epoxide Total 1966 0.67 ND ND ND 1.20 1.25 2.45 0.40 0.90 1.30 1967 0.43 0.06 0.01 0.07 1.32 0.49 1.81 0.08 0.34 0.42 1968 0.41 0.06 0.04 0.10 0.25 0.10 0.35 0.09 0.07 0.16 1969 1.20 — — — 1.68 0.14 1.82 0.54 0.10 0.64 1970 — 0.06 0.06 0.12 — — - - - - ^ See Table 3 for treatment and sampling dates. NOTE: ND = No detectable residue at 0.01 ppm. 22 Pesticides Monitoring Journal TABLE 6.- -Aldrin-dieldrin residues in soil of irrigated cornfield (Bench 3b) receiving annual soil applications of aldrin at approximate maximum recommended rates Treatment Average Residues in PPM Year Pretreatment ^ Posttreatment Harvest ' lb/acre (Spring) (Spring) (Fall) Aldrin DiELDRIN Total Aldrin DiELDRIN Total Aldrin DiELDRIN Total 1965 1.0 ND ND ND — — — 0.14 0.14 0.28 1966 1.2 0.08 0.05 0.13 2.06 0.21 2.27 0.94 0.16 1.10 1967 0.74 0.09 0.11 0.20 1.23 0.14 1.37 0.42 0.20 0.62 1968 0.30 0.13 0.17 0.30 0.91 0.29 1.20 0.23 0.22 0.45 1969 1.08 — — — 1.09 0.24 1.33 0.37 0.48 0.85 1970 - ND 0.26 0.26 — — — — — - 1 See Table 3 for treatment and sampling dates. NOTE: ND = No detectable residue at 0.01 ppm. aldrin and 0.14 to 0.29 ppm of dieldrin were recovered (Table 6). Total aldrin-dieldrin residues in the soil at harvest varied from 0.28 to 1.10 ppm with no cumula- tive trend over a 4-year period. Approximately 50% of the spring treatment, plus residues carried over from the previous year, remained in the soil at harvest time. Data from one year to the next showed 80 to 90% loss of residue by the following spring, a month before the next application. Dieldrin residues at harvest and in the winter carryover tended to increase from year to year. Dieldrin avaraged 36% of the total residue at harvest and 52% by the following spring. The total spring posttreatment residue converted to dieldrin by harvest averaged about 19%. In 1965 a single heavy soil application of aldrin at about 4 times the maximum recommended rate was made to Bench 4a (Table 7). The soil was sampled both fall and spring throughout the 5 years. No spring posttreatment samples were obtained the first year, but the combined aldrin-dieldrin residue in the fall was 0.53 ppm, with dieldrin nearly double the aldrin concentration. By the following spring, a year after initial treatment, more than 50% of the total fall residue had disappeared. The dieldrin concentration was 10 to 20 times greater than aldrin during the second year. Aldrin residues were well below the 0.01 ppm level the third year, but dieldrin TABLE 7. — Residues of aldrin and dieldrin in soil of an irrigated cornfield (Bench 4a) for indicated years treated once with aldrin at 3.9 lb/acre in 1965 Sam- pling Time' Average Residues in PPM TICIDE 1965 1966 1967 1968 1969 1970 Aldrin Spring FaU 0.18 0.01 0.01 0.01 ND ND ND ND ND ND Dieldrin Spring FaU 0.35 0.20 0.13 0.18 0.17 0.12 0.20 0.10 O.U Total Spring Fall 0.53 0.21 0.14 0.19 0.17 0.12 0.20 0.10 o.n ^ See Table 3 for treatment and sampling dates. 2 No insecticide residues were found prior to the first year of treat- ment; no posttreatment samples were obtained in 1965. NOTE: ND = No detectable residue at 0.01 ppm. Vol. 5, No. 1, June 1971 residues remained relatively persistent at 0.1-0.2 ppm throughout the remaining 4 years. Lichtenstein et al. (14) reported on the disappearance of aldrin from two soil types in Kansas. Aldrin was found to disappear most rapidly under conditions of high rain- fall and low organic matter content. No aldrin residues were detected the second year following treatment at 2 lb/acre; no dieldrin residues were detected after AVi years (checked by bioassay). However, dieldrin ptersisted 4'/2 years (0.16-0.17 ppm) when the aldrin was applied at 20 lb/acre. A single aldrin treatment of nearly 4 lb/ acre in our study resulted in dieldrin residues of about 0.1 ppm after 5 years, indicating that widely vary- ing treatment rates and field conditions may result in similar levels of dieldrin in the soil after a few years of weathering and degradation. Lichtenstein et al. (16), however, found much higher levels of dieldrin (0.69 ppm) 10 years after treatment of Wisconsin loam soil following treatment at 25 lb/ acre of aldrin. Decker et al. (1) surveyed Illinois cornfields where aldrin had been used at recommended rates of % to 3 lb/ acre for up to 10 years. They concluded that 10 to 15% of the total aldrin-dieldrin residue was carried over to the following spring and that repeated annual applications at recommended rates should not result in residues ex- ceeding annual rates by the following year. Our study, although carried out under considerably different con- ditions of climate, soil type, and irrigation, confirms their general conclusions. Corn foliage residues resulting from foliar applications of diazinon, endrin, and methyl parathion Com grown in soil treated with diazinon at planting time also received a diazinon and endrin foliar spray at silk- ing time. Foliage samples collected soon after spraying showed diazinon levels of approximately 2 to 3 ppm and endrin levels from 0.9 to nearly 6 ppm (Table 8). Diazinon persisted in the foliage at harvest time from 0.02 to 0.05 ppm. Endrin residues (except in 1968) were 23 more persistent, as expected, ranging from 0.06 to 2.43 ppm. Diazinon soil treatments left no detectable foliage residues in early August in samples collected just before foliar treatment. Methyl parathion applied to com foliage at silking gave residues of 0.12 to 6.81 ppm after treatment. These dissipated to below 0.01 ppm by harvest except for 0.07 ppm detected in 1967. Spring soil treatments of para- thion left no detectable residues in August corn foliage samples. El-Refai and Hopkins (2) have shown that little para- thion is translocated from roots of bean plants into the foliage even when roots accumulated high concentra- tions. Diazinon likewise was poorly translocated into the foligae from roots, and translocated residues were rapidly hydrolyzed in the leaves (11). Therefore, soil treatments with organophosphorus insecticides with little systemic activity, like parathion or diazinon, do not appear to contribute significant residues to field foliage. No residues of diazinon, endrin, parathion or methyl parathion were detected in com grain sampled at harvest. Corn foliage residues resulting from heptachlor and aldrin soil treatments Foliage was sampled from corn plants grown in Benches 2 and 3b that recived annual soil treatments of aldrin and heptachlor, respectively. Samples were collected twice in August to correspond to foliar pretreatment and posttreatment sampling times and at harvest in Septem- ber or October. No heptachlor or aldrin was detected in foliage samples during the 4 years (Table 9). However, low levels of heptachlor epoxide or dieldrin sometimes TABLE 8. — Foliar residues of insecticides in an irrigated cornfield (Benches 1 and 3a) receiving soil and foliage applications at approximate maximum recommended rates Soil Treatment Foliar treatment Sampling TlMEl Average Residues in PPM Diaziiioii Diazinon Pretreatment ND ND ND (0.6-2.05 lb/acre) (1.0-1,4 lb/acre) Posttreatment 2.90 2.16 3.24 — Harvest 0.02 0.05 0.02 — Endrin Pretreatment ND ND KD _ (0.3-0.4 lb/acre) Posttreatment 5.75 2.73 2.26 0.90 Harvest 2.43 0.21 0.06 0.38 Parathion ' Methyl parathion Pretreatment ND ND ND — (0.79-1.4 lb/acre) (0.4-0.6 lb/acre) Posttreatment 0.12 2.25 6.81 — Harvest ND 0.07 ND - ^ See Table 3 for treatment and sampling dates. * No detectable levels of parathion at 0.01 ppm were present in foliage samples. NOTE: ND = No detectable residue at 0.01 ppm. TABLE 9. — Foliar residues resulting from annual heptachlor and aldrin soil treatments to an irrigated cornfield (Benches 2 and 3b) at approximate maximum recommended rates [T = trace <0.01 ppm] Sampling TlMEl Average Residues in PPM 1966 1967 1968 1969 TREATMENT Hepta- chlor Hepta- chlor EPOXIDE Hepta- chlor Hepta- chlor EPOXIDE Hepta- chlor Hepta- chlor EPOXIDE Hepta- chlor Hepta- chlor EPOXIDB Heptachlor Pretreatment 0.00 0.00 O.OO 0.00 0.00 0.00 _ — (0.41-1.20 lb/acre) Posttreatment 0.00 0.07 0.00 T 0.00 0.00 0.00 0.00 Harvest 0.00 0.01 0.00 T 0.00 T — - BENCH 3B Aldrin Dieldrin Aldrin Dieldrin ALDRIN Dieldrin Aldrin Dieldrin Aldrin Pretreatment 0.00 0.00 0.00 0.01 0.00 0.00 — _ (0.30-1.2 lb/acre) Posttreatmeni — — 0.00 T 0.00 T 0.00 0.01 Harvest 0.00 0.01 0.00 0.01 0.00 0.01 — — ' See Table 3 for treatment and sampling dates. 24 Pesticides Monttorino Journal were detected. Heptachlor epoxide varied from 0.07 to less than 0.01 ppm, while dieldrin concentrations did not exceed 0.01 ppm. Com grain sampled at harvest con- tained no detectable residues of aldrin, heptachlor, or their respective epoxides. Ef)oxides of aldrin and heptachlor have been detected in corn and other crops grown on treated soil, but residues in aerial parts of the plant are typically very low. Wood et al. (23) detected 0.02 ppm dieldrin and trace amounts of heptachlor epoxide in corn grown on soil treated with aldrin and heptachlor at 1 lb/ acre the previous fall. Wheeler et al. (22) determined that dieldrin was trans- located to aerial parts of young plants from treated soil; however, less was translocated to corn than to wheat or alfalfa. Harris and Sans (8) also detected dieldrin in com and other forage crops grown on aldrin-treated soil. No aldrin was present in the foliage residues; dieldrin resi- dues in the corn foliage ranged from 0.01 to 0.02 ppm, comparing closely to levels that are reported here. Water analysis Results of 18 samplings during 1966 through 1969 showed no residues at the 0.1 ppb level in water or at 0.001 ppm in silt in either well or surface water collec- tions. Traces of certain insecticides at the parts per trillion level were detected irregularly during 1966, 1967, and 1968, but not in 1969. Wells Endrin, applied to Bench 1, was never detected. Heptachlor, applied to Bench 2 only, was detected in trace amounts in all wells once or twice during 1966 and 1967, generally at 1 to 2 ppt; heptachlor epoxide was detected in four instances at 2 to 5 ppt. The traces were predominantly in the wells located in berms ad- jacent to treated areas. Aldrin, applied yearly to Bench 3b, and heavily in 1965 to Bench 4a, was detected in trace amounts three times during 1966 and 1967 at 2 ppt. Though not applied in the treated field, dieldrin was detected in most wells sometime during 1966 and 1967, generally at 2 or 3 ppt. Individual levels of 14, 18, 27 and 30 ppt were de- tected, perhaps when the sampling hose accidentally touched the ground prior to sampling. Dieldrin was most commonly detected in wells adjacent to aldrin applica- tions. It was the only insecticide detected in wells in 1968. We concluded that traces of insecticides detected in wells resulted from contaminated hoses used for sampling. All trace amounts were detected in 1966 and 1967, except one in 1968, and no residues were detected in 1969 when the sampling technique was improved by using a bail. Traces were detected somewhat more often in deeper Vol. 5, No. 1, June 1971 wells, when longer sampling equipment extensions were used. In addition, residues were not detected in soil deeper than 12 inches from the surface; therefore, ground water at deeper levels would not be expected to contain residues. Eye (3) concluded that dieldrin does not move signi- ficantly through soils into subsurface water by infiltra- tion. Nicholson (18). in a summary article, pointed out that the potential for pesticide contamination of ground water is very much less than for surface water and re- ported examining many well water samples from south- eastern States with only a few cases of contamination by chlorinated hydrocarbon insecticides. Direct contamina- tion seemed to be the cause in all but two cases. In summary, our findings substantiate those of others and indicate that insecticides applied at recommended maxi- mum rates for 5 years on the treated field, used on ad- jacent dryland, and in the newly developed irrigation district did not contaminate ground water. Surface water of experimental field Samples of water entering the treated field from the irrigation canal were obtained July 16 and August 16, 1966; August 22 and September 12, 1967; May 1 and August 14, 1968; and August 5, 1969. No residues were detected at the 0.1 ppb level in the water or at the 1 ppb level in the silt. Insecticides in water runoff from the treated field oc- curred rarely in trace amounts in water from buckets sunk to ground level at the lower end of Benches 3a, 3b, 4a and 4b (Fig. 1). Traces of dieldrin (12 to 22 ppt) were detected in water and 1 3 ppb in silt at the end of 3a and 3b. Dieldrin was detected three times at the extreme lower end of 4a and 4b, ranging from 9 to 49 ppt in the water; heptachlor epoxide was detected once at 5 ppt in the water. Cedar Bluff Reservoir and Smoky Hill River During 1966, 1967, and 1968 traces of dieldrin were detected in the reservoir in 6 of 18 samples; levels ranged from 3 to 51 ppt in the water. Dieldrin was detected once in silt at 6 ppb. Traces of endrin in the water were de- tected once at 13 ppt; heptachlor once at 1 ppt; hep- tachlor epoxide once at 6 ppt; and aldrin once at 14 ppt. DDE was found once at 4 ppb in sUt. During the first 3 years, heptachlor was detected 3 times in river water at 1 to 2 ppt. No heptachlor epoxide or aldrin was detected. Dieldrin was detected in 6 of 18 samples, at 3 1 ppt once and ranging from 3 to 9 ppt the other five times. Dieldrin was detected twice in the silt at 3 and 4 ppb. Endrin was detected twice in the water at 3 and 12 ppt. DDE was detected twice in the silt at 6 ppb. 25 During 1969, no residues were detected in either the reservoir or the river in silt or water, probably because use of organochlorines continually decreased. In summary, infrequent trace levels of indicated insecti- cides demonstrated no significant contamination in any of the surface waters. A cknowledgments Appreciation is expressed to the following personnel from the Kansas Agricultural Experiment Station: C. W. Pitts and Gerald Wilde for general assistance; James Leiker for field work; and to W. W. Duitsman for help in establishing the study site. Philip H. Marvin helped initiate the field studies under contract. Gratitude is also expressed to M. W. Gray and G. A. Stoltenberg of the Environmental Health Services, Kansas State Department of Health; to Robert B. Leonard of the Water Resources Division, U. S. Geo- logical Survey; and to the State Geological Survey of Kansas, for cooperation in making wells available for water sampling and for geohydrological data. The fol- lowing research assistants helped prepare and analyze the samples: Larry Cox, Ted Macy, Marie Finnochio, Dale Mosher, Charles Anderson TIL and Evelyn White. Milton E. Meier conducted the pesticide-use surveys, and the cooperation of growers supplying information was commendable. Vernon W. Moore provided the treated experimental field and significant cooperation and assistance beyond provisions in the contract. Robert J. Schamel, Superintendent, Cedar Bluff' Irrigation Dis- trict No. 6, supplied information on water use in the District and on the treated field. Mrs. Donna Irvin supplied a portion of the rainfall data. Contributions of insecticides by Monsanto Company, Shell Chemical Company, Geigy Chemical Corporation, and Velsicol Chemical Corporation are gratefully ac- knowledged. See Appendix for chemical names of compounds mentioned in. this paper. Supported in part by North Central Regional Project NC-85, Reduc- tion of Hazards Associated with the Presence of Insecticidal Chemicals in the Environment; by North Central Regional Project MCM-37, Trace Levels of Pesticide Residues in Agricultural Commodities in Marketing Channels; and by the U. S. Department of the Interior, OfSce of Water Resources Research. 26 LITERATURE CITED (1) Decker, G. C, W. N. Bruce, J. H. Bigger. 1965. The accumulation and dissipation of residues resulting from the use of aldrin in soils. J. Econ. Entomol. 58:266-71. (2) El-Refai, A. and T. L. Hopkins. 1966. Parathion absorp- tion, translocation, and conversion to paraoxon in bean plants. J. Agr. Food Chem. 14:588-92. (3) Eye, J. D. 1968. Aqueous transport of dieldrin residues in soils. J. Water PoUut. Conf. Fed., Res. Suppl. 40(8): R316-R332. (4) Getzin, L. W. 1967. Metabolism of diazinon and zino- phos in soils. J. Econ. Entomol. 60:505-8. (5) Getzin, L. W. 1968. Persistence of diazinon and zinophos in soil; effects of autoclaving, temperature, moisture, and acidity. J. Econ. Entomol. 61:1560-5. (6) Getzin. L. W. and 1. Rosefield. 1968. Organophosphorus insecticide degradation by heat-labUe substances in soil. J. Agr. Food Chem. 16:598-601. (7) Harris, C. R. 1969. Laboratory studies on the persistence of biological activity of some insecticides in soils. J. Econ. Entomol. 62:1437-41. (8) Harris, C. R. and W. W. Sans. 1969. Absorption of organochlorine insecticide residues from agricultural soils by crops used for animal feed. Pesticides Monit. J. 3(3):182-5. (9) Kadoum, A. M. 1967. A rapid micromethod of sample cleanup for gas chromatographic analysis of insecticidal residues in plant, animal, soil, and surface and ground water extraction. Bull. Environ. Contamination Toxicol. 2:264-73. (10) Kadoum, A. M. 1968. Application of the sample cleanup for gas chromatographic analysis of common organic pesticides in ground water, soil, plant and animal ex- tracts. Bull. Environ. Contamination Toxicol. 3:65-70. (11) Kansouh, A. S. H. and T. L. Hopkins. 1968. Diazinon absorption, translocation, and metabolism in bean plants. J. Agri. Food Chem. 16:446-50. (12) Leonard, R. B. 1969. Variations in the chemical quality of ground water beneath an irrigated field. Cedar Bluff Irrigation District, Kansas. An interim report. Kans. State Dep. Health Environ. Health Serv. Bull., Topeka, 1-11, 20 p. (13) Leonard, R. B. 1970. Effect of irrigation on the chemical quality of ground and surface water. Cedar Bluff Irriga- tion District, Kansas. In Relationship of agriculture to soil and water pollution. Agr. Water Manage. Conf., Cornell Univ. p. 147-163. (14) Lichtenstein. E. P.. L. J. DePew, E. L. Eshbaugh, and P. D. Sleesman. 1960. Persistence of DDT, aldrin, and lindane in some midwestem soils. 1. Econ. Entomol. 53:136-42. (15) Lichtenstein, E. P. and K. R. Schulz. 1964. The effects of moisture and microorganisms on the persistence and metabolism of some organophosphorus insecticides in soil with special emphasis on parathion. J. Econ. En- tomol. 57:618-27. (16) Lichtenstein, E. P., K. R. Schulz T. W. Fuhremann, and T. T. Liang. 1970. Degradation of aldrin and heptachlor in field soils during a ten-year period translocadon into crops. J. Agr. Food Chem. 18:100-6. (17) Miles, J. R. W., C. M. Tu, and C. R. Harris. 1969. Metabolism of heptachlor and its degradation products by soil microorganisms. J. Econ. Entomol. 62:1334-8. (18) Nicholson, H. P. 1969. Occurrence and significance of pesticide residues in water. I. Wash. Acad. Sci. 59(4-5): 77-85. Pesticides Monitoring Joitrnal (19) Read, D. C. 1969. Persistence of some newer insecti- (22) Wheeler, W. B., D. E. H. Frear, R. O. Mumma, R. H. cides in mineral soils measured by bioassay. J. Econ. Hamilton, and R. C. Cotner. 1967. Absorption and Entomol. 62:1338-42. translocation of dieldrin by forage crops. J. Agr. Food (20) Sethunathan, N. and I. C. MacRae. 1969. Resistanc^ '^Z^TkX J. Ambrust. G. G. Gyrisco, W. H. and biodegradation of diazmon m submerged soils. J. Cutenmann. D. J. Lisk. 1966. The presence and per- Agr. Food Chem. 17:221-25. . , r u . ui -j j T- u • r ° sistence of heptachlor epoxide and dieldnn on forage (21) Sethunathan, N. and T. Yoshida. 1969. Fate of diazinon crops in New York. J. Econ. Entomol. 59:131-2. in submerged soil. Accumulation of hydrolysis product. (24) Young, W. R. and W. A. Rawlins. 1958. TTie persistence J. Agr. Food Chem. 17:1192-95. of heptachlor in soils. J. Econ. Entomol. 51:11-18. Vol. 5, No. 1, Jiwe 1971 ^"^ Organochlorine Insecticide Residues in Soil From Vegetable Farms in Saskatchewan^ Jadu G. Saha^ and Arthur K. Sumner' ABSTRACT Forty-one agricultural soil samples from 21 vegetable farms in Saskatchewan were analyzed for organochlorine insecti- cide residues. All but 2 of the 41 samples had more than 0.01 ppm of total organochlorine insecticide residues, with a maximum of 6.87 ppm. DDT, DDE, and DDD were pres- ent in 63% of the samples with a maximum of 6.75 ppm in one sample. Aldrin and/or dieldrin were present in 61% of the samples at levels between 0.01 to 0.77 ppm, while similar amounts of heptachlor and heptachlor epoxide were present in 24% of the samples. Chlordane residues were present in 17% of the samples up to a maximum level of 3.91 ppm. Introduction Organochlorine insecticides have been used in agricul- ture for more than 20 years, and much is known about their persistence in the environment. It is known, for example, that their continued use will lead to the buildup of residues in soils with a potential hazard of contami- nation of subsequent crops. The magnitude of these soil residues is known for only three areas in Canada, and much more information is necessary. A limited survey by Harris et al. (3J showed significant amounts of organochlorine insecticide residues in agri- cultural soils in southwestern Ontario. Soils used for the production of sugar beets, corn, forage, and cereal crops Contribution No. 429, Canada Agriculture Research Station, Saska- toon, Saskatchewan, Canada. ' Canada Agriculture Research Station, University Campus, Saskatoon, Saskatchewan, Canada. ' College of Home Economics, University of Saskatchewan, Saskatoon, Saskatchewan, Canada. 28 contained 0.4 to 1.8 ppm of total organochlorine in- secticide residues, while vegetable farm soils contained an average of 9.5 ppm. The highest level of residues, mostly DDT and its degradation products, was found in orchard soils where an average of 61.8 ppm was found. Duffy and Wong (I) studied the occurrence of organo- chlorine insecticide residues in 38 vegetable and orchard soils in the 3 Atlantic Provinces of Canada. Forty-five percent of the samples contained 1 to 9 ppm of DDT and its degradation products; 32% of the samples con- tained more than 0.75 ppm aldrin plus dieldrin; and 9% of the samples contained 0.06 to 0.86 ppm of heptachlor plus heptachlor epoxide. Saha et at. (6) analyzed soil and legume crop samples from 20 farms in northeastern Saskatchewan. Eighty percent of the soil samples contained 0.01 to 0.3 ppm dieldrin. Although low levels (0.01 to 0.04 ppm) of heptachlor, heptachlor epoxide, and endrin were ob- served in some soils, DDT and its degradation products were not detected in any of the samples. These three studies indicated a relationship between soil residue levels and the pesticide use patterns on the particular crops being grown. Cereal and forage crop sou contained the least amount of residues; vegetable crop soils contained intermediate amounts; and orchard soils contained the highest amount. Although Saskatche- wan is a predominantly cereal-growing area, vegetable crops are grown on many farms in the province. The object of this study was to determine the levels of or- ganochlorine insecticide residues in soils from vegetable farms in Saskatchewan. PEsncroES Monitoring Journal Sampling Procedure Forty-one soil samples were collected from 21 vegetable farms in Saskatchewan during May and June 1970. A soil sample consisted of 20 to 30 cores (6 inches deep) taken at random throughout the field. Each soil sample was partially air-dried so that it could be mixed thoroughly, screened through a 20-mesh screen, and stored in a plastic bag at — 18°C until analyzed 2 to 8 weeks later. Analytical Procedure One hundred grams of soil (average moisture content 12 to 16%) was shaken with 200 ml of a 1:1 hexane: acetone mixture for 1 hour and filtered. The solid residue was re-extracted twice with 50-ml portions of the same solvent mixture and filtered. The combined filtrate was partitioned into petroleum ether after dilution with 500 ml of a 2% solution of sodium chloride. The pet- roleum ether layer was dried with sodium sulfate and concentrated to about 10 ml. The concentrated solution was then eluted on a 20-g alumina (grade III) column with 250 ml of 15% benzene in hexane. The eluent was concentrated to about 75 ml and made up to 100 ml. The samples were analyzed on an Aerograph Hi-Fi Model 600-D gas chromatograph with an electron capture de- tector. Operating conditions were as follows: Column: 5' x Va" aluminum tube packed with 4% SE-30 + 6% QF-1 on Chromosorb W, preconditioned for 72 hours at 220° C. Temperature: Column 175°C Detector 200 °C Injector 190°C Carrier gas: Oxygen-free nitrogen at 60 ml/minute. A known volume of each sample (2 to 6 ^1) was in- jected into the gas chromatograph, and the concentra- tions of lindane, aldrin, dieldrin, heptachlor, heptachlor epoxide, chlordane, endrin, p.p'-DDT, o,p'-DDT, p.p'- DDE p,p'-DDD were determined by comparing their peak heights with those of standards. All samples in- dicating more than 0.05 ppm of any residue were an- alyzed by thin layer chromatography according to Kovacs (4). The identity of a suspected insecticide was established by comparing its Rf value with that of the standard. Further proof of the identities of suspected compounds was obtained by chemical conversion tech- niques (2). Recoveries of lindane, heptachlor, aldrin, heptachlor epoxide, technical chlordane, dieldrin, endrin, p,p'-DDT, p,p'-DDE, o,p'-DDT and p,p'-DDD at 0.1 and 0.05 ppm added to soil were 90-100%. This method also gave 92-98% recovery of aged dieldrin-i*C irrespective of the soil type (7). The lower level of detectabUity for Vol. 5, No. 1, June 1971 these compounds was 0.005 ppm except in the case of DDT and its metabolites where the lower level was 0.01 ppm. Although residues could be detected in concen- trations as low as 0.005 ppm, quantitative detenninations were made only for residues present in concentrations of 0.01 ppm or more. Soil moisture contents were determined by air-drying at 1 10°C for 4 hours, and residue levels were calculated on a dry- weight basis (Table 1). All experiments were carried out in duplicate. Results and Discussion All but 2 of the 41 samples had more than 0.01 ppm of total organochlorine insecticide residues (Table 1). Con- centrations ranged from less than 0.01 ppm to 6.87 ppm. Thirty-five of the soil samples contained less than 1.00 ppm of total organochlorine insecticide residues, but four of the samples contained 1.01 to 5.00 ppm, and the remaining two had residue concentrations of over 5.00 ppm. DDT, and/or its metabolites were present in 26 (63.3%) of the soil samples. While most of the samples contained less than 1.00 ppm total DDT, three samples contained 1.01 to 5.00 ppm, and two contained more than 5.00 ppm. Aldrin and/ or dieldrin were present in 25 (61%) of the samples, but their concentrations were low. Their total concentration was 0.01 to 0.10 ppm in 15 samples, 0.11 to 0.50 ppm in 9, and only one sample contained greater than 0.50 ppm. The highest levels of aldrin and dieldrin encountered were 0.28 and 0.77 ppm, respectively. Heptachlor and/or heptachlor epoxide were found in 10 (24%) of the samples. A total concentration of 0.01 to 0.10 ppm occurred in 5 samples, 0.11 to 0.50 ppm in 4, and only one sample contained greater than 0.50 ppm. Chlordane occurred in seven (17%) of the samples of which three contained 0.01 to 0.10 ppm, three contained 0.11 to 0.50 ppm, and the remaining sample contained 3.91 ppm. Lindane was found in one of the samples at a level of 0.05 ppm, while endrin was present in one sample at a concentration of 0.48 ppm. This survey indicates that organochlorine insecticide residues are present in some vegetable farm soil in Saskatchewan in significant amounts. Twelve percent of the samples contained total DDT residues in excess of 1 .00 ppm, 24% more than 0.10 ppm total aldrin and dieldrin, 12% more than 0.10 ppm heptachlor and heptachlor epoxide, and two samples each (2%) con- tained 3.91 and 0.48 ppm chlordane and endrin, re- spectively. Crops (especially root crops) grovra in these 29 soils would absorb significant amounts of these residues. Whether the levels of such residues would be greater than the tolerance levels established for human consump- tion would depend on the crop, the specific insecticide involved, its concentration in the soil, soil type, and ■ climate (5). However, crops grown in some of these soils or their waste products such as beet, carrot and turnip tops, culled potatoes, and cabbage trimmings if fed to livestock might result in residues occurring in animal products in excess of the tolerances established for human consumption. Thus, the insecticide residues found in some of these soils may be a hazard to food and feed production. A cknowledgments The authors wish to thank the Saskatchewan Research Council for a research grant to support this work. Thanks are also due Robert Boudreau and Shirley Remmen for technical assistance and the many district agricultural representatives who collected most of the soil samples. See Appendix for chemical names of compounds mentioned in this paper. LITERATURE CITED (1) Duffy, J. R. and N. Wong. 1967. Residues of organo- chlorine insecticides and their metabolites in soils in the atlantic provinces of Canada. J. Agr. Food Chem. 15:457-464. (2) Hamence, J. //.. P. S. Hall, and D. J. Caverly. 1965. The identification and determination of chlorinated pesticide residues. Analyst 90:649-656. (3) Harris, C. R., W. W. Sans, and J. R. W. Miles. 1966. Exploratory studies on occurrence of organochlorine insecticide residues in agricultural soils in southwestern Ontario. J. Agr. Food Chem. 14:398-403. (4) Kovacs, M. F.. Jr. 1963. Thin layer chromatography for chlorinated pesticide residue analysis. J. Ass. Office. Anal. Chem. 46:884-893. (5) Lichtenstein, E. P. 1965. Problems associated with in- secticidal residues in soil. In "Research in Pesticides", Academic Press, New York, N.Y. p. 199-204. (6) Saha, J. C, C. H. Craig, and W. K. Janzen. 1968. Organochlorine insecticide residues in agricultural soil and legume crops in northeastern Saskatchewan. J. Agr. Food Chem. 16:617-619. (7) Saha. J. G., B. Bhavaraju, Y. W. Lee, and R. L. Randell. 1969. Factors affecting extraction of dieldrin-i'^C from soil. J. Agr. Food Chem. 17:877-882. TABLE 1. — Organochlorine insecticide residues in some vegetable farm soils in Saskatchewan in 1970 [ — = absent or less than 0.01 ppm] Residues in PPM (oven dry) <2z § "o, D "a Q Q Q z z i i i g |2 2 Z i z z 3 4 z < lg 1 0.21 — — — 0.21 0.04 0.04 0.28 0.34 — — — 0.91 2 0.16 — — — 0.16 0.28 0.03 0.11 0.25 — — _ 0.83 3 0.02 — — — 0.02 0,04 0.03 0.08 0.15 — — — 0.32 4 0.02 — — — 0.02 — — 0.01 0.01 — — — 0.04 5 — — — — — 0.05 0.02 0.02 0.02 — — — 0.11 6 0.25 0.04 0.08 0.03 0.40 — — — — — — — 0.40 7 0.21 0.03 0.07 0.02 0.33 — — — — — — — 0.33 8 0.41 0.06 0.13 0.04 0.64 — 0.02 — 0.09 — — — 0.75 9 10 11 — — - 0.10 0.10 - - - - - - 0.10 _ _ _ _ _ 0.02 0.03 0.13 _ _ _ 0.18 12 0.57 — 0.05 — 0.62 0.20 0.04 — — — — — 0.86 13 0.78 0.04 0.14 — 0.96 — 0.03 — — — — — 0.99 14 — — — — — 0.21 0.04 — — — — — 0.25 15 — — — — — 0.21 0.09 — — — 0.49 — 0.79 16 5.57 0.10 0.70 — 6.37 — — — — — — — 6.37 17 0.33 0.11 — — 0.44 — 0.49 — — — — — 0.93 18 0.10 — — — 0.10 0.06 0.28 — — — — — 0.44 19 — — — — — 0.06 0.11 — — — — — 0.17 20 0.21 0.06 — — 0.27 — — — — 0.48 3.91 0.05 4.71 21 — — — — — — 0.02 — — — — — 0.02 22 2.61 037 0.65 — 3.63 — — — — — — — 3.63 23 0.20 0.02 0.05 — 0.27 _ — _ _ _ — — 0.27 30 Pesticides MomTORiNG Journal TABLE 1. — Organochlorine insecticide residues in some vegetable farm soils in Saskatchewan in 1970 — Continued [ — = absent or less than 0.01 ppm] Residues in PPM (oven dry) 1 g o. a ft. 0 § "o. ex II D 1 t\ 1 g < g ,3 4 5 II 24 3.04 0.98 0.95 — 4.97 _ — — — — — _ 4.97 25 0.04 — — — 0.04 — — — — — 0.13 — 0.17 26 1.46 0.26 0.37 — 2.09 — 0.17 0.03 0.21 — — — 2.50 27 28 29 5.06 0.58 1.11 - 6.75 0.06 0.06 — — - - - 6.87 _ _ _ _ _ _ 0.77 _ _ _ 0.02 _ 0.79 30 0.18 0.03 0.05 — 0.26 — 0.04 — — — — — 0.30 31 — — — — — — 0.01 — — — — — 0.01 32 0.03 — — — 0.03 — — — — — — — 0.03 33 0.17 0.03 0.06 — 0.26 — — — — — — — 0.26 34 0.05 0.02 — — 0.07 — 0.02 — — — — — 0.09 35 — — — — ~ — 0.02 — 0.02 — — — 0.04 36 0.04 — — — 0.04 — 0.02 — 0.01 — — — 0.07 37 — — — — — — — — — — 0.03 — 0.03 38 — — — — — — 0.05 — — — 0.14 — 0.19 39 — — — — — — 0.09 — — — 0.03 — 0.12 40 0.32 0.03 0.20 — 0.55 — — — — — — — 0.55 41 - — - - - - 0.03 - — - - - 0.03 Vol. 5, No. 1, June 1971 31 BRIEFS Preliminary Study of Mercury Residues in Soils Where Mercury Seed Treatments Have Been Used p. F. Santf, G. B. Wiersma', H. Tai', and L. J. Stevens* ABSTRACT Soil samples collected in 1968 from the small-grain pro- ducing areas of the North Central United States were an- alyzed for mercury residues. Half the samples were from areas where mercury-treated seed had been used in 1968 and the other half were from areas of no use. Mercury was found in almost all soil samples. A significant difference was found in mean levels between areas of use and no use, with the higher residues occurring in areas where mercury had not been used in 1968. Introduction Warren and Delavault (3) estimated that mercury resi- dues normally exp)ected in British agricultural soils would range between 0.01 and 0.06 ppm. Ericksson (2) reported that soils with organic matter contained ap- proximately 1.3 lb of mercury i>er acre in a layer of soil 3 feet deep. Converting this to parts per million for an acre of soil 3 inches deep gives 0. 1 1 ppm. Ericksson, however, does not specify the sampling methods used in arriving at his figures. Andersson (1) analyzed 100 soil samples from Sweden for mercury residues. He found the values ranged between 0.20 ng/g (0.020 ppm) to 920 ng/g (0.920 ppm), with an average of 70 ng/g (0.070 ppm). ' Plant Protection Division, Agricultural Research Service, U. S. Department of Agriculture, Hayattsville, Md. 20782. • Environmental Quality Branch, Environmental Protection Agency, Hyattsville, Md.; formerly, Plant Protection Division, Agri'-ultural Research Service, U. S. Department of Agriculture, Hyattsville, Md. 20782. ' Environmental Quality Branch, Environmental Protection Agency, Gulfport, Miss.; formerly Plant Protection Division, Agricultural Research Service, U. S. Department of Agriculture, Gulfport, Miss. » Plant Protection Division, Gypsy Moth Methods Development Lab- oratory, Otis Air Force Base, Mass.; formerly. Plant Protection Division, Agricultural Research Service, U. S. Department of Agriculture, Hyattsville, Md. 20782. 32 The objective of this study was to determine if residues were present in cropland soils of the North Central States where mercury seed treatments have been com- monly used and whether or not additional work on mercury residues in soil should be carried on. Materials and Methods Soil samples used were a part of the nationwide soil monitoring program. A random selection of samples was made from the States of North Dakota, South Dakota, Nebraska, Wisconsin, Minnesota, Iowa, and Illinois. The samples were sent to a commercial laboratory for an- alysis. A total of 93 samples collected in 1968 were chosen from the seven States. Of these, 50 were from sample sites with a record of mercury use in the summer of 1968, and 43 were from sample sites with no record of mercury use that season. Soil samples were analyzed for mercury by neutron activation analysis as follows: (1) Mercury was distilled from the soil samples by heating with a mixture of copper and calcium oxide and collecting the distillate in nitric acid. (2) The acid solution was made up to an exact volume, and an exact f>ortion was sealed in a quartz ampoule for irradiation in a Hanford reactor [neutron flux 101^ neutrons (Am 2/ sec)]. (3) After irradiation and a 5-day "cooling" period, the ampoule was dissolved in a mixture of hydrofluoric and nitric acid, made up to a known volume. (4) This solution was then counted on a Ge(Li)diode coupled to a pulse height analyzer for the 279.17 Key gamma emission of Mercury 230. Pesticides Monitoring Journal The sensitivity limit for this method was 0.001 ppm. Seven of the samples were duplicated so a check could be made of analytical procedures. The average differ- ence between members of each of the seven pairs was 0.199 ppm. The difference ranged between 0.037 ppm and 0.655 ppm. This indicates that there is a fair amount of variability in the results due to the analytical tech- nique. Results The sample sites were primarily drawn to give two ap- proximately equal samples, one from areas on which mercury had been used during the year of sampling and the other where it had not. TTie results summarized in Table 1 cannot be interpreted as being estimates of mercury levels in each State. They are presented by State only to give an idea of the numbers of sites sampled, and the relative differences in distribution. The overall mean of mercury on areas where it was used was 0.114 ppm. The individual values ranged be- tween a trace (less than 0.01 ppm) and 1.388 ppm, and 88% of the sample sites had residues of 0.01 ppm or greater. The areas on which no mercury was used the year of sampling had an overall mean of 0.195 ppm; the in- dividual values ranged from 0.017 ppm to 2.050 ppm. Mercury residues equal to or greater than 0.01 ppm were found on 97.7% of the sample sites which received no treatment the year of sampling. Analysis of the results using a "T" test for unequal num- bers of observations indicated a significant difference at the 95% confidence level between the two areas. TTie higher residues were found on the areas which had no mercury applied the year samples were taken. Not too much significance should be attached to the apparent difference in mean levels of mercury. First, although there was no record of mercury used in the summer of 1968, mercury might have been used in prior years. Second, the paired check samples, indicated there was considerable variation resulting from the analytical techniques. Warren and Delavault (3) considered soil residues greater than 0.25 ppm as anomalous but gave no reasons for using this level. In addition, their estimated residue levels in British agricultural soils of 0.01 to 0.06 ppm are considerably below the levels detected in this study. The residue levels found by Andersson (1) for Swedish soils are also below the levels in this study, although they agree quite well with the figures given by Warren and Delavault (3). Only Ericksson's (2) estimates are close to the mean residue levels detected in this study. Based on the above references, mercury residue levels detected in the wheat belt of the United States seem to be equal to or higher than residue levels found or esti- mated in various foreign soils. This fact, along with the statistical results presented above, indicate a need for more extensive sampling of soil for mercury residues. These extended sampling designs should have as their objective the establishment of creditable background levels of mercury and finding areas where mercury levels in soil may be sufficiently high to present a potential for contamination of other components of the environment. LITERATURE CITED (1) Andersson, A. 1967. Mercury in Swedish soils. Oikos (Supplement 9) p. 13-15. (2) Ericksson. E. 1967. Mercury in nature. Oikos (Supple- ment 9) p. 13. (3) Warren, H. V. and R. E. Delavault. 1969. Mercury content of some British soils. Oikos 20:537-539. TABLE 1. — Results of analysis of soil samples for mercury residues Mercury Used — 1968 No Mercury Used— 1968 State No. OF Samples Mean Range % OF Samples WTTH Residues No. OF Samples Mean Range % OF Samples wrra Residues N. Dakota 38 0.131 T-1.388 86.8 0.079 0.067-0.085 100 S. Dakota 5 0.080 0.045-0.195 100 7 0.070 0.026-0.157 100 Nebraska 7 0.044 T-0.124 85.7 11 0.240 0.027-1.960 100 Wisconsin 4 0.403 0.100-1.159 100 Iowa 0.069 0.052-0.114 85.7 niinois 0.356 0.017-2.050 100 Minnesota 0.103 0.09(M).129 100 AU States 50 0.114 T-1.388 88.0 43 0 195 0.017-2.050 97.7 NOTE: Blanks indicate no sample collected; T = Trace <0.0I ppm. Vol. 5, No. 1, June 1971 33 APPENDIX Chemical Names of Compounds Mentioned in Preceding Papers ALDRIN BHC BUX TEN CARBARYL CHLORDANE a-CHLORDANE 7-CHLORDANE CRUFOMATE DDE DDT (including Its isomers and dehydrochlorination products) DIAZINON DIELDRIN DIOXATHION ENDRIN FENSULFOTHION HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE MALATHION MERCURY METHOXYCHLOR METHYL PARATHION PARATHION POLYCHLORINATED BIPHENYLS (PCB's) PHORATE PYRETHRINS RONNEL ROTENONE TDE (DDD) (including its isomers and dehydroclilorina- tion products) TOXAPMENE Not less than 95% of l,2,3,4,10,10-hexachloro-l,4,4a,S,8,8a-hexahydro-l,4-enifo-eAco-S,8-dimethanonaphthalene 1,2,3,4,5,6-hexachlorocyclohexane, mixed isomers m-(l-methylbutyl) phenyl methylcarbamate mixture with approximately 4:1 proportions of m-(l-ethylpropyl) phenyl methylcarbamate 1-naphthyl methylcarbamate 1, 2,4,5,6,7 ,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-methanoindane , alpha isomer — — — — , gamma isomer 4-/e«-butyl-2-chlorophenylmethyI methylphosphoramidite 1 , 1 -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 the o,p'-isomer (in a ratio of about 3 or 4 to 1 ) 0,0-diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate Not less than 85% of l,2,3,4,10,10-hexachloro(6,7-epoxy-l,4,4a,5,6,7,8,8a-oclahydro-l,4-?ndo-K<:o-5,8-dimethano= naphthalene 5,5'-p-dioxane-2,3-diyl 0,0-diethyl phosphorodithioate (cis and trans isomers) 1,2,3 ,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l,4-fndo-endo-5,8-dimethanonaphthalene 0,0-diethyl 0-p- (methylsulfinyl) phenyl phosphorothioate I,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 1,2,3,4,5,6-hexachlorocyclohexane, 99% or more gamma isomer diethyl mercaptosuccinate, S-ester with 0,0-dimethyl phosphorodithioate l,l,l-tiichloro-2,2-bis(p-methoxyphenyl)ethane 0,0-dimethyl O-p-nitrophenyl phosphorothioate 0,0-diethyl O-p-nitrophenyl phosphorothioate Mixtures of chlorinated biphenyl compounds having variotis percentages of chlorination 0,0-diethyl S-(ethylthio)methyl phosphorodithioate principally from plant species Chrysanthemum cinariaefolium 0,0-dimethyl 0-2,4,5-trichlorophenyl phosphorothioate from plant species Derris and Lonchocarpus l,]-dichIoro-2,2-bis(p-chlorophenyl)ethane; technical TDE contains some e,p'-isomer also chlorinated camphene containing 67% to 69% chlorine 34 Pesticides Monitoring Journal NATIONAL PESTICIDE MONITORING PROGRAM (Revised) Introduction The National Pesticide Monitoring Program was first described in the Pesticides Monitoring Journal. Vol. 1. No. 1 (1967). The Program was initially designed on the basis of the minimum monitoring needed to establish baseline levels of pesticides in substrates of food and feed, humans, soU. water, air, wildlife, fish, and estu- aries and to assess changes in these levels. Monitoring activities are subject to changes — changes to incorporate research investigations, utilize improved methodology, reflect changes in program emphasis, and to accommo- date findings within existing programs. In 1968, a review of the components of the National Pesticide Monitoring Program was initiated by the original Subcommittee on Monitoring; the review has been completed by the Sub- committee's successor, the Monitoring Panel of the Working Group on Pesticides responsible to the Council on Environmental Quality. Vol. 5, No. 1, June 1971 Recent realignments have been made in the pesticide activities of the Federal agencies. The focal point of Federal policies and activities for pesticides is within the Environmental Protection Agency. However, many of the monitoring activities on pesticides have remained in other agencies, and the need still exists for a co- ordinated approach to pesticide monitoring. The Panel notes that the scope of the existing estuarine monitoring program is limited compared to other substrates, which is due in part to the responsible agency's primary mission and resources. Also, there is no operational National Monitoring Program for pesticides in air, and no com- prehensive information on this important substrate is developed in other programs. The statement on air monitoring outlines a program needed to develop mini- mal data which can be correlated with data from other parts of the National Pesticide Monitoring Program. R. E. Duggan Chairman, Monitoring Panel 35 Criteria for Defining Pesticide Levels To Be Considered an Alert to Potential Problems Panel on Pesticide Monitoring Working Group on Pesticides' (W. S. Murray, Executive Secretary) The objective of the National Pesticide Monitoring Pro- gram is to determine levels and trends of pesticides in the various substrates sampled. The establishment of mean levels of specific pesticides through the NPMP provides baselines necesary for determining whether levels of specific pesticides are high or low. We have not yet determined, however, just what would be considered the levels of concern for each pesticide in certain environmental components. For example, we know what the actionable level of DDT is in human food, but there has been no level established for DDT in human tissues that would result in action to reduce exposure. On the other hand, for some elements of the environment, there have been maximum allowable levels set baeed on known adverse effects, although these levels may include a built-in margin of safety. The following criteria may be used to define jjesticide levels to be considered an alert to potential problems: Environiriental Component Criteria for Identifying Potential Problems (1) Any concentration of a pesticide known to be potentially harmful (based on research demonstratiBg barm). (2) Increasing trends. (1) Any concentration of a pesticide known to be potentially harmful (based on research demonstrating harm). (2) Evidence of exceeding established levels. (3) Increasing trends. Soil Water Food and Feed Humans (1) Evidence of exceeding established levels in soil-associated items. (2) Increasing trends. (1) Evidence of exceeding established water quality standards. (2) Increasing trends. (1) Evidence of exceeding established levels and standards. (2) Increasing trends. (1 ) Increasing trends. (2) Recognition of adverse effects. Condensed even further, the five bases for concern are: (1) Any concentration of a pesticide known to be potentially harmful. (2) Increasing trends. (3) Exceeding standards. (4) Recognition of adverse effects in humans. (5) Erratic variability* Some combinations of these criteria are apparently al- ready used to distinguish possible problem areas. Dif- ferent combinations of the five may be desirable for different environmental components. Formulas for the bases of concern for each component and a more precise definition of what comprises each in terms of each component of the NPMP appear to be the next logical step. For example, depressed choline- sterase cases represent a basis for concern in human monitoring. These five are the bases of concern that may be under- stood by scientists, administrators, and the public. In accord with research advances, agencies should develop specific possible problem-area definitions for each medi- um being monitored. ' Responsible to the Council on Environmental Quality. 36 A statistically oriented observation that is potentially common to each of the stratum sampled. Pesticides Monitoring Journal National Food and Feed Monitoring Program R. E. Duggan' and H. R. Cook' ABSTRACT The Federal program for monitoring pesticide residues in food and feed is comprised of suneillance programs main- tained by the Food and Drug Administration, U. S. Depart- ment of Health, Education, and Welfare and by the Con- sumer Protection Program, Consumer and Marketing Serv- ice, U. S. Department of Agriculture. The Department of Agriculture is responsible for the sampling of meat and poultry, and DHEW is responsible for raw agricultural products and the Market Basket Studies. Monitoring Objective The objective of this program is to determine the levels of pesticide residues in unprocessed and commercially processed consumer food commodities, animal feeds, and composites of food items prepared for human consump- tion. Programs being carried out to accomplish this objective include (1) a continuing Market Basket Study to determine pesticide residues in the basic 2-week diet of a 16-to- 19-year-old male, statistically the Nation's largest eater, (2) nationwide surveillance of unprocessed food and feed, and (3) the surveillance program of the Consumer Protection Program, Consumer and Market- ing Service, U. S. Department of Agriculture, for the analysis of meat and poultry samples taken from animals at slaughter. An emerging and very important objective of this pro- gram is to determine levels of contaminants not directly attributable to pesticide application e.g. mercury, poly- chlorinated biphenyls, cadmium, etc. To the extent that methodology and p ogram mechanics are interrelated with pesticides, determination of such contaminants has become an automatic objective of this program. Office of Associate Commissioner for Compliance, Food and Drug Administration, U. S. Department of Health, Education, and Welfare, Rockville. Md. 20852. Consumer and Marketing Service, U. S. Department of Agri- culture, WashinBton, D. C. 20250. Vol. 5, No. 1, June 1971 Factors Influencing Program Design Numerous interrelated factors necessarily have been con- sidered and evaluated in defining a minimum monitor- ing effort for pesticide residues in food and feed. Many individual commodities entering the Nation's food supply are produced in various geographical areas under a broad range of growing conditions. Because the distri- bution system which brings these commodities to market is rapid, a constant shifting of commodity origins exists within a given consumption area. Since there are no crossroads in time or geography to permit concentrated or highly selective sampling which could be considered sufficiently representative of the food supply, monitoring of residues in food and feed must be programmed on a continuing and broadly geographical basis. It should be recognized that the important impact of pesticide residues in human and animal food, insofar as environmental effects are concerned, lies in th<;ir con- sumption. Therefore, the examination of foods as they are prepared and ready for consumption is of special interest to this monitoring program. Residues in wastes from food processing, of course, may be of concern with regard to soil, water, or the atmosphere, depending uf)on their final disposition. Their effect on tfiese ele- ments of the environment, however, would be detected by other monitoring programs. Because no uniformity may be expected within even a single food item due to extreme variations in local growing, harvesting, and processing procedures, <;ampl- ing patterns taking geographical and seasonal variables into account must be used. Moreover, examination of the 120 individual food items in the Market Basket Survey was considered impractical because of the spec- trum of unknown residues potentially present and the 37 limitations in analytical methods to detect and measure more than one class of residues. The dilution factor, technical problems in methodology, and variations in dietary habits suggested that composites representing a "total diet" also would be unsatisfactory. To minimize these problems, a practical compromise was reached, that is, the compositing of foods by classes, e.g., meats, dairy products, green vegetables, etc. Data yielded by this method may be used to calculate the approximate residue intake associated with any diet pattern but is more useful to determine trends in in- cidence and levels of residues nationally and by geo- graphic location. One very important factor considered in determining modifications of the program is the large amount of data collected in this area for the past 6 years. These data allow establishment of baselines for groups of products so that by statistical consideration of results being ob- tained currently, trends or changes in these base levels may be detected. Brief Descriptions of the Programs 1. The Market Basket Program on Total Diet Studies has been uf)dated this year. The composition of the baskets has been changed to reflect the latest U.S. De- partment of Agriculture (1965) information on food consumption. A total of 1 1 7 items are now included in each basket, and regional variations are recognized in the composition of the baskets collected by the different participating Districts. There has been no change in the areas where Market Basket samples are collected nor has there been any change in the frequency of sampling. A change has been made to obtain information on several food categories as purchased in the market for comparison with the ready-to-eat composite. The items now included in the Market Basket samples are given in Appendix A with the regional variations indicated. 2. The other major program of the Food and Drug Administration to be utilized in accomplishing the ob- jectives of the National Monitoring Program is the new FDA surveillance program for pesticide residues. This new program replaces the former monitoring program which was based on food classes and the older surveil- lance activities based on sampling at destination. This current program is designed to determine pesticide resi- due levels of individual corrmiodities on a geographical basis through the use of a sampling plan developed and based on sound statistical principles. The new program requires sampling individual items of food or crops at their origin. Each of the 17 field Districts of the Food and Drug Administration will sample and examine the major food and feed items produced within its area to 38 determine the current levels of pesticide residues. For example, the Minneapolis District will be expected to devote a considerable portion of its effort to dairy prod- ucts and Los Angeles and Atlanta Districts wUl be more heavily involved in the area of fresh fruits and vege- tables. Headquarters program analysis units will analyze the results obtained by the field Districts to produce the national picture. 3. The Consumer Protection Program, Consumer and Marketing Service, U. S. Department of Agriculture, has primary responsibility for sampling meats and poultry. This program will involve sampling at about 1,200 slaughtering plants. The instructions for sampling pro- vide that samples should be selected from animals originating in the State in which the plant is located and, to the extent possible, samples from each location should be derived from different originating premises. Geographical Distribution of Sampling Stations 1. Sampling in the Market Basket Survey (for analysis of composites of food items prepared for consumption) is carried out in five regions representing the North- eastern, Southeastern, North Central, Central, and West- em United States. Five FDA District offices are in- volved (Boston, Baltimore, Minneapolis, Kansas City, and Los Angeles). Sampling sites within each region are chosen from different cities, one representing a standard metropolitan statistical area and one representing a smaller population center (less than 50,000 population). 2. Samples in the nationwide surveillance of unpro- cessed foods are collected at all major growing, proces- sing, and marketing centers. Animal food ready for consumption is included in this part of the program. Collection headquarters are in each of the 17 Regional Districts of the Food and Drug Administration, with offices in Boston, New York City, Buffalo, Philadelphia, Baltimore, Atlanta, Cincinnati, Detroit, Chicago, New Orleans, Minneapolis, Kansas City, Dallas, Denver, Los Angeles, San Francisco, and Seattle. 3. Meat samples at slaughter will be taken at 1,200 of the Nation's major meat processing centers. Sampling Frequency , Number of Samples 1. Market Basket samples are collected six times per year in each of the five geographic regions mentioned above, making a total of 30 Market Basket samples annually. 2. The surveillance program encompasses an estimated 2.5 million carloads of raw agricultural products an- nually shipped in interstate commerce. In addition, there are thousands of lots of other foods, e.g., milk, eggs, fish, and processed animal feeds, produced each year. Pesticides Monitoring Journal It is not possible to estimate accurately at this time the number of samples which will be collected annually under the new surveillance program, although it is expected to be approximately 10,000-12,000. Sampling Schedule The sampling schedule, as given below, has been de- veloped for the surveillance program on a national basis. This program has been designed to provide information on specific products on a point-of-origin rather than a destination basis in order to integrate the District sur- veillance program into the national program. It can be used on a local or District basis (1) to gather intelligence about a crop as a whole by taking one sample from each of 12 growers, (2) to evaluate a grower by taking one sample from each of 12 available lots of the same commodity, and (3) to evaluate one orchard (or field) by taking 12 samples at random through the area; or it can be used nationally (1) to compare the results on a prod- uct from several regions of the country, (2) to evaluate the results on a national basis, and (3) to compare the results with previous years to determine or discern trends. The sampling plan has been designed to allow statistical estimates of the incidence of residues in the population to be made with a 95% confidence that the sample esti- mate will be within dz 2-5% (depending upon the actual incidence and number of samples examined) of the population parameter. Recommended CoMMODrriES Minimum Number OF Samples Large Fruits. Beans, Vine and Ear Vegetables 12 Grains and Cereals, Nuts. Root Vegetables 12 Small Fruits, Eggs, Fluid Milk 12 Dairy Products 12 Leaf and Stem Vegetables 18 Processed Foods 28 The Consumer and Marketing Service will sample and examine meat and poultry according to the following schedule: Animal Poultry Month Year Month Year Chlorinated Hydrocarbons Organophosphates* Carbamates' Heavy Metals 292 25 25 3500 300 300 3700 250 0 0 3000 0 0 500 • These programs may b ; reduced or held i n abeyance since past results indicate little problem in this area. Commodities to be Sampled 1. In the Market Basket Survey, samples are collected according to a series of 117 items listed by commodity groups in Appendix A. Adjustments are made in this list to reflect local dietary patterns in each geographic area. Vol. 5, No. 1, June 1971 The list also will continue to be evaluated periodically and changed as necessary to reflect changes in dietary patterns, particularly in the area of "convenience" and frozen foods. 2. Commodities sampled under the national surveillance program for unprocessed foods and feeds are listed in Appendix C. A sampling schedule for these commodi- ties is included in Appendix D 3. The commodities to be sampled are meat and poultry. Sample Preparation 1. Market Basket items which normally require further processing by cooking, such as fresh meats and certain raw vegetables, or preparation for eating raw, such as tomatoes, carrots, celery, lettuce, cucumber, cabbage, and fresh fruits, are delivered to a diet kitchen for preparation under the direction of a dietician. Some food items, e.g., cabbage, are included in both the raw and cooked forms. Instructions to the diet kitchen for pre- paring these food items are contained in Appendix B. Market Basket items normally consumed as purchased or which do not otherwise require further processing, e.g., dairy products, luncheon meats and frankfurthers, canned meats, some fruits and vegetables, potato chips, canned fruit juices, concentrated fruit juices, and frozen fruits, are to be retained by the examining laboratory for compositing by commodity groups with the foods prepared by the diet kitchen. 2. and 3. Guidelines for compositing food items sampled in the surveillance of unprocessed foods are given in Appendix E. Sample Analysis Procedures All analytical procedures used in this program are described in the Food and Drug Administration s Pesti- cide Analytical Manual. 1. For the Market Basket Survey, procedures for ex- amining each commodity group are outlined as follows: Chlorinated Organic Pesticides. Examine all commodity groups at sensitivity levels equivalent to 0.003 parts per million heptachlor epoxide using electron capture, gas- liquid chromatography. Residues above these limits are to be checked by tests such as thin layer chromatography element-specific GLC detectors, p-values, derivatization, etc., beyond E'^-GLC and results reported to the nearest 0.001 ppm. When the presence of polychlorinated bi- phenyls is indicated by the EC chromatogram, analyze for PCB and organochlorine pesticides after separation by the method described in JAOAC 53(4)761-768. 39 Multiple detection procedures are to be used to detect the chlorinated organic compounds included in Ap- pendix F. Organic Phosphate Pesticides. Examine all commodity groups simultaneously with chlorinated organic residue analyses using a dual detection system at a sensitivity level of 0.01 ppm (parathion) based on whole weight of sample. Confirm residues described for chlorinated or- ganic compounds. Herbicides. Examine all commodity groups by Dohr- mann GLC; confirm by thin layer chromatography. Carbamates. Examine all commodity groups for car- baryl, except groups 1, 2, and 10, Appendix A, and confirm positive findings. The fungicide ortho-phenyl^ phenol is determined along with carbaryl in the TLC method employed. Arsenic. Examine all commodity groups. Cadmium. Examine all commodity groups. Cadmium has no pesticidal usage but is currently being determined to obtain information regarding its dietary intake. Mercury. Examine all commodity groups at a sensitivity of 0.02 ppm using flameless atomic absorption [JAOAC 54(2):466-467(1971)]. Confirmation and greater sensitiv- ity by neutron activation analysis can be provided by FDA's Bureau of Foods where composites are also sent for research/ support purposes. Polychlorinated Biphenyl Residues. Analyze Groups I and II. (Indication of PCB's in other groups should be followed by similar analysis for PCB's in these groups). Separate PCB's from the 6% eluate used for analysis for organochlorine and organophosphorus residues. Use the silicic acid column as described by Armour and Burke, [JAOAC, 53(4):761-768 (1970)]. Determine residues by electron capture GLC versus ap- propriate Aroclor standard. Inject 100 mg sample at the same instrument sensitivity specified for organochlorine residues to provide method sensitivity of 0.05 ppm PCB. 2. For the nationwide surveillance of unprocessed food and feed, all samples are to be examined for chlorinated organic pesticides and organic phosphate pesticides (see Appendix F) by procedures at sensitivity levels equival- ent to 0.03 ppm heptachlor epoxide using dual electron capture and thermionic detection, gas-liquid chroma- tography. Individual samples selected at random are to be examined for residues of chlorophenoxy compounds, carbaryl, and carbamates. Analytical procedures are described in FDA's Pesticide Analytical Manual. 40 3. The samples are to be examined for chlorinated organic pesticide residues by methods in FDA's Pesti- cide Analytical Manual. The analyses will be made on the edible fat. Heavy metals (mercury, lead, cadmium, copper, and arsenic) are determined by atomic adsorption methods as follows: Cattle: muscle, liver, and kidney Poultry: muscle, liver, and kidney Imports: canned pork products and frozen boneless beef Dairy cattle: muscle, liver, kidney, and hair from tail. APPENDIX A Market Basket Composition By Commodity Groups 1. Dairy Products Milk, fresh fluid whole Evaporated milk Nonfat dry milk Ice cream Cottage cheese Processed cheese (American) Natural cheese Butter Margarine Skim milk Ice milk (Baltimore and Los Angeles only) Buttermilk (Baltimore only) 2. Meat, Fish, and Poultry Lamb (Boston and Los Angeles only) Roast beef Ground beef Pork chops Bacon Chicken (eviscerated — fresh or frozen) Fish fillet, fresh or frozen Tuna or salmon, canned Luncheon meat Frankfurters Liver, beef Eggs, large Ham. cured Round steak Veal, chops, or cutlets (Baltimore and Boston only) Raw shrimp, fresh or frozen (Baltimore and Boston only) 3. Grains and Cereal Prodoct^ ' Flour, general purpose Flour, self-rising (Baltimore only) Pancake mix Corn flakes Shredded wheat or wheat cereal Rice flakes or puffed rice Oatmeal Rice Corn meal Com grits (Baltimore only) Macaroni, elbow Bread, white enriched Bread, whole wheat Rolls (sweet, cinnamon, bismarcks, etc.) Snack Items (pretzels, corn chips, crackers, etc.) Cookies, plain (w/o nuts or chocolate) Buns, frankfurter or hamburger Pie crust (fruit filling in Item 9) Cake mix Wheat cereal, uncooked (all except Baltimore) Corn, raw, canned or frozen Potatoes, white (bake V2) Potatoes, white (boil V4) Potatoes, white (fry V4) Potato chips Frozen french fries Dehydrated potatoes (all except "Boston) Sweet potatoes or yams, fresh or canned 5. Leafy Vegetables CoUards, spinach or mustard greens (fresh, frozen, or canned) Celery, raw Lettuce, raw Cabbage (raw V4) Cabbage (boil V4) Broccoli, fresh or frozen Asparagus, fresh, frozen, or canned Cauliflower, fresh or frozen (Kansas City, Los Angeles, and Minneapolis only) 6. Legume Vegetables Peas, fresh, frozen, or canned Green Beans, fresh, frozen, or canned Beans w/pork, canned Lima beans, frozen Pesticides Monitoring Journal 7. Root Vegetables Carrots, fresh or canned, tops Onions dry (raw V4) Onions, dry (boil Vi) Beets, fresh or canned, w/o tops Green onions 8. Garden Fruits Green peppers, fresh Tomatoes, fresh Tomatoes, canned Catsup Cucumbers, fresh Pickles, dill or sweet Vegetable soup, canned condensed Tomato soup, canned condensed Fruit filling from pie (see Item 3) Oranges, fresh Citrus juice, frozen concentrated Citrus juice, fresh or canned Bananas Raisins Peaches, fresh or canned Apples, fresh Strawberries, fresh or frozen Prunes Grapefruit, fresh Fruit juice, non-citrus, canned Apricots, fresh or canned Cherries, fresh or canned Grapes, fresh Pears, fresh or canned Pineapple, fresh or canned Rhubarb, w/o tops, fresh (all except Baltimore) Watermelon Cantaloupe Fruit cocktail 10. Oils, Fats and Shortening Salad dressing, french Salad dressing, mayonnaise Salad dressing, salad Shortening, hydrogenated Peanut butter 11. Sugar and Adjuncts White sugar JeUy Pudding mix Syrup, blended cane-maple Jam Candy bars Baicing powder Salt Vinegar Tea leaves Cola soft drink Coffee, ground Non-Cola soft drink Cocoa, plain (not drink powder) Coffee, instant APPENDIX B Instructions For Food Preparation and Check List Of Items In Sample (Market Basket Survey) The food items listed below are those requiring preparation. The preparation may consist of roasting, baking, broiling, frying, or boiling. Use the shortening provided in the "market basket" during preparation. Some vegetables are to be prepared to eat raw. After processing, wrap in alumi- num foil or place in labeled containers. Food Item Instructions Chuck roast Groimd beef Pork chops Bacon Chicken Roast, medium-well done. Remove bone and discard. Save drippings. Make into patties, broil, save drippings. Broil. Remove bone and discard. Save drippings. Broil. Roast. Discard neck and taU portion before cooking. Remove edible meat from bone after roasting. Save drippings. Fish fillet Liver, beef Ham Round steak Veal, chops or cutlets Roast, lamb Raw shrimp Potatoes, white Frozen french fries Tomatoes, fresh Oranges, raw Grapefruit Carrots, raw Greens (collards mustard, spinach) Green pepper Broccoli Sweet potatoes Olery Lettuce Cucumber Cabbage Onions, dry Onions, green Peas Green beans Com, sweet Peaches, raw Apples Strawberries Other vegetables Asparagus Beets Lima beans Cauliflower Otber fruits Apricots Cherries Grapes Pears Initnictions Broil. Broil. Save drippings. Roast, medium-well done. Remove 'bone and discard. Save drippings. Broil, medium-well done. Remove bone and discard. Save drippings. Broil. Remove bone and discard. Save drippings. Roast, medium-well done. Remove bone and discard. Save drippings. Boil water, add shrimp until done. Remove shell and devein. Bake. Leave skin on. (W of total) Fry. (Va of total) Boil. Peel and discard sltin before boiling. (V4 of total) Discard cooking water. Heat in oven. Follow package label instructions. Wash, remove core, do not peel. Remove peel and seeds. Remove peel and seeds. Wash, scrape, slice ready-to-eat raw. Fresh or frozen. Wash, trim, cook fresh item. Cook frozen item. Discard cooking water. Pepper, fresh. Prepare to eat raw. Fresh broccoli washed, trimmed, and cooked. Frozen broccoli cooked. Cooking water discarded. Wash, peel, and bake. Wash, trim, cut ready-to-eat. Trim, quarter ready-to-eat. Wash to remove wax. (1) Raw. Trim and chop for slaw. (2) Cook after trimming. Discard cooking water. (1) Raw. Clean and quarter. (2) Cook. Clean and boil. Discard cooking water. Wash, trim ready-to-eat. Fresh peas in season. Remove pods, cook. Frozen peas cook. Discard cooking water from both. Fresh beans if available. Wash, and cook fresh or frozen. Discard cooking water. Fresh if available. Remove husk, trim, cook in boil- ing water. Discard water. Remove cooked com from ear. Cook frozen corn and discard water. Discard cobs. Fresh when available. Wash, peel, remove pits and halve. Wash, remove core, do not peel. Fresh in season. Wash, remove stems. Halve. Fresh and frozen vegetables will be cooked . Fresh in season. Wash and cook. Frozen to be cooked. Discard cooking water. Fresh beets. Wash, trim, and cook. Discard cooking water. Frozen to be cooked. Discard cooking wat< r. Wash, trim, and cook fresh cauliflower. Cook frozen cauliflower. Discard cooking water. Fresh fruits only lo be processed. Wash and pit. Wash and pit. Wash, remove seeds and stems. Wash and core. Pineapple Trim and core. Rhubarb Trim. Watermelon Trim and remove seeds. Cantaloupe Trim and remove seeds and pulp. Shortening (Unused shortening to be returned with processed foods and included in composite.) Vol. 5, No. 1, June 1971 41 APPENDIX C Nationwide Surveillance Commodities Large fruit Small fruit Leaf and stem vegetables Vine and ear vegetables Beans Root vegetables Nuts Hay and silage Wheat Corn Oats Rye Sorghum Barley Flax Rice Soybeans Fluid milk Shell eggs Fish and oysters Meats (beef, pork, mutton, lamb and poultry) Mfd. animal feed Vegetable oil Fish liver oil Other [e.g., coffee beans, cocoa beans, spices (black pepper, paprika), etc.] APPENDIX D Sampling Schedule For Nationwide Surveillance Commodities Treat each identifiable grower's mark or lot number in the shipment as a separate sample. Sample, as a single lot, ship- ments containing commingled and unidentifiable lots from several growers. Be careful not to collect more than the proportional amount from facing layers. When sampling from loading cars, select subsamples at intervals to obtain a sample representative of the carload. For bulk lots select subs at random throughout the lot. Collect a composite sample closely approximating 20 lb by taking a 2-lb sub from each of 10 different shipping con- tainers selected at random. DO NOT cut or divide individual produce items to adjust sub weights. SPECIAL NOTE: Some produce items weighing 2 lb or more each, such as melons, pineapples, large heads of cabbage, large cauliflower, large celery stalks, large ruta- bagas, etc., do not lend themselves to the above sampling approaches. In such cases, collect a total composite sample of 10 subs taking one item from each shipping container. For light bulky produce, e.g., collards, spinach, leaf lettuce, other leafy products, hay, etc., collect a 10-lb composite sample taking 1 lb from each of 10 different shipping con- tainers selected at random. Hold samples in cold storage until ready to be shipped or de- livered to the laboratory only if normally held or shipped under refrigeration in commercial practice. APPENDIX E Guidelines For Compositing Unprocessed Food Samples Animal tissue Dairy products Eggs Fruits Large Small Grains Hay Milk Nuts Oils Seeds Spices Vegetables Head Leafy Pod Root Stalk Grind about half of each sub (meat grinder); com- posite 100 g from each sub and grind again. Equal weight from each sub. Grind, dice, or blend. Equal number of units from each sub, for total of 6-12. Blend. 200 g from each sub (quarter subs down to 200 g where necessary); wet feeds (silage) 100 g from each sub. Quarter each sub down to 200 g; composite 200 g from each sub. Chop fine. Where necessary, grind in Wiley Mill without screen; then with screen in. (apples, pears, tomatoes, etc.). Equal number of units from each sub. Chop or blend. 200 g from each sub. Chop or blend. 100 g from each sub. Grind in Wiley Mill or equiv- alent. 200 g from each sub. Chop or grind. 100 g (ml) from each sub after thorough shaking. Remove shells. Composite equal number of units (equal weight) from each sub. Chop or grind. Equal weight or volume from each sub. 100 g from each sub. Grind. 200 g from each sub. Grind or chop. Quarter each head in the sub. Take two opposite quarters from each head and chop into 1- to 2-inch pieces with a knife. Mix well. Composite 200 g of chopped product from each sub and chop entire composite in a food chopper. Leaf Cut — Mix sub well and select leaves at random until a 200-g portion is obtained. Composite in a food chopper. (beans, peas, etc.. also asparagus) 200 g from each sub. Chop or grind. Equal number of units from each sub. Chop or grind. (celery, broccoli, etc.) Quarter each sub length- wise and proceed as in "Head Vegetables." APPENDIX F Quantitative and Qualitative Common or Trade Name Chemical Name Aldrin BHC (benzene hexachloride) Bulan® Butoxyethanol ester, 2.4-d Butoxyethanol ester. 2,4,5-T Butylether ester. 2,4-D n-Butyl ester. 2.4-D «-Butyl ester, 2,4,5-T Chlorbenside Chlordane l,2,3.4,10,10-hexachloro-I,4,4a.5,8,8a-hexahydro-l,4-en£io-exc>-5,8-dimethanonaphthalene 1,2,3,4,5.6-hexachlorocyclohexane 2-nitro- 1 . 1-bis ( p-chlorophenyl ) butane butoxyethanol ester of 2,4-dichIorophenoxyacetic acid butoxyethanol ester of 2.4.5-trichlorophenoxyacetic acid butyl ether ester of 2.4-dichlorophenoxyacetic acid n-butyl ester of 2.4-dichlorophenoxyacetic acid n-butyl ester of 2.4,5-trichlorophenoxyacetic acid p-chlorobenzyl- p-chlorophenyl sulfide l,2,3,5,6,7,8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene 42 Pesticides Monitoring Journal Common or Trade Name Chemical Name 11. Chlordecone decacWorooctahydro-l,3,4-metheno-2//-cyclobutatcd] pentalen-2-one 12. Chlorinated naphthalenes 13. Chlorobenzilate ethyl 4,4'-dichlorobenzilate 14. Chlorothion (?,0-dimethyl 0( 3-chloro-4-nitrophenyl ) phosphorothioate 15. CIPC isopropyl N- ( 3-chlorophenyl ) carbamate 16. Dacthal® (DCPA) dimethyl 2,3,5,6-tetrachloroterephthalate 17. DDE dichlorodiphenyl dichloroethylene 18. DDT (o.p' + p.p'; o.p': p.p') dichlorodiphenyl trichloroethane 19. Diazinon 0,0-diethyl 0-(2-isopropyl-4-methyl-6-pyrimidyl ) phosphorothioate 20. Dichloran 2,6-dichloro-4-nilroaniline 21. Dieldrin I,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l,4-cnrfo-eio-5,8-dimelhanonaphthalene 22. Photodieldrin 23. Dilan* (See Bulan and Prolan®) 24. Dyrene® 2,4-dichloro-6-(p-chloroarilino)-s-triazine 25. Endrin 1,2,3 ,4,10, 10-hexachloro-6,7-epoxy-l,4,4a.5,6,7.8,8a-octahydro-I,4-cn(;o-ef;rfo-5,8-dimethanon.iphthaIene 26. Endrin alcohol 27. Endrin aldehyde 28. Endrin ketone 29. Ethion 0,0,0',0'-telraethyl-S-5'-methylene bis-phosphorodithioate 30. Ethyl hexyl ester, 2,4-D ethyl hexyl ester of 2,4-dichIorophenoxyacetic acid 31. EPN 0-ethyl 0-p-nitrophenyl phenylphosphonothioate 32. Folpet /^-trichloromethylthiophthalimide 33. Heptachlor l,4,5,6,7,8.8-heptachloro-3a,4,7,7a-tetrahydro-4,7-endo-methanoindene 34. Heptachlor epoxide l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 35. Hexachlorobenzene Same 36. Isobutyl ester. 2,4-D isobutyl ester of 2,4-dichlorophenoxyacetic acid 37. Iso-octyl ester, 2,4,5-T iso-octyl ester of 2,4.5-trichlorophenoxyacetic acid 38. Iso-octyl ester, 2,4-D iso-octyl ester of 2,4-dichlorophenoxyacetic acid 39. Isopropyl ester, 2,4,5-T isopropyl ester of 2,4.5-trichlorophenoxyacetic acid 40. Isopropyl ester, 2,4-D isopropyl ester of 2,4-dichlorophenoxyacetic acid 41. Kelthane® (dicofol) l,l-bis(p-chlorophenyl)-2,2,2-trichloroethanol 42. Lindane y isomer of benzene hexachloride 43. Malathion 5-[l,2-bis(ethoxycarbonyl)ethyll0,0-dimethyl phosphorodithioate 44. Merphos tributyl phosphorotrithioite 45. Methoxychlor l,l,l-trichloro-2,2-bis(p-methoxyphenyl) ethane 46. Methyl parathion 0.0-dimethyl 0-p-nitrophenyl phosphorothioate 47. Mirex dodecachlorooctahydro-l,3,4-metheno-2W-cyclobuta[cd]pentalene; GC-1.283(allied); ENT 25, 719 48. Octachlor epoxide (oxychlordane) 49. Ovex p.-.^ C7~ ^'» PUERTO Sampling Procedures WATER SAMPLES All samples are to be collected in 1 -liter glass bottles fur- nished by the laboratory performing the analyses. Prior to collection, scrupulous cleansing of sample containers is required. Chromic acid cleaning solution or other suitable agents are to be used, followed by seveial rins- ings with organic-free distilled water. Containers are to be further treated as necessary to destroy remaining traces of organic matter. Heating overnight at 300°C has been found to be satisfactory. Bottles are to be capped immediately to prevent airborne contamination. The sample must have no contact with rubber, cork, and most plastics; Teflon, however, will not contaminate the sample. Samples are collected in prepared containers by lowering them in an appropriate sampler in a vertical sect-on of the stream which is representative of the stream cross section. The bottle is to be lowered as close as possible to the bottom of the stream, or to a maximum depth of 100 feet, and returned to the surface at an equal transit rate so that all points in the vertical section are repre- sented in the sample. Prior reconnaissance of selected 55 water quality parameters at several vertical sections of the stream may be required to determine degree of uni- formity in the cross section. If lack of complete mixing is suspected, the station should be moved to a site where a representative sample may be easily obtained. To prevent contamination, it is important that the sample not be transferred from one container to another. Sepa- rate containers must be used for determination of any parameters that may be desired in addition to pesticides. A sample tag or label providing appropriate identifica- tion is to be completed and firmly affixed to each sample container. Recorded information includes river flow or stage, temperature, measured water properties such as conductivity, pH, dissolved oxygen, etc., physical ap- pearance of the water, and unusual physical stream features. Samples are to be shipped in protective packing cases to the laboratory as soon as possible after collection, using air parcel post, railway express, overnight bus service, or air express. It is highly desirable that samples arrive at the laboratory and extraction be commenced within 24 hours after collection. Extractions should be made upon arrival at the laboratory and the extracts stored in a refrigerator just above freezing until analysis can be started. BOTTOM SEDIMENTS It is well documented that pesticides entering many streams are associated with soil particles. Fluvial mate- rials settle out during periods of low streamflow, and solids accumulated on the streambed mav contain up to 2,500 times the quantities of pesticides measured in the overlying water (10, 11). Organic debris may have pesti- cide residues several thousand times the concentrations found in water (12). Keith and Hunt (13) report residues in particulates that are 10,000 to 100,000 times higher than measured values from filtrates. Therefore, it is im- portant to analyze the bottom materials concurrently with the overlying water to provide data for a meaningful assessment. Pesticides in sediments accumulated from nmoff of the previous spring and summer would be in the freshly deposited layer of the streambed. Hence, every effort should be made to collect only fresh deposition or that material in the upper 3 inches of the bottom deposits. These samples may well be an important index of gen- eral pesticide levels in the hydrologic environment. Care should be taken to minimize loss of the lightweight deposits during the sampling process. This requires the use of a bottom sampler capable of trapping the "fines" with a high degree of success. Bed-material samplers such as the US BMH 60, piston type, and commercial core samplers, appear to be adequate for this purpose. Cores 56 may be taken with a metal tube sampler and composited. When extreme difficulty in sampling bed material is en- countered, an alternative is the collection of moist bank deposits with a tool such as a small, chrome-plated garden spade. At times of very low discharge when streams may be waded, deposits may be taken directly from the streambed using a hand sampler. Following collection, the bottom sample should be placed in a wide-mouth glass jar meeting the same cleansing requirements described for the water sample bottles. Sample handling and shipment should be the same as for water samples. Sediment samples should be refrigerated and extracted as soon as possible, although the timing is not quite as critical as for the liquid phase. Sampling Frequency The optimum sampling frequency required to define pesticide levels in the waters of the Nation depends on the variability in pesticide concentrations throughout the year. In a statistical sense, there is no answer to the question of how many samples are needed over the period of a year without foreknowledge of the variability in concentration of the pesticides being measured. Thus, a rather arbitrary frequency must be set initially, and adjusted at a later date after sufficient data have been evaluated. Because of very limited manpower and funds, the num- ber of samples collected must he held to a minimum. Thus, it is imperative that sampling be conducted at periods that will yield the greatest amount of informa- tion. The number of fish kills that occurred each month dur- ing the 1965-69 period as a result of pesticides con- tamination, indicates that highest concentrations of pesti- cides in water might occur during July and August, and lowest concentrations during November (14). This infor- mation is summarized in the following tabulation: Number of documented fish kills resulting from pesticides, in the United States, 1965-69 Months Year Totals J F M A M J J A S O N D 1965 0 2 1 4 3 14 23 24 1 0 1 1 74 1966 1 2 3 1 4 8 12 17 2 0 0 1 51 1967 1 0 1 2 7 5 10 12 1 1 0 0 40 1968 0 1 1 3 6 4 14 8 7 1 0 2 M8 1969 3 0 2 3 10 11 15 13 6 5 1 1 =80 Totals 5 5 g 13 30 42 74 74 17 7 2 5 293 ^ Month of occurrence of one kill not given. 2 Month of occurrence of 10 kills not given. Since most pesticides are introduced into the hydrologic system between early spring and late summer, highest levels in the bottom sediment might ordinarily be ex- pected several months later. A majority of streams are Pesticides Monitoring Journal at low flow during October and November; hence, most of the erosion products transported during and im- mediately following the pesticide application season would be deposited in the stream beds by this time. Rel- atively little of this material would have had an op- portunity to pass from subbasins to coastal waters. In April and May, the majority of streams are at high flow, transporting a near maximum suspended sediment load just prior to the pesticide application season. Re- sults might be indicative of the residual eff'ect of the previous year's (or years') application (s) of pesticides. Based upon these hypotheses, it is recommended that as a minimal program, water samples be collected at all stations four times a year — the first weeks of November, February, May, and August. An annual mean of the pesticide level at each station can thus be obtained. Collection schedules may be adjusted slightly to be com- patible with a regularly scheduled visit to the accounting stations. A bottom sediment sample should be collected at each station concurrent with the November and May sampling. As soon as sufficient data are available from this pro- gram, and periodically thereafter, an assessment should be made of the number of stations, the pesticides being identified, and the sampling frequency so that adjust- ments can be made as necessary to maintain an eflfective program. Identification Schedule Pesticides of current interest continue to be largely the compounds indicated in the primary monitoring list pre- pared by Schechter in 1967 (15). Concern over levels of the DDT family in particular, and persistent chlorinated hydrocarbons in general, has culminated in severe re- strictions upon and prohibition of use of certain formu- lations by Federal and State agencies. Ecologists and environmentalists continually express concern over use and toxicological eff'ects of pesticides in scientific journals and at national meetings of professional societies. Based upon the number of reported positive identifica- tions, and with due consideration to those pesticides used in significant quantities and listings in the "Revised Chemicals Monitoring Guide for the National Pesticide Monitoring Program" (16), the minimum analytical schedule should include the following determinations: Insecticides Herbicides Aldrin Heptachlor 2.4-D Chlordane Lindane 2,4.5-T DDD Malathion Silvex DDE Methoxychlor DDT Methyl parathion Dieldrin Parathion Endrin Toxaphene Vol. 5, No. 1, June 1971 All significant peaks on chromatograms should be identi- fied and quantified if possible and a report made of metabolites or breakdown products which are pesticidal or toxic. The schedule should be thoroughly evaluated every 2 years in accordance with revisions of the Chemicals Monitoring Guide, positive identifications, laboratory experience, advances in technology, compatability with other components of the National Pesticide Monitoring Program, and objectives of the Monitoring Panel. In- terim adjustments, such as surmounting the interfer- ences caused by polychlorinated biphenyl compounds (PCB's) should be made as necessary, and eff'ort ex- pended to identify and quantitate those compounds. Analytical Methods CHLORINATED INSECTICIDES IN WATER Upon receipt from the field, water samples are refrig- erated until extracted, normally within 1 to 2 days. One liter (or larger) samples are extracted. The basic pro- cedures are described by Lamar, Goerlitz, and Law (17) and the Federal Water Pollution Control Administration (18), now the Water Quality Office. Environmental Pro- tection Agency. Solvent extracts are to be concentrated and analyzed by dual column electron capture gas chromatography (ECGC) as minimum identification. Microcoulometry, or mass spectrometry coupled with gas chromatography (GC/MS), may be used for con- firmation. If the concentrated sample appears "dirty," i.e., colored, cloudy, viscous, or is believed to contain materials which may interfere with measurement, column cleanup or thin layer chromatography (TLC) (18) will be required. A microcolumn cleanup using a suitable adsorbent should routinely be used as a final step before analysis by ECGC (19). The instrumental analysis is performed with extracts in- jected into two columns having different retentii^in prop- erties. Typical columns used are pyrex glass, packed with special solid supports treated with DC-200 which is a non-polar column, and QF-1, a polar column. Posi- tive identification can usually be obtained by corrobora- tion of results using at least two types of GC columns. Additional confirmation, when required, can be made using specific detectors such as chloride, sul'iur, or nitrogen microcoulometry, and GC phosphorous detec- tors. Analysis by a third column with different retention times can be quite helpful, and if infrarred or mass spectroscopy are available, special techniques applied to separated materials can aid substantially in positive identification. 57 CHLORINATED HERBICIDES IN WATER Screening for the phenoxyacetic and propionic acid herbicides, 2,4-D, 2,4,5-T, and silvex, is presently ac- complished on water samples using the method de- veloped by Goeriitz and Lamar (20). Each sample is acidified at time of collection or immediately upon re- ceipt to pH 2 or less with redistilled, reagent grade sulfuric acid, and stored in a refrigerator at 5-6 °C. The extraction should be carried out within 1-2 days to pre- vent any additional decomposition of the herbicides. Herbicide extraction is performed with ethyl ether, followed by alkaline hydrolysis with potassium hy- droxide, cleanup with ether, acidification, and re-extrac- tion of the acids with ether. After an evaporation step, the herbicide acids are esterified with boron trifluoride- methanol reagent. The methyl esters of the herbicides are cleaned up on Florisil and concentrated in benzene solution to 2 ml/or less. Extracts are analyzed by dual column ECGC. Recoveries of spiked samples average 85-110%. Insecticide and herbicide concentrations of 0.01 jug/liter can be determined routinely in most waters by these techniques. Special sample handling will allow determination at the 0.005 ^g/liter level, and in some cases 0.001 /xg/liter. Reportable values should be re- stricted to an excess of twice the background noise levels. CHLORINATED INSECTICIDES IN SEDIMENTS Bottom sediments are normally collected and shipped in wide-mouth glass containers. Upon receipt in the labora- tory, they are refrigerated until extracted. The analytical procedure is described in a techniques manual by Goer- iitz and Brown (21). Moist sediments can be extracted by an acetone-hexane technique. Following column cleanup, the extract is analyzed by dual column ECGC and/or microcoulometry. Confirmation techniques can be used as described for the water samples. Only moist samples of sediment are extracted and quantitation for common base compari- sons is achieved by performing moisture determinations on all samples. If very dry sediments are submitted, samples must be moistened with organic-free distilled water. CHLORINATED HERBICIDES IN SEDIMENTS A procedure for the separation and identification of phenoxy acid herbicides in bottom material is also con- tained in the "Techniques Manual" (21). The general approach is acidification of a moist sample to pH 1-2, refrigeration if necessitated by workload, and extraction with acetone-ether. Following cleanup, minimum an- alysis is performed by dual column ECGC and/or micro- coulometric techniques. 58 NEED FOR STANDARDIZED PROCEDURES For the proposed program to be effective, a specific set of procedures should be followed by all participants. In addition, the set of methods employed should be ac- ceptable to all agencies that intend to make use of the data. It is therefore recommended that agreement on and standardization of sampling, analytical, and quality con- trol procedures, be the first steps taken by the Federal agencies that are to make use of data provided by this monitoring program. It is further recommended that this be accomplished through formation of a group or subcommittee consisting of representatives of each of these agencies and who have responsibility for selecting their agency's analytical methods. Until uniform methodolgy is agreed upon, procedures currently employed by individual agencies should be used to insure program continuity. Data Evaluation Annual reporting should be made to the Monitoring Panel, Working Group on Pesticides, which is responsi- ble to the Council on Environmental Quality. A com- prehensive, biennial assessment should be reported in the Pesticides Monitoring Journal. In consideration of recommendations made by the Na- tional Research Council of the National Academy of Sciences (22). the Report of the Subcommittee on En- vironmental Improvement of the American Chemical Society (23). the objectives of the OWDC and the Moni- toring Panel, data evaluations should be presented in forms most useful for those interested in pesticide as- sessments. Reporting high. low. and median pesticide levels for the major drainage areas defined by the Water Resources Council on a map similar to Fig. 1 seems to meet most all requirements. Tabular data for the subbasins would identify possible problem areas for intensive surveillance consideration. Interpretation of the pesticide data re- lated to other measured parameters at the hydrologic stations is in order. Correlation with streamflow, sedi- ment discharge, particle size, inorganic constituents, total organic carbon, and physical characteristics should be attempted. Recommendations should be made and steps taken to alter the program to allow proper assessment of suspected problem areas. Program Funding The estimated annual cost of the proposed program, consisting of the collection and analysis of four water samples and two bottom samples per station per year, is $195,000. Pesticides Monitoring Igurnal This monitoring program will assist in providing for the continuing-type data needs of several Federal agencies and, of course, many State agencies and other investiga- tive organizations. The proposed program clearly meets requirements of Bureau of the Budget Circular A-67, and accordingly, it is recommended that the program be implemented through the National Network commencing with the 1972 fiscal year. LITERATURE CITED (1) Green. R. S., and S. K. Love. 1967. Network to monitor hydrologic environment covers major drainage rivers. Pesticides Monit. J. Kl): 13-16. (2) Weaver, Leo. C. G. Gitnnerson, A. W. Brcidenbiich. and J. J. Lichtenherg. 1965. Chlorinated hydrocarbon pesticides in major U. S. river basins. Public Health Rep. 80(6):481-493. (3) Green, R. S.. C. G. Giinnersnn. and J. J. Lichtenherg. 1966. Pesticides in our national waters. Presented at Amer. Ass. Advance. Sci. Symp. "Agriculture and the Quality of Our Environment," Washington, D. C. (4) Breidenbach, A. W., C. G. Giinner.son, F. K. Kawahara. ]. J. Lichtenherg. and R. S. Green. 1967. Chlorinated hydrocarbon pesticides in major river basins, 1957-1965. Public Health Rep. 82(2): 139-156. (5) Lichtenherg, 1. }., ]. W . Eichelherger, R. C. Dressman, and J. E. Longhottom. 1970. Pesticides in surface waters of the United States — a 5-year summary, 1964-1968. Pesticides Monit. J. 4(2):71-86. (6) Brown, E.. and Y. A. Nishioka. 1967. Pesticides in selected western streams — a contribution to the National Program. Pesticides Monit. J. l(2):28-46. (7) Manigold. D. B.. and J. A. Schidze. 1969. Pesticides in selected western streams — a progress report. Pesticides Monit. J. 3(2): 124-135. (8) Manigold. D. B. and J. A. Schidze. 1971. Pesticides in selected western streams — a progress report 1969-1970. To be published. (9) United States Water Resources Council. 1968. The Nation's water resources. U. S. Govt. Printing Office, Washington, D. C. (10) Bailey. T. E.. and J. H. Hannum. 1967. Distribution of pesticides in California. Amer. Soc. Civil Eng. Proc, J. Sanit. Eng. Div. 93(SA5):27-43. (ID King P. H. 1968. A discussion on "Distribution of pesti- cides in California," by T. E. Bailey and J. H. Hannum. J. Sanit. Eng. Div. 93(SA5). (12) Odiim, W. E.. G. M. Woodnell. and C. E. Wurster. 1969. DDT residues absorbed from organic detritus by fiddler crabs. Science 16413879): $16-511. (13) Keith, J. O.. and E. G. Hunt. 1966. N. Amer. Wildlife Natur. Resources Conf. Trans. 31, p. 150-177. (14) U. S. Department of llic Interior. Federal Water Pollu- tion Control Administration. Pollution caused fish kills, 1966, 1967, 1968. 1969, and 1970. (15) Schcchter, M. 1967. Chemicals monitoring guide for national pesticide monitoring program. Pesticides Monit. J. 1(0:20-21. (16) Schcchter, Milton S. 1971. Revised chemicals moni- toring guide for the National Pesticide Monitoring Program. Pesticides Monit. J. (This issue). (17) Lamar, W. L., D. E. Goerlitz. and L. M. Law. 1965. Identification and measurement of chlorinated organic pesticides in water by electron capture gas chromatog- raphy. U. S. Geol. Surv. Water-Supply Paper 181 7-B. (IS) V. S. Department of the Interior. Federal Water Pollu- tion Control Administration. 1969. FWPCA method for chlorinated hydrocarbon pesticides in water and waste water. April 1969. (19) Law. LcRoy A/., and Donald E. Goerlitz. 1970. Micro- column chromatographic cleanup for the analysis of pesticides in water. J. Ass. Offic. Anal. Chem. 53(6): 1276-1286. (20) Goerlitz. D. F., and W. L. Lamar. 1967. Determination of phenoxy acid herbicides in water by electron capture and microcoulometric gas chromatography. U. S. Geol. Surv. Waler-Supply Paper 1817-C. " (21) Goerlitz, Donald F.. and Eugene Brown. Methods for analysis of organic substances in water. Book 5. Chap. A3, Techniques of Water-Resources Investigations of the U. S. Geol. Surv. In press. (22) National Academy of Sciences National Research Council. 1969. Report on persistent pesticides. Chem. Eng. News p. 32-33. (23) American Chemical Society. 1969. Cleaning our En- vironment— The Chemical Basis for Action: Report of the Committee on Chemistry and Public Affairs, 249 p. TABLE 1 . — Station descriptions for National Pesticides Water Monitoring Network WRC Accounting UNO- Station Name OWDC Catalog = OWDC Region i Unit Sub-Unit Number 01 01 Aroostook River at Washburn, Maine 01 C 13912 01 03 Merrimack River below Concord River at Lowell. Mass. 02 D 56786 01 05 Hudson River at Poughkeepsie, N.Y. 03 G 54070 01 07 Raritan River at Bound Brook, N.J. 03 J 51165 01 09 Delaware River at Trenton. N.J. 04 D 53966 01 10 Susquehanna River at Harrisburg, Pa. 04 Q 5'!044 01 11 Choptank River near Greensboro, Md. 05 C 54245 01 13 Pamunky River near Hanover, Va. 05 M SWi 02 01 Blackwater River near Franklin, Va. 06 A 11947 02 03 Roanoke River near Scotland Neck. N.C. 06 G 52130 02 05 Neuse River at Kinston, N.C. 06 M 52198 02 07 Pee Dee River near Rockingham, N.C. 07 I 52371 Vol. 5, No. 1, June 1971 59 TABLE 1. — Station descriptions jor National Pesticides Water Monitoring Network — Continued OWDC Catalog • OWDC WRC Region > Accounting Unit Site Number Station Name Unit Sub-Unft 02 09 Black River at Kingstree, S.C. 07 H 53468 02 11 Edisto River near Givhans, S.C. 07 W 53536 02 13 Savannah River near Clyo, Ga. 08 G 51016 02 15 Altamaha River at Doctortown, Ga. 08 O 51018 02 17 St. Mary's River near Gross, Fla. 09 C 61668 02 19 Main Canal at Vero Beach, Fla. 10 A 53137 02 22 Peace River at Arcadia, Fla. 10 F 53204 02 23 Hillsborough River near Zephyr Hills, Fla. 10 G 53223 02 25 Ochlockonee River near Havana, Fla. 11 C 53275 02 26 Chattahoochee River at Lanett, Ala. 11 D 55019 02 27 Choctawhatchee River near Bruce, Fla. 12 C 13653 02 29 Big Coldwater Creek near Milton, Fla. 12 F 61961 02 31 Tombigbee River near Jackson, Ala. 13 M 50128 02 33 Boque Chitio near Bush, La. 13 U 53945 03 01 St. Louis River at Scanlon, Minn. 29 D 57120 03 03 Tahquamenon River near Tahquamenon Para., Mich. 23 E 09067 03 05 Kalomazoo River at Saugatuck, Mich. 22 D 60213 03 07 Fox River at Green Bay. Wis. 23 Q 57802 03 09 Manistee River at Manistee, Mich. 22 L 60206 03 11 Cheboygan (Black) River at Cheboygan, Mich. 23 V 60203 03 13 Chnton River below Mt. Clemens, Mich. 22 X 60191 03 15 Cuyahoga River at Independence, Ohio 21 z 50917 03 17 Black River at Watertown, N.Y. 03 p 54105 03 19 Lake Champlain, N.Y. 02 u 61435 04 01 Allegheny River at Natrona, Pa. 21 F 53955 04 03 Beaver River, Pa. 21 o 61372 04 05 Muskingum River at McConnelsville, Ohio 21 u 50776 04 07 Hocking River at Athens, Ohio 21 W 50782 04 09 Kanawha River at Charleston, W. Va. 19 F 54284 04 11 Big Sandy River at Louisa, Ky. 19 J 50156 04 13 Ohio River at Cincinnati, Ohio 19 V 54973 04 15 Licking River at McKJnneysburg, Ky. 19 P 50159 04 16 Great Miami River at Elizabethtown, Ohio 19 R 50878 04 19 Ohio River at Louisville. Ky. 17 C 55058 04 21 Ohio River at Evansville, Ind. 17 D 55047 04 23 White River near Hazelton, Ind. 17 S 57579 04 25 Cumberland River near Grand Rivers, Ky. 18 O 50190 05 01 Tennessee River at South Pittsburg, Tenn. 18 R 58515 06 01 Mississippi River near Royalton, Minn. 28 W 57095 06 03 Minnesota River near Carver, Minn. 28 V 52750 06 05 Chippewa River, 3 mi E. of Pepin. Wis. 27 M 57815 06 07 Wisconsin River at Muscoda, Wis. 27 W 51226 06 09 Rock River at Rt. 92 Bridge, Joslin, lU. 26 M 59456 06 11 Des Moines River at Kcosauqua, Iowa 25 N 06796 06 13 Illinois River at Rt. 104 Bridge, Meredosia, 111. 24 O 59575 06 15 Mississippi River at Cape Girardeau, Mo. 16 F 55076 06 17 Big Muddy River at Murphysboro Water Intake, 111. 16 E 59535 07 01 Mississippi River at West Memphis, Ark. 16 R 55021 07 03 St. Francis River at Marked Tree, Ark. 16 Q 51074 07 05 Yazoo River at Greenwood, Miss. 15 J 1682S 07 07 Ouachita River at Camden. Ark. 15 N 16741 60 Pesticides Monitoring , TABLE 1. — Station descriptions for National Pesticides Water Monitoring Network — Continued WRC Region ' Accounting Unit Station Name OWDC Catalog = OWDC Srre Number Unit Sub-Unit 07 09 Little River near RocheUe, I^. 15 Z 53801 07 11 Mississippi River at Tarbert Landing, Miss. 14 E 54880 07 13 Calcasieu River near Kinder, La. 14 O 53928 08 03 Red River of the North at Grand Forks, N. Dak. 30 W 50541 08 05 Roseau River near Caribou, Minn. 30 V 57135 08 06 Souris River near Westhope (outflow), N. Dak. 39 c 56367 09 01 Missouri River at Toston, Mont. 41 I 03293 09 03 Marias River near Loma, Mont. 41 o 03356 09 05 Musselshell River near Mosby, Mont. 40 c 51108 09 07 Missouri River near Culbertson, Mont. 40 s 51115 09 09 Yellowstone River at Billings, Mont. 43 Q 51122 09 11 Yellowstone River near Sidney, Mont. 42 M 55086 09 13 Missouri River below Garrison Dam, N. Dak. 39 M 54719 09 15 Grand River at Little Eagle, S. Dak. 39 s 54753 09 17 Cheyenne River near Eagle Butte, S. Dak. 38 J 54745 09 19 White River near Oacoma, S. Dak. 37 D 54747 09 21 James River near Scotland, S. Dak. 36 H 50549 09 23 Big Sioux River at Akron, Iowa 36 L 56371 09 25 Missouri River at Omaha, Nebr. 35 Q 55100 09 26 North Platte River near Glenrock, Wyo. 34 F 51054 09 27 South Platte River at julesburg, Colo. 33 G 51244 09 29 Platte River near South Bend, Nebr. 35 M 54751 09 31 Missouri River at St. Joseph, Mo. 31 E 54662 09 33 Smoky Hill River at Enterprise, Kans. 32 M 50250 09 35 Kansas River at Bonner Springs, Kans. 31 G 50262 09 38 Missouri River at Hermann, Mo. 24 P 54659 10 01 Arkansas River near Coolidge, Kans. 47 F 50267 10 03 Arkansas River at Arkansas City, Kans. 46 K 50285 10 05 Cimarron River near Guy, N. Mex. 47 E 52532 10 07 Verdigris River near Inola, Okla. 45 D 51846 10 10 Canadian River near Amarillo, Tex. 47 T 52763 10 13 North Canadian River at Woodward, Okla. 46 U 05959 10 15 Canadian River at Calvin, Okla. 45 o 51854 10 17 Arkansas River at Van Buren, Ark. 45 R 51082 10 19 White River at Calico Rock, Ark. 44 J 07543 10 21 White River at De Vails Bluff, Ark. 44 M 51080 10 23 Prairie Dog Town Fork near Childress, Tex. 50 E 12432 10 25 Red River near Burkburnett, Tex. 50 s 54960 10 27 Red River at Denison Dam near Denison, Tex. 49 H 52765 10 29 Red River near Hosston, La. 49 T 53727 11 01 Sabine River near Ruliff, Tex. 51 C 52768 11 03 Trinity River near Oakwood, Tex. 51 o 12635 11 05 West Fork San Jacinto River n«ar Conroe, Tex. 51 Q 52782 11 07 Brazos River at Seymour, Tex. 54 G 52792 11 09 Brazos River near Juliff, Tex. 52 B 52812 11 11 Colorado River at Ballinger, Tex. 54 S 52819 11 13 Colorado River at Wharton, Tex. 52 I 52825 11 15 San Antonio River at Goliad, Tex. 52 Q 52828 11 16 Nueces River near Mathis, Tex. 52 AB 52831 12 01 Rio Grande below Alamosa, Colo. 48 Q 55034 12 03 Rio Grande below Elephant Butte Reservoir, N. Mex. 57 G 55548 12 05 Rio Grande above Rio Conchos near Presidio, Tex. 56 A 55829 Vol. 5, No. 1, June 1971 61 TABLE 1. — Station descriptions for National Pesticides Water Monitoring Network — Continued WRC Accounting Unit Station Name OWDC Catalog = OWDC Site Number RroioN • Unit Sub-Unit 12 07 Pecos River at Santa Rosa. N. Mex. 58 I 52568 12 08 Pecos River at Red Bluff, N, Mex. 56 Q 52585 12 09 Pecos River at Sliumla, Tex. 56 T 55833 12 11 Rio Grande at Ft. Ringgold, Tex. 55 M 55841 13 01 Green River near Greendale, Utah 64 P 50937 13 03 Green River near Ouray, Utah 64 T 50941 13 05 Colorado River near Cameo, Colo. 63 J 51251 13 07 Colorado River near Cisco, Utah 63 M 50932 13 09 San Juan River near Bluff, Utah 61 J 50945 14 01 Little Colorado near Cameron, Ariz. 61 W 54397 14 03 BUI Williams River near Alamo, Ariz. 59 P 02472 14 05 Gila River below Coolidge Dam, Ariz. 60 P 57876 14 07 Gila River near Laveen, Ariz. 60 P 02514 14 09 Santa Cruz River near Laveen. Ariz. 60 H 02531 14 11 Colorado River at Southerly International Boundary near San Luis. Ariz. 59 L 55855 15 01 Bear River below Stewart Dam near Montpelier, Id.iho 65 A 52053 15 03 Weber River near Plain City, Utah 65 D 02947 15 06 Sevior River near Lynndyl, Utah 66 D 50929 15 09 Humbolt River at Carlin, Nev. 68 I 51090 15 U Truckee River at Floriston, Calif. 68 N 56327 15 13 Walker River at JJ Ranch. Nev. 69 G 57248 16 01 Kootenai River at Porthill, Idaho 76 D 52082 16 03 Spokane River at Long Lake, Wash. 76 W 51977 16 05 Snake River above Reservoir near Alpine, Wyo. 79 J 51070 16 07 Snake River near Murphy, Idaho 78 H 55737 16 09 Salmon River at White Bird, Idaho 78 X 52084 16 11 Yakima River at Kiona, Wash. 75 s 51996 16 13 John Day River at McDonald Ferry, Oreg. 74 E 54230 16 15 Tualatin River at West Linn, Oreg. 74 T 54191 16 19 Nehlam River near Foss, Oreg. 74 AB 14722 16 17 Elwha River at McDonald Bridge near Pt. Angeles, Wash. 75 A 51917 16 20 Rogue River near Agness, Oreg. 73 U 54238 17 01 Santa Ana River at Santa Ana, Calif. 70 K 00733 17 02 Salinas River near Spreckels. Calif. 71 I 51444 17 03 Klamath River near Klamath, Calif. 73 K 51679 17 04 Sacramento River at Band. Calif. 72 E 51552 17 05 Kaweah River at Three Rivers, Calif. 71 O 51470 17 07 Sacramento River at Pittsburg, Calif. 72 R 55584 17 09 Owens River near Big Pine, Calif. 69 C 00575 18 - Yukon River at Ruby, Alaska 84 NQ 54052 18 - Campbell Creek near Spenard, Alaska 84 NP 56877 19 - Kalihi Stream at Kalihi, Hawaii 85 - 56868 19 - Waikele Stream at Woipahu, Hawaii 85 - 56867 20 - Rio Tanama near Utado. P.R. 94 - 54346 20 - Rio Grande de Zoiza at Caguss. P.R. 94 - 54344 20 - Rio Guanajibo near Horinegueros. PR. 94 - 54335 ^ Selected Reference number 9. - U.S. Dept. of the Interior. 1967. Geol. Survey, Office of Water Data Co Quality Stations. 62 rdination, Index to Catalog of Information on Water Data — Water Pesticides Monitoring Journal A Sampling Design to Determine Pesticide Residue Levels in Soils of the Conterminous United States G. B. Wiersma ' P. F. Sand ' and E. L. Cox' Introduction The agricultural pesticides monitoring program was in- itiated in 1964 with the establishment of large-scale study areas in the Mississippi Delta; Grand Forks, N. Dak. and Yuma, Ariz. The determination of pesticide residue levels in the soil was an integral part of the study. An additional large-scale study area was established at Mobile, Ala. in the spring of 1965. Also during 1965, the soils phase of the program was expanded to include sampling sites in 17 high-use, 16 low-use, and 18 no-use areas across the United States (1). The large-scale study areas were phased out at the end of 1967. Selected fields in these areas and the high-, low-, and no-use areas will be resampled periodically. Results of these pilot studies, including analytical data for soybeans, carrots, peanuts, and potatoes, indicated a need for a nationwide monitoring program to assess the pesticide residue levels in the soils more thoroughly. The soil is one of the most important components of the environment from the standpoint of storing pesticide residues. Certain pesticide residues in the soil can con- taminate crops through direct contact or by transloca- tion into the systems of plants grown on it. Residues in soil may be carried into surface water by runoff, and pesticides which are readily leached may be carried into the subsoil and possibly into ground water supplies. Knowledge of the pesticide levels in soils provides a basis for determining the need for changing pest control recommendations, cropping practices, and registration or labeling of pesticides. It will also serve as a basis for future monitoring of otber kinds of environmental con- taminants. 1 Environmental Quality Branch, Pesticides Regulation Division. Pesti- cides Office, Environmental Protection Agency, Washington, D. C. = Plant Protection Division. Agricultural Research Service. U. S. De- partment of Agriculture, Hyattsville. Md. 20782. ' Biometrical Services Staff. Agricultural Research Service, U. partment of Agriculture, Beltsville. Md. 20705. Vol. 5, No. 1, June 1971 De- The objectives of the soil monitoring program are as follows: (1) To determine levels of pesticide residues and major pollutants in soils in major land-use areas and other areas in the United States and through periodic sampling, to determine changes in these levels. (2) To determine the levels of pesticide residues in crops grown on treated soil and other components of the environment directly related to the soil. (3) To determine the level of pesticide residues in runoff water of certain agricultural lands. (4) To provide a basis for initiation of special studies on demonstrated problem areas. (5) To publish the results for appropriate distribution. Design of the Program Using information obtained from the Conservation Needs Inventory (CNI) Survey design used by the Soil Conservation Service, USDA, and with the technical assistance of the Statistical Reporting Service and the Biometrical Services Staff of the Agricultural Research Service, USDA, the following plan of action was de- veloped. Soils of the conterminous United States are designated in one or the other of two land-use catetjories: Cropland — Includes land in corn, wheat, other grain, soybeans, hay, vegetables and potatoes, orchards, sugar beets and sugar cane, tobacco, cotton, and other crops. This area covers about 400 million acres. 63 Noncropland — Includes woodland, pastures, grazing land, and all other lands not defined as cropland. This area covers about I'/i billion acres. Sample sites for the monitoring program were selected from the sample segments used in the CNI. These seg- ments are based on a stratified random design with an average sampling density of about 2% of each land-use category, although variation in sampling rates occur. The CNI segments arc generally 100 or 160 acres in size, but some are 40, 400, or 640 acres. Land-use and other information is reported at 18 to 25 points within the 100-acre segments with proportionately more for 160- acre segments. In the soil monitoring program, cropland is sampled at 0.025% or one 10-acre block for every 40,000 acres of cropland. This provides for 9,468 cropland sample sites. Noncropland will be sampled at a rate of 0.0025% or one-tenth of that for cropland. This provides for 3,832 noncropland sample sites. A random method of selecting sample segments from the CNI was devised. A method of selecting a 10-acre site within the CNI segment was applied with the aid of data available for points within the segment. Two points are selected about which a 10-acre sampling site is located for the soil monitoring program. The number of sampling sites per state is presented in Table 1. After the two points are selected, a designation is made on an aerial photo or other map of a 10-acre site with these points centrally located. Attention is given to mak- ing boundaries conform with natural physical features such as: (a) boundaries between cropland and noncropland (as defined) (b) roads and railroads (c) hedgerows, stone fences, etc. (d) streams, brooks, rivers, runs, creeks, etc. Records will he prepared so that the site can be defined and readily located with the same boundaries for sub- sequent samplings at 4-year intervals. A well-documented map or sketch of the location will be recorded. In addi- tion to the guidelines already enumerated, the location will contain no less than 8 acres of available land. SAMPLING SCHEDULE One-fourth of the sites in each State (selected in a random manner) will be sampled each year. Each site will probably be sampled a minimum of three times at 4-year intervals. On cropland, soil and crop samples will be taken at harvest. Initial soil samples from noncrop- land can be taken any time during the year; however, subsequent sampling of all locations will be accomplished 64 at approximately the same time of the year the first sample was taken. SOIL SAMPLING PROCEDURE Fifty cores, 2 inches in diameter and 3 inches deep, are taken in a grid pattern from each 10-acre block. These cores are composited, sieved, thoroughly mixed, and a 2-quart sample taken. The sample is labeled, packaged for shipping, and sent to the analytical laboratory. CHEMICAL ANALYSES OF SAMPLES All soil samples will be analyzed for chlorinated hydro- carbons, organophosphate pesticides, arsenic, and mer- cury (Table 2). Analyses for other pesticides will be made largely on the basis of records of their use. To insure reliable results quality controls will be carried out on the analytical and sampling techniques. CROPPING AND PESTICIDE USE INFORMATION Data collected at the time of sampling and every year between sampling periods include: (1) kinds and amounts of pesticides applied per acre; (2) formulation of pesti- cides applied and method of application; (3) crop grown on the land; and (4) the number of acre-inches of water applied if land is irrigated. A general history of pesticide use prior to the initial sampling is obtained as far back as possible for each site. SAMPLING OF OTHER MATERIAL A predetermined number of water and sediment samples will be collected after the sites for soil sampling are established. Samples of corn, sorghum, soybeans, cotton, hay, and forage will he collected (when available) from the soil sampling sites. Reliability of Estimates The laboratory analyses of the soil samples will provide values from which mean residue levels for various cropping areas of the United States can be estimated, j Subsequent samples from the same areas at 4-year in- tervals will give future mean pesticide residue levels. With the incorporation of associated information on soil type, cropping practices, climate, rainfall, etc., these averages will provide information about the status of chemical residues in a cropping area. The design described above utilizes information, relative to the proposed monitoring program, that has been ob- tained by other Agencies by tested sampling procedures. As a probability sample, it will provide unbiased esti- mates of residues on both cropland and noncropland. LITERATURE CITED (/) Sand. P. F.. J. W. Gentry. J. Boiighcrf;. and M. S. Schecliter. 1967. National Soil Monitoring Program studies high-, low-, and nonuse areas. Pesticides Monit. J. 1(1):16-^19. Pesticides Monitoring Journal TABLE 1. — Approximate number of sample sites by State that will be sampled from cropland and noncropland States Listed BY Region Unfted States Number of Sampling Sites Cropland (9,468) Noncropland (3,832) Total (13,300) NEW ENGLAND Maine 32 48 80 New Hampshire 8 12 20 Vermont 20 12 32 Massachusetts 8 12 20 Rhode Island 4 4 8 Connecticut 8 8 16 Total 80 96 176 MIDDLE ATLANTIC New York New Jersey Pennsylvania 152 20 148 60 12 56 212 32 204 Total 320 128 448 EAST-NORTH CENTRAL Ohio 276 36 312 Indiana 312 28 340 Illinois S68 32 600 Michigan 220 68 288 Wisconsin 272 60 332 Total 1,648 224 1,872 PACIFIC Washington Oregon California 180 152 268 92 140 224 272 292 492 Total 600 456 1,056 WEST-NORTH CENTRAL Minnesota 488 80 568 Iowa 608 28 636 Missouri 328 76 404 North Dakota 636 48 684 South Dakota 424 80 504 Nebraska 428 80 508 Kansas 684 64 748 Total 3,596 456 4,052 SOUTH ATLANTIC Delaware 12 4 16 Maryland 52 12 64 Virginia 84 56 140 West Virginia 24 36 60 North Carolina 124 68 192 South Carolina 68 40 108 Georgia 120 80 200 Florida 72 80 152 Total 556 376 932 EAST-SOUTH CENTRAL Kentucky 124 52 176 Tennessee 112 56 168 Alabama 92 72 154 Mississippi 124 64 188 Total 452 244 696 65 TABLE 1. — Approximate number of sample sites by State that will be sampled from cropland and noncropland — Continued States Listed Number of Sampling Sites BY Region United States Cropland (9,468) Noncropland (3,832) Total (13,300) WEST-SOUTH CENTRAL Arkansas 188 64 252 Louisiana 108 60 168 Oklahoma 260 84 344 Texas 744 344 1,088 Total 1,300 552 1,852 Montana 340 200 540 Idaho 132 120 252 Wyoming 68 148 216 Colorado 240 140 380 New Mexico 40 192 232 Arizona 36 196 232 Utah 48 128 176 Nevada 12 176 188 Total 916 1,298 2,216 TABLE 2. — Compounds that will be analyzed for in the sod monitoring program I. CHLORINATED HYDROCARBON INSECTICIDES aldrin BHC binapacryl Bulan chlordane o.p'-DDE p.p'-DDE o.p'-DDT p.p'-DDT dicofol dieldrin Dilan dinocap endosLiIfan I, II, and sulfate endrin, its aldehvde and ketone Genite 923 heptachlor and its epoxide hydroxy chlordene isobenzan (Telodrin) isodrin Kepone lindane methoxychlor mi rex oxythioqiiinox (Morestan) nonachlor PCNB Perthane Prolan o,p'-TDE p./''-TDE tetradifon toxaphene/Strobane II. ORGANOPHOSPHATES azinphosethvl diazinon malathion parathion azinphosmethvl dioxathion Merphos phorale carbophenothion disulfoton methyl parathion prolate coumaphos EPN methyl carbophenothion ronnel DEF ethion naled sulfotepp demeton fenthion in. HERBICIDES atrazine monuron propanil 2,4,5-T 2,4-D nitralin propazine 2,3,6-TBA diuron picloram simazine triflur,ilin fenac IV. OTHER All samples routinely analyzed for chlorinated hydrocarbon and organo phosphate pesticides, arsenic, and mercury. Other pesticides listed will be analyzed for if treatment records indicate they have been used. 66 Pesticides Monitoring Journal National Monitoring Program for Air Anne R. Yobsi Data on pesticides in air should be developed without special consideration for any one sector of the environ- ment such as man, wildlife, etc. In order to do this the country should be divided on an arbitrary basis, i.e. along longitudinal and latitudinal lines or by some other grid mechanism constructed of x number of equally spaced lines east-west and y number of lines north-south across the country. Sampling should be conducted at approxi- mately 60 sites selected by random design. A rough design for air monitoring can still he devised; however, the limitations of the sampling equipment and analytical procedures selected for use will influence the length of sampling intervals and the time required for analysis of a sample. These factors will critically affect the number of samples which can be analyzed by a laboratory in a specific period of time. Air should be sampled intermittently on a year-round basis, at least three 24-hour samples to the month, with sampling equipment remaining in the same location for a minimum 12-month period. All sites should follow a uniform sampling schedule devised according to random design. Equipment should be located 15-40 feet above ground, and one location should be classified according to land usage although such classification should not in- fluence site selection. Data on weather conditions in effect at the sampling location during each sampling period should be recorded including maximum-minimum temperatures, wind speed and direction, humidity, and precipitation. If equipment is limited, sample periods may be of 12 hours duration or less, but data should be Si.ite Services Branch. Division of Pesticide Community Studies. Pes- ticides OiBce, Environmental Protection Agency, 4770 Buford High- way, Chamblee, Ga. 30341. Vol. 5, No. 1, June 1971 compiled for 24-hour periods. All data should be re- ported as weight of pesticide per volume of air sampled. For the foreseeable future, regardless of sampling tech- nique, chemical analysis will be primarily by gas-liquid chromatography with appropriate detectors. Identifica- tion by GLC should be confirmed whenever amounts captured are sufficient to permit such procedures. In the case of heavy metals, especially mercury, flameless atomic absorption would be the method of choice. TTie monitoring effort should include chlorinated hydro- carbons, organophosphates, phenoxyacetate derivatives, polychlorinated biphenyls. and certain other compounds that are widely used or are heavily used in restricted areas or on limited crops. Such inclusion will, of course, increase the laboratory support required and consequently also increase budget requirements, especially when analylical procedures do not apply to more than one compound or group of compounds or require large amounts of time for com- pletion. Such a program will develop minimal data on pesticides in air which can be correlated with data from other parts of the National Pesticide Monitoring Program. It will also provide valuable background information for problem-oriented or other ambient air sampling. In addition, provision must be made for research sup- port for such an air monitoring program. This would include methodology development, equipment evalua- tion and development, as well as investigation of associa- tion of other parameters. 67 Revised Chemicals Monitoring Guide for the National Pesticide Monitoring Program ^ Milton S. Schechter' A list of pesticides was promulgated several years ago in this Journal [Pesticides Monti. J. 7(1). 20-21 (1967)] as a guide to Federal agencies participating in the National Pesticide Monitoring Program. The Hst contained chem- icals believed to be of most interest because of their (1) extent and/or volume of usage and/or (2) degree of hazard to man, fish, and wildlife and/or (3) degree of persistence. The Monitoring Panel of the Working Group on Pesti- cides responsible to the Council on Environmental Quality has suggested that the list be revised to take into account new pesticides which have been developed and changes in the use patterns of older pesticides. As men- tioned in the previous article, these lists are suggested only as guides and are not to be considered as exclusive; all identifiable pesticide residues found in significant quantities in monitoring studies should be reported, in- cluding metabolic and/or breakdown products which are pesticidal or toxic. In addition to the pesticides listed on the primary and secondary lists, there are some chemicals which, although not considered as pesticides per se, deserve special men- tion. One group of such chemicals (first identified as environmental pollutants in Sweden) are the PCB's or polychlorobiphenyls. which have been widely used as transformer oils, plasticizers. heat-exchange liquids, ink vehicles, etc. The PCB's have become spread through- out the environment and have been detected in fish and 1 This revised guide was drawn up after consultation with representa- tives from the U.S. Departments of Agriculture. Defense, the In- terior, and Health, Education, and Welfare, and the Environmental Protection Agency, under the sponsorship of the Monitoring Panel of the Working Group. ' U.S. Department of Agriculture, Agricultural Research Service. Entomology Research Division, Pesticide Chemicals Research Branch, Agricultural Research Center, Beltsville, Md. 20705. 68 birds. When present in an environmental sample, the polychlorobiphenyls give rise to a complex series of peaks on gas chromatograms, and some of the peaks overlap or coincide with those given by some of the common organochlorine pesticides. The PCB's are relatively persistent toxic chemicals and, because of their adverse ecological effects, should be reported whenever detected in monitoring samples. Another class of compounds which merits comment are the "dioxins." These are polychlorodibenzo-p-dioxins which have been found to occur as byproduct impurities in technical 2.4.5-T and pentachlorophenol. The dioxins are highly toxic chemicals which have been implicated in chick edema disease in chickens, in chloracne of in- dustrial workers, and as teratogens in experimental ani- mals. Because 2,4,5-T especially has been used on such a large scale, any of the dioxins detected in environ- mental samples should be reported, although little is known at present concerning the presence or persistence of dioxins in the environment. Current production of 2.4.5-T has been improved so that the level of tetra- chlorodibenzo-p-dioxin is below 0.5 ppm in the tech- nical product. In addition, many of the uses of 2,4,5-T have been suspended pending the outcome of hearings which are being held concerning the herbicide by the Environmental Protection Agency. The problem of pollution of the environment by mercury is currently of tremendous interest. Instances of such pollution had been known in Japan ("Minimata disease" caused by eating fish contaminated with methyl mercury from industrial discharge into Minimata Bay and at Niigata) and in Sweden (primarily from paper mill slimi- cide treatments). Although mercury-containing jjesti- cides (inorganic and organic) were listed on the initial Pesticides Monitoring Journal Primary List of Chemicals for Monitoring, compara- tively little monitoring for mercury in environmental samples had been done in the United States until the recent discovery of widespread pollution of certain rivers and lakes by this element (chiefly from electrolytic chlor-alkali plants), its conversion to methyl mercury by microorganisms, and the absorption or ingestion of the latter mercury compound by fish. It should be noted that such pollution does not seem to be due primarily to agricultural usage but instead is from industrial and natural sources. Monitoring for mercury in the environment will no doubt continue to be carried out on a large scale until pollution by this toxic material and its compounds has been fully evaluated and brought under control, and the hazards to fish, wildlife, and man have been reduced to a tolerable level. Problems of industrial pollution from chemicals which are not pesticides, such as PCB's and mercury, illu- strate some of the complexities in the analysis of pesti- cide residues in environmental samples. Even more diflncult is the interpretation of biological effects due to interactions of multiple pollutants and stresses on bio- logical organisms. Clearly, a broader view of monitoring environmental samples must be taken than just a search for individual pesticide residues alone. To reflect the increasing utilization of herbicides, a number of the important ones have been added, and atrazine has been moved from the secondary to the primary list because of its increased use. Some herbicides should be monitored on a specific crop or regional basis rather than countrywide, as for example fenac, which is a persistent, mobile herbicide used mainly on sugar cane, and propanil which is used mainly on rice. Still important is the following statement quoted from the previous article that "Because of difficulties involved in screening samples for a multiplicity of pesticides and their important metabolites and degradation products, care should be used not only in the sampling and quanti- tative aspects of monitoring studies but especially in the identification aspects in order to assure reliability of re- ported results." Primary list of cliemicals for monitoring ' ' Common or Trade Name Chemical Name Aldrin not less than 95% of 1,2,3,4, 10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-endo-«io-5,8-dimethanonaph= thalene Amitrole 3-amino-s-triazole Arsenic-containing pesticides (Inorganic and organic) Atrazine 2-chloro-4-(ethylamino)-6-(isopropylamino)-j-triazine Azinphosmethyl (Guthion®) 0,0-dimethyl phosphorodithioate 5-ester with 3-(mercaplomcthyl)-1.2,3-benzotriazin-4(3W)-one Benzene hexachloride (BHC) 1,2.3.4, 5.6-hexachlorocyclohexane, consisting of several isomers and containing a specified percentage of gamma isomer ^ Captan iV-[ (trichloromethyl ) thio]-4-cyclohexene-l ,2-dicarboximide Chlordane at least 60% of l,2.4.5,6.7,8.8-octachloro-3a,4.7,7a-tetrahydro-4,7-methanoindan and not over 40% of related compounds 2,4-D (including salts, esters, and other derivatives) 2,4-dichlorophenoxyacetic acid DDT (including its isomers and dehydrochlorination products) l,l,l-trichloro-2,2-bis(p-chlorophenyl)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 ) Dicamba 3.6-dichloro-o-anisic acid Dieldrin not less than 85% of l,2,3,4,I0,10-hexachloro-6,7-epoxy-l,4,4a,5,6.7,S,8a-octahydro-l,4-enrfo-cxo-5,8-di= methanonaphthalene Dithiocarbamate pesticides: Maneb; Ferbam; Zineb; etc. [ethylenebis(dithiocarbamato)]manganese; tris ( dimethyldithiocarbamato ) iron; [ethylenebis ( dithiocarbamato ) ]zinc ; Endrin l,2,3.4,10.10-hexachJoro-6.7-epoxy-l,4,4a,5,6,7.8,8a-octahydro-l,4-endo-pndo-5.8-dimethanonaphthalene Heptachlor l,4,5.6,7,8.8-heptachloro-3a.4.7.7a-tetrahydro-4,7-methanoindene Heptachlor epoxide 1.4.5.6.7.8.8-heptachloro-2.3-epoxy-3a,4.7.7a-tetrahydro-4,7-methanoindan Lindane 1,2,3,4,5,6-hexachlorocyclohexane. gamma isomer of not less than 99% purity Malathion diethyl mercaptosuccinate i'-ester with 0,0-dimethyl phosphorodithioate Mercury-containing pesticides (inorganic and organic) Methoxychlor l,I,l-trichloro-2,2-bis(p-methoxyphenynethane; technical methoxychlor contains some o,p'-isomer also Vol. 5, No. 1, June 1971 69 Primary list of ctiemicals for monitoring ^-^ — Continued Common or Trade Name Chemical Name Methyl parathion 0,0-dimethyl O-(p-nitrophenyl) phosphorothioate Mirex dodecachlorooctahydro-l,3.4-metiieno-l//-cyclobutalcf/]pentalene Nitralin (Planavin®) 4-(methylsulfonyl)-2,6-dinitro-A',N-dipropylaniline Parathion 0,0-diethyl O-(p-nitrophenyl) phosphorothioate PCNB pentachloronitrobenzene Picloram 4-amino-3,5,6-trichloropicolinic acid Silvex (including salts, esters, and other derivatives) 2-(2,4,5-trichIorophenoxy) propionic acid Strobane® terpene polychlorinates containing 65% chlorine 2,4,5-T (including salts, esters, and other derivatives) 2,4,5-trichlorophenoxyacetic acid TDE (DDD) (including its isomers and dehydrocUorination products) l,l-dichloro-2,2-bis(p-chIorophenyl)ethane; technical TDE contains some o,p' -isomer also Toxaphene chlorinated camphene containing 67-69% chlorine Trifluralin a,a,a-trifluoro-2,6-dinitro-N.Af-dipropyl-p-toIuidine Secondary list of chemicals for monitoring Common or Trade Name Chemical Name DCNA (Botran®) 2,6-dichloro-4-nitroaniline Carbaryl 1-naphthyl methylcarbamate Demeton (Systox®) mixture of 0,0-diethyl 5(and 0) -12- (ethylthio) ethyl] phosphorothioates Diazinon 0,0-diethyI 0-(2-isopropyl-6-methyI-4-pyrimidinyl ) phosphorothioate Disulfoton (Di-Syston®) 0,0-diethyl 5-[2-(ethylthio)ethylI phosphorodithioate Diuron 3-(3,4-dichlorophenyl)-I,l-dunethylurea Endosulfan (Thiodan®) l,4,5,6,7,7-hexachloro-5-norbomene-2,3-diinethanol cyclic sulfite Fenac * (2,3,6-trichlorophenyl) acetic acid Fluometuron l,l-dimethyl-3-(a,Q!,a-trifluoro-m-tolyl)urea Inorganic bromide from bromine- containing pesticides Lead-containing pesticides such as lead arsenate Linuron 3-(3,4-dichlorophenyl)-l-methoxy 1-methylurea PCP pentachlorophenol Propanil * 3',4'-dichloropropionanilide Triazine-type herbicides: ^ Simazine; 2-chloro-4,6-bis(ethylamino)-j-triazine; Propazine; 2-chloro-4,6-bis(isopropylamino)-5-triazine; Prometryne, etc. 2,4-bis ( isopropylamino ) -6-(methylthio ) -j-triazine TBA 2,3,6-trichIorobenzoic acid, usually available as mixed isomers List of special chemicals for monitoring ° Common or Trade Name Chemical Name Polychlorobiphenyls (PCB's) Polychlorodibenzo-p-dioxins Mixtures of chlorinated biphenyl compounds having various percentages of chlorination Dibenzo-p-dioxins having various degrees of chlorination such as the tetra-, hexa-, or octachlorodibenzo- p-dioxins, present as impurities in various chlorine-containing phenols and early samples of 2,4,5-T Chemical names are in accordance with Chemical Abstracts. An equal sign ( = ) at the end of a line signifies that the rest of the chemical name is to be joined without a space or hyphen at that point. Report individual isomers when possible. Some compounds are used primarily on one or two crops or in certain regions rather than countrywide; for example, the herbicides fenac and propanil are used mainly on sugar cane and rice, respectively. Note that atrazine has been moved to the Primary List. This list contains chemicals whioh, although not considered to be pesticides themselves, are of special interest in monitoring studies. 70 Pesticides Monitoring Journal The author consulted the following Federal departments and individuals in revising the list of pesticides for monitoring: U.S. Department of Agriciiltiire H. Rex Thomas E. E. Fleck P. C. Kearney Paul F. Sand Warren C. Shaw D. Graham D. L. Klingman L. L. Danielson W. B. Ennis J. M. Good K. C. Walker J. T. Holstun S. A. Hall P. R. Miller R. L. Busbey (presently retired) Fred H. Tschirley U.S. Department of Health, Edncatlon, and Welfare Henry Fischbach William M. Upholt Reo Duggan J. G. Ciunmings J. W. Cook Jerry Alpert (presently retired) U.S. Department of the Interior Herman Feltz E. H. Dustman Vol. 5, No. 1, June 1971 71 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 sampling 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- laboratory checks. The procedure employed should be referenced 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 72 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 he 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 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 1 00 reprints. J 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. Pesticides Office, Environmental Protec tion Agency, 4770 Buford Highway, Bldg. 29, Cham- blee, Ga. 30341. ii us. GOVERNMENT PRINTING OFFICE: 1971—435.594/4 Pesticides Monitoring Journal The Pesticides Monitoring Journal is published quarterly under the auspices of the WORKING GROUP on Pesticides (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, E.xtension Senice, Forest Service, Department of Defense, Fish and Wildlife Service, Geological Survey, Food and Drug Administration, Environmental Protection Agency, 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 principal sources of data and interpretive articles. However, pertinent data /'/; summarized form, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and com- munity monitoring programs, universities, hospitals, and nongovernmental research institutions, 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 Andrew W. Breidenbach, 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 5 September 1971 Number 2 Page RESIDUES IN FOOD AND FEED Pesticide residue levels in foods in the United Slates from July 1 , 1963 to June 30. 1969 73 R. E. Duggan, G. Q. Lipscomb, E. L. Cox, R. E. Heatwole, and R. C. Kling RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Short-term effects of 2,4-D on aquatic organisms in the Nakwasina River Watershed, southeastern Alaska 213 Howard S. Sears and William R. Meehan PESTICIDES IN SOIL Effects of a cover crop versus soil cultivation on the fate and vertical distribution of insecticide residues in soil 7 to 11 years after soil treatment 218 E. P. Lichtenstein, K. R. Schultz. and T. W. Fuhremann National soils monitoring program — six States, 1967 223 G. B. Wiersma, P. F. Sand, and R. L. Schutzmann BRIEFS Chlorinated hydrocarbons in livers of fishes from the northeastern Pacific Ocean 228 Thomas W. Duke and Alfred J. Wilson, Jr. APPENDIX Chemical names of compounds discussed in this issue 233 RESIDUES IN FOOD AND FEED Pesticide Residue Levels in Foods in the United States from July 1 , 1963 to June 30, 1969 R. E. Diiggan', G. Q. Lipscomb', E. L. Cox", R. E. Heatwole". and R. C. Kling' AUTHORS' NOTE: In lieu of an acknowledgment al the end of lliis article, tlie authors are taking this initial oppor- tunity to give credit to chemists in tlie District Laboratories of the Food and Drug Administration and tliose in tlie Con- sumer and Marketing Service Laboratories of tlie U.S. Department of Agriculture for their e.xccllent analytical work and sustained interest in the not-so-glamorous task of repetitive analyses. Regrettably, the cliemists are too num- erous to mention by name. The autltors do wish to speci- fically mention the collaboration of K. C. Walker. Fred A. Schultz, and T. Cooper of the U. S. Department of Agricul- ture in the planning of the summation and the statistical tests used in this article. Introduction The Food and Drug Administration. Department of Health, Education, and Welfare, monitors pesticide residues in the Nation's food supply through two pro- grams. One program, commonly known as the "total diet program," involves the e.xamination of food ready to be eaten. This investigation measures the amount of pesticide chemicals found in a high-consumption varied diet. The samples are collected in retail markets and prepared for consumption before analysis. The other program involves the examination of large numbers of samples, obtained when lots are shipped in interstate commerce, to determine compliance with tolerances. These analyses are complemented by observation and investigations in the growing areas to determine the actual practices being followed in the use of pesticide chemicals. The Consumer and Marketing Service, U.S. Department of Agriculture, conducts monitoring pro- grams on red meat and poultry as responsibilities under the Meat Inspection Act and the Poultry Products In- spection Act. These programs represent the National Monitoring Program for Food and Feed (/). An earlier report (2) presented data on FDA's programs for a 4-year period beginning July 1, 1963. The dual purpose of this article is to report FDA data for 2 addi- tional years (beginning July 1. 1967) and report data obtained by the USDA on red meat for the period July ' Food and Drug Administration, DHEW, Rockville. Md. 20852. - Deceased. Formerly with Food and Drug Administration. DHEW, Rockville. Md. = Agriculture Research Service, USDA, Washington, D.C. 00258. 1. 1964 to June 30. 1969 and on poultry for the period July 1, 1967 to June 30. 1969. Sampling and Analytical Procedures A majority of the samples collected in these programs were categorized as "objective" samples. Objective samples are those collected where there is no suspicion of excessive residues or misuse of the pesticide chemicals. All samples of imported foods and fish are categorized as "objective" samples even though there may be reason to believe excessive residues may be found on successive lots of these food categories. Market basket samples for the total diet studies are purchased from retail stores, bimonthly, in five regions of the United States. A shopping guide totaling 117 foods for all regions is used, but not all foods are repre- sented in all regions because of differences in regional dietary patterns. The food items are separated into 12 classes of similar foods and prepared for consumption bv dieticians in institutional kitchens. After preparation, the food items are composited into 12 classes of similar foods (e.g., dairy products: meat, fish and poultry; legume vegetables; and garden fruits) for more reliable analysis and to minimize the dilution factor. Each class in each sample is a "composite." The food items and the pro- portion of each used in the study was developed in co- operation with the Household Economics Research Division, USDA, and represents the high-consumption level of a 16- to 19-year-old male. Each sample repre- sents a 2-week supply of food. Surveillance samples are generally collected at major harvesting and distribution centers throughout the U.S. and examined in 16 FD.^ District laboratories. Some samples may be collected in the fields immediately prior to harvest. Surveillance samples are not obtained in retail markets. Samples of imported food are collected when offered for entry into the United States. Meat and poultry sampler are obtained from animals and poultry slaughtered in all federally inspected estab- lishments and from shipments offered for entry into the United States. The samples are examined in seven lab- oratories of the Consumer and Marketing Service, USDA. Vol. 5, No. 2, September 1971 73 Quantitative multiresidue gas-liquid chiromatographic methiods of analysis at routine sensitivity levels of 0.03 ppm* on most fruits and vegetables and at 0.01 ppm on meat and poultry are used. The total diet samples arc examined at sensitivity levels substantially lower, 0.00.^ ppm.* Sensitivity of analysis varies with the individual pesticide even within the chlorinated group, and this statement is intended to identify the depth of analysis in general terms. Confirmatory tests, using thin layer chro- matography or different GLC columns, were made on all determinations where the residue exceeded the action level or tolerance for objective samples. All residues re- ported in the total diet study are confirmed. Precise in- formation can be obtained from the analytical proced- ures (3) prescribed for these programs. Statistical Treatment of Data The numbers of samples falling into the various ranges of level of residue were accumulated from the "none found" to the most highly contaminated. The cumulative counts were converted to percentages. Such percentages may be stated as the "percent of samples containing not more than [the stated upper boundary of a class] parts per million." Tables of the cumulative percentages were constructed. These suggest that the normal function could be used to relate the logarithm of the pesticide level to the cumulative percentages. P.= l_ /"/-% (iLzJiy b\ll'n J -i \ '' I dv. where y z= In x, P, = percent of contaminated samples up to the level a:,, and a and h are constants to be de- termined. The parameters of the function were estimated using an iterative nonlinear least squares technique.** The mean square residual. =.z (observed, — COMPUTED,) - was used as a measure of the agreement between the observations and the computed functions. Small values of Sy. ^ indicate a good fit. Results and Discussion TOTAL DIET PROGRAM The frequency of occurrence, as well as the sensitivity of the method for a specific pesticide chemical, must be considered in attaching significance to the calculated daily intake. Where a method is relatively insensitive, a * Instrument sensitivity producing i- scale deflection for 1 ng hepta- chlor epoxide; 20 mg objective samples and 100 mg of more rigorous cleanup total diet samples. ** The working details of this procedure which include many inter- esting innovations may be obtained on request from the Biometrical Services Staff. few positive findings will unduly influence the calculated value, even though the frequency of positive findings does not justify recognition as a common component in the dietary intake of pesticide chemicals. The results obtained during the 5-year period, June 1964 — April 1969, are compared; Table 1, with the acceptable daily intake (ADD established by the FAO- WHO Expert Committee (4). The amounts of these pesticide chemicals calculated from this high-consump- tion diet, approximately twice that consumed by a normal individual, arc well below the daily intake re- garded as safe by the FAO-WHO Expert Committee, except for the combined residues of aldrin and dieldrin. The calculated daily intake of these chemicals has ap- proached the ADI during this period. Table 2 shows the distribution of total chlorinated pesticides in the twelve classes of food. Over the 5-year period, the largest amount of these pesticides, about 35%, was from the meat, fish and poultry component of the diet. Approxi- mately equal amounts, about 15% each, were from the dairy product and fruit component of the diet. The garden fruit and grain and cereal components of the diet contributed about 10% each. The other components were responsible for the remaining 15%. Table 3 com- pares the incidence and daily intake in milligrams of the 22 pesticide chemicals most frequently found in these samples for each of the 5 years. This list includes those pesticide chemicals found in 1 % or more of the com- posites examined during any 2 years. Residues of arsenic and bromides are not included because of the natural occurrence of these elements in foods. The chi-square test of independence for incidence of positive findings occurring from year to year was calculated for the various pesticides. The following were found to be significant at the probability level indicated: 0.001 carbaryl diazinon DDT, DDE. and TDE combined 0.01 DDT dieldrin 2.4-D 0.05 TDE malathion difocol (Kelthane) The significances for DDT and TDE and similarity of behavior for DDE. the other DDT compound, would seem to indicate that the incidence of DDT compounds is increasing in these 12 classes of foods. The daily in- take, however, seems to be decreasing. While BHC seems to be behaving in somewhat the same manner as the DDT compounds the chi-square test was not signif- icant— possibly due to the much smaller numbers of contaminations involved. RAW AGRICULTURAL PRODUCTS Residues of 83 different pesticide chemicals have been found in the 111,296 samples of domestic food ex- amined during the period July 1, 1963 — June 30, 1969. 74 Pesticides Monitoring Journal Many of these compounds were found infrequently. This report includes all pesticide chemicals found in 1 % or more of the samples in a food class in 1 or more years, even though the incidence was reached in only 1 year. Thirty pesticide chemicals were found at this level. The DDT compounds, dieldrin and lindane are reported for all food groups. Others, such as Perthane, tetradi- fon, PCP, carbophenothion, pentachloronitorobenzene (PCNB), chlorbenside, DCPA (Dacthal). chloromethyl- phenoxyacetic acid (MCP), are reported for only one food group. Aldrin, BHC, heptachlor epoxide, toxa- phene, endrin and chlordane are reported in a majority of the food groups. In general, during the past 6 years, more than half of the samples of fruits, vegetables, dairy products, and animal feeds, contained residues of one or more pesti- cide chemicals. Although the incidence of residues was high, most of the residues were at very low levels. Over 75% of the individual residues found were below 0.11 ppm, and 95% were below 0.51 ppm. This general pattern of residue levels is observed when the data are considered by specific pesticide chemical, food category, domestic or imported food, or on an annual basis. Not only was the average level of residues within a food category quite low, but too few individual lots of food contained levels above 2 ppm to justify categories in higher range. Furthermore, the residue levels reported on fruits and vegetables were reduced in the normal food preparation and processing employed prior to con- sumption. The incidence of residues in fish, red meat, and poultry was generally higher than that found in fruits and vegetables. Even though a majority of the residues were below 0.11 ppm, higher levels of residues were gener- ally present in fish, red meat, and poultry than in other food classes. TTie average levels, calculated from all samples within a food class, of the individual chemicals were very low and do not approach the legal tolerances in those instances where tolerances have been estab- lished. The average for most pesticide chemicals was below 0.01 ppm, including the fish, meat, and poultry food classes. However, in these specific food classes, the averages of certain common pesticides, for example, DDT compounds, BHC, dieldrin, and heptachlor epoxide, commonly exceeded 0.01 ppm. For the purposes of this report, the data have been summarized into the following food classes: Dairy Products — Table 4,5,6 Large Fruits — Table 7 Small Fruits — Table 8 Grains and Cereals (Human) — Table 9 Leaf and Stem Vegetables — Table 10 Vine and Ear Vegetables — Table 1 1 Root Vegetables— Table 12 Beans — Table 13 Red Meat — Table 14 Poultry— Table 15 Eggs — Table 16 Fish— Table 17 Shellfish— Table 18 Grains (animal) — Table 19 Infant and lunior Foods — Table 20 Tree Nuts — Table 21 Vegetable Oil Products— Table 22-27 Summary tables (4-27) have been prepared for each food class from data obtained from samples as shipped in interstate commerce and as imported into the United States during FY 1964-1969. Averages in ppm for each pesticide chemical are shown for the raw product and for that composite of the total diet sample most closely related to the raw product. This relationship is per- missible through the use of dairy products as a check- point. The results on milk and dairy product samples in both investigations are reported on a fat basis. There are no significant processing changes in the composition of fat of dairy products from the objective samples to the total diet samples. The investigations are made at different points in the food distribution chain, and there are great differences in the depth of sampling. The data from which the summary tables were prepared are given in more detail in Tables 4A, 5A. and 7A-25A, which list the incidence and ranges of levels for each pesticide chemical as in previous reports. Only the totals of the FY 1964-1967 data are included in these tables. When sufficient positive findings were available for statistical tests, graphs were prepared to accompany the tables — these graphs show the incidence of positive findings at the trace level and at levels greater than 0.03 ppm by year. TTie significance level of the chi-square test for independence, provided there were enough positive findings for the test, and the lower confidence limit (95%) for percent of samples with residue levels of 0.1 ppm, 0.5 ppm and 1.0 ppm, are shown on each graph. This kind of information can be used to identify po- tential problems with lead time for corrective actions to avoid unnecessary health hazards and economic hard- ship. DAIRY PRODUCTS Table 4, Fluid Milk, and Table 5, Dairy Products, show that seven chlorinated organic pesticides were commonly found in milk fat in addition to the DDT compounds. It is noteworthy that the imported dairy products con- tained the same pesticide chemicals as those produced in the United States. The average residue levels of the specific pesticide chemicals were not significantly differ- ent between imported and domestic dairy products, except for BHC. This difference is due to the classifica- tion of all samples of imported food as objective samples Vol. 5, No. 2, September 1971 75 as discussed above. In this instance, the rate of samphng of imported cheese was increased because of excessive residues of BHC. Table 6 compares the average residue levels in the surveillance (objective) samples with those in the total diet samples and shows remarkably good agreement between the two sets of values. The incidence of samples at various ranges of residue levels for each pesticide are given for fluid milk in Table 4A and for dairy products in Table 5A. These tables are accompanied by bar graphs indicating the annual per- cent of positive sample, together with statistical informa- tion. From these data it can be seen that there have not been significant increases in the incidence or levels of chlorinated organic pesticide chemicals in fluid milk or dairy products. A general trend appears to be that the trace levels remain about the same or perhaps a bit higher, and that the incidence of samples above 0.03 ppm is lower, particularly during the past 3 years. Statistical tests indicate that, except for residues of BHC in imported dairy products and DDE in dairy products and fluid milk, the residue level of a specific pesticide chemical (fat basis) does not exceed 0.1 ppm in 90% or more of the samples (95% confidence). The BHC residue level does not exceed 0.1 ppm (fat basis) in 74% of the dairy product samples. The DDE residue level does not exceed 0.1 ppm (fat basis) in 85% of the domestic samples of fluid milk and dairy products and 88% of the imported samples of dairy products. LARGE FRUITS Table 7 lists 15 pesticide chemicals, in addition to the DDT compounds commonly found in large fruits in food distribution channels. Except for carbaryl, these same chemicals are found in imported fruits. Not all of these chemicals were found in the fruit composite of the total diet sample. No residues of endrin, toxaphene, parathion, diazinon, or carbophenothion were reported in the ready-to-eat food. No residues of pesticide chemicals were found in the total diet samples which were not re- ported in the raw food surveillance program. The data in this table indicate generally that the average residue level in the total diet composites are about one order of magnitude lower than those found on the raw fruit. The incidence of residues in the total diet composites is much higher, which is attributed to the greater analytical sensitivity used in the total diet program. Inspection of Table 7A and the accompanying figures shows that there is no readily observable trend in the incidence of trace levels of the chlorinated organic pesticides in or on large fruit. There does appear to be a trend toward a lower incidence of lots containing meas- urable amounts (>0.03 ppm) of the chlorinated organic pesticides during the last 2 or 3 years. The incidence of 76 residues of organic phosphate pesticides shows increases at trace and higher levels of residues. Statistical tests indicate that the residue level of a spe- cific pesticide chemical does not exceed 0.1 ppm in 90% or more of domestic and imported samples (95% con- fidence). SMALL FRUITS Table 8 lists 13 pesticide chemicals in addition to the DDT compounds commonly found in small fruits in food distribution channels. There are no significant dif- ferences in the kind, incidence, or levels of pesticide chemicals on domestic and imported foods, except that residues of Perthane and endosulfan were not found on imported small fruits. Inspection of Table 8A and accompanying figures shows that the incidence at trace and measurable levels of chlorinated organic pesticides has tended to be lower except for dicofol and endosulfan during the past sev- eral years. Tlie trend of organic phosphate pesticide chemicals appears to be increasing at the trace level. There were not sufl^cient positive samples containing measurable amounts of organic phosphate pesticide residues (>0.03 ppm) to determine a statistical signif- icance level. Statistical tests indicate that, except for DDT, the residue level of a specific pesticide chemical in domestic and imported small fruits does not exceed 0.1 ppm in 95% or more of the samples (95% confidence). The DDT residues level does not exceed 0.1 ppm in 90% of the domestic samples and 88% of the imported samples. The assumption of normality and the use of the mean square residual as an estimate of error variance pro- vided a basis for the construction of the confidence statements relating to Tables 4A. 5A, and 7A-26A. As an example of how these data may be used, note that in the graphic illustrations for Table 14A, Red Meat, Diel- drin. Imported, we find under the headings 0.1 ppm, 0.5 ppm. 1.0 ppm, and s^ ^i the following numerical values: 76.09, 87.54. 90.01, and 0.03424. This means that the lower 95% confidence limit for the percentage of samples having not more than 0.1 ppm of dieldrin is 76.09%. Confidence statements of this type indicate the expectation that 1 time out of 20 the true percentage will be greater than the specified value. Similarly, the lower 95% confidence limits for the percentage of samples having not more than 0.5 ppm and 1.0 ppm of dieldrin are 87.54 and 90.01 percent, respectively. Fin- ally, the mean square residual is 0.03424. The chi-square test of independence was used to an- alyze the year-to-year changes in the frequency of con- tamination. When it is noted, "SIGNIFICANCE LEVEL Pesticides Monitoring Journal OF CHI-SQUARE TEST STATISTIC < 0.00 1"— <0.01 or <0.05 — a different distribution is indicated for at least 1 year. Different distributions among years were not detected when it is noted, "SIGNIFANCE LEVEL OF CHI-SQUARE TEST STATISTIC NON- SIGNIFICANT." If no notation is made concerning the CHI-SQUARE STATISTIC, there were too few con- taminated samples to perform the test. Further examina- tion of the data indicated that in some cases significance is due to irregular behavior rather than definable trends. GRAINS AND CEREALS (HUMAN) Table 9 lists 15 pesticide chemicals, in addition to the DDT compounds, commonly found in grains and cereals for human use. Eight of these were not found in im- ported grains and cereals. The incidence and levels of the pesticide chemicals found in imported grains and cereals are comparable to the domestic commodities. Many of the products examined in the ready-to-eat grain and cereal composite contain other ingredients which affect the residue content. It is worthy of note, however, that the average levels of DDT. malathion, and methoxychlor in the ready-to-eat food are of a lower order of magni- tude than the averages in the surveillance samples, even though other ingredients may have contributed to the total residue in the ready-to-eat food. Inspection of Table 9A and the accompanying figures indicates the incidence of chlorinated organic pesticides has been decreasing during the past several years. There were insufficient measurable positive residues of chlori- nated organic pesticides, except for DDT, for statistical testing. Malathion residues are increasing in incidence and levels. Statistical tests indicate that, except for malathion resi- dues, the residue level of a specific pesticide chemical in domestic samples of this food class does not exceed 0.1 ppm in 95% or more of the samples (95% confidence). The malathion residue does not exceed 0.1 ppm in 89% of the samples. LEAF AND STEM VEGETABLES Table 10 lists 15 pesticide chemicals in addition to the DDT compounds found in leaf and steam vegetables in food distribution channels. Except for methyl parathion and DCPA (Dacthal), these same pesticide chemicals were found in leaf and stem vegetables imported into the United States. PCNB was reported in the samples of raw vegetables, but not in the total diet composites of this food category. All other pesticides reported in the raw foods were found in the ready-to-eat composite of leaf and stem vegetables. Nine of these pesticide chemi- cals contained average levels exceeding 0.01 ppm in the raw food. The higher incidence of most residues in the total diet composites is attributed to the greater an- alytical sensitivity used in the total diet program. The data in this table indicate that the average residue levels in the total diet composite are about one order of magnitude lower than those found on the raw vegeta- bles. Inspection of Table IDA and accompanying figures shows that the incidence of trace and measurable levels of most chlorinated organic pesticide residues has de- clined during the past several years. Toxaphene has shown some increase while no significant change is ob- served in DDT and BHC residues. The incidence of trace and measurable levels for each of the organic phosphate residues has shown a trend toward higher incidences of residues in almost every case. The limited number of imported lots of leaf and stem vegetables did not result in enough samples for statistical evaluation. Statistical tests indicate that, except for residues of DDT. the residue level of a specific pesticide chemical in domestic and imported samples of this class of food does not exceed 0.1 ppm in 93% or more of the samples (95% confidence). The DDT residues do not exceed 0.1 ppm in 86% of the samples. VINE AND EAR VEGETABLES Table 11 lists 11 pesticide chemicals, in addition to the DDT compounds, commonly found in vine and ear vegetables in food distribution channels. These same pesticide chemicals were found in imported vegetables and in the ready-to-eat composites in the total diet samples. The greater incidence of residues in the total diet samples is attributed to the greater analytical sen- sitivity used in the total diet program. The average levels of residues in the ready-to-eat food approximates that found in the raw foods, particularly of the com- pounds having a high incidence of residues. Inspection of Table llA and the accompanying figures shows that the incidence of trace and measurable levels (>0.03 ppm) of DDT compounds, dieldrin, and para- thion have increased during this 6-year period. Statistical tests indicate that, except for residues of DDT, the residue level in domestic and imported samples in this class of food of a specific pesticide chemical does not exceed 0.1 ppm in 96% or more of the samples (95% confidence). The DDT residues do not exceed 0.1 ppm in 94% of the domestic samples and in 78% of the imported samples. ROOT VEGETABLES Table 12 lists 12 pesticide chemicals, in addition to the DDT compounds commonly found in root vegetables in food distribution channels. Except for toxaphene, these same pesticide chemicals were found in root vegetables imported into the United States. Two separate com- posites are used for root vegetables in the total diet samples; potatoes form one composite, and all other Vol. 5, No. 2, September 1971 77 root vegetables are placed in another composite. Not all pesticide chemicals found in the raw products are found in the ready-to-eat foods. The incidence of resi- dues in the raw and ready-to-eat foods are approximately the same. The average levels of residues in the ready-to- eat food is about one order of magnitude lower than the average found in the surveillance samples. Inspection of Table 12A and accompanying figures shows that the incidence of residues at trace and measur- able (>0.03 ppm) levels has decreased for most pesticide chemicals, although there have been no significant changes in the incidence of DDT compounds. The in- cidence of trace levels of BHC in domestic and im- ported root vegetables has increased. Statistical tests indicate that, except for residues of DDT, the residue level of a specific pesticide chemical in domestic and imported samples in this food class docs not exceed 0.1 ppm in 95% or more of the samples (95% confidence). The DDT residues do not exceed 0.1 ppm in 92% of domestic samples and in 91% of imported samples. BEANS Table 13 lists nine pesticide chemicals, in addition to the DDT compounds commonly found in beans and other legume vegetables. Diazinon was not found on imported foods in this category. Except for diazinon and endrin, these same chemicals were found in the ready-to-eat composites of legume vegetables at substantially lower average levels. This class of food represents a small por- tion of the diet, about 2.5%, as measured by the market basket program and contributes to the dietary intake of pesticide chemicals in about the same proportion. Table 13A and the accompanying figures show that the incidence of trace and measurable (>0.03 ppm) levels of DDT has become somewhat lower during the past several years. There were insufficient positive samples of pesticides other than DDT and DDE for statistical testing. Statistical tests indicate that, except for DDT, the residue level of a specific pesticide chemical in samples of domestic and imported beans does not exceed 0.1 ppm in 94% or more of the samples (95% confidence). The DDT residues do not exceed 0.1 ppm in 90% of the domestic samples and in 77% of the imported samples. RED MEAT Table 14 lists 10 pesticide chemicals in addition to DDT compounds commonly found in the fat of red meat, from domestic and imported sources, in food distribu- tion channels. The incidence and levels in imported foods, except for BHC, are not significantly different from domestic meat. Except for methoxychlor, these same chemicals are found in the ready-to-eat meat, fish. and poultry composites of the total diet samples. The higher incidences of positive samples in the total diet program may be due to the greater analytical sensitivity used in that program and to the inclusion of other foods in the composite. Because the results are given on a fat basis, the differences in the average levels in the ready- to-eat food and the raw foods may be attributed to dilution with foods having lower average levels of pesticide chemicals. Reduction in the dietary intake of pesticide chemicals from this source would be associated with removal of fat. Table 14A and accompanying figures show that the incidence of trace and measurable levels of most chlori- nated organic pesticides in the fat of meat have either not changed significantly or have declined in the past several years. The most notable exception is the in- cidence of measurable levels of DDT compounds, in the ranges between trace and 0.1 ppm. Statistical tests indicate that the residue level for most specific pesticide chemicals in meat does not exceed 0.1 ppm (fat basis) in 97% of the samples of domestic and imported red meats (95% confidence). The residue levels of DDT compounds, dieldrin, and chloromethyl- phenoxy acetic acid (MCP) in imported meats do not exceed 0.1 ppm in a much lower percentage of the samples. POULTRY Table 15 lists eight pesticide chemicals in addition to the DDT compounds commonly found in the fat of poultry during the 2-year period reported. The incidences of DDT, dieldrin, and heptachlor — heptachlor epoxide exceed those found in any other class of foods. The period, FY 1968—1969, reported in Table 15A and accompanying figures is too short to depict trends. Except for the lower incidence of samples containing measurable levels of heptachlor — heptachlor epoxide in FY 1969, there do not seem to be significant differences in the residues found in poultry fat during the 2-year period. Statistical tests indicate that, except for DDT com- pounds, the residue level of a specific pesticide chemical does not exceed 0.1 ppm in 99% or more of the samples of domestic eggs (95% confidence). The DDT compound residue levels do not exceed 0.1 ppm in 77% of the samples. Table 16 lists seven pesticide chemicals, in addition to the DDT compounds, commonly found in the edible portion of shell eggs and frozen eggs in food distribu- tion channels. Three of these pesticide chemicals, aldrin, endrin and toxaphene, were not reported in the relatively few samples of imported eggs. Eggs are included in the 78 Pesticides Monitoring Journal meat composite of the total diet samples. All of the pesticide chemicals reported in the surveillance samples of eggs are found in the ready-to-eat meat composite. Inspection of Table 16A and accompanying figures shows that the incidence of trace levels of most chlori- nated organic compounds has not changed significantly during this period. Lower incidence of findings at meas- urable levels (>0.03 ppm) are observed for most pesticide chemicals with the exception of dieldrin which shows an increasing incidence of measurable residues. Statistical tests indicate that the residue level of a spe- cific pesticide does not exceed 0.1 ppm in 95% or more of the samples of domestic and imported eggs (95% confidence). FISH Table 17 lists eight chlorinated organic pesticide chemi- cals, in addition to the DDT compounds, commonly found in domestic and imported fish in food distribution channels. The incidence and levels of residues in im- ported fish are apparently lower than those reported in samples of domestic origin. This apparent difference may be due to the arbitrary classification of all fish samples as "objective," including samples which have been collected repeatedly from locations known to con- tain significant residues, e.g.. Lake Michigan. This bias must be considered in any uses made of these data. Table 17A and accompanying figures do not indicate any significant (by an order of magnitude) trends rec- ognizing the bias in the sampling, particularly in the last 2 years of the investigation. Statistical tests indicate that, except for DDT com- pounds, the residue level of a specific pesticide chemical does not exceed 0.1 ppm in 95% or more of the domestic and imported samples (95% confidence). The residue levels of DDT, DDE, and TDE do not exceed 0.1 ppm in a much lower percentage of the samples. SHELLFISH Table 18 lists eight pesticide chemicals, in addition to the DDT compounds, commonly found in shellfish in food distribution channels. Four of these compounds, heptachlor, heptachlor epoxide, aldrin, and chlordane were not reported in samples of imported shellfish. The incidence and average levels were lower in the im- ported products. Inspection of Table ISA and accompanying figures shows that there have been no significant changes in the incidence of trace levels of these compounds and that there were too few samples with measurable levels (>0.03 ppm) for statistical testing. Statistical tests indicate that the residue level of a specific pesticide chemical does not exceed 0.1 ppm in 96% or more of domestic and imported samples (95% confidence). GRAINS (ANIMAL) Table 19 lists seven pesticide chemicals, in addition to the DDT compounds, commonly found in grains in- tended for animal consumption. Only DDT, lindane, and aldrin were found on the small number of samples of grains imported for this purpose. Inspection of Table 19A and the accompanying figures does not show significant changes in the incidence of residues at the trace or measurable (>0.03 ppm) levels where there were sufficient positive samples for statistical testing. Statistical tests indicate that, except for malathion, the residue level of a specific pesticide chemical will not exceed 0.1 ppm in 96% or more of domestic and im- ported samples (95% confidence). The level of malathion residues does not exceed 0.1 ppm in 90% of the samples. INFANT AND JUNIOR FOODS (PREPARED) Table 20 lists four pesticide chemicals in addition to the DDT compounds commonly found in infant and junior foods. Table 20A shows the detailed data by year on each of the pesticide chemicals. There were not suffi- cient positive samples for any chemical at trace or measurable (>0.03 ppm) levels for statistical testing for trends. Statistical tests indicate that the residue level of a specific pesticide chemical does not exceed 0.1 ppm in 98% or more of the samples. TREE NUTS (EDIBLE PORTION) Table 21 lists seven pesticide chemicals, in addition to the DDT compounds, commonly found in tree nuts. Except for endrin and heptachlor epoxide, the same pesticide chemicals are found in the imported and domestic food. The incidence and levels found in im- ported tree nuts are somewhat higher than reported in the domestic surveillance program. Table 21 A provides detailed data on each of the pesti- cide chemicals. There were not sufficient positive sam- ples for any chemical at trace or measurable (>0.03 ppm) levels for statistical testing for trends. Statistical tests indicate that except for BHC. DDT, and DDE resi- dues, the residue level of a specific pesticide chemical in domestic and imported nuts does not exceed 0.1 ppm in 96% of the samples (95% confidence). The BHC residue does not exceed 0.1 ppm in 87% of the samples of imported nuts. The DDT residue does not exceed 0.1 ppm in 95% of the imported samples. The DDE residue does not exceed 0.1 ppm in 83% of the im- ported samples. Vol. 5, No. 2, September 1971 79 VEGETABLE OIL SEED AND PRODUCTS Tables 22-26 show the average levels and incidences of pesticide chemicals reported in the major vegetable oil seeds, crude oils, meal or cake, refined oils and oleo- margarine. Six chlorinated organic pesticide chemicals were commonly found in these products. Tables 22A- 25A list detailed incidence and ranges of pesticides in the oil seed. Tables 22B-25B list detailed incidence and ranges in the crude oils. Tables 22C-24C list detailed incidence and ranges in the oil seed meal or cake, except for corn. Tables 22D-25D list detailed incidence and ranges in the refined oil. No statistical tests were made on these data. Relatively few samples were examined during the 1968-1969 period. Table 27 is a summary of average levels of chlorinated pesticide residues, by compound, in the different vegetable oil seeds and products. The DDT compounds, dieldrin. lindane, and BHC residues were found in all oil seed. Toxaphene was found in all oil seeds except corn. These residues and endrin and chlordane residues were found in most oil seed products. Average residues were higher in the crude oils than in the original oil seed. The average residues in the oil meal or cake were approximately the same as in the oil seed. Most residues were substantially lower in the refined oil than in the crude oil and in many in- stances exceed the residue level in oil seed, even though the refining process removes substantial amounts of the chlorinated organic compounds. Inspection of the detailed data on the incidence and range of specific pesticide chemicals in these products shows that such relatively few samples are not likely to reflect any changes over the period of time studied. LITERATURE CITED (1) Duggan, R. E., and McFarland, F. ]., 1967. Assess- ments include raw food and feed commodities, market basket items prepared for consumption, meat samples taken at slaughter. Pestic. Monit. J. 1(1): 1-5. (2) Duggan, R. E. 1968. Pesticide residue levels in foods in the United States from July 1, 1963 to June 30, 1967. Pestic. Monit. J. 2(l):2-46. {3} Food and Drug Administration. U.S. Department of Healtli, Education, and Welfare. Pesticide Analytical Manual, Vol. I and II. Washington, D.C. 20204. (4) Food and Agriculture Organization of the United Na- tions— World Healtli Organization. 1970. 1969 Evalua- tions of some pesticide residues in foods. FAO:PL: 1969/M/17/1 WHO/Food Add./70.38 221-236. TABLE I. — Dietary intake of pesticide chemicals FAO-WHO- acceptarle Daily Intake Milligrams/Kilogram Body Weight/Day Total Diet Studies 1964-1965 1965-1966 1966-1967 1967-1968 1968-1969 5-Year Average Aldrin Dieldrin TOTAL 0.0001 0.00001 0.00008 0.00009 0.00004 0.00009 0.0001 0.00001 0.00005 0.00006 0.00001 0.00005 0.00006 0.0000001 0.00007 0.00007 0.00001 0.00007 0.00008 Carbaryl 0.02 0.002 0.0005 0.0001 0.00004 0.0005 DDT DDE TDE TOTAL 0.01 0.0004 0.0003 0.0002 0.0009 0.0005 0.0003 0.0002 0.00 1 0.0004 0.0002 0.0002 0.0008 0.0003 0.0002 0.0002 0.0007 0.0002 0.0002 0.0001 0.0005 0.0004 0.0003 0.0002 0.0008 0.004 0.125 0.0125 Gamma BHC (Lindane) 0.00007 0.00006 0.00007 0.00004 0.00002 0.00005 Bromide 1.0 »0.39 10.22 10.29 10.41 10.24 10.31 Heptachlor Heptachlor epoxide TOTAL 0.0005 0.000003 0.00003 0.00003 0.00005 0.00005 0.000001 0.00002 0.00002 0.000001 0.00003 0.00003 0.000001 0.00003 0.00003 0.000002 0.00003 0.00003 Malathion Dia2inon Parathion 0.02 0.002 0.005 0.000001 0.0001 0.00002 0.000005 0.0002 0.000001 0.00001 0.00004 0.000001 0.0002 0.000004 0.00001 0.0001 0.00001 0.00001 BHC Dicofol (Kelthane) Endrin 0.00003 0.00004 0.000009 0.00004 0.0001 0.000004 0.00003 0.0002 0.000004 0.00004 0.0001 0.00001 0.00002 0.0001 0.000004 0.00003 0.0001 0.000006 Total Chlorinated Organics Total Organophosphates Total Herbicides 0.0012 0.00012 0.0016 0.00014 0.00022 0.0012 0.00025 0.00005 0.0010 0.00007 0.00006 0.0008 0.00023 0.00005 0.0012 0.0002 0.0001 Total bromide present — includes naturally occurring bromides. Pesticides Monitoring Journal TABLE 2. — Chlorinated pesticides in ready-to-eal foods, total diet samples — Food and Drug Administration [Figures in parentlieses = Percent of daily intake; T = <0.001 mg] Average Milligrams Per Day 1965 1966 1967 1968 1969 I. D^ iry Products 0.010 (12.2) 0.018 (14.5) 0.014 (17.5) 0.015 (20.8) 0.010 (17.9) II. Meat, Fish, tnd Poultry 0.032 (39.0) 0.058 (46.8) 0.028 (35.0) 0.018 (25.0) 0.015 (26.8) III. Grains and Cereal 0.008 (9.8) 0.009 (7.3) 0.006 (7.5) 0.008 (11.1) o.no6 (10.7) IV. Potatoes 0.002 (2.4) 0.003 (2.4) 0.001 (1.3) 0.001 (1.4) 0.002 (3.6) V. Leafy Vegetables 0.004 (4.9) 0.004 (3.2) 0.002 (2.5) 0.003 (4.2) 0.007 (12.5) VI. Legume Vegetables 0.003 (3.7) 0.001 (0.8) T 0.002 (2.8) 0.001 (1.8) VII. Root Vegetables 0.002 (2.4) O.OOI (0.8) T T T VIII. Garden Fruits 0.010 (12.2) O.OU (8.9) 0.008 (10.0) 0.009 (12.5) 0.005 (8.9) IX. Fruits 0.007 (8.5) 0.015 (12.1) 0.018 (22.5) O.OU (15.3) 0.009 (16.1) X. Oils, Fats, and Shortening 0.003 (3.7) 0.004 (3.2) 0.002 (2.5) 0.006 (8.3) 0.001 (1.8) XI. Sugar and Adjuncts 0.001 (1.2) T T T T XII. Beverages TABLE 3. — Average incident and daily intake of 22 pesticide chemicals IT = <0.001 mg] 1964-1965 1965- 966 1966-1967 1967-1968 1968-1969 Percent PERCENT Percent Percent Percent Compounds POSETIVE Daily Positive Daily Positive Daily Positive Daily Positive Daily Com- Intake Com- Intake Com- Intake Com- Intake Com- Intake posites' (MG) posites = (MG) posites ■' (MG) posites ■" (MC) posites •' (MG) DDT 37.5 0.031 37.3 0.041 38.6 0.026 44.2 0.019 48.9 0.016 DDE 31.5 0.018 33.0 0.028 31.1 0.017 37.5 0.015 39.4 0.011 TDE 19.4 0.013 25.7 0.018 28.9 0.013 31.1 0.011 28.1 0.005 Dieldrin 18.5 0.005 21.3 0.007 15.3 0.004 15.6 0.004 25.3 0.005 Lindane 15.8 0.004 12.3 0.004 10.6 0.005 15.3 0.003 13.3 0.001 Heptachlor epoxide 13.4 0.002 12.0 0.003 8.9 0.001 13.1 0.002 12.2 BHC 6.5 0.002 6.0 0.004 8.9 0.002 9.7 0.003 10.6 O.OOI Mnlnthion — — 5.3 0.009 3.6 0.010 1.9 0.003 5.8 0.012 Carbaryl 7.4 0.15 2.7 0.026 1.1 0.007 — — 0.8 0.003 Aldrin 5.6 O.OOI 3.7 0.002 3.3 0.001 3.9 T 1.4 T 2,4-D 4.2 0.005 3.0 0.002 1.7 0.001 0.8 0.001 0.3 T Diazinon — — 3.0 O.OOI 0.3 T 0.3 T 3.9 T Dicofol (Kellhane) 0.5 0.003 3.7 0.002 5.6 0.012 4.7 0.010 3.6 0.007 PCP 1.4 T 3.3 0.006 2.2 0.001 1.9 O.OOI 2.8 0.002 Endrin 2.8 T 2.0 T 1.7 T 1.1 0.001 3.3 T Methoxychlor — — 1.6 T 0.8 O.OOI I.l 0.001 0.3 T Vol. 5, No. 2, September 1971 TABLE 3. — Average incident and daily intake of 22 pesticide chemicals — Continued [T = <0.001 mg] 1964-1965 1965- 1966 1966-1967 1967- 1968 1968-1969 Percent Percent Percent Percent Percent Compounds Positive Daily Positive Daily Positive Daily Positive Daily Positive Daily Com- Intake Com- Intake Com- Intake Com- Intake Com- Intake posites 1 (MG) posites = (MG) posites ^ (mc) posites ■■' (mg) posites ' (MG) Heptachlor 1.9 T _ _ 0.3 T 0.3 T 1.7 T Toxaphene — — 1.0 0.002 — — 1.1 0.002 3.6 0.004 Penhjne 0.5 T 1.3 0.001 — — 0.6 0.001 1.1 0.004 Parathion — — 1.0 T 1.4 0.001 0,6 T 3.3 T Endosulfan — — 1.6 T 0.3 T 0.8 T 4.2 0.001 Ethion — — 0.3 T 1.1 0.002 1.7 0.001 1.7 0.003 216 composites examined. 312 composites examined. 360 composites examined. TABLE 4. — Pesticide residues in fluid milk (fat basis) Fiscal Years 1964-69 1 — Domestic No. Samples Examined: 12,989 Compounds Percent With Residues: 59.2 Domestic Incidence Average Percent PPM DDT 25.5 0.03 DDE 44.3 0.07 TDE 16.5 0.02 Lindane 3.9 T Dieldrin 28.0 0.04 Aldrin 2.2 T Heptachlor epoxide 21.2 0.03 BHC 10.8 T Heptachlor 0.7 T Methoxychlor 0.9 T T = <0.005 ppm. TABLE 5, — Pesticide residues in dairy products (fat basis) T = <0.005 ppm. 82 Fiscal Years 1964-69 Manufactured Dairy Products: Butler, Cheese, Ice Cream. Etc. Domestic Imported Compounds No. Samples Examined: 6,231 1,981 Percent With Residues: 56.4 67.7 Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDT 24.8 0.03 21.8 0.07 DDE 43.2 0.06 30.2 0.05 TDE 18.4 0.02 14.1 0.03 Lindane 5.3 T 9.8 0.02 Dieldrin 23.7 0.02 17.1 0.01 Aldrin 1.4 T 2.3 T Heptachlor epoxide 18.0 0.02 3.8 0.01 BHC 15.3 0.02 49.3 0.76 Heptachlor 0.6 T 0.2 T Methoxychlor 0.5 T 0.1 T Pesticides Monitoring Journal TABLE 6. — Average levels of pesticide chemicals in dairy products (1) Average findings for FY 1964-66 (2) Average findings for FY 1967 (3) Average findings for FY 1968 (4) Average findings for FY 1969 (5) Total Diet samples, June 1964 — April 1966 Total Diet samples. June 1966 — April 1967 Total Diet samples. June 1967 — April 1968 Total Diet samples, June 1968— April 1969 ■ Parts Per Mai-iON — Fat Basis Compounds OBJEtmvE Samples Total Diet Samples (1) (2) (3) (4) (5) (6) (7) (8) DDE 0.066 0.087 0.069 0.058 0.074 0.050 0.063 0.048 Dieldrin 0.042 0.017 0.011 0.008 0.016 0.019 0.012 0.019 DDT 0.042 0.033 0.014 0.009 0.037 0.032 0.030 0.023 Heptachlor epoxide 0.036 0.005 0.003 0.005 0.010 0.006 0.012 0.012 TDE 0.026 0.017 0.011 0.007 0.013 0.022 0.019 0.010 BHC 0.007 0.018 0.006 0.013 0.008 0.01 1 0.021 0.007 Lindane 0.004 0.006 0.001 0.001 0.005 0.003 T 0.00 1 Aldrin 0.001 0.001 0.001 T 0.001 0.001 — — Heptachlor 0.002 T T T — 0.001 — T Methoxychlor 0.001 0.00 1 0.002 0.005 0.002 0.005 0.004 — T = <0.001 ppm. TABLE 7. — Pesticide residues in large fruits Fiscal Years 1964-69 June 1964— April 1969 Raw Agricultural Products: Apples, Oranges, Pears, Peaches. Et c. Total Diet Samples — Ready-to-Eat Food Compounds No. Samples Examined: Percent With Residues: Domestic 6.763 49.7 Imported 2.495 54.1 Fruit Composites: Oranges. Orange Juice, Raisins. Peaches. Strawberries. Apricots. Cherries. Pineapple. Grapes. Bananas. Etc. Domestic Imported 134 COMPOSTTES Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 29.7 0.10 17.4 0.04 53.0 0.008 DDE 16.8 T 7.9 0.01 44.0 0.002 TDE 7.5 0.01 3.6 T 25.4 0.002 Lindane 1.8 T 3.1 T 6.0 TT Dieldrin 10.8 T 23.0 0.01 7.5 TT Aldrin 5.3 T 0.9 T 17.9 0.002 BHC 0.6 T 1.3 T 1.5 TT Endrin 2.0 T 30.6 0.01 — — Heptachlor epoxide 0.6 T 0.6 T 3.0 TT Toxaphene 0.2 T 0.4 0.02 — _ Endosulfan (Thiodan) 0.8 T 0.4 T 2.2 TT Carbaryl •4.1 0.02 • — 6.0 0.011 Dicofol (Kelthane) 8.6 0.02 4.0 0.01 44.0 0.030 •4.4 T •1.0 T — — Tetradifon (Tedion) 2.0 T 1.9 0.01 3.0 0.001 Ethion •10.5 0.02 •1.0 T 11.9 0.004 Diazinon •2.3 T •<0.1 T — — Carbophenothion (Trithion) •1.3 T •0.2 T — — Perihane — — — — 3.0 0.001 T = <0.005 ppm. TT = < 0.001 ppm. • Not included in analytical i ethod FY 1964-1965. Vol. 5, No. 2, September 1971 83 TABLE 8. — Pesticide residues in small fruits^ Fiscal Years 1964-69 Raw Agricultural Products: Strawberries, Cherries, Plums, Grapes, Cranberries, Etc. Domestic Imported No. Samples Examined: 2,695 496 Percent With Residues: 53.4 43.8 Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDT 32.3 0.05 28.8 0.05 DDE 19.8 T 15.5 0.01 TDE 8.3 0.01 5.0 T Lindane 1.1 T 1.0 T Dieldrin 7.8 T 3.6 T Aldrin 2.0 T 2.4 T BHC 0.5 T 3.0 T Endrin 1.5 T 4.4 T Heplachlor epoxide 0.8 T 0.6 T Toxaphene 0.9 0.01 0.2 T Dicofol (Kelthane) 6.2 0,04 5.7 0.04 Perthane 1.9 0.04 — — Endosulfan (Thiodan) 2.0 r 2.4 T P; rathion •4.4 T •0.6 T Ethion •4.0 0.02 •5.2 0.02 Tetradifon (Tedion) •2.0 0.01 - - 1 Small fruits included in Fruit Composites of Total Diet samples. T = < 0.005 ppm. • Not included in analytical method FY 1964-1965. TABLE 9. — Pesticide residues in grains and cereals for human use Fiscal Years 1964-69 June 1964 — April 1969 Raw Agricultural Products: Total Diet Samples— Wheat. Grain Corn. Rice. Etc.^ Ready-to-Eat Food — Grain and Cereal CoMposriES: Compounds Domestic Imported Flour. Bread. Corn Meal, No. Samples Examined: 8,005 104 Vegetable Corn. Rice. Percent With Residues: 33.6 19.2 Macaroni, Pie Crust, Etc. Domestic Imported 134 CoMPosrrES Incidence Average Incidence Average Incidence Average Percent PPM Percent PPM Percent PPM DDT 19.5 0.02 10.6 0.01 59.7 0.005 DDE 8.7 T 1.9 T 31.3 0.001 TDE 2.4 T — — 18.7 0.001 Lindane 7.7 T 10.6 T 67.2 0.006 Dieldrin 3.6 T 1.9 T 29.1 0.003 Aldrin 2.0 T 2.9 T 6.0 TT BHC 1.5 T 1.9 T 3.0 TT Endrin 0.3 T 1.0 T 1.5 IT Heptachlor epoxide 0.3 T 1.0 T 6.0 TT Toxaphene 0.4 T — — — — Malathion •22.1 0.56 — — 28.4 0.012 Carbaryl •1.4 T — — 3.0 0.009 PCP •24.1 T 6.7 0.001 Methoxychlor 2.4 0.01 — — 3.0 TT Chlordane 0.6 T 2.9 T — — Heptachlor 0.3 T 2.9 T 2.2 TT Diazinon •0.5 T — — 6.0 0.001 Parathion •0.7 T — — — — ' Includes animal grains FY 1964-1965. T = <0.005 ppm. TT = <0.001 ppm. • Not included in analytical method FY 1964-1965. 84 Pesticides Monitoring Journal TABLE 10. — Pesticide residues in leaf and stem vegetables Fiscal Years 1964-69 June 1964 — April 1969 Raw Agriclh-tural Products: Total Diet Samples — Spinach. Mustard, Celery, Broccoli, Cabbage Kate. Etc. Ready-to-Eat Food Leafy Vegetable Composttes: Domestic Imported Beet tops. Collards. Mustard, No. Samples Examined: 13,864 153 Spinach. Celery. Cabbage, Percent with Residues: 61.0 52.9 Broccoli, Mushrooms. Cauliflower Domestic Imported 134 Composttes Incidence Average Incidence Average Incidence Average Percent PPM Percent PPM Percent PPM DDT 37.3 0.14 29.8 0.53 60.4 0.013 DDE 24.0 0.01 13.9 0.01 38.8 0.004 TDE 6.9 0.01 1.3 T 29.1 0.006 Lindane 3.8 T 4.6 T 11.9 TT Dieldrin 8.8 T 10.6 T 6.7 TT Aldrin 2.1 T 3.3 T 2.2 TT BHC 1.5 T 0.7 T 5.2 TT Endrin 4.0 T 2.0 T 3.7 0.001 Heptachlor epoxide 2.6 T 4.0 O.OI 1.5 TT Toxaphene 7.9 0.20 2.7 1.24 3.7 0.006 Parathion •16.0 0.03 •1.6 T 9.7 0.003 Bndosulfan (Thiodan) 4.9 0.01 4.0 0.03 7.5 0.001 PCNB 0.7 0.01 3.3 T — — Methoxychlor 0.1 T 2.0 0.01 0.7 TT Chlorbenside (Mitox) 0.2 T 1.3 T 3.7 0.001 Diazinon •6.9 0.01 •14.5 0.03 4.5 TT Methyl parathion •6.1 0.01 — — 4.5 TT DCPA (Dacthal) 0.5 T — 3.0 TT • Not included in ai T = <0.005 ppm. TT = < 0.001 ppm. lalytical method FY 1964-1965. TABLE 1 1 . — Pesticide residues in vine and ear vegetables Fiscal Years 1964-69 June 1964 — April 1969 Raw Agricultural Products: Tomatoes. Corn, Squash. Eggplant. Etc. Total Diet Samples— Ready-lo-Eat Food Compounds Domestlc No. Samples Examined: 8,072 Percent With Residues: 44.7 Imported 1,791 78.2_ Garden Fruit Composites: Pepper (raw). Tomatoes, Catsup, Cucumbers, Eggplant, Squash Domestic Imported 134 Composites Incidence Average Percent PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 21.8 0.03 56.3 0.10 67.2 0.029 DDE 9.3 T 33.3 0.01 41.0 0.003 TDE 6.7 0.01 2.6 T 53.0 0.013 Lindane 3.0 T 5.9 T 29.9 0.002 Dieldrin 18.0 0.01 24.1 0.01 32.1 0.002 Aldrin 1.2 T 1.4 T 4.5 TT BHC 0.7 T 1.0 T 0.7 TT Endrin 3.5 T 8.8 T 3.0 TT Heptachlor epoxide Toxaphene 2.1 T 1.3 0.01 2.7 5.0 T 0.02 5.2 7.5 TT 0.007 Chlordane 1.7 T 0.2 T 1.5 TT Endosulfan (Thiodan) Parathion 1.4 T •2.9 T 6.7 •10.3 T 0.01 6.0 5.2 TT 0.001 Diazinon •0.9 T •0.6 T 3.0 TT T = <0.005 ppm. TT = <0.001 ppm. • Not included in analytical method FY 1964-1965. Vol. 5, No. 2, September 1971 85 TABLE 12. — Pesticide residues in root vegetables Fiscal Years 1964-69 June 1964 — April 1969 Raw Agricultural Products: Carrots, Beets, Potatoes, Onions, Turnips, Etc. Total Diet Samples — Ready-to-Eat Food Compounds Domestic Imported No. Samples Examined; 13.561 533 Percent With Residues: 50.4 55.3 Root Vegetable and Potato Composttes : Carrots. Onions. Beets. Turnips, Etc., White Potatoes, Sweet Potatoes, Potato chips. Etc. Domestic Imported 134 CoMPosrres Root Vegetables Potatoes Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 33.9 0.04 26.0 0.03 20.1 0.003 26.1 0.002 DDE 31.3 0.02 9.4 T 30.6 0.003 20.9 0.001 TDE 7.9 T 2.3 T 8.2 0.001 8.2 TT Lindane 2.3 T 6.1 T 1.5 TT 7.5 TT Dieldrin 23.9 0.01 14.7 0.01 10.4 0.001 19.4 0.001 Aldrin 2.5 T 8.0 T 0.7 TT 0.7 TT BHC 1.0 T 13.9 0.02 — — 0.7 TT Endrin 5.5 T 1.5 T 2.2 TT 14.2 0.001 Heptachlor epoxide 3.2 T 5.3 T 0.7 TT 6.7 TT Toxaphene 1.4 0.01 — — 0.7 TT — — Chlordane 1.8 T 0.4 T — — 1.5 0.001 Heptachlor Diazinon 0.7 •1.1 T T 3.8 •13.1 T 0.01 1.5 TT 0.7 TT Parathion •1.3 T •1.2 T — _ 0.7 TT Methyl parathion •0.4 T •0.9 T — — — — T = < 0.005 ppm. TT = < 0.001 ppm. • Not included in analytical method FY 1964-1965. TABLE 13. — Pesticide residues in beans Fiscal Years 1964-69 June 1964 — April 1969 Raw Agricultural Products: Peas, Green Beans, Lima Beans. Etc Total Diet Samples — Ready-to-Eat Food Compounds Domestic No. Samples Examined: 1,492 \_Percent With Residues: 31.0 Imported 144 80.6 Legume Vegetable Composttes : Peas, Green Beans. Lima Beans Domestic Imported 134 Composttes Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 21.4 0.08 63.9 0.12 23.1 0.010 DDE 9.6 T 47.9 0.01 21.6 0.001 TDE 3.3 T 2.1 T 20.9 0.003 Lindane 1.2 T 12.5 T 2.2 TT Dieldrin 6.2 T 10.4 T 3.0 TT Aldrin 0.6 T 2.1 T 3.0 TT BHC 0.9 T 3.5 T 0.7 TT Endrin 0.3 T 1.4 T — — Heptachlor epoxide 0.3 T 2.1 T 0.7 TT Toxaphene 1.1 0.01 1.4 T 1.5 0.001 Parathion •1.3 T •19.2 0.02 0.7 TT Diazinon •0.7 T — — — — T = < 0.005 ppm. TT = <0.001 ppm. • Not included in analytical method FY 1964-1965. Pesticides Monitoring Journal TABLE 14. — Pesticide residues in meats (fat basis Fiscal Years 1964-69 JuNF 1964— April 1969 Meat Products: Total Diet Samples — Beef. Pork, Etc. Ready~to-Eat Food Meat, Fish, and Poultry Composites; Roast Beef. Ground beet. Compounds Domestic Imported ' No. Samples Examined: 12,146 3,674 Pork chops, f is/? fillets. Eggs, Frankfurters, etc. Domestic Imported 134 Composites Incidence Average Incidence Average Incidence Average Percent PPM Percent PPM Percent PPM DDT* 75.4 0.33 83.9 0.41 88.1 0.182 DDE* 92.5 0.168 TDE* 80.6 0.092 Dieldrin 31.3 0.05 46.7 0.10 61.9 0.026 Heptjchlor epoxide*' ♦21.6 0.02 10.2 0.01 53.7 0.016 Heptachlor** 9.6 0.01 1.1 T 3.0 TT Lindane 6.6 0.01 12.4 0.01 19.4 0.006 BHC "20.2 0.02 ■63.2 0.15 50.0 0.018 Aldrin 0.1 T 2 1.4 T 0.7 TT Endrin 0.4 T 1.0 T 1.5 TT Methoxychlor 1.8 0.01 0.6 T — — Toxaphene 1.4 0.01 0.1 T 1.5 0.004 MCP m.8 0.02 «45.1 0.10 0.7 TT 1 Import samples for FY 1967, 1968, and 1969 only. 'FY 1968 and 1969 only, 4,012 domestic samples and 1,773 import samples. >FY 1965, 1966 and 1967 only, 8,134 domestic samples. 'FY 1967 only, 3,098 domestic samples, 1,901 import samples. = < 0.005 ppm. T = <0.001 ppm. DDT includes DDE and TDE. * Heptachlor includes Heptachlor epoxide except FY 1967 (domestic samples only). TABLE 15. — Pesticide residues in poultry ' Fiscal Years 1968 and 1969 Domestic Compounds No. Samples Examined: 3,414 Domestic Incidence Average Percent PPM DDT* 99.1 0.15 Aldrin 0.2 T BHC 20.3 T Chlordane 0.1 T Dieldrin 79.9 0.02 Endrin 4.4 T Heptachlor** 26.3 0.01 Lindane 9.3 T Methoxychlor 1.4 T 1 Poultry included in the Meat, Fish, and Poultry composites of Total Diet samples. T = <0.005 ppm. Includes DDE and TDE. * Includes Heptachlor epoxide. TABLE 16. — Pesticide residues in eggs' Fiscal Years 1964-69 Raw AoRicuLTimAL Products: Shell eggs Domestic Imported Compounds No. Samples Examined: 4,046 Percent With Residues: 70.5 121 54.5 Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDT 42.1 0.03 17.4 0.01 DDE 65.2 0.03 28.9 0.01 TDE 7.8 T 0.8 T Lindane 5.0 T 9.1 T Dieldrin 20.7 0.01 5.8 T Aldrin 0.5 T — — BHC 2.4 T 0.8 T Endrin 0.9 T — — Heptachlor epoxide 3.1 T 3.3 T Toxaphene 0.1 T — — 1 Eggs included in Meat, Fish, and Poultry composites of Total Diet samples. T = < 0.005 ppm. Vol. 5, No. 2, September 1971 87 TABLE 17. — Pesticide residues in fish ' Fiscal Years 1964-69 Products: Fillets: Fresh, Frozen, Canned, Etc. Domestic Imported Compounds No. Samples Examined: 2,150 378 Percent With Residues: 74.4 56.1 _| Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDE 66.3 0.49 49.1 0.06 DDT 54.7 0.22 44.0 0.08 TDE 41.2 0.13 25.5 0.03 Dieldrin 27.9 0.02 14.1 T BHC 8.0 T 13.0 0.02 Endrin 5.7 T 2.9 T Heptachlor epoxide 3.4 T 3.7 T Toxaphene 1.9 0.04 0.8 T Lindane 1.8 T 3.5 T Aldrin 1.8 T 1.1 T Heptachlor 0.6 T 0.3 T ^ Fish included in Meat, Fish, and Poultry composites of Total Diet samples, T = <0.005 ppm. TABLE IS.— Pesticide residues in shellfish Fiscal Years 1964-69 Products: Shrimp, Oysters, Lobster, Crabmeat, Etc. Domestic Imported Compounds No. Samples Examined: 830 167 Percent With Residues: 48.3 16.8 Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDE 38.9 0.02 10.2 T TDE 23.3 0.01 10.2 0.01 DDT 18.9 0.01 7.2 T Dieldrin 18.3 0.01 4.2 T Heptachlor epoxide 3.5 T — — BHC 3.4 T 6.0 T Endrin 2.5 T 2.4 T Lindane 1.3 T 1.2 T Aldrin 0.8 T — — Chlordane 0.8 T — — Heptachlor 0.5 T — — T = < 0.005 ppm. TABLE \9.— Pesticide residues in grains (animal) Fiscal Years 1966-69 Raw Agricultural Products: Wheat, Grain Corn, Milo, Etc. Domestic Imported Compounds No. Samples Examined: 1,168 60 Percent With Residues: 40.6 18.3 _ Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDT 21.5 0.02 10.0 T DDE 9.9 T — — TDE 4.6 T — — Lindane 3.5 T 6.7 T Dieldrin 7.1 T — — Aldrin 1.5 T 1.7 T BHC 2.7 T — — Endrin 0.4 T — — Heptachlor epoxide 2.1 T — — Malathion •18.3 0.12 — — ■ = <0.005 ppm. Not examined for in all samples. Pesticides Monitoring Journal TABLE 20. — Peslicide residues in infant and junior foods Fiscal Years 1964-69 Products: Prepared Baby Foods, Pureed or Prepared Formulae. Etc. Diced. Compounds No. Samples Examined: Percent With Residues: Domestic 2,078 25.5 Domestic Incidence Percent Average PPM DDE DDT TDE Dicldrin Aldrin Lind:ine Htpijchlor epoxide 12.7 9.3 8.4 4.7 1.5 1.6 I.l 0.01 T 0.01 T T T T T = <0.005 ppm. TABLE 21. — Pesticide residues in tree nuts Fiscal Years 1964-69 Raw Agricultural Products: Pecans. Filberts, Walnuts. Etc. Domestic Imported Compounds No. Samples Examined: 418 Percent With Residues: 21.5 128 49.2 Domestic Imported Incidence Average Incidence Average Percent PPM Percent PPM DDT 0.02 10.6 0.03 22.1 DDE n.n5 9.4 T 22.1 TDE 0.01 3.8 T 11.8 Lindane O.OI 1.9 T 8.7 Dieldrin T 4.1 0.05 7.9 Aldrin T 1.0 T 0.8 BHC 0.04 1.9 T 21.3 Endrin — 0.7 T Heptachlor epoxide — 0.5 T Toxaphene T 0.2 T 1.6 T = <0.005 ppm. TABLE 22. — Average levels and incidence of specific pesticide residues in peanut products Fiscal Years 1964-69 Nuts Crude On. Meal (Cake) Refined Oil No. Samples Examined: 229 41 36 11 Percent With Residues: 31.0 75.6 58.3 36.4 Incidence Average Incidence Average Incidence Average Incidence Average Compounds Percent PPM Percent PPM Percent PPM Percent PPM DDT 16.6 0.050 65.9 0.500 38.9 0.121 27.3 0.073 TDE 6.1 0.002 43.9 0.131 22.2 0.024 36.4 0.025 DDE 14.8 0.003 58.5 0.081 36.1 0.025 27.3 0.033 Dieldrin 7.4 0.006 17.1 0.015 19.4 0.005 9.1 0.006 Lindane 3.1 0.002 14.8 0.001 2.8 T Toxaphene 1.3 0.005 2.4 0.008 Endrin 0.9 T 2.4 0.007 BHC 0.9 0.005 7.3 0.002 11.1 0.005 9.1 0.002 T = <0.001 ppm. Vol. 5, No. 2. September 1971 89 TABLE 23. — Average levels and incidence of specific pesticide residues in cottonseed products Fiscal Years 1964-69 Seed Crude Oil Meal (Cake) Refined Oil No. Samples Examined: Percent IVilh Residues: 31 64.5 282 51.4 287 38.0 48 41.7 Compounds Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 54.8 0.114 28.0 0.064 28.9 0.091 14.6 0.036 TDE 9.7 0.022 34.7 0.085 18.1 0.027 16.7 0.016 DDE 12.9 0.004 14.5 0.010 13.2 0.012 16.7 0.009 Dieldrin 19.3 0.016 2.8 T 2.8 T 2.1 T Lindane 3.2 0.002 8.2 0.009 7.3 0.002 2.1 0.015 Toxaphene 29.0 0.017 1.1 0.008 3.5 0.002 10.4 0.120 BHC 19.3 0.013 2.5 0.003 4.9 0.005 2.1 T Chlordane 6.5 0.003 1.8 0.014 5.6 0.008 2.1 0.006 Endrin — — — — 1.4 T — — <0.001 ppm. TABLE 24. — A verage levels and incidence of specific pesticide residues in soybean products Fiscal Years 1964-69 Soybeans Crude Oil Meal (Cake) Refined Oil No. Samples Examined: Percent With Residues: 690 31.9 118 37.3 248 16.9 34 14.7 Compounds Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT TDE DDE Dieldrin Lindane Toxaphene Endrin BHC Chlordane 9.3 0.9 3.2 13.2 1.7 7.1 9.6 3.3 0.9 0.005 T T 0.002 T 0.006 0.007 T T 18.6 8.5 5.9 16.1 2.5 8.5 9.3 12.7 0.014 0.006 0.002 0.011 T 0.114 0.028 0.004 8.1 2.0 3.6 3.6 4.0 0.8 1.6 0.4 0.003 T 0.001 T 0.001 T 0.001 T 11.8 2.9 2.9 2.9 2.9 0.002 T T T T TABLE 25. — Average levels and incidence of specific pesticide residues in corn products Fiscal Years 1964-69 Grain Crude Oil Refined Oil No. Samples Examined: Percent With Residues: 1,314 23.7 28 25.0 10 20.0 Compounds Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT 7.2 0.007 14.3 0.065 10.0 0.030 TDE 1.4 0.002 10.7 0.058 — — DDE 4.1 T 10.7 0.015 _ — Dieldrin 8.9 0.002 10.7 0.013 _ — Lindane 2.5 0.001 — _ — _ Toxaphene — — — — — _ Endrin 0.4 T _ — — _ Chlordane 0.2 T 3.6 0.077 _ _ BHC 0.5 T - - - - T= <0.O0I ppm. 90 Pesticides Monitoring Journal TABLE 26. — Incidence of specific residues in oleomargarine (1) Average Findings for FY 1964-65 (2) Average Findings for FY 1967 (3) Average Findings for FY 1968 (4) Average Findings for FY 1969 No. Samples Examined: Percent With Residues: (1) 53 18.9 (2) 23 17.4 (3) 4 0.0 (4) 5 0.0 TOTAL 85 16.5 Compounds Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM Incidence Percent Average PPM DDT TOE DDE BHC Dieldrin 18.9 5.7 7.5 3.8 n.026 0.002 0.001 T 13.0 13.0 8.7 4.3 4.3 0.014 0.014 0.034 0.001 T - - - - 15.3 7.1 7.1 3.5 1.2 0.018 0.003 0.007 T T TABLE 27. — Average levels of chlorinated pesticide residues in vegetable oil seeds and products Whole Product Fiscal Years 1964-69 (Residues in PPM) Meal OR Cake Oleo- margarine Total Diet Composites* Soybean 0.005 0.014 0.003 0.002 Cottonseed 0.114 0.064 0.091 0.036 Peanut 0.050 0.500 0.121 0.073 Corn 0.007 0.065 — 0.030 TOTAL 0.009 0.090 0.055 0.026 0.018 0.005 Soybean T 0.006 T T Cottonseed 0.022 0.085 0.027 0.016 Peanut 0.002 0.131 0.024 0.025 Corn 0.002 0.058 — — TOTAL 0.002 0.067 0.015 0.008 0.003 1 0.009 Soybean T 0.002 0.001 T Cottonseed 0.004 0.010 0.012 0.009 Peanut 0.003 0.081 0.025 0.033 Com T 0.015 — — TOTAL 0.001 0.014 0.008 0.007 0.007 0.005 Soybean 0.002 0.011 T T Cottonseed 0.016 T T T Peanut 0.006 0.015 0.005 0.006 Corn 0.002 0.013 — — TOTAL 0.003 0.005 T 0.001 T 0.002 Soybean T T O.OOI — Cottonseed 0.002 0.009 0.002 0.015 Peanut 0.002 0.001 T — Com O.OOI — — — TOTAL 0.001 0.005 0.002 0.007 — 0.001 TOXAPHENE Soybean 0.006 0.114 _ T Cottonseed 0.017 0.008 0.002 0.120 Peanut 0.005 0.008 — — Corn — — — — TOTAL 0.002 0.034 0.001 0.056 — — Vol. 5, No. 2, Septembeji 1971 91 TABLE 27. — Average levels of clilorinatcd pesticide residues in vegetable oil seeds and products — Continued Fiscal Years 1964-69 (Residues in PPM) Whole Product Crude Oil Meal OR Cake Refined Oil Oleo- margarine Composites Total Diet* Soybean 0.007 0.028 T _ Cottonseed — — T — Peanut T 0.007 — — Corn T — — — TOTAL 0.002 0.008 T — — 0.002 Soybean T 0.004 0.001 _ Cottonseed 0.013 0.003 0.005 T Peanut 0.005 0.002 0.005 0.002 Corn T — — — TOTAL O.OOI 0.003 0.004 T T 0.001 CHLORDANE Soybean T — T — Cottonseed 0.003 0.014 0.008 0.006 Peanut — — — — Corn T 0.077 — — TOTAL T 0.013 0.004 0.003 - - ■ = < 0.001 ppm. Salad dressings, salad oil, mayonnaise, shortening and peanut butter. TABLE 4 A — Fluid Milk: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total 92 Pesticides Monitoring Journal TABLE 4A — Fluid Milk: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued 1T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 84.0 80.58 81.09 83.48 9.45 14.41 16.17 10.40 3.79 2.46 1.55 3.51 2.28 1.94 .95 2.16 No. Samples 10807 1339 841 12987 None found 95.56 98.81 98.10 96.07 Trace-0.03 2.88 .90 1.66 2.60 0.04-0.10 .98 .07 .12 .83 0.11-0.50 .48 .22 .42 0.51-1.00 .05 .12 .05 1.01-1.50 .01 1.51-2.00 Above 2.00 .01 .02 Average PPM T T T T DIELDRIN No. Samples 10807 1336 841 12984 None found 71.18 75.30 78.00 72.05 Trace-0.03 12.09 16.77 14.98 12.76 _ 0.04-0.10 7.75 4.72 4.28 7.22 0.11-0.50 8.04 2.62 2.38 7.12 0.51-1.00 .78 .45 .24 .72 1.01-1.50 .04 .15 .12 06 1.51-2.00 .02 .02 Above 2.00 .06 .05 -— Average PPM .04 T T .04 _ ALDRIN Vol.. 5, No. 2, September 1971 93 TABLE 4 A — Fluid Milk: Percent distribution of residues, hy fiscal year, in different quantitative ranges — Continued [T=<.005 PPMl Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total BHC No. Samples None found Tracc-0.3 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 0.70 79,31 85.97 89.22 6.79 15.91 12.13 8,08 1.64 4.18 1.66 1.91 HEPTACHLOR EPOXIDE HEPTACHLOR No. Samples 10807 1339 841 12987 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1,01-1.50 1.51-2.00 Above 2.00 99.15 99.78 99.88 99.27 .50 .22 .12 .45 .18 .15 •" - '^ .01 Average PPM T T T T METHOXYCHLOR 94 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 4 A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) Vol. 5, No. 2. Sfptfmber 1971 95 STATISTICAL TREATMENT OF DATA IN TABLE 4/)— Continued DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00l Lower Confidence Limit (95%) BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM r^ I IS( \l ■» I \K ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) HEPTACHI OR EPOXIDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM -J,.. n n F.»..il Vc:in dIS,. •ivr tii 96 Pesticides Monitoring Joltrnal STATISTICAL TREATMENT OF DATA IN TABLE -//4— Continued HEPTACHI.OR SIGNIFICANCE LE\EL OF CHI-SQL ARE TEST STATISTIC < 0.001 Lower Confidence Limit (95';r) METHOXYCHLOR SIGNIFICANCE LE\ EL OF CHI-SQUARE TEST STATISTIC <0.05 Lower Confidence Limit (95?r) i'-/ln TABLE 5 A — Dairy Products: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DDT No. Samples 4489 1088 654 6231 1182 177 620 1978 None found 74.42 76.75 78.29 75.24 75.38 77.40 83.71 78.17 Trace-0.03 12.58 15.99 17.28 13.67 8.20 11.30 11.13 9.40 0.04-0.10 4.98 3.77 2.91 4.56 3.80 3.95 .48 2.78 0.11-0.50 7.26 3.22 1.53 5.95 10.15 6.21 4.19 7.93 0.51-1.00 S.l .18 .42 1.77 1.13 .32 1.26 I. 01-1.50 .11 .08 .50 .30 1.51-2.00 .06 .05 Above 2.00 .02 .09 .03 .16 .16 .15 Average PPM .04 T T T .09 T .05 .07 No. Samples 4489 1088 654 6231 1182 179 620 1981 None found 56.35 56.62 60.24 56.81 66.49 72.63 75.16 69.76 Trace-0.03 18.71 23.62 22.63 19 98 12.18 12.29 16.13 13.43 0.04-0.10 10.93 7.90 4.89 9.77 7.19 6.15 2.74 5.70 0.11-0.50 12.76 10.39 10.09 12.07 11.25 8.38 5.32 9.14 0.51-1.00 1.06 1.19 1.99 1.19 2.28 .56 .32 1.51 1.01-1.50 .08 .28 .15 .13 .50 .30 1.51-2.00 .06 .05 Above 2.00 ..._.. .08 .32 .15 Average PPM .06 .04 .05 .06 .07 T T .05 Vol. .";, No. 2. September 1<)71 97 TABLE 5A — Dairy Products: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued IT=<.005 PPM) Range PPM Percent Disthibution of Samples Domestic 1968 1969 Imported 1968 1969 TDE No. Samples 4489 1088 654 6231 1182 177 620 1979 None found 80.19 83.46 88.23 81.61 83.84 84.75 90.15 85.90 Trace-0.03 9.82 11.67 9.79 10.14 7.19 11.86 8.06 7.88 0.04-0.10 5.56 1.84 1.07 4.45 3.63 1.69 .16 2.37 0.11-0.50 4.12 2.85 .76 3.55 4.31 1.69 1.29 3.13 0.51-1.00 .24 .09 .15 .21 .50 .32 .40 1.01-1.50 .04 .09 .05 .16 .10 1.51-2.00 .08 .05 Above 2.00 .25 .15 Average PPM .02 T T T .06 T T .04 No. Samples 4489 1088 654 6231 1182 177 620 1979 None found 93.58 97.52 98.01 94.74 93.73 87.01 84.52 90.25 Trace-0.03 4.47 1.93 1.53 3.72 3.46 4.52 9.19 5.36 0.04-0.10 1.18 .09 .15 .88 .84 3.39 2.90 1.72 O.n-0.50 .62 .28 .31 .53 1.60 3.95 2.90 2.22 0.51-1 00 .11 .18 .11 .08 .16 .10 1.01-1.50 .02 .02 .08 .05 1.51-2.00 Above 2.00 .16 1.13 .32 .30 Average PPM T T T T .01 .07 T T DIELDRIN No. Samples 4489 1088 654 6231 1182 175 620 1977 None found 74.96 77.85 83.18 76.33 85.44 87.43 76.94 82.95 Trace-0.03 11.04 16.64 13.15 12.25 6.85 7.43 13.39 8.95 0.04-0-10 7.61 4.32 2.14 6.47 5.07 4.00 4.19 4.70 0.11-0.50 6.03 1.19 1.53 4.72 2.36 1.14 5.00 3.09 0.51-1.00 .22 .16 .16 .48 .25 1.01-1.50 .04 .03 08 .05 1.51-2.00 .06 .05 Above 2.00 --— .._-... Average PPM .03 T T T .01 T T T 98 ALDRIN No. Samples 4489 1088 654 6231 1182 177 620 1979 None found 98.59 98.35 98.78 98.57 96.78 99.44 99.03 97.73 Trace-0.03 1.33 1.29 1.07 1.30 2.45 .56 .97 1.82 0.04-0.10 .04 .28 .15 .10 .25 .15 0.11-0.50 .02 .09 .03 .50 .30 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 '-— ...._.. Average PPM T T T T T T T T Pesticides Monitorino Journ.^l TABLE 5A — Dairy Products: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPMl Range PPM Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 BHC No. Samples 4489 1088 654 6231 1182 178 620 1980 None found 87.14 79.50 76.30 84.67 73.43 56.74 5.48 50.66 Trace-0.03 7.52 15.35 15.90 9.77 5.32 13.48 24.68 12.12 0.04-0.10 3.16 3.13 3.82 3.23 7.10 12.92 25.97 13.54 O.n-0.50 1.87 1.93 3.21 2.02 9.30 16.29 34.68 17.88 0.51-1.00 .20 .09 .46 .21 2.87 4.84 3.23 1.01-1.50 .15 .02 .50 .56 2.42 1.11 1.51-2.00 .50 .65 .51 Above 2.00 .08 .15 .08 .93 1.29 .96 Average PPM .02 T T T .14 .05 2.15 .76 HEPTACHLOR EPOXIDE No. Samples 4489 1088 654 6231 1182 177 620 1979 None found 78.74 89.89 90.83 81.96 97.03 96.05 94.68 96.21 Trace-0.03 10.40 8.18 7.95 9.76 1.18 .56 2.90 1.67 0.04-0.10 5.27 1.47 .76 4.14 .84 1.13 1.13 .96 0.11-0.50 5.48 .46 .31 4.06 .93 1.69 1.29 1.11 0.51-1.00 .08 .06 1.01-1.50 1.51-2.00 Above 2.00 .15 .02 .56 .05 Average PPM .02 T T T T T T T HEPTACHLOR No. Samples 4489 1088 654 6231 1182 177 620 1979 None Found 99.24 99.82 99.85 99.41 99.91 98.87 99.84 99.80 Trace-0.03 .57 .15 .43 .08 .56 .10 0.04-0.10 .08 .06 .56 .16 .10 0.11-0.50 .08 .18 .10 D.51-1.00 1.01-1.50 1.51-2.00 - Above 2.00 Average PPM T T T T T T T T METHOXYCHLOR Vol. 5, No. 2, September 1971 No. Samples 4489 1088 654 6231 1182 177 620 1979 None found 99.59 99.36 98.93 99.49 100.00 99.44 100.00 99.95 Trace-0.03 .08 .55 .15 .18 .56 .05 0.04-0.10 .06 .09 .06 O.n-0.50 .20 .92 .24 0.51-1.00 .04 .03 1.01-1.50 1.51-2.00 Above 2.00 ._.-... Average PPM T T T T T T 99 STATISTICAL TREATMENT OF DATA IN TABLE 5 A SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 93.09 90.00 96.98 94.53 97.54 95.53 0.00999 0.01473 96.05 95.89 98.62 98.13 98.95 98.49 0.00399 0.00568 FISCAL YEAR FISCAL YEAR DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 85.94 88.46 94.41 94.62 95.78 95.83 0.01524 0.01349 99.31 97.11 99.66 98.68 99.69 98.95 0.00149 0.00368 100 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 5^— Continued DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM I.O PPM Sy.x Domestic Imported 94.79 96.45 98.35 98.92 98.82 99.25 0.00414 0.00241 97.56 74.56 99.05 87.40 99.18 90.48 0.00374 0.02512 ^ ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 HEPTACHLOR EPOXIDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00r Lower Confidence Limit (95%) •Domestic ••Imported Lower Confidence Limit (95% 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.97 99.71 99.98 99.78 99.98 99.79 0.0001 1 0.00105 95.64 98.71 98.29 99.36 98.66 99.49 0.00522 0.00166 n F1SC\L YF^R ^ HEPTACHLOR Lower Confidence Limit (95%) METHOXYCHLOR Lower Confidence Limit (95%) Domestic Imported 99.90 99.94 99.94 99.96 Vol. 5, No, 2, September 1971 99.94 99.97 0.00027 0.00015 101 TABLE 7 A — Large Fruits: Percent distribution of residues, by fiscal year in different quantitative ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DDT No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 68.28 79.00 72.87 71.27 85.29 52.47 69.15 82.62 Trace-003 13.41 12.64 17.42 13.74 9.22 12.96 15.96 9.71 0.04-0.10 6.81 3.95 3.79 5.80 2.04 9.88 5.32 2.66 0.11-0.50 8.54 3.62 5.57 7.07 2.26 8.64 9.57 2.94 0.51-1.00 1.77 .59 1.29 .78 8.02 1.21 1.01-1.50 .47 .07 .12 .34 .26 2.47 .39 1.51-2.00 .27 .18 .13 1.23 .20 Above 2.00 .40 .13 .24 .33 4.32 .27 Average PPM .14 .02 .02 .10 .02 .35 .03 .04 DDE No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 81.08 87.43 86.49 83.19 93.43 72.22 93.62 92.09 Trace-0.03 16.52 11.98 13.27 15.10 6.08 5.56 5.32 6.03 0.04-0.10 1.95 .53 .24 1.42 .34 4.32 .59 0.11-0.50 .38 .07 .27 .13 11.73 1.06 .90 0.51-1.00 .02 .01 4.94 .31 1.01-1.50 1.23 .08 1.51-2.00 Above 2.00 .02 .01 Average PPM .01 T T T T .08 T .01 TDE No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 91.45 94.67 94.19 92.52 97.52 87.65 82.98 96.36 Trace-0.03 5.06 3.23 2.49 4,33 2.04 2.47 3.19 2.11 0.04-0.10 1.90 1.32 1.42 1.72 .17 4.32 3.19 .55 0.11-0.50 1.38 .53 1.66 1.23 .13 4.94 5.32 .63 0.51-1.00 .09 .20 .12 .12 .08 .62 4.26 .27 1.01-1.50 .02 .07 .03 .04 1.06 .08 1.51-2.00 .02 .12 .03 Above 2.00 .04 .03 ....... ..._.-. Average PPM .01 T .01 .01 T .02 .05 T LINDANE No. Samples 4399 1520 844 6763 2299 162 94 2555 None found 98.29 97.96 98.46 98.24 96.91 98.77 94.68 96.95 Trace-0.03 1.50 1.97 1.42 1.60 2.74 1.23 4.26 2.70 0.04-0.10 .13 .07 .10 .34 1.06 .35 0.11-0.50 .04 .03 0,51-1.00 .12 .01 1.01-1.50 .02 .01 1.51-2.00 Above 2.00 Average PPM T T T T T T T T 102 Pesticides Monitoring Journal TABLE 7 A — Large Fruits: Percent distribution of residues, by fiscal year in different quantitative ranges — Continued IT=<.005 PPM] Percent Distribution of Samples Imported 1968 1969 Total DIELDRIN No. Samples 4399 1517 844 6760 2299 163 94 2556 None found 86.65 93.80 93.84 89.16 75.64 87.12 93.62 77.03 Trace-0.03 11.86 5.74 5.69 9.72 22,79 8.59 5.32 21.24 0.04-0.10 1.36 .40 .36 1.02 1.52 4.29 1.06 1.68 0.11-0.50 .11 .12 .09 0.51-1.00 .07 .01 1.01-1.50 1.51-2.00 _. Above 2.00 _...._ ..._... .04 .04 Average PPM T T T T .01 T T .01 ALDRIN No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 93.15 97.50 97.39 94.66 99.08 lOO.OO 97.87 99.10 Trace-0.03 5.36 2.11 2.61 4.29 .52 2.13 .55 0.04-0.10 1.27 .39 .92 .30 .27 0.11-0.50 .20 .13 .08 .08 0.51-1.00 1.01-1.50 _ 1.51-2.00 Above 2.00 -_.- Average PPM T T T T T T T T BHC No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 99.65 98.95 98.70 99.38 99.26 95.06 91.49 98.71 Trace-0.03 .31 .92 1.30 .58 .39 3.70 8.51 .90 0.04-0.10 .07 .01 .26 1.23 .31 0.11-0.50 .02 .07 .03 .08 .08 0.51-1.00 1.01-1.50 1.51-2,00 Above 2.00 __... Average PPM T T T T T T T T ENDRIN Vol. 5, No. 2, September 1971 No. Samples 4399 1517 844 6760 2299 163 94 2556 None found 98.63 95.98 98.70 98.05 67.50 79.14 100.00 69.44 Trace-0.03 1.25 4.02 1.18 1.86 24.44 6.75 22.42 0.04-0.10 .09 .12 .07 7.78 9.82 7.63 0.11-0.50 .02 .01 .26 3.68 .47 0.51-1.00 .61 .04 1.01-1.50 1.51-2,00 Above 2.00 ---- Average PPM T T T T .01 .02 .01 103 TABLE 7 A — Large Fruits: Percent distribution of residues, by fiscal year in different quantitative ranges — Continued 1T=<.005 PPM] Percent Distxibution of Samples Domestic 1968 1969 Imported 1968 1969 HEPTACHLOR EPOXIDE No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 93.34 99.41 99.41 99.36 99.30 99.38 100.00 99.33 Trace-0.03 .59 .59 .59 .59 .69 .62 .67 0.04-0.10 .04 .03 0.11-0.50 .02 .01 0.51-1.00 1.01-1.50 1.51-2.00 . Above 2.00 Average PPM T T T T T T T TOXAPHENE No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 99.74 99.74 100.00 99.78 99.91 95.06 100.00 99.61 Trace-0.03 .15 .07 .12 .08 .08 0.04-0.10 .02 .01 0.11-0.50 .04 .07 .04 0.51-1.00 .02 .13 .04 1.01-1.50 1.51-2.00 Above 2.00 --- 4.94 .31 Average PPM T T T T .39 T .02 ENDOSULFAN No. Samples 4399 1517 844 6760 2299 163 94 2556 None found 98.81 99.80 99.88 99.17 99.65 98.16 100.00 99.57 Trace-0.03 .84 .20 .12 .61 .21 .61 .23 0.04-0.10 .27 .18 .08 1.23 .16 0.11-0.50 .06 .04 .04 .04 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T 104 DICOFOL No. Samples 4399 1519 844 6762 2299 162 94 2555 None found 91.45 91.97 89.93 91.38 96.73 87.65 93.62 96.05 Tracc-0.03 1.43 1.18 1.54 1.39 .43 3.09 2.13 .67 0.04-0.10 1.93 1.38 3.20 1.97 .47 1.23 1.06 .55 0.11-0.50 4.06 4.74 4.03 4.21 1.95 7.41 3.19 2.35 0.51-1.00 .84 .72 .95 .83 .21 .62 .23 1.01-1.50 .15 .24 .13 .13 .12 1.51-2.00 .06 .12 .06 .04 .04 Above 2.00 .04 .03 Average PPM .02 .02 .02 .02 .01 .02 .01 .01 Pfsticides Monitoring Journai TABLE 7 A — Large Fruits: Percenl distribution of residues, by fiscal year in different quantitative ranges — Continued (T=<.005 PPM] Percent Distkibution of Samples Domestic 1968 1969 Imported 1968 1969 TETRADIFON Percent Distribution of Samples No. Samples 4399 1517 844 6760 2299 163 94 2556 None found 97.63 98.75 98.58 98.00 98.04 97.55 100.00 98.08 Trace-0.03 .52 .33 .71 .50 .21 .20 0.04-O.10 .75 .33 .12 .58 .34 1.23 .39 0.11-0.50 .95 .46 .59 .80 1.17 .61 1.10 0.51-1.00 .11 .13 .10 .21 .61 .23 1.01-1.50 .02 .01 1.51-2.00 Above 200 Average PPM T T T T .01 .01 .01 Domestic 1968 1969 Imported 1968 1969 CARBARYL 322 88.82 3.42 2.80 3,11 1.24 95.87 1.08 PARATHION No. Samples 2361 1512 844 4717 2018 155 94 2267 None found 96.86 94.97 93.36 95.63 99.50 92.26 98.94 98.99 Trace-0,03 1.56 2.71 4,38 2,44 .29 1.29 1.06 .40 0.04-0.10 .80 1,52 ,95 1,06 .09 2.58 .26 0.11-0.50 .72 .60 1.18 .76 .09 1.94 .22 0.5I-1.OO .04 .20 .12 .11 1,29 .09 1.01-1.50 .65 .04 1.51-2.00 Above 2.00 Average PPM T T T T T .03 T T ETHION No, Samples 2361 1513 844 4718 2018 154 94 2266 None found 95.04 82.35 86.97 89.53 99.50 95.45 93.62 98.98 Trace-0.03 1.44 3.37 3.44 2.42 .09 .65 2.13 .22 0.04-0.10 1.27 5.95 4.15 3.29 .19 1.95 2.13 .40 0.11-0.50 1.82 7.14 4,98 4.09 .14 1,30 2.13 .31 0.51-1.0O .29 1.06 .24 .53 .04 .65 .09 1.01-1.50 .08 .07 .24 .11 1.51-2.00 .04 .02 Above 2.00 .07 .02 Average PPM .01 .03 .02 .02 T .01 m T Vol. 5, No. 2, September 1 97 1 105 TABLE 7 A — Large Fruits: Percent distribution of residues, by fiscal year in different quantitative ranges — Continued 1T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIAZINON No. Samples 2361 1512 844 4717 2018 155 94 2267 None found 98.60 96.89 97.51 97.86 99.95 100.00 100.00 99.96 Trace-0.03 1.14 2.45 2.25 1.76 0.04-0.10 .12 .40 .12 .21 0.11-0.50 .08 .20 .12 .13 .04 .04 0.51-1.00 1.01-1.50 1.51-2.00 .04 .07 .04 ■ ZI Above 2.00 ■■-- — Average PPM T T T T T .._„. T CARBOPHENOTHION No. Samples 2361 1513 844 4718 2018 154 94 2266 None found 99.19 97.49 99.64 98.73 99.95 99.35 96.81 99.78 Trace-0.03 46 .40 .36 .04 .04 0.04-0.10 21 .66 .12 .34 0.11-0.50 12 1.32 .24 .53 3.19 .13 0.51-1.00 „ .07 .02 .65 .04 1.01-1.50 _ ._. 1.51-2.00 _ -.. _ Above 2.00 - .07 .02 Average PPM T .01 T T T T .01 T STATISTICAL TREATMENT OF DATA IN TABLE 7 A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidenc E Limit (95%) Domestic Imported Lower Confidence Limit (95%) O.I PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 90.35 93.91 95.90 96.94 96.94 97.50 0.00944 0.00920 99.72 98.63 99.76 99.04 99.76 99.06 0.00119 0.00462 m FISCAL YEAR 106 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 7^— Continued TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.0OI DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95% 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 98.53 98.90 99.49 99.45 99.62 99.54 0.00138 0.00172 99.91 99.91 99.94 99.92 99.94 99.92 0.00032 0.00038 FISCAL YEAR LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confide NCE Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.94 99.97 99.94 99.99 99.94 99.99 0.00028 0.00007 99.87 99.87 99.98 99.96 99.98 99.97 0.00010 0.00014 S 5. FISCAL YEAR Vol. 5, No. 2, September 1971 1 107 STATISTICAL TREATMENT OF DATA IN TABLE 7/4— Continued BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 99.97 99.91 99.97 99.98 99.97 99.99 HEPTACHLOR EPOXIDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.05 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM 0.00013 0.00005 FISCAL YEAR FISCAL YEAR ENDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM Domestic Imported 99.99 98.82 99.99 99.66 99.99 99.67 0.00004 0.00163 TOXAPHENE Lower Confidence Limit (95%) S 5- n J 108 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 7/4— Continued ENDOSULFAN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 TETRADIFON SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x O.I PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.96 99.91 99.99 99.96 100.00 99.96 0.00002 0.00015 98.89 98.44 99.30 98.88 99.39 99.00 0.00206 0.00350 •'^'X FIWAL YEAR n FISCAL YEAR DICOFOL SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT Lower Confidence Limit (95%) Domestic Imported 93.94 96.95 95.94 97.86 96.46 98.10 0.01178 0.00653 CARBARYL SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 LowFjt Confidence Limit (95%) O.I 0.5 1.0 PPM PPM PPM - Yea 965 Vol. 5, No. 2, September 1971 109 STATISTICAL TREATMENT OF DATA IN TABLE 7^— Continued PARATHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported 0.5 PPM 1.0 PPM 99.09 99.60 99.67 99.79 99.76 99.83 0.00080 0.00046 DIAZINON SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) g 5. J\ ETHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported CARBOPHENOTHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.32 99.80 99.58 99.85 99.64 99.87 0.00122 0.00046 n no Pesticides Monitoring Journal TABLE 8A — Small Fruits: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total No. Samples 1912 400 383 2695 294 58 144 496 None found 64.33 80.50 71.02 67.68 64.96 82.76 79.17 71.17 Trace-O.03 16.16 11.75 15.67 15.44 12.24 10.34 11.11 11.69 0.04-0.10 8.52 4.50 7.05 7.72 7.48 3.45 3.47 5.85 0.11-0.50 8.05 2.00 5.22 6.75 11.90 3.45 4.17 8.67 0.51-1.00 2.19 .50 1.04 1.78 2.72 2.08 2.22 1.01-1.50 .36 .25 .30 .68 .40 1.51-2.00 .31 .25 .26 Above 2.00 .05 .25 .07 Average PPM .06 .03 .02 .05 .07 .01 .03 .05 No. Samples 1912 400 383 2695 294 58 144 496 None found 79.23 84.50 80.68 80.22 82.65 84.48 88.19 84.48 Trace-0.03 18.04 14.75 18.02 17.55 15.30 15.52 11.81 14.31 0.04-0.10 2.45 .50 1.04 1.97 0.11-0.50 .26 .25 .26 .26 2.04 1.21 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM .01 T T T .01 T T .01 TDE No. Samples 1912 400 383 2695 294 58 144 496 None found 91.21 93.25 92.43 91.69 95.23 89.66 96.53 94.96 Trace-0.03 6.38 4.75 6.01 6.09 3.06 10.34 1.39 3.43 0.04-0.10 1.30 1.00 .52 1.15 1.02 1.39 1.01 O.n-0.50 1.04 .75 1.04 1.00 .68 .69 .60 0.51-1.00 1.01-1.50 .25 .04 1.51-2.00 Above 2.00 .05 .04 Average PPM .01 .01 T .01 T T T T LINDANE Vol. 5. No. 2, September 1971 No. Samples 1912 400 383 2695 294 58 144 496 None found 98.74 99.00 99.48 98.89 98.63 100.00 99.31 98.99 Trace-0.03 1.25 1.00 .52 l.U 1.36 .69 1.01 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 _._... ..._... Average PPM T T T T T T T T 111 TABLE 8 A — Small Fruits: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total DIELDRIN No. Samples 1912 399 383 2694 294 58 144 496 None found 90.63 97.24 96.34 92.43 97.27 94.83 95.14 96.37 Trace-0.03 8.73 2.76 3.66 7.13 2.72 5.17 4.86 3.63 0.04-0.10 .52 .37 0.11-0.50 .10 .07 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T T. ALDRIN No. Samples 1912 400 383 2695 294 58 144 496 None found 97.80 97.00 99.74 97.96 97.61 98.28 97.22 97.58 Trace-0.03 1.88 2.75 .26 1.78 2.04 1.39 1.61 0.04-0.10 .20 .25 .19 .34 1.72 1.39 .81 0.11-0.50 .10 .07 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 .„_... Average PPM T T T T T T T T BHC No. Samples 1912 400 383 2695 294 58 144 496 None found 99.89 98.00 99.22 99.52 97.95 93.10 96.53 96.98 Trace-0.03 .10 1.75 .26 .37 2.04 6.90 2.08 2.62 0.04-0.10 .25 .52 .11 1.39 .40 0.11-0.50 0.51-1.00 _ _ 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T T ENDRIN No. Samples 1912 399 383 2694 294 58 144 496 None found 99.47 98.25 93.99 98.52 98.63 89.66 91.67 95.56 Trace-0.03 .47 1.50 2.35 .89 1.36 10.34 5.56 3.63 0.04-0.10 .05 2.87 .45 1.39 .40 0.11-0.50 .78 .11 1.39 .40 0.51-1.00 .25 .04 1.01-1.50 1.51-2.00 Above 2.00 __.._ __^.. Average PPM T T T T T T .01 T 112 Pesticides Monitoring Journal TABLE 8A — Small Fruits: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Range PPM Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 HEPTACHLOR EPOXIDE No. Samples 1912 400 383 2695 294 58 144 496 None found 99.00 99.75 99.74 99.22 99.31 98.28 100.00 99.40 Trace-0.03 .78 .25 .26 .63 .68 1.72 60 0.04-0.10 .10 _ .07 0.11-0.50 .10 .07 ._ _.. 0.51-1.00 I. 01-1.50 _ ._. 1.51-2.00 Above 2.00 — Average PPM T T T T T T T TOXAPHENE No. Samples 1912 400 383 2695 294 58 144 496 None found 98.74 100.00 99.74 99.07 99.65 100.00 100.00 99.80 Trace-0.03 .10 .07 0.04-0.10 .05 .26 .07 .34 .20 0.11-0.50 .36 .26 D.51-1.00 .52 .37 1.01-1.50 .05 .04 , 1.51-2.00 .10 .07 Above 2.00 .05 .04 — Average PPM .01 T .01 T --- T DICOFOL No. Samples 1912 400 383 2695 294 58 144 496 None found 94.92 90.50 91.91 93.84 97.95 81.03 92.36 94.35 Trace-0.03 .62 1.25 .52 .71 12.07 .69 1.61 0.04-0.10 .99 .75 1.31 1.00 0.11-0.50 1.83 2.75 3.39 2.19 .34 3.45 3.47 1.61 0.51-1.00 .83 2.50 1.57 1.19 .68 1.72 .69 .81 1.01-1.50 .31 .50 .52 .37 .34 1.72 1.39 .81 1.51-2.00 .20 1.25 .26 .37 .68 .40 Above 2.00 .26 .50 .52 .33 1.39 .40 Average PPM .03 .06 .05 .04 .02 .05 .07 .04 PERTHANE Vol. 5, No. 2, September 1971 113 TABLE 8A — Small Fruits: Percent dislrihution of residues, by fiscal year, in different quantitative ranges — Continued 1T=<.005 PPM] <,E PPM Percent Distribution of Samples Domestic 1968 1969 ENDOSULFAN No. Samples 1912 399 383 2694 294 58 144 496 None found 98.58 98.75 93.99 97.96 97.95 98.28 96.53 97.58 trace-0.03 .94 1.00 2.87 1.22 1.02 1.72 2.08 1.41 0.04-0.10 .36 .25 1.83 .56 .68 1.39 .81 0.11-0.50 .10 1.31 .26 0.51-1.00 1.01-1.50 .34 .20 1.51-2.00 Above 2.00 Average PPM T T T T T T T T PARATHION No. Samples 825 398 384 1607 123 57 144 324 None found 95.75 95.48 95.57 95.64 99.18 100.00 99.31 99.38 Trace-0.03 2.18 3.77 2.60 2.68 .69 .31 0.04-0.10 1.33 .50 1.04 1.06 0.11-0.50 .60 .25 .78 .56 .81 .31 0.51-1.00 .12 .06 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T — T T No. Samples 825 399 384 1608 123 57 144 324 None found 98.30 95.24 91.93 96.02 98.37 91.23 93.06 94.75 Trace-0.03 .12 1.25 2.08 .87 .81 1.75 1.39 1.23 0.04-0.10 .72 .25 .52 .56 .81 1.75 .69 .93 0.11-0.50 .84 1.75 1.82 1.31 1.75 1.39 .93 0.51-1.00 .75 1.56 .56 1.75 1.39 .93 1.01-1,50 .50 .26 .19 1.75 2.08 1.23 1.51-2.00 .78 .19 Above 2.00 .25 1.04 .31 Average PPM T .03 .06 .02 T .03 .04 .02 114 TETRADIFON No. Samples 825 399 383 1607 123 58 144 325 None found 97.09 98.75 98.96 97.95 100.00 100.00 100.00 100.00 Trace-0.03 .12 .06 0.04-0.10 .48 .25 0.11-0.50 1.93 1.00 .78 1.43 ... 0.51-1.00 .24 .25 .26 .25 1.01-1.50 1.51-2.00 .12 .06 Above 2.00 Average PPM .0! .01 T .01 Pesticides Monitoring JouRN.^L STATISTICAL TREATMENT OF DATA IN TABLE 8 A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00l TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (959!-) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 90.28 88.15 96.35 94.25 97.38 95.53 0.00804 0.01370 98.90 99.39 99.37 99.76 99.40 99.79 0.00296 0.00096 J^lil FISCAl MAR DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 99.76 98.91 99.81 98.92 0.00093 0.00534 m u^ Vol. 5, No. 2, Sfptembf.r 1971 115 STATISTICAL TREATMENT OF DATA IN TABLE 5/1— Continued ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.OI Lower Confidence Limit (95%) 0.: 0.5 1.0 PPM PPM PPM TOXAPHENE Domestic Imported Lower Confidence Limit (95% ) 99.93 99.69 99.95 99.83 99.85 99.84 0.00024 0.00078 Domestic Imported 99.07 99.85 99.28 99.89 99.35 99.89 0.00184 0.00047 DICOFOL SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 95.02 95.56 96.46 96.76 96.89 97.13 0.00797 0,00665 BHC Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.97 99.96 99.98 99.98 99.99 99.98 0.00007 0.00010 PERTHANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 ENDRIN Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.79 99.62 99.94 99.71 99.95 99.72 0.00017 n.00140 HEPTACHLOR EPOXIDE Lower Confidence Limit (95%) 116 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 5/1— Continued ENDOSULFAN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 ETHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.0OI Lower Confidence Limit (95'7r) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99,70 99.45 99.91 99.71 99.93 99.74 0.00023 0.001 15 97.29 96.02 98.17 97.18 98.43 97.52 0.00345 0.00696 Fist AL YEAR PARATHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.01 Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.36 99.67 99.82 99.78 99.87 99.81 0.00050 0.00074 TETRADIFON SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATLSTIC <0.01 Lower Confidence Limit (95%) S 5_ I. nsr.At. \?.\R Vol. 5, No. 2, September 1971 TABLE 9 A — Grains and Cereal for Human Use: Percent distribution of residues, by fiscal year, in different quantitative ranges IT=<,005 PPMl Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DDT No. Samples 6513 888 584 7985 92 8 4 104 None found 79.27 84.35 88.18 80.49 88.04 100.00 100.00 89.42 Trace-0.03 12.43 10.59 8.22 11.92 5.43 4.81 0.04-0.10 4.79 2.59 2.57 4.38 3.26 2.88 0.11-0.50 3.16 2.36 1.03 2.92 3.26 2.88 0.51-1.00 .21 .11 .19 1.01-1.50 .03 .03 1.51-2.00 .04 .04 Above 2.00 .04 ..._... .04 ..._... Average PPM .03 T T T .01 T DDE No. Samples 6513 888 854 7985 92 8 4 104 None found 90.41 93.81 97.43 91.31 98.91 87.50 100.00 98.08 Trace-0.03 9.31 5.74 2.57 8.43 12.50 .96 0.04-0.10 .21 .34 .21 1.08 .96 0.11-0.50 .04 .11 .05 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T TDE No. Samples 6513 888 584 7985 92 8 4 104 None found 97.38 97.97 99.49 97.61 100.00 100.00 100.00 100.00 Trace-0.03 2.27 1.80 .51 2.09 0.04-0.10 .19 .16 0.11-0.50 .13 .23 .14 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T LINDANE No. Samples 6513 888 584 7985 92 8 4 104 None found 91.41 95.72 96.92 92.30 90.21 75.00 100.00 89.42 Trace-0.03 7.84 3.60 2.74 7.00 8.69 25.00 9.62 0.04-0.10 .46 .68 .34 .48 1.08 .96 0.11-0.50 .18 .15 0.51-1.00 .04 .04 1.01-1.50 .04 .04 1.51-2.00 Above 2.00 Average PPM T T T T T T T 118 Pesticides Monitoring Journal TABLE 9 A — Grains and Cereal for Human Use: Percent distribution of residues, by fiscal year, in differenrrquantitative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIELDRIN No. Samples 6513 888 584 7985 92 8 4 104 None found 96.43 94.93 98.12 96.39 98.91 87.50 100.00 98.08 Trace-0.03 3.40 4.95 1.54 3.44 12.50 .96 0.04-0.10 .13 .11 .34 .15 .96 0.11-0.50 1.08 0.51-1.00 .01 .01 1.01-I.5O 1.51-2.00 Above 2.00 Average PPM T T T T T T T ALDRIN No. Samples 6513 888 584 7985 92 8 4 104 None found 97.81 98.87 98.12 97.96 96.73 100.00 100.00 97.12 Trace-0.03 1.91 1.13 .86 1.75 3.26 2.88 0.04-0.10 .16 1.03 .21 0.11-0.50 .04 .04 0.51-1.00 .03 .03 1.01-1.50 .01 .01 1.51-2.00 Above 2.00 ....... Average PPM T T T T T T BHC No Samples 6513 888 584 7985 92 8 4 104 None found 98.46 99.10 98.63 98.55 98.91 87.50 100.00 98.08 Trace-0.03 1.44 .90 1.37 1.38 1.08 12.50 1.92 0.04-0.10 .07 .06 O.I 1-0.50 0.51-1.00 1.01-1.50 1.51-2.00 .01 .01 Above 2.00 ...-_.. -._-... Average PPM T T T T T T T No. Samples 6513 888 584 7985 92 8 4 104 None found 99.80 99.10 99.66 99.71 98.91 100.00 100.00 99.04 Trace-0.03 .16 .90 .34 .26 0.04-0.10 1.08 .96 0.11-0.50 .03 .03 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 .__... Average PPM T T T T T T Vol. 5, No. 2, September 1971 119 TABLE 9A — Grains and Cereal for Human Use: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM) Percent Distkibution of Samples Domestic 1968 1969 Imported 1968 1969 HEPTACHLOR EPOXIDE No. Samples 6513 888 584 7985 92 8 4 104 None found 99.75 99.55 99.83 99.74 100.00 87.50 100.00 99.04 Trace-0.03 .23 .45 .17 .25 12.50 .96 0.04-0.10 .01 .01 O.n-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T TOXAPHENE No. Samples 6513 888 584 7985 92 8 4 104 None found 99.66 99.21 99.49 99.60 100.00 100.00 100.00 100.00 Trace-0.03 .07 .34 .10 0.04-0.10 .03 .03 0.11-0.50 .19 .11 .34 .20 0.51-1.00 .01 .11 .03 1.01-1.50 1.51-2.00 .11 .01 Above 2.00 .01 .11 .17 .04 „.-_.- Average PPM T T T T CHLORDANE No. Samples 6513 888 584 7985 92 8 4 104 None found 99.35 99.77 99.83 99.44 96.73 100.00 100.00 97.12 Trace-0.03 .33 .11 .29 2.17 1.92 0.04-0.10 .15 .13 1.08 .96 0.11-0.50 .13 .17 .13 0.51-1.00 .11 .01 1.01-1.50 1,51-2.0 Above 2.00 .01 .01 Average PPM T T T T T T CARBARYL 120 Pesticides Monitoring Journal TABLE 9A — Grains and Cereal for Human Use: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPMl Percent DisTRiBirriON of Samples Domestic 1968 1969 Imported 1968 1969 PCP No. Samples 17 12 29 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 100.00 41.67 75.86 58.33 24.14 - Average PPM -. T T - METHOXYCHLOR No. Samples 6513 888 584 7985 92 8 4 104 None found 97.62 96.62 98.29 97.56 100.00 100.00 100.00 100.00 Trace-0.03 .70 .68 .86 .71 0.04-0.10 .35 .79 .17 .39 0.11-0.50 1.01 1.24 .51 1.00 0.51-1.00 .15 .34 .17 .18 _ 1.01-1.50 .04 .04 1.51-2.00 .09 .11 .09 Above 2.00 .01 .23 .04 Average PPM .01 T T T HEPTACHLOR Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 6513 888 584 7985 92 8 4 104 None found 99.73 99.66 100.00 99.75 96.73 100.00 100.00 97.12 Trace-0.03 .23 .23 .21 2.17 1.92 0.04-0.10 1.08 .96 0.11-0.50 .01 .11 .03 0.51-1.00 .01 .01 1.01-1.50 1.51-2.00 Above 2.00 ..._... Average PPM T T T T T MALATHION No. Samples 2107 359 234 2700 20 20 None found 89.93 38.72 29.49 77.89 100.00 100.00 Trace-0.03 4.41 22.01 27.35 8.74 0.04-0.10 .99 10.31 10.26 3.04 0.11-0.50 2.37 14.76 16.24 5.22 _ 0.51-1.00 .80 5.01 5.56 1.78 1.01-1.50 .37 1.95 3.85 .89 1.51-2.00 1.67 2.56 .44 Above 2.00 1.09 5.57 4.70 2.00 Average PPM .55 .68 .56 .56 ~ - „_-. Vol. 5, No. 2, September 1971 121 TABLE 9A — Grains and Cereal for Human Use: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued IT=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIAZINON No. Samples 2107 877 581 3565 20 8 4 32 None found 99.76 99.09 99.31 99.52 100.00 100.00 100.00 100.00 Trace-0.03 .04 .68 .69 .31 0.04-0.10 .09 .11 .08 0.11-0.50 .04 .11 .06 0.51-1.00 1.01-1.50 1.51-2.00 .04 .03 Above 2.00 Average PPM T T T T PARATHION No. Samples 2107 877 581 3565 20 8 4 32 None found 99.57 98.75 99.14 99.30 100.00 100.00 100.00 100.00 Trace-0.03 .33 1.14 .86 .62 0.04-0.10 .09 .06 0.11-0.50 .11 .03 — 0.51-1.00 1.01-1.50 — 1.51-2.00 — Above 2.00 --- Average PPM T T T T STATISTICAL TREATMENT OF DATA IN TABLE 9 A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 LovreR Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95rc) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM I.O PPM Sy.x Domestic Imported 96.66 96.71 98.80 98.49 99.00 98.81 0.00443 0.00420 99.95 99.48 99.96 99.68 99.96 99.70 0.00022 0.00140 FISCAL Yf^AR FISCAL ■VCAR 122 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 9/1— Continued TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM I.O PPM Sy.x Domestic Imported 99.99 99,48 99.99 99.68 99.99 99.70 0.00006 0.00140 LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95% ) ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.01 Lower Confidence Limit (95%) Domestic Imported 99.77 99.96 99.79 99.98 99.79 99.98 0.00103 0.00009 FISCAL m:ar Vol. 5, No. 2, September 1971 Fist AL MAR 123 STATISTICAL TREATMENT OF DATA IN TABLE 9^— Continued BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC < 0.001 Lower Confidence Limit (95%) METHOXYCHLOR SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT Lower Confidence Limit (95%) ;CAL YEAR ENDRIN Lower Confidence Limit (95%) -^ FISCAL YEAR HEPTACHLOR Domestic 99.97 99.97 99.97 99.28 99.46 99.50 HEPTACHLOR EPOXIDE 0.00013 0.00224 Domestic Imported Lower Confidence Limit (95%) Imported 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 99.96 99.63 99.97 99.80 99.97 99.81 0.00016 0.00092 Lower Confidence Limit (95%) TOXAPHENE Lower Confidence Limit (95%) MALATHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 PPM 124 CHLORDANE Lower Confidence Limit (95% ) 0.1 0.5 PPM PPM 1.0 PPM Sy.x Domestic Imported 99.84 99.93 99.63 99.80 99.95 99.81 0.00013 0.00092 CARBARYL Lower Confidence Limit (95%) 0.1 0.5 PPM PPM 1.0 PPM Sy.x Domestic 98.87 99.18 99.26 0.00275 r FISCAL YE-VR Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 9/1— Continued DIAZINON PARATHION Lower Confidence Limit (95%) 0.5 1.0 Lower Confidence Limit (95%) 0.1 0.5 TABLE 10 A — Leaf and Stem Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges 1T=<.005 PPM) Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 9789 2292 1782 13863 122 10 19 151 None found 63.97 60.03 58.75 62.66 74.59 60.00 47.37 70.20 Trace-0.03 15.42 18.19 18.35 16.26 15.57 20.00 10.53 15.23 0.04-0.10 8.54 9.16 11.11 8.97 3.27 20.00 5.26 4.64 0.11-0.50 8.11 9.03 7.74 8.22 4.09 15.79 5.30 0.51-1.00 1.94 1.79 1.35 1.84 .81 5.26 1.32 1.01-1.50 .54 .61 .79 .58 .81 .66 1.51-2.00 .34 .13 .51 .33 5.26 .66 Above 2.00 1.11 1.05 1.40 1.14 .81 10.53 1.99 Average PPM .14 .15 .16 .14 .06 .01 3.88 .53 DDE TDE Vol. 5, No. 2, September 1971 No. Samples 9879 2292 1781 13862 122 10 19 151 None found 75.61 73.25 81.64 76.00 89.34 70.00 73.68 86.09 Trace-0.03 18.01 20.51 14.60 17.98 8.19 30.00 10.53 9.93 0.04-0.10 4.60 4.19 2.64 4.29 1.63 10.53 2.65 0.11-0.50 1.58 1.92 .95 1.56 .81 .66 0.51-1.00 .17 .13 .11 .16 1.01-1.50 5.26 .66 1.51-2.00 .01 .01 Above 2.00 .06 .01 Average PPM .01 .01 .01 .01 .01 T .07 .01 No. Samples 9789 2292 1781 13862 122 10 19 151 None found 92.43 93.15 96.80 93.11 99.18 90.00 100.00 98.68 Trace-0.03 5.54 5.10 2.30 5.06 .81 10.00 1.32 0.04-0.10 1.10 .74 .51 .97 0.11-0.50 .66 .65 .28 .61 0.51-1.00 .14 .17 .13 1.01-1.50 .03 .02 1.51-2.00 .02 .06 .02 Above 2.00 .06 .17 .06 .08 ...._.. Average PPM .01 .02 T .01 T T T 125 TABLE lOA — Leaf and Stem Veaetabtcs: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued IT=<.OOS PPM) Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 LINDANE No. Samples 9789 2292 1781 13862 122 10 19 151 None found 96.30 95.81 96.52 96.25 95.08 90.00 100.00 95.36 Trace-0.03 2.60 3.53 3.20 2.84 2.45 10.00 2.65 0.04-0.10 .63 .26 .28 .53 1.63 1.32 0.11-0.50 .23 .31 .22 .81 .66 0.51-1.0O .13 .04 .10 1.01-1.50 .01 .04 .01 1.51-2.00 Above 2.00 .08 .06 Average PPM .01 T T T T T T DIELDRIN No. Samples 9789 2289 1781 13859 122 10 19 151 None found 89.89 93.88 94.78 91.18 86.88 100.00 100.00 89.40 Trace-0.03 8.84 5.11 4.66 7.69 9.01 7.28 0.04-0.10 1.00 .87 .39 .90 3.27 2.65 0.11-0.50 .24 .13 .17 .22 .81 .66 0.51-1.00 .01 .01 _ 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T .01 .01 No. Samples 9789 2292 1781 13862 122 10 19 151 None found 97.64 98.30 98.99 97.92 95.90 lOO.OO 100.00 96.69 Trace-0.03 2.01 1.57 .90 1.80 2.45 J. 99 0.04-0.10 .25 .04 .11 .20 .81 .66 0.11-0.50 .09 .09 .08 .81 .66 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T BHC No. Samples 9789 2292 1781 13862 122 10 19 151 None found 98.74 98.08 97.81 98.51 99.18 100.00 100.00 99.34 Trace-0,03 .63 1.31 1.29 .83 .81 .66 0.04-0.10 .30 .26 .06 .27 0.11-0.50 .22 .31 .51 .27 0.51-1.00 .04 .17 .05 1.01-1.50 .01 .01 1.51-2.00 .01 .11 .02 Above 2.00 .03 .04 .06 .04 .-.._.- Average PPM T .01 .01 T T T 126 Pesticides Monitoring Journal TABLE 10 A — Lcaj and Stem \'egclables: Percent distribulion of residues, by fiscal year, in different quanritative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 ENDRIN No. Samples 9789 2289 1781 13859 122 10 19 151 None found 95.44 96.16 98.54 95.96 97.54 100.00 100.00 98.01 Trace-0.03 3.62 3.23 1.35 3.27 2.45 1.99 0.04-0.10 .62 .39 .51 0.11-0.50 .26 .17 .11 .23 0.51-1.00 .02 .04 .02 1.01-1.50 .02 .01 1.51-2.00 Above 2.00 Average PPM T T T T T T HEPTACHLOR EPOXIDE No. Samples 9879 2292 1781 13862 122 10 19 151 None found 97.00 97.82 99.44 97.45 97.62 80.00 100.00 96.03 Trace-0.03 2.76 1.83 .45 2.32 20.00 1.32 0.04-0.10 .21 .22 .11 .20 1.63 1.32 0.11-0.50 .01 .13 .03 1 63 1.32 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T .01 T .01 TOXAPHENE No. Samples 9879 2292 1781 13862 122 10 19 151 None found 93.63 88.70 87.82 92.07 98.18 100.00 84.21 97.35 Trace-0.03 .82 1.70 3.03 1.26 0.04-0.10 .24 .52 .26 0.11-0.50 1.26 3.93 2.08 1.81 .81 .66 0.51-1.00 1.17 2.09 2.02 1.44 5.26 .66 1.01-1.50 .55 1.00 1.07 .69 1.51-2.00 .34 .39 .56 .38 Above 2.00 1.95 1.66 3.43 2.09 10.53 1.32 Average PPM .18 .23 .33 .20 T 9.84 1.24 ENDOSULFAN Vol. 5, No. 2, September 1971 No. Samples 9879 2289 1781 13859 122 10 19 151 None found 97.07 95.24 84.45 95.15 97.62 90.00 94.74 96.03 Trace-0.03 1.50 2.14 3.87 1.91 1.63 10.00 1.99 0.04-0.10 .61 1.18 4.38 1.19 .81 .66 0.11-0.50 .64 1.14 6.06 1.42 .81 .66 0.51-1.00 .09 .26 .90 .22 1.01-1.50 .02 .04 .28 .06 1.51-2.00 .03 .06 .03 Above 2.00 .02 .01 5.26 .66 Average PPM .01 .01 .03 .01 T T .25 .03 127 TABLE lOA — Leaj and Stem Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 PCNB No. Samples 9879 2292 1781 13862 122 10 19 151 None found 99.09 99.69 99.94 99.30 99.18 100.00 78.95 96.69 Trace-0.03 .42 .17 .33 .81 10.53 1.99 0.04-0.10 .11 .09 .09 10.53 1.32 0.11-0.50 .08 .06 .06 0.51-1.00 .10 .07 1.01-1.50 .04 .04 .04 1.51-2.00 — Above 2.00 .14 .10 Average PPM .01 T T .01 T .01 T METHOXYCHLOR No. Samples 9789 2292 1781 13862 122 10 19 151 None found 99.85 99.96 100.00 99.89 97.54 100.00 100.00 98.01 Trace-0.03 .06 .04 .05 0.04-0.10 .03 .02 0.11-0.50 2.45 1.99 0.51-1.00 .03 .02 1.01-1.50 1.51-2.00 Above 2.00 .02 .01 Average PPM T T T .01 .01 CHLORBENSIDE No. Samples 9879 2292 1781 13862 122 10 19 151 None found 99.80 99.91 lOO.OO 99.85 98.36 100.00 100.00 98.68 Trace-0.03 .09 .04 .07 .81 .66 0.04-0.10 .08 .06 .81 .66 0.11-0.50 .02 .04 .02 0.51-1.00 1.01-1.50 — 1.51-2.00 — Above 2.00 — Average PPM T T T T DCPA No. Samples 9879 2289 1781 13859 122 10 19 151 None found 99.45 99.74 99.72 99.54 100.00 100.00 100.00 100.00 Trace-0.03 .35 .13 .11 .29 0.04-0.10 .06 09 .06 0.11-0.50 .10 .04 .08 - 0.51-1.00 .02 .01 1.01-1.50 .17 .02 1.51-2.00 Above 2.00 ..._... — Average PPM T T T T -— - -~- 128 Pesticides Monitoring Journal TABLE lOA — Leaf and Stem Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 HEPTACHLOR N6. Samples 5780 2251 1782 9813 35 8 19 62 None found 88.14 80.36 75.08 83.99 100.00 100.00 94.74 98.39 Trace-0.03 4.15 9.02 9.60 6.26 5.26 1.61 0.04-0-10 2.49 5.29 6.34 3.83 0.11-0.50 3.94 4.09 7.24 4.58 0.51-1.00 .76 .89 .84 .81 1.01-1.50 .27 .18 .39 .28 1.51-2.00 .06 .09 .22 .10 Above 2.00 .15 .09 .28 .16 --- Average PPM .03 .03 .05 .03 T T DIAZINON No. Samples 5780 2251 1782 9813 35 8 19 62 None found 94.20 91.56 91.58 93.12 91.42 100.00 68.42 85.48 Trace-0.03 3.33 4.66 4.26 3.81 5.71 15.79 8.06 0.04-0.10 .91 1.82 2.08 1.33 2.85 1.61 0.11-0.50 l.IO 1.73 1.63 1.35 10.53 3.23 0.51-1.00 .22 .22 .17 .21 1.01-1.50 .06 .06 .05 1.51-2.00 .01 .06 .02 5.26 1.61 Above 2.00 .12 .17 .10 Average PPM .01 .01 .02 .01 T .11 .03 PARATHION No. Samples 5780 2251 1782 9813 35 8 19 62 None found 88.14 80.36 75.08 83.99 100.00 100.00 94.74 98.39 Trace-0-03 4.15 9.02 9.60 6.26 5.26 1.61 0.04-0.10 2.49 5.29 6.34 3.83 0.11-0.50 3.94 4.09 7.24 4.58 0.51-1.00 .76 .89 .84 .81 1.01-1.50 .27 .18 .39 .28 1.51-2.00 .06 .09 .22 .10 Above 2.00 .15 .09 .28 .16 --- Average PPM .03 .03 .05 .03 T T METHYL PARATHION No. Samples 5780 2251 1782 9813 35 8 19 62 None found 95.69 91.60 90.85 93.88 100.00 100.00 100.00 100.00 Trace-0.03 1.31 3.78 3.87 2.34 0.04-0.10 .96 2.18 2.19 1.47 0.11-0.50 1.73 2.09 2.97 2.04 0.51-1.00 .22 .31 .06 .21 1.01-1.50 .06 .04 .05 1.51-2.00 Above 2.00 _..„. .06 .01 _.-_. „.._.. Average PPM .01 .01 .01 .01 --" Vol. 5, No. 2, September 1971 129 STATISTICAL TREATMENT OF DATA IN TABLE lOA DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0,001 Lower Confidence Limit (95%) Domestic Imported 86.92 86.44 94.81 92.55 96.41 93.98 0.00821 0.01863 ^5. FISCAL 'lEAR FISCAL YEAR DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95% 0.1 PPM 0.5 PPM 1.0 PPM Sy.x O.I PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 98.30 98.22 99.06 98.98 99.07 99.01 0.00460 0.00486 99.54 99.23 99.72 99.76 99.73 99.83 0,00134 0.00061 -P-^ ^ y 130 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 70^— Continued DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95% ) BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95'3>) Domestic Imported 99.80 99.31 99.85 99.92 99.85 99.95 ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 0.00076 0.00019 Domestic Imported Lower Confidence Limit (95%) 99.93 99.31 99.94 99.70 99.94 99.75 0.00028 0.00100 F1SC-\L YEAR ENDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) FISCAL VE^R FISCAL YEAR Vol. 5, No. 2, September 1971 131 STATISTICAL TREATMENT OF DATA IN TABLE 70/4— Continued HEPTACHI OR EPOXIDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (959r) ENDOSULFAN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported ^ 99.97 98.27 99.98 99.01 99.98 99.17 0.00010 0.00297 3—1966 4—1967 5—1968 Domestic Imported FISCAL YEAR TOXAPHENE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 PCNB SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confide NCE Limit (95%) Domestic Imported Lower Confidence Limit (95 7c) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x O.I PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 93.15 97.19 94.67 97.62 95.21 97.78 0.00737 0.00314 99.61 99.41 99.74 99.66 99.78 99.68 0.00049 0.00153 FISCAL YEAR t>. n i 132 FISCAL YEAR Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 70/1— Continued CHLORBENSIDE METHOXYCHLOR -OWER Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.96 99.64 99.98 99.78 99.98 99.79 0.00007 0.00097 99.94 97.76 99.96 98.25 99.96 98.39 0.00010 0.00611 DCPA SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) PARATHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) s ,. J] FrSCAL YEAR 12 3 4 5 6 FISCAL YEAR DIAZINON SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95% ) METHYL PARATHION SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 98.17 93.69 99.22 96.40 99.40 96.98 0.00205 0.01056 100- 50- 1 10- I '■ r^ 2 r £ i_i 0 5- Fiscal Yean 1—1964 2—1965 3—1966 -- 's„°Lr 4—1967 5—1968 6—1969 FISCAL YEAR Vol. 5, No. 2, September 1971 133 TABLE 11 A—Vine and Ear Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPMl Percent Distribution of Samples Domestic 1968 1969 Imported 1964-67 1968 1969 Total 6163 1067 848 8078 1187 300 280 1767 81.66 61.39 74.53 78.24 49.03 34.33 31.43 43.75 10.14 16.49 13.09 11.29 23.25 24.67 19.29 22.86 3.60 10.78 5.31 4.73 11.71 15.67 13.21 12.62 3.73 10.03 6,01 4.80 12.29 20.00 29.64 16.36 .47 1.03 .59 .56 2.44 4.33 5.71 3.28 .22 .09 .24 .21 .42 1.00 .71 .57 .09 .09 .09 .42 .28 .06 .09 .24 .09 .42 .28 .03 .04 .03 .03 .09 .09 .13 .10 No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 6163 94.38 3.19 1.21 1.08 1067 88.75 6.19 2.62 2.25 .19 TDE 91.15 3.54 2.36 8077 93.30 3.63 1.52 1.39 .11 96.96 2.69 97.33 2.67 99.29 .71 97.40 2.38 No. Samples None found Trace-0,03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 134 97.63 2.04 94.28 4.22 1.50 LINDANE 95.75 3.18 96.99 2.45 .50 95.02 4.38 89.00 10.33 95.36 4.64 94.06 5.43 Pesticides Monitoring Journal TABLE 11 A — Vine and Ear Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIELDRIN No. Samples 6163 1065 849 8077 1187 300 280 1767 None found 81.47 83.76 83.39 81.97 79.27 65.67 72.50 75.89 Trace-0.03 13.92 12.68 12.72 13.63 17.10 32.67 20.36 20.26 0.04-0.10 3.92 3.19 3.65 3.80 3.36 1.67 7.14 3.68 0.11-0.50 .66 .38 .24 .58 .16 .11 0.51-1.00 .08 .06 1.01-1.50 .01 .01 1.51-2.00 Above 2.00 Average PPM .01 T T .01 .01 T .01 .01 ALDRIN No. Samples 6163 1067 847 8077 1187 300 280 1767 None found 98.81 99.16 98.58 98.84 98.82 98.00 98.21 98.59 Trace-0.03 1.15 .75 1.42 1.13 1.09 2.00 1.79 1.36 0.04-0.10 .01 .09 .02 .08 .06 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 .01 .01 . Above 2.00 .._.... ..._.„ Average PPM T T T T T T T T BHC No. Samples 6163 1067 847 8077 1187 300 280 1767 None found 99.44 98.03 99.17 99.23 98.90 98.67 100.00 99.04 Trace-0.03 .37 1.78 .71 .59 .92 .33 .68 0.04-0.10 .14 .09 .12 .14 .08 .67 .17 0.11-0.50 .03 .09 .04 .08 .33 .11 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ....__ Average PPM T T T T T T T ENDRIN No. Samples 6163 1065 847 8075 1187 300 280 1767 None found 96.75 94.93 96.46 96.48 90.48 90.67 95.00 91.23 Trace-0.03 2.28 4.51 3.07 2.66 8.08 8.33 2.50 7.24 0.04-0.10 .76 .38 .24 .66 1.01 100 1.79 1.13 0.11-0.50 .19 .19 .24 .20 .42 7.1 .40 0.51-1.00 1.01-1.50 1.51-2.00 _ Above 2.00 _._-.- _._... Average PPM T T T T T T T T Vol. 5, No. 2, September 1971 135 TABLE 11 A — Vine and Ear Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Percent Disthibution of Samples Domestic 1968 1969 Imported 1968 1969 HEPTACHLOR EPOXIDE 97.72 2.10 93.33 6.67 97.28 2.60 No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM TOXAPHENE 847 96.67 1.33 80.71 10.00 95.02 2.15 CHLORDANE No. Samples 6163 1067 847 8077 1187 300 280 1767 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 97.95 .87 .55 .61 99.53 .19 .09 .19 99.17 .24 .12 .47 98.29 .72 .45 .54 99.74 .08 .16 100.00 100.00 99.83 .06 .11 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T 136 ENDOSULFAN No. Samples 6163 1065 847 8075 1187 300 280 1767 None found Trace-0.03 98.83 .82 98.22 1.13 97.05 1.89 98.56 .98 96.71 2.69 86.67 6.67 85.71 8.57 93.27 4.30 .21 .56 .94 .33 .58 5.33 5.00 2.09 0.11-0.50 0.51-1.00 .09 .01 .09 .12 .10 .01 1.33 .71 .34 1.01-1.50 .01 .01 1.51-2.00 Above 2.00 ...._.. Average PPM T T T T T .01 .01 T Pesticides Monitoring Journal TABLE 1 1 A — Vine and Ear Vegetables: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIAZINON No. Samjles 4401 1059 848 5308 1040 254 280 1574 None found 99.35 98.39 99.17 99.13 99;80 97.64 99.64 99.43 Trace-0.03 .49 1.51 .71 .73 .09 2.36 .36 .51 0.04-0.10 .09 .12 .04 .09 .06 0.11-0.50 .14 .09 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T T PARATHION No. Samjles 4401 1059 848 5308 1040 254 280 1574 None found 98.44 94.62 94.69 97.08 95.09 83.46 75.00 89.64 Trace-0.03 .88 3.97 3.18 1.87 2.88 11.81 18,93 7.18 0.04-0.10 .38 1.04 1.42 0.68 1.44 3.94 2.86 2.10 0.11-0.50 .23 .38 .71 .34 .48 .79 2.86 .95 0.51-1.00 .02 .02 .09 .36 .13 1.01-1.50 1.51-2.00 .02 .02 Above 2.00 ....... _...... Average PPM T T T T T .01 .01 .01 STATISTICAL TREATMENT OF DATA IN TABLE IIA DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported 94.01 78.35 97.65 91.39 0.00615 0.01874 DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM Domestic Imported 99.80 99.66 99.83 99.66 99.83 99.66 i-J L ^ J 1^ Fi«;il Vcr. ^-. ^".ZT' ,-L J— 1M7 Vol. 5, No. 2, September 1971 137 STATISTICAL TREATMENT OF DATA IN TABLE 7 //I— Continued TDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 98.39 99.83 99.36 99.83 99.51 99.83 0.00166 0.00082 99.41 99.78 99.92 99.95 99.92 99.95 0.00037 0.00027 S 5. FISCAL Vt\R nri J FISCAL YEAR LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT Lower Confidence Limit (957c) Domestic Imported 99.94 99.75 100.00 99.76 100.00 99.76 0.00002 0.00120 fiscal ^far 138 oj-rm Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE / 7^— Continued BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0,001 HEPTACHLOR EPOXIDE SIGNIFICANT LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confide tAR METHYL PARATHION Lower Confidence Limit (9 TABLE ISA — Beans: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPM I Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 1307 106 81 1494 86 34 24 144 None found 77.96 79.25 87.65 78.58 39.53 32.35 29.17 36.11 Trace-0.03 8.11 7.55 7.41 8.03 29.06 8.82 12.50 21.53 0.04-0.10 3.90 8.49 3.70 4.22 12.79 50.00 8.33 20.83 0.11-0.50 7.03 3.77 6.43 11.62 8.82 41.67 15.97 0.51-1.00 1.75 .94 1.61 3.48 8.33 3.47 1.01-1.50 .91 .80 2.32 1.39 1.51-2.00 .15 .13 Above 2.00 .15 1.23 .20 1.16 .69 Average PPM .09 .02 .06 .08 .13 .04 .16 .12 148 Pesticides Monitoring Journal TABLE 13A — Beans: Percent distribution of residues, by fiscal year, in dif}erent quantitative ranges — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 1307 106 81 1494 86 34 24 144 None found 90.51 88.68 91.36 90.43 53.48 32.35 75.00 52.08 Trac«-0.03 8.56 11.32 7.41 8.70 41.86 67.65 25.00 45.14 0.04-0.10 .76 1.23 .74 4.65 2.78 0.11-0.50 .07 .07 0.51-1.00 .07 .07 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T .01 .01 T .01 TDE No. Samples 1307 106 81 1494 86 34 24 144 None found 97.70 95.28 100.00 97.66 96.51 100.00 100.00 97.92 Trace-0.03 1.22 4.72 1.41 2.32 1.39 0.04-0.10 .68 .60 0.11-0.50 .30 .27 1.16 .69 0.5I-I.0O .07 .07 1.01-1.50 1.51-2.00 Above 2.00 _._... Average PPM T T T T T LINDANE No. Samples 1307 106 81 1494 86 34 24 144 None found 98.85 98.11 98.77 98.80 89.53 73.53 100.00 87.50 Trace-0.03 .99 1.89 1.23 1.07 6.97 23.53 9.72 0.04-0.10 .07 .07 3.48 2.94 2.78 0.11-0.50 .07 .07 0.51-1.00 1.0I-I.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T DIELDRIN Vol. 5. No. 2, September 1971 No. Samples 1307 106 81 1494 86 34 24 144 None found 93.34 100.00 93.83 93.84 89.53 82.35 100.00 89.58 Trace-0.03 6.19 6.17 5.76 10.46 14.71 9.72 0.04-0.10 .22 .20 2.94 .69 0.11-0.50 .22 .20 0. 51-1.00 1.01-1.50 _ — 1.51-2.00 Above 2.00 .._._- _-.... _-..... „.._ --- Average PPM T T T T T T 149 TABLE I3A — Beans: Percent distribution of residues, by fiscal year, in different quantitative ra«gei— Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported ALDRIN No. Samples 1307 106 81 1494 86 34 24 144 None found 99.46 99.06 98.77 99.40 97.67 97.06 100.00 97.92 Trace-0.03 .53 .94 1.23 .60 2.32 2.94 2.08 0.04-0.10 0.11-0.50 0.5I-I.00 _ 1.01-1.50 1.51-;.00 Above 2.00 _..„_ Average PPM T T T T T T T BHC No. Samples 1307 106 81 1494 86 34 24 144 None found 99.31 97.17 98.77 99.13 95.34 100.00 95.83 96.53 Trace-0.03 .61 2.83 1.23 .80 3.48 4.17 2.78 0.04-0.10 0.11-0.50 1.16 .69 0.51-1.00 .07 .07 1.01-1.50 1.51-2.00 Above 2.00 _.___.. Average PPM T T T T T T T ENDRIN No. Samples 1307 106 81 1494 86 34 24 144 None found 99.69 100.00 100.00 99.73 98.83 100.00 95.83 98.61 Trace-0.03 .22 .20 1.16 4.17 1.39 0.04-0.10 .07 .07 _ 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T 150 HEPTACHLOR EPOXIDE No. Samples 1307 106 81 1494 86 34 24 144 None found 99.61 100.00 100.00 99.67 98.83 94.12 100.00 97.92 Trace-0.03 .38 .33 1.16 5.88 2.08 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ...^... Average PPM T T T T T Pesticides Monitoring Journal TABLE 13A — Beans: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=:<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 TOXAPHENE No. Samples 1307 106 81 1494 86 34 24 144 None found 99.08 95,28 100.00 98.86 98.83 100.00 95.83 98.61 Trace-0.03 .15 .94 .20 4.17 .69 0.04-0.10 .07 .07 0.11-0.50 .30 .94 .33 1.16 .69 0.51-1.00 .38 .94 .40 1.01-1.50 1.89 .13 1.51-2.00 Above 2.00 Average PPM T .03 .01 T T T Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 PARATHION No. Samples 681 106 81 868 79 27 24 130 None found 98.82 99.06 97.53 98.73 87.34 74.07 66.67 80.77 Trace-0.03 .29 2.47 .46 6.32 11.11 16.67 9.23 0.04-0.10 .73 .94 .69 3.79 II. II 8.33 6.15 0.11-0.50 .14 .12 2.53 3.70 4.17 3.08 0.51-1.00 4.17 .77 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T .01 .01 .04 .02 DIAZINON No. Samples 681 106 81 868 79 27 24 130 None found 99.26 99.06 100.00 99.31 100.00 100.00 100.00 100.00 Trace-0.03 .58 94 .58 0.04-0.10 .14 .12 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ........ Average PPM T T T Vol. 5, No. 2, September 1971 151 STATISTICAL TREATMENT OF DATA IN TABLE 13 A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.05 LINDANE Domestic Imported Lower Confidence Limit (95%) 0.1 0.5 PPM PPM 1.0 PPM Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM Sy.x 99.94 99.94 99.47 99,74 DIELDRIN 99,94 99.74 0.00028 Domestic Imported 90.44 95.06 96.14 77.83 93.66 96.52 0.01021 0.00486 Fiscal Yean 2-1965 4—1967 5— I96li 6—1969 100- / Domestic Imported Lower Confidence Limit (95%) 50- 0.1 0.5 PPM PPM 1.0 PPM Sv.x K 99.82 99.82 99.99 99.99 ALDRIN 99.82 99.99 0.00087 0.00003 s Imported Lower Confidence Limit (95%) z O.I 0.5 PPM PPM 1.0 PPM Sy.x OS- 94.16 94.16 BHC 94.16 0.02898 Domestic Imported Lower Confidence Limit (95%) 0.1 0.5 PPM PPM 1.0 PPM DDE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC NONSIGNIFICANT Sy.x 99.91 99.91 99.32 99.47 ENDRIN 99.91 99.48 0.00044 0.00258 Domestic Lower Confidence Limit (95%) I riwnu f"r.i.ji:inPMri: I t^4iT CQSr' 1 0.1 0.5 PPM PPM I.O PPM 0.1 0.5 1.0 PPM PPM PPM Sy.x Sy.x 99.98 99.99 99.99 HEPTACHLOR EPOXIDE Domestic Imported 99.86 99.88 99.88 99.99 100.00 100.00 0.00059 0.00002 Fiscal Yeats 1-1964 2-1965 1—1966 5—1968 100 -| Imported Lower Confidence Limit (95%) 50- 0.1 0.5 PPM PPM 1.0 PPM Sy.x 94.16 94.16 TOXAPHENE 94.16 0.02898 S S '" ^ I 5- Domestic Imported Lower Confidence Limit (95%) o 0.1 0.5 PPM PPM 1.0 PPM Sy.x gl.O- 0,5- 98.96 99.22 99.27 99.52 PARATHION 99.29 99.58 0.00220 0.00163 Domestic Imported Lower Confidence Limit (95%) 0.1 0.5 PPM PPM 1.0 PPM 1 2 .1 FISCAL YEAR TDE Sy.x 99.52 99.71 95.63 98.67 DIAZINON 99.74 99.12 0.00111 0.00246 T ^u/co r^rixiciriCKjr-n T ix*t-r tQ^Of Domestic Lower Confidence Limit (95%) 0.1 0.5 1.0 PPM PPM PPM Sy.x 0.1 0.5 PPM PPM 1.0 PPM Sy.x Domestic Imported QQ fi< OQ 01 QO QJ 0.00018 0.00190 99.26 99.53 99.57 99.98 99.99 99.99 0.00005 152 Pesticides Monitoring Journal TABLE 14A — Red Meat: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 BHC No. Samples 2713 1299 4012 1274 499 1773 None found 76.30 86.99 79.76 35.01 41.28 36.77 Trace-0.03 21.23 11.24 18.00 29.04 35.67 30.91 0.04-0.10 1.81 1.31 1.65 29.98 19.64 27.07 0.11-0.50 .37 .23 .32 4.71 2.81 4.17 0.51-1.00 .15 .08 .12 .86 .60 .79 1.01-1.50 .07 .05 1.51-2.00 .07 .08 .07 .16 .11 Above 2.00 .08 .02 .24 .17 Average PPM .02 .03 .03 .17 .11 .15 Percent DisraiBLrTioN of Samples Domestic 1968 1969 Imported 1968 1969 DDT No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 29.01 17.40 12.39 24.64 15.78 16.95 15.23 16.11 Trace-0.03 32.99 26.83 29.48 31.24 27.46 28.65 25.85 27.65 0.04-0.10 23.59 39.81 44.03 29.47 33.56 39.17 40.28 36.42 0.11-0.50 7.04 9.33 7.93 7.65 12.41 8.87 9.02 10.72 0.51-1.00 2.48 2.21 3.31 2.51 4.10 2.35 4.81 3.59 1.01-1.50 1.64 1.58 1.00 1.56 2.05 1.73 1.20 1.82 1.51-2.00 1.49 1.36 1.54 1.47 2.63 1.26 1.20 1.96 Above 2.00 1.66 1.47 .31 1.47 2.00 1.02 2.40 1.71 Average PPM .32 .37 .32 .34 .46 .34 .42 .41 DIELDRIN No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 73.60 57.54 61.43 68.71 53.50 49.92 60.92 53.27 Trace-0.03 11.15 35.50 33.41 18.97 25.30 20.96 27.86 24 14 0.04-0.10 14.85 6.67 4.85 11.95 19.25 25.59 1042 :n ;•; 0.11-0.50 .16 .22 .23 .18 1.53 2.98 .80 1 Ml 0.51-1.00 .06 .04 .05 .16 .31 JQ 1.01-1.50 .10 .04 .08 .08 .16 .24 ,16 1.51-2.00 .02 .02 Above 2.00 .05 .03 .11 .05 Average PPM .06 .04 .04 .05 .09 .12 .05 .10 LINDANE Vol. 5, No. 2, September 1971 No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 94.82 90.75 90.15 93.41 91.90 85.64 76.55 87.64 Trace 0.03 3.68 7.45 8.16 5.00 6.10 11.30 20.84 9.91 0.04-0.10 1.09 1.58 1.69 1.27 1.53 2.98 2.61 2.18 0.11-0.50 .21 .18 .18 .21 .08 .14 0.51-1.00 .10 .04 .07 .21 .11 1.01-1.50 .04 .02 .05 .03 1.51-2.00 .06 .04 Above 2.00 ----- Average PPM .01 .01 .01 .01 .01 .02 .02 .01 153 TABLE 14A — Red Meat: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total ALDRIN No. Samples 8134 2713 1299 12146 1274 499 1773 None found 99.99 99.85 99.92 99.95 99.22 96.99 98.59 Trace-0.03 .11 .08 .03 .71 2.61 1.24 0.04-0.10 .04 .01 .08 .40 .17 0.11-0.50 .01 .01 0.5I-I.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T T No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 99.90 99.23 98.46 99.60 99.21 99.76 96.39 99.02 Trace-0.03 .04 .63 1.54 .33 .42 .24 3.41 .76 0.04-0.10 .06 .15 .07 .32 .20 .19 0.11-0.50 .05 .03 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T . T T T T T T METHOXYCHLOR No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 98.51 97.97 97.00 98.23 99.32 99.76 98.60 99.37 Trace-0.03 .68 .22 1.23 .63 .42 .08 .60 .33 0.04-0.10 .38 1.40 1.77 .76 .16 .60 .16 0.11-0.50 .28 .37 .27 .05 .16 .20 .11 0.51-1.00 .05 .03 .05 .03 1.01-1.50 .06 .04 1.51-2.00 .04 .02 Above 2.00 .04 .01 Average PPM T .01 .01 .01 T T T T 154 TOXAPHENE No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 97.98 99.85 99.92 98.61 99.89 100.00 100.00 99.95 Trace 0.03 .73 .08 .49 0.04-0.10 .63 .42 0.11-0.50 .33 .22 0.51-1.00 .06 .04 1.01-1.50 .16 .11 1.51-2.00 .07 .04 .06 _. Above 2.00 .04 .11 .05 .11 .05 Average PPM .01 .01 T .01 T T Pesticides Monitoring Journal TABLE I4A — Red Meat: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPMJ Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 Total CHLOROMETHYLPHENOXY ACETIC ACID (MCP) No. Samples 8134 8134 1044 1044 None found 88.16 88.16 54.92 54.92 Trace-0.03 9.91 9.91 29.67 29.67 0.04-0.10 1.55 1.55 11.26 11.26 0.11-0.50 .20 .20 2.74 2.74 0.51-1.00 .07 .07 .74 .74 1.01-1.50 .02 .02 .26 .26 1.51-2.00 .04 .04 .16 .16 Above 2.00 .05 .05 .26 .26 Average PPM .02 .02 .10 .10 HEPTACHLOR No. Samples 8134 2713 1299 12146 1901 1274 499 3674 None found 97.98 72.61 80.37 90.43 99.74 97.57 99.00 98.88 Trace-0.03 1.66 23.15 16.40 8.04 .26 1.02 .40 .54 0.04-0.10 .36 4.02 3.23 1.48 I.4I .60 .57 0.11-0.50 .18 .04 0.51-1.00 .04 .01 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T .03 .02 .01 T T T T Percent Distribution of Samples Domestic 1968 1969 Total Imported 1968 1969 HEPTACHLOR EPOXIDE No. Samples 3098 3098 1901 1274 499 3674 None found 78.41 78.41 90.16 91.13 85.37 89.85 Trace-0.03 19.37 19.37 8.47 7.38 12.02 8.57 0.04-0.10 1 .94 1 .94 1.37 1.49 2.61 1.58 0.11-0.50 .10 .10 _ _ 0.51-1.00 .06 .06 1.01-1.50 1.51-2.00 .06 .06 Above 2,00 .06 .06 Average PPM .02 .02 .01 .01 .01 .01 September 1971 155 STATISTICAL TREATMENT OF DATA IN TABLE 14A BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.OOI DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 0.5 PPM 1.0 PPM Sy.x Domestic Imported 97.27 66.02 99.36 83.64 99.53 87.50 0.00189 0.04027 86.72 76.09 93.31 87.54 94.60 90.01 0.01917 0.03424 1 T^ T. 2-1965 £1L ^^?ir ,-?^. -,"„-:?' 5-IQM n FISl AL Vi:.\R DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001* < NONSIGNIFICANT" LINDANE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 54.55 40.89 0.5 PPM I.O PPM Sy.x O.I PPM 0.5 PPM 1.0 PPM Sy.x •Domestic ♦♦Imported 78.50 72.32 84.88 81.13 0.03127 0.03920 98.34 97.42 99.41 99.22 99.59 99.48 0.00095 0.00146 ^ J^ HS( AL "i I \R 156 Pesticides Monitoring Journal STATISTICAL TREATMENT OF DATA IN TABLE 14 A- ALDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit {95':i) METHOXYCHLOR SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 98.80 99.66 99.18 99.79 99.28 99.82 0.00228 0.00056 ENDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95% ) TOXAPHENE SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) Domestic Imported 99.92 99.76 99.97 99.90 99.98 99.93 0.00008 0.00023 n FISCAL YEAR Vol. 5, No. 2, September 1971 157 STATISTICAL TREATMENT OF DATA IN TABLE 1 4 A— Continued CHLOROMETHYLPHENOXYACETIC ACID (MCP) SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 HEPTACHLOR SIGNIFICANT LEVEL OF CHI-SQUARE TEST STATISTIC <0.00I Lower Confidence Limit (95%) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 98.02 84.02 99.60 94.19 99.80 96.20 0.00019 0.00780 98.34 99.39 99.52 99.60 99.66 99.65 0.00115 0.00132 n r ' 1 — 1964 ■>— 1 9fi5 .1—1966 J n 01 PPM 4_i967 D.-mc.lic D.>nic>rrv 5—1968 6—1969 n^ t HEPTACHLOR EPOXIDE SIGNIFICANT LEVEL OF CHI-SQUARE TEST STATISTIC <0.01 Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 97.54 98.27 99.59 99.49 99.74 99.63 0.00098 0.00133 n^ 158 Pesticides Monitoring Journal TABLE ISA — Poultry: Percent distribution of residues, by fiscal year, in different quantilalive ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 2679 735 3414 None found Trace-0.03 0.04-0.10 0.11-0.50 0,51-1.00 1.01-1.50 1.51-2.00 Above 2.00 .49 2.45 .91 15.15 12.65 14.62 66.48 67.35 66.67 13.48 13.61 13.50 2.43 2.31 2.40 .93 .82 .91 .52 .14 .44 .52 .68 .56 - - - Average PPM .15 .15 .15 No. Samples 2679 735 3414 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1,50 1.51-2.00 Above 2.00 99.85 99.46 99.77 .15 .27 .18 ,27 .06 Average PPM TXT - BHC No. Samples 2679 735 3414 None found Trace-0.03 0,04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 76.78 90.34 79.70 22.40 8.84 19.48 .82 .82 .82 Average PPM T T T CHLORDANE No. Samples 2679 735 3414 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 99.93 100.00 99.94 .04 .03 .04 .03 — -- Average PPM T T Vol. 5, No. 2, September 1971 159 TABLE 15A — Poultry: Percent distribittion of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM) Range PPM Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 DIELDRIN No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 14.78 73.16 11.87 39.32 55.10 5.44 20.06 69.27 10.49 ENDRIN HEPTACHLOR LINDANE 160 Pesticides Monitoring Journal TABLE 15A — Poultry: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T = <.005 PPM] Range PPM Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 METHOXYCHLOR No. Samples 2679 735 3414 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 98.92 97.69 98 .11 .82 .63 1.36 .26 .14 .04 .04 65 26 79 23 03 03 Average PPM T T T STATISTICAL TREATMENT OF DATA IN TABLE I5A DDT SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) BHC SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95%) n Vol. 5, No. 2, September 1971 161 STATISTICAL TREATMENT OF DATA IN TABLE /.5^— Continued ALDRIN Lower Confidence Limit (95% ) DIELDRIN SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.O0I Lower Confidence Limit (QS'";- ) HEPTACHLOR SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC <0.001 Lower Confidence Limit (95':!' ) ru SIGNIFICANCE LEVEL OF CHI-SQUARE TEST STATISTIC rr Distribution of Samples Domestic 1967 LINDANE No. Samples 256 16 40 372 951 443 2078 None found 97.66 100.00 95.00 97.85 98.42 99.32 98.36 Trace-0.03 1.95 5.00 2.15 1.58 .68 1.59 0.04-0,10 .39 .05 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T T HEPTACHLOR EPOXIDE No. Samples 256 16 40 372 951 443 2078 None found 100.00 100.00 95.00 98.92 99.05 98.42 98.94 Trace-0.03 2.50 1.08 .95 1.58 1.01 0.04-0.10 2.50 .05 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T STATISTICAL TREATMENT OF DATA IN TABLE 20 A DDE DIELDRIN Lower Confidence Limit (95%) Lower Confidence Limit (95%) DDT Lower Confidence Limit (95%) Lower Confidence Limtt (95%) Lower Confidence Limit (95%) LINDANE Lower Confidence Limit (95% ) HEPTACHLOR EPOXIDE Lower Confidence Limit (95% ) 182 Pesticides Monitoring Journal TABLE 21 A — Tree Nuts: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=r<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 1969 No. Samples 373 31 13 417 122 2 3 127 None found 88.47 96.77 100.00 89.45 78.68 50.00 66.67 77.95 Trace-0.03 8.04 7.19 13.11 50.00 33.33 14.17 0.04-0.10 1.87 3.23 1.92 3.27 3.15 0.11-0.50 .80 .72 4.09 3.94 0.51-1.00 .26 .24 .81 .79 1.01-1.50 .26 .24 1,51-2.00 Above 2.00 .26 .24 Average PPM .03 T T .02 T .01 .02 DDE No. Samples 373 31 13 417 122 2 3 127 None found 91.15 87.10 84.62 90.65 77.04 100.00 100.00 77.95 Trace-0.03 6.70 6.45 15.38 6.95 2.45 2.36 0.04-0.10 1.07 6.45 1.44 5.73 5.51 0.11-0.50 1.07 .96 14.75 14.17 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 .._.... .._.„. Average PPM .01 T T T .05 .05 TDE No. Samples 373 31 13 417 122 2 3 127 None found 95.97 96.77 100.00 96.16 87.70 100.00 100.00 88.19 Trace-0.03 3.48 3.23 3.36 7.37 7.09 0.04-0.10 .26 .24 2.45 2.36 0.11-0.50 .26 .24 2.45 2.36 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T .01 T LINDANE No. Samples 373 31 13 417 122 2 3 127 None found 98.39 93.55 100.00 98.08 91.80 100.00 66.67 91.34 Trace-0.03 1.34 6.45 1.68 4.09 33.33 4.72 0.04-0.10 .81 .79 0.11-0.50 .26 .24 3.27 _ 3.15 0.51-1.00 1.01-1.50 _ 1.51-2.00 Above 2.00 _.-.-. _.--„ Average PPM T T T .01 _..._._ T T Vol. 5, No. 2, September 1971 183 TABLE 21 A — Tree Nuts: Percent lUstrihiilion of residues, hy fiscal yeiir, in tliffercnl qiiiinlilulive ranges — Continued 1T=<.005 PPM] Percent DisTRrBunoN of Samples Domestic Imported 1968 1969 No. Samples 373 31 13 417 122 2 3 127 None found 95.71 96.77 100.00 95.92 91.80 100.00 100.00 92.13 Trace-0.03 2.94 3.23 2.88 6.55 6.30 0.04-0.10 .26 .24 .81 .79 0.11-0.50 .80 .72 .81 .79 0.51-1,00 1.01-1.50 1.51-2.00 Above 2.00 .26 .24 Average PPM .06 T .05 T T No. Samples 373 31 13 417 122 2 3 127 None found 98.92 100.00 100.00 99.04 99.18 100.00 100.00 99.21 Trace-0.03 1.07 .96 .81 .79 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T No. Samples 373 31 13 417 122 2 3 127 None found 98.39 93.55 100.00 98.08 77.86 100.00 100.00 78.74 Trace-0.03 1.34 3.23 1.44 4.09 3.94 0.04-0.10 7.37 7.09 0.11-0.50 3.23 .24 9.01 8.66 0.51-1.00 1.63 1.57 1.01-1.50 .26 .24 1.51-2.00 Above 2.00 Average PPM T T T .05 — - .04 184 ENDRIN No. Samples 373 31 13 417 122 2 3 127 None found 99.19 100.00 100.00 99.28 100.00 100.00 100.00 100.00 Trace-0.03 .80 .72 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 _ 1.51-2.00 _ Above 2.00 ....... — _.... Average PPM T T — - Pesticides Monitoring Journal 21 A — Tree Nuls: Percent distribulion of residues, by fiscal year, in difjcrenl quantitative ranges — Continued [T=<.005 FPM] Percent Distribution of Samples Domestic 1968 1969 HEPTACHLOR EPOXIDE No. Samples 373 31 13 417 122 2 3 127 None found 99.46 100.00 100.00 99.52 100.00 100.00 100.00 100.00 Trace-0.03 .53 .48 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ___.. _.._.. Average PPM T T TOXAPHENE No. Samples 373 31 13 417 122 2 3 127 None found 99.73 100.00 100.00 99.76 98.36 100.00 100.00 98.43 Trace-0.03 .26 .24 0.04-0.10 0.11-0.50 1.63 1.57 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T STATISTICAL TREATMEN T OF DATA IN TABLE 21 A DDT LINDANE Lower Confidence Limit (95% ) Domestic Imported Lower Confidence Limit (95% ) 0.1 PPM 0.5 PPM 1.0 PPM Sv.x O.I PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 98.08 94.85 98.95 97.39 DDE 99.01 97.64 0.00475 0.01105 99.78 96.65 99.80 98.10 DIELDRIN 99.80 98.36 0.00 1 00 0.00653 Lower Confidence Limit (95% ) Domestic Imported Lower Confidence Limit (95%) 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.04 83.02 99.47 88.57 TDE 99.49 89.95 0.00252 0.03745 98.79 99.24 99.24 99.44 BHC 99.29 99.45 0.00329 0.00273 0.1 Lower Confidence Limit (95% ) 0.5 1.0 PPM PPM Domestic Imported Lower Confidence Limit (95% ) Sy.x 0.1 PPM 0.5 PPM 1.0 PPM Sy.x Domestic Imported 99.78 97.52 99.81 98.96 99.81 99.13 0.00095 0.00374 TOXA 99.33 87.32 99.53 92.33 99.56 93.5! 0.00209 0.02234 PHENE Imported Lower Confidence Limit (95% 0.1 PPM 0.5 PPM 1.0 PPM Sy.x 98.23 98.62 98.73 0.00483 Vol. 5, No. 2, September 1971 185 Vegetable Oil Seed and Products TABLE 22A — Peanuts: Percent distribution of residues, by fiscal year, in different quantitative ranges [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 DDT No. Samples 177 29 10 13 229 None found Trace-0.03 ().()4-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 86.45 55.17 90.00 100.00 83.41 6.22 34.48 _ 9.17 3.96 10.00 3.49 1.70 6.90 ._ _ 2.18 1.13 _ .87 .57 .._. .44 3.45 .44 - Average PPM .03 .24 .01 .05 ■- ~ No. Samples None found Trace-0.03 0.04-0.10 0.11-0,50 0,51-1.00 1.01-1.50 1.51-2.00 Above 2.00 98.31 1.70 65.52 27.59 3.45 3.45 90.00 10.00 93.89 5.24 Average PPM No. Samples 177 29 10 13 229 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 92.66 48.28 60.00 84.62 85.16 3.96 44.83 20.00 15.38 10.48 .57 3.45 20.00 1.75 2.83 3.45 .. 2.62 Average PPM T .01 .01 T T DIELDRIN No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0,51-1.00 1.01-1.50 1.51-2.00 Above 2.00 92.10 93.10 90.00 5.09 6.90 10.00 .57 2.26 92.58 5.24 Pesticides Monitoring Journ.al TABLE 22A — Peanuts: Percent distribution of residues, by fiscal year, in different quantitative ranges — Continued [T=<.005 PPM] Range PPM Percent Distribution of Samples Domestic Imported 1964-66 1967 1968 1969 Total 1964-66 1967 1968 1969 Total LINDANE No. Samples 177 29 10 13 229 None found 97.18 100.00 80.00 100.00 96.95 Tracc-0.03 1.70 20.00 2.18 0.04-0.10 .57 .44 0.11-0.50 0.51-1.00 .57 .44 1.51-2.00 Above 2.00 Average PPM T T T TOXAPHENE No. Samples 177 29 10 13 229 None found 98.31 100.00 100.00 100.00 98.69 Trace-0.03 .57 .44 0.04-0.10 O.n-0.50 .57 .44 0.51-1.00 .57 .44 1.0I-I.50 1.51-2.00 Above 2.00 _„._ — - Average PPM .01 — .01 __.._ ENDRIN No. Samples 177 29 10 13 229 .._.._ None found 98.88 100.00 100.00 100.00 99.13 Trace-0.03 1.13 .87 0.04-0. 10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 — -- II Above 2.00 — — Average PPM T — — T _ -. — - BHC No. Samples 177 29 10 13 229 - . None found 98.88 100.00 100.00 100.00 99.13 Trace-0.03 .57 .44 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 ---- .57 .44 1.51-2.00 Above 2.00 — Average PPM .01 „__.. — .01 . Vol. 5, No. 2, S EPTEMBER 1971 187 TABLE 22B— Crude Peamil Oil [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 DDT No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 33.33 25.00 5.56 2.78 22.22 22.22 25.00 8.33 25.00 2.78 25.00 2.78 34.15 4.88 2.44 19.51 21.95 9.76 2.44 Average PPM TDE No. Samples 36 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 I.0I-1.50 1.51-2.00 Above 2.00 55.56 11.11 11.11 13.89 5.56 2.78 50.00 25.00 56.10 12.20 9.76 12.20 7.32 2.44 DDE No. Samples 41 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 41.67 25.00 16.67 50.00 16.67 25.00 25.00 41.46 19.51 17.07 21.95 DIELDRIN Pesticides Monitoring Journal TABLE 22B— Crude Peanul O/V— Continued [T=<.005 PPM] Percent DisniiBimoN of Samples Domestic 1968 Imported 1967 1968 LINDANE 41 75.00 25.00 2.78 2.78 85.37 9.76 2.44 2.44 TOXAPHENE BHC No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 i.01-1.50 1.51-2.00 Above 2.00 94.44 2.78 Average PPM Vol. 5, No. 2, September 1971 189 TABLE 22C— Peanut Meal [T=<.005 PPM] Percent Distribution of Samples Range PPM Domestic Imported 1964-66 1967 1968 1969 Total 1964-66 1967 1968 1969 Total DDT No. Samples 31 5 36 None found 54.84 100.00 61.11 Trace-0.03 6.45 5.56 0.04-0.10 16.13 13.89 0.11-0.50 12.90 11.11 0.51-1.00 6.45 5.56 1.01-1.50 3.23 2.78 1.51-2.00 Above 2.00 _.„_. Average PPM .14 .- .12 TDE No. Samples 31 5 36 ....... None found 77.42 80.00 77.78 Trace-0.03 9.68 8.33 0.04-0.10 6.45 20.00 8.33 0.11-0.50 6.45 5.56 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 - - Average PPM .03 .01 .02 DDE DIELDRIN 190 Pesticides Monitoring Journal TABLE 2 2C— Peanut A/f a/— Continued [T=<.(X)5 PPM] Percent Distribution of Samples Range PPM Domestic Imported 1964-66 1967 1968 1969 Total 1964-66 1967 1968 1969 Total LINDANE No. Samples 30 5 35 None found 96.77 100.00 97.22 Trace-0.03 3.23 2.78 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 -- ' ■--- Above 2.00 --- ...._.. - Average PPM T T BHC No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 87.10 6.45 6.45 88.89 5.56 5.56 Average PPM TABLE 22D— Refined Peanut Oil [T=<.005 PPM) Percent Distribution of Samples Domestic 1968 Imported 1968 DDT No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 20.00 100,00 Vol. 5. No. 2, September 1971 191 TABLE 22 D— Refined Peanut O//— Continued 1T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 TDE No. Samples None found Trace-0.30 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 70.00 30.00 63.64 27.27 DDE No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 80.00 10.00 72.73 9.09 9.09 9.09 DIELDRIN No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 90.00 10.00 90.91 9.09 BHC No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 90.00 10.00 90.91 9.09 192 Pesticides Monitoring Journal TABLE 23 A — Vegetable Oil Seed and Products: Cottonseed [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 SPORTED 1968 DDT No. Samples 23 4 1 3 31 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 30.43 75.00 100.00 100.00 45.16 8.70 25.00 _ 9.68 13.04 9.68 47.83 35.48 -- Average PPM .15 T _ .11 -—- 86.96 75.00 8.70 25.00 4.35 100.00 87.10 9.68 3.23 Vol. 5, No. 2, September 1971 193 TABLE 23 A — VcgcUibIc Oil Seed ami Products: Collonsced — Continued [T=<.005 PPM] Percent Distoibution of Samples Domestic 1968 Imported 1967 1968 LINDANE No. Samples None found Tr;ice-0.n3 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 95.65 4.35 100.00 96.77 3.23 TOXAPHENE No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 60.87 8.70 70.97 6.45 BHC No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 72.91 100.00 21.74 80.65 16.13 CHLORDANE 194 Pesticides Monitoring Journal TABLE 23 B— Crude Cottonseed Oil [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1967 1968 70.80 75.00 81.82 77.78 13.72 19.44 18.18 11.11 4.42 11.11 7.96 5.56 1.33 71.99 14.54 3.90 7.09 1.06 TDE 226 64.16 12.39 3.10 18.58 1.33 58.33 22.22 90.91 9.09 16.67 2.78 65.25 13.12 17.38 1.42 84.95 91.67 81.82 77.78 85.46 10.18 5.56 18.18 11.11 9.93 3.10 2.78 11.11 3.13 1.77 1.42 97.34 2.21 94.44 2.78 2.78 97.16 2.13 5, No. 2, September 1971 195 TABLE 23 B — Crude Collonseecl Oil — Continued IT=<.005 PPM] Percent Distribittion of Samples Range PPM Domestic Imported 1964-66 1967 1968 1969 Total 1964-66 1967 1968 1969 Total LINDANE No. Samples 226 36 11 9 282 . None found 91.15 94.44 90.91 100.00 91.84 Trace-0.03 4.87 3.90 0.04-0.10 2.21 1.77 0.11-0.50 1.77 5.56 9.09 2.48 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 .. .. . ^ Average PPM .01 .01 .02 .01 TOXAPHENE No. Samples 226 36 n 9 282 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 98.67 100.00 100.00 100.00 98.94 .44 .35 .44 _ .35 .44 _. .35 ' Average PPM .01 .01 BHC No. Samples 226 36 11 9 282 - None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 97.34 97.22 100.00 100.00 97.52 1.77 2.78 1.77 .44 -- - .35 .44 .35 ~ Average PPM T T T CHLORDANE 196 Pesticides Monitoring Journal TABLE 23C—Col!onseed Meal [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 DDT No. Samples 186 61 22 18 287 .._.„. None found 71.51 67.21 68.18 83.33 71.08 Trace-0.03 18.28 24.59 18.18 16.67 19.51 0.04-0.10 6.99 3.28 9.09 5.92 O.U-0.50 2.15 3.28 4.55 2.44 0.51-1.00 .54 .35 1.01-1.50 1.51-2.00 .54 .35 Above 2.00 --- 1.64 .35 Average PPM .03 .37 .01 T .09 TDE No. Samples 186 61 22 18 287 None found 83.33 70.49 86.36 100.00 81.88 Trace-0.03 16.13 26.23 13.64 17.07 0.04-0.10 1.64 .35 0.11-0.50 .54 .35 0.51-1.00 1.01-1.50 ._ 1.51-2.00 _ Above 2.00 1.64 _-.. ..__.. .35 Average PPM T .12 T .03 DDE 87.63 80.33 86.36 10.75 18.03 13.64 1.08 86.76 11.85 DIELDRIN Vol. 5, No. 2, September 1971 197 TABLE 23C — Cottonseed Meal — Continued [T=<.005 PPM] Percent Distribution of Samples 1964-66 1967 Domestic 1968 1969 Total 1964-66 1967 Imported 1968 1969 Total LINDANE No. Samples 186 61 22 18 287 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 91.40 7.53 .54 .54 95.08 4.92 95.45 4.55 94.44 5.56 92.68 6.27 .35 .70 Average PPM T T .01 T T TOXAPHENE No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM 18 287 ?8.36 100.00 100.00 96.52 1.64 in, No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM BHC 18 287 95.16 91.80 100.00 100.00 95.12 3-23 8.20 3.83 CHLORDANE Pesticides Monitoring Journal TABLE 23C — Cottonseed Meal — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1958 Imported 1968 ENDRIN TABLE 23D— Refined Cottonseed Oil [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1968 1969 Total No. Samples None found Trace-n.03 0.04-0.10 0.11-0.50 0,51-1.00 1.01-1.50 1.51-2.00 Above 2.00 87.80 2.44 60.00 20.00 85.42 4.17 TDE Vol. 5, No. 2, September 1971 199 TABLE 23 D— Refined Collonseed Oil — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 I MPORTED 1967 1968 DDE No. Samples None found Trace 0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 40.00 100.00 60.00 83.33 12.50 2.44 2.44 DIELDRIN No. Samples 41 5 2 48 None found Tr,ice-0.03 0.04-0.10 97.56 2.44 100.00 100.00 97.92 2.08 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T .._.... T LINDANE No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 97.56 100.00 100.00 Average PPM TOXAPHENE No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 87.80 100.00 100.00 2.44 9.76 200 Pesticides Monitoring Journal TABLE 23D— Refined Collonseed O//— Continued [T=<.005 PPM] Range PPM Percent Distoibution of Samples Domestic Imported 1967 1968 1969 Total BHC CHLORDANE TABLE 24A — Vegetable Oil Seed and Products: Soybeans [T=<.005 PPM] Percent Disthibution of Samples Domestic 1968 Imported 1968 DDT No. Samples 90 None found Trace-0.03 0.04-0.10 O.U-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 90.36 6.91 1.82 92.22 3.33 3.33 1.11 93.75 3.13 3.13 90.72 6.38 2.03 Vol. 5, No. 2, September 1971 201 TABLE 24 A — Vegetable Oil Seed and Products: Soybeans — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1968 TDE No. Samples None found Trace-0.03 0.04-0.10 O.n-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 97.27 2.73 94.44 5.56 96.87 3.13 94.44 5.56 96.81 3.19 Average PPM DIELDRIN 202 Pesticides NfoNiTORiNc Journal TABLE 24 A — Vegetable Oil Seed and Products: Soybeans — Continued [T=<.005 PPM] Percent DiSTTtiBurioN of Samples Domestic 1968 Imported 1968 TOXAPHENE 92.00 2.36 94.44 5.56 92.90 1.74 ENDRIN 550 90.18 2.91 5.82 1.09 86.67 10.00 90.44 3.62 4.64 BHC 96.73 94.44 5.56 100.00 100.00 96.67 .72 3.27 2.61 CHLORDANE 90 32 1.89 100.00 Vol. 5, No. 2, September 1971 203 TABLE 24B— Crude Soybeans IT=<.005 PPM] Percent DisreiBUTioN of Samples Domestic 1968 Imported 1967 1968 DDT No. Samples 98 17 2 1 118 None found 83.67 64.71 100.00 100.00 81.36 Trace-0.03 11.22 23.53 12.71 0.04-0.10 3.06 5.88 3.39 0.11-0.50 1.02 5.88 1.69 0.51-1.00 1.02 .85 1.01-1.50 1.51-2.00 Above 2.00 -- ~z zi 11 :z Average PPM .02 .01 .01 - TDE No. Samples 98 17 2 1 118 .... None found 92.86 82.35 100.00 100.00 91.53 Trace-0.03 3.06 11.76 4.24 0.04-0.10 3.06 2.54 " 0.11-0.50 1.02 5.88 1.69 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 — - I" II II Average PPM T .01 T No. Samples 98 17 2 1 118 None found 93.88 94.12 100.00 100.00 94.07 Trace-0.03 5.10 5.88 5.08 .... 0.04-0.10 1.02 .85 0.11-0.50 ' 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T DIELDRIN No. Samples 98 17 2 1 118 None found 82.65 88.24 100.00 100.00 83.90 Tracc-0.03 8.16 11.76 8.47 0.04-0.10 7.14 5.93 0.11-0.50 2.04 1,69 0.51-1.00 1.01-1.50 --■ 1.51-2.00 Above 2.00 — II Average PPM .01 T -- .01 -..- 204 Pesticides Monitoring Journ.al TABLE 24B — Crude Soybeans — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 LINDANE No. Samples 98 17 2 1 118 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 97.96 1.02 1.02 94.12 5.88 100.00 100.00 97.46 .85 1.69 Average PPM T T T TOXAPHENE 95.92 64.71 1.02 5.88 1.02 1.02 1.02 11.76 17.65 1.69 2.54 ENDRIN No. Samples 98 17 2 1 118 „ None found 93.88 70.59 100.00 100.00 90.68 Trace-0.03 2.04 5.88 2.54 0.04-0.10 0.11-0.50 4.08 5.88 4.24 0.51-1.00 17.65 2.54 1.01-1.50 1.51-2.00 Above 2.00 Average PPM .01 .12 .03 ...._ BHC -'5, No. 2, September 1971 205 TABLE 24CSoybean Meal [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1968 No. Samples 143 58 32 15 248 - None found 93.01 89.66 87.50 100.00 91.94 Tr;ice-0.03 5.59 8.62 12.50 6.85 0.(14-0.10 1.72 .40 0.11-0.50 1.40 _ .81 _ 0.51-1.00 _ _ 1.01-1.50 1.51-2.00 Above 2.00 --- Average PPM T T T T No. Samples 143 58 32 15 248 None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 98.60 96.55 96.88 100.00 97.98 .70 3.45 3.12 1.61 .70 .40 — - Average PPM T T T T No. Samples None found Tr,ice-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 94.83 5.17 DIELDRIN No. Samples 143 58 32 15 248 None found 98.60 93.10 93.75 93.33 96.37 Tracc-0.n3 1.40 6.90 6.25 6.67 3.63 0.04-0.10 0.11-0.50 0.51-1.00 _ 1.01-1.50 _ 1.51-2.00 _ Above 2.00 Average PPM T T T T T 206 Pesticides Monitoring Journal TABLE 24C—Soybcan A/f a/— Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Imported 1968 LINDANE No. Samples 143 58 32 15 248 None found 95.10 98.28 93.75 100.00 95.97 Trace-0.03 4.90 6.25 3.63 0.04-0.10 1.72 .40 O.I 1-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ■•-- --- Average PPM T T T T „..„.. ENDRIN BHC CHLORDANE Vol. 5, No. 2, September 1971 207 TABLE 24D — Refined Soybean Oil [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 No. Samples 23 10 1 - 34 -■-- None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 86.96 90.00 100.00 88.24 13.04 10.00 - 11.76 - Average PPM T T T - No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 90.00 10.00 97.06 2.94 Average PPM No. Samples 23 10 1 34 --• None found 100.00 90.00 100.00 97.06 Trace-0.03 10.00 2.94 0.04-0.10 — 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 ...._.. Average PPM T T DIELDRIN No. Samples 23 10 1 34 ...._ None found 95.65 100.00 100.00 97.06 Trace-0.03 4.35 2.94 0.04-0.10 0.11-0.50 — 0.51-1.00 1.01-1.50 — - 1.51-2.00 Above 2.00 -_.... „.... -— Average PPM T T -- —- -— 208 Pesticides Monitoring Journal TABLE 24D — Refined Soybean Oil — Continued 1T=<.005 PPMl Percent Distribution of Samples Domestic 1968 Imported 1968 TOXAPHENE TABLE 25 A — Vegetable Oil Seed and Products: Corn [T=<.005 PPM) Percent Distribution of Samples Domestic 1968 Imported 1968 94.38 3.66 1.34 86.14 10.40 92.43 5.41 94.44 4.63 92.85 5.02 1.14 TDE 98.78 1.10 96.53 3.47 98.63 1.29 Vol. 5, No. 2, September 1971 209 TABLE 25A~Vegelable Oil Seed and Products: Com — Continued [T=<.005 PPM) Percent Distribution of Samples Domestic 1968 Imported 1967 1968 DDE No. Samples 819 202 185 108 1314 None found Trace-0.03 0.04-0.10 0.11-0.50 97.19 2.81 95.54 4.46 91.89 7.57 .54 93.52 6.48 95.89 4.03 .08 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM T T T T T _^__ DIELDRIN No. Samples 819 202 185 108 1314 None found Trace-0.03 0.04-0.10 0.11-0.50 95.85 4.15 73.27 23.27 2.97 88.11 11.35 .54 93.52 5.56 .93 91.10 8.22 .61 0.51-1.00 1.01-1.50 .50 .08 - 1.51-2.00 Above 2.00 .._.... Average PPM T .01 T T T LINDANE No. Samples 819 202 185 108 1314 None found 97,44 97.03 98.38 97.22 97.49 Trace-0.03 2.56 1.98 1.08 1.85 2.21 0.04-0.10 .54 .93 .15 0.11-0.50 .99 .15 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 — - Average PPM T T T T T ENDRIN 210 Pesticides Monitoring Journal TABLE 25A — Vegetable Oil Seed and Products: Corn — Continued [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1967 1968 CHLORDANE TABLE 25B— Crude Corn Oil IT=<.005 PPM] Percent Distribution of Samples Domestic 1968 1969 Total DDT 28 85.71 3.57 3.57 7.14 Imported 1967 1968 85.19 3.70 3.70 7.41 Vol. 5, No. 2, September 1971 211 No. Samples None found Trace-0.03 0.04-0.10 0.11-0.50 0.51-1.00 1.01-1.50 1.51-2.00 Above 2.00 Average PPM TABLE 25 B— Crude Corn 0;7— Continued [T=<,005 PPM] Percent Distribution of Samples Range PPM 1964-66 1967 Domestic 1968 1969 Total 1964-66 1967 Imported 1968 1969 Total DDE No. Samples 27 1 28 None found Trace-0.03 88.89 100.00 89.29 0.04-0.10 0.11-0.50 0.51-1.00 7.41 3.70 7.14 3.57 E 1.01-1.50 1.51-2.00 — — Above 2.00 II II Average PPM .02 .02 DIELDRIN No. Samples 27 1 28 None found Trace-0.03 0.04-0.10 88.89 7.41 100.00 89.29 7.14 — 0.11-0.50 0.51-1.00 3.70 3.57 1.01-1.50 1.51-2.00 Above 2,00 Average PPM .01 .01 CHLORDANE No. Samples 27 1 28 __„_.. None found Trace-0.03 93.63 100.00 96.43 ...._.. 0.04-0.10 0.11-0.50 ■ 0.51-1.00 1.01-1.50 — 1.51-2.00 Above 2.00 3.70 3.57 Average PPM .08 .08 TABLE 25 D— Refined Corn Oil [T=<.005 PPM] Percent Distribution of Samples Domestic 1968 Imported 1968 DDT 212 Pesticides Monitoring Journal RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Short-Term Effects of 2,4-D on Aquatic Organisms in the Nakwasina River Watershed, Southeastern Alaska^ Howard S. Sears" and William R. Meehan' ABSTRACT Approximalely 400 acres of cutover land on tlie Nakwasina River watershed in southeastern Alaska were treated with 2,4-D to inhibit the growth of broad-leaved plants. No im- mediate mortality to salmonid fishes or aquatic inverte- brates was attributable to the spray. Samples of water and fish had concentrations of 2,4-D well below the level gen- erally considered to be lethal to aquatic organisms. The re- sults were considered inconclusive because of the lack of information on the pretreatmenl condition of the test ani- mals. Further research is required to assess the immediate and long-term effects of these spray operations in Alaska. Introduction This paper reports methods and results of a study to monitor effects of spraying on salmonid fishes and aquatic invertebrates in the Nakwasina River watershed in southeast Alaska. The study was a cooperative pro- gram of the National Marine Fisheries Service, U.S. Department of Commerce; the Forest Service, U.S. De- partment of Agriculture: and the Alaska State Depart- ment of Fish and Game. The objective was to determine the impact of spray operations on the quality of the aquatic environment. Although some monitoring of chemical brush control operations on forest lands had been conducted in the Pacific Northwest (5), this study marked the first attempt to monitor herbicide applica- tion in southeastern Alaska. One method of accelerating initial growth of conifer trees after clearcut logging is to control development of ^ This publication reports research involving pesticides. It does not contain recommendations for their use nor does it imply that the uses discussed here have been registered. All uses of pesticides must be registered by appropriate State or Federal agencies before they can be recommended. ■ National Marine Fisheries Service Biological Laboratory. Auke Bay, Alaska 99821. 3 Institute of Northern Forestry, Pacific Northwest Forest and Range E.\periment Station, Forest Service, U.S. Department of Agriculture, June:--., Alaska 99801. fast-growing broad-leaved plants that sometimes rapidly invade cutover areas. Herbicides commonly used for such control include various formulations of 2,4-D. On June 6 and 7, 1968, the U.S. Forest Service sprayed 2,4-D over the Nakwasina River drainage on Baranof Island in southeastern Alaska to control growth of red alder (Alnus rubra) in clearcut forest lands of Sitka spruce (Picea sitchensis) and western hemlock (Tsiiga heterophylla). The objective of the spraying project was to promote growth of seedlings of spruce and hemlock by retarding growth of fast-growing broad-leaved plants. About 400 acres of cutover land were treated with butyl 2,4-dichloropheno.\yacetate at the rate of 2 lb/ acre acid equivalent. Design and supervision of the spraying operation were handled by personnel of the U.S. Forest Service. The herbicide was sprayed from a helicopter equipped with a special tank and spray bars. The susceptibility of aquatic organisms to various formu- lations of 2,4-D is extremely variable. In some instances these compounds may be hazardous to fish (2). Harris- son and Rees {3) found the safe upper limits of 2,4-D concentrations to be 1,500 parts per million (ppm) for minnows (Cyprinodontidae), 500 ppm for sunfish (Eupomotis gibbosus). and an estimated 500 ppm for catfish (Ameriurus nebidosus). To.xicity tests by Apple- gate et al. (1) indicated that concentrations of 5 ppm of a butyl ester of 2,4-D were lethal to rainbow trout (Salmo gairdnerii) and bluegills (Lepomis macrochirits) after 12-hour exposure. McKee and Wolf (4), in sum- marizing other studies, stated that concentrations of 1 and 5 ppm of 2,4-D butyl ester produced mortalities of 40 and 100%, respectively, in fingerling bluegills and that the organisms consumed by fish were also suscep- tible to 2,4-D but were more resistant to a mixture of propylene glycol and butyl esters of 2,4-D. Vol. 5, No. 2, September 1971 213 The Study Area In addition to the sprayed area of the Nakwasina River watershed, the study included an unsprayed adjacent area, Noxon Creek watershed, that was used as a con- trol. Both watersheds are on the northwestern side of Baranof Island (Fig. 1). They are rather steep sided and their boundary ridges have elevations of 2,000 to 3,000 feet. Most of the Nakwasina watershed is separated from the Noxon Creek watershed by a ridge about 2,800 feet in elevation. The valley of the main stream in each watershed is fairly level but narrow — from % to 1 mile wide. The valleys and lower elevations are covered with mature stands of Sitka spruce and western hemlock. Cutover areas, natural openings, and streambanks are often covered by dense stands of red alder. Devil's club (Oplopanax horridus), salmonberry (Rubus spectabilis), and other broad-leaved shrubs and ferns and mosses make up most of the undergrowth. The brush to be sprayed in the Nakwasina River drain- age was separated by an uncut strip of timber into two distinct parts, designated for study purposes as upper (U) and lower (L) areas. Several age classes of resident Dolly Varden (Sahelinus malma), two age classes of juvenile coho salmon {Oncorhynchus kisuich), and sub- stantial numbers of emigrant fry of pink salmon (O. gorbuscha) and chum salmon (O. keta) were in the streams during the spraying. FIGURE 1. — Sampling stations in Nakwasina River water- shed (spray area) and Noxon Creek (control), Baranof Island, southeastern Alaska. Weather records from nearby Sitka indicate that the area has an annual precipitation of about 90 to 100 inches, most of which generally occurs during fall and early winter months. Streams in the Nakwasina River drainage and the main stem of Noxom Creek were clear and quite fast flowing during the sampling period. Stream bottoms were pri- marily clean gravel or sand. Aquatic vegetation, includ- ing algae, was not common. Water chemistry at the stations of the study streams is shown in Table 1. TABLE 1. — Water chemistry at live-box stations in Noxon Creek and Nakwasina River watersheds shortly before spraying started on June 6, 1968 Dissolved Total Carbon Oxygen Hardness Acidity Dioxide Station ' (PPM) pH (PPM) (PPM) (PPM) Noxon Creek 12 6.5-7.0 17.1 0.33 5 L-0 n 7.5 51.3 0.33 0 L-1 11 7.0 51.3 = 0.33 5 L-3 8 6.0 34.2 0.67 10 L-* 11 7.0 68.4 0.33 10 L-5 9 6.0 34.2 5.0 15 L-6 11 7.0 34.2 0.33 10 L-7 13 6.5-7.0 34.2 0.33 0 L-8 12 6.5 34.2 0.33 0 L-10 11 7.0 34.2 0.33 5 1 Water chemistry determinations not made at stations L-2, L-9, and at upper river sites. ^ Free acidity was also 0.33; free acidity of all other samples was 0. Spraying Operation Spraying began late in the afternoon of June 6, 1968, in the lower area and was completed in the upper area late in the afternoon of June 7. Areas to be sprayed had previously been flagged with surface markers for easy identification. A 100-foot-wide strip was left unsprayed on each side of the main course of the Nakwasina River, but no attempt was made to prevent spray from falling directly into smaller lateral streams. The strip was in- tended to prevent drifting spray from falling into the main river; but because of wind currents during most of the spraying operation, it was not effective, and some spray fell into the river. The 2,4-D was diluted with water to give an acid equivalent of 2 lb/ acre when applied at 10 gal/ acre. A surfactant was added at ilie rate of IVi pints per 100 gal of solution. The solution was mixed at one site in the lower area and one in the upper. At each site an intake hose was run 200 feet inland from the stream to a pump where a helicopter landing area had been cleared. Water was pumped and spray mixed and loaded into tanks on the helicopter at these two loca- tions. The helicopter carried a maximum of 90 gal of spray, enough for about 2 to IVi min of spraying. To achieve a uniform spray and a full 10 gal/ acre, the helicopter flew at 35 to 40 miles per hour. 214 Pesticides Monitoring Journal Study of Fish and Insects Before spraying began, 21 stations (Fig. 1) for biological sampling were established in the Nakwasina River drain- age and 2 on Noxon Creek. At some of the stations, more than one sampling site was established, and live- boxes to hold the test organisms were installed at each site. Young coho salmon and Dolly Varden were placed in the live-boxes at every site; and at most sites imma- ture stoneflies and mayflies (Plecoptera and Ephemerop- tera) were also put in the live-boxes. Insects were first put in metal cylinders, about 4 inches long and Wi inches in diameter, with fine-meshed nylon netting over the ends. All of the test animals except test fish for the upper area were taken from the stream close to the sampling site where they were held. Because of the scarcity of fish in the upper area, the fish were captured in the lower area and flown to the upper area by helicopter. In some instances test fish may not have had time to adapt to the live-boxes or to show possible effects of handling. The insects were collected in drift nets placed in the stream. The nets were made of 0.8-mm mesh nylon netting and were 1 by 1 foot square. They were attached to metal frames held in place by metal rods driven into the streambed. The sampling stations were visited at least once and usually twice daily — in the morning and again in the late afternoon or early evening. At each visit, fish and insects in the live-boxes were checked for apparent con- dition. The nets were emptied, and the animal contents were identified and counted. Survival of Test Animals The number of fish and aquatic insects used in both spray areas on the Nakwasina River watershed and un- sprayed Noxon Creek and number surviving for the duration of each sampling period are shown in Table 2. SPRAY AREA A total of 19 live-boxes containing test fish were placed in 1 1 locations in the lower spray area. After removal of fish that died from handling or other causes, 265 juvenile coho salmon and Dolly Varden of several age classes remained. One box installed in the main river at station L-1 on June 4 was washed out 4 days later, but none of the 15 fish in this live-box died while it was in place. Only two fish in the lower area died from June 4 to 10. Three boxes, two at L-0 and one at L-1, were left in place until June 27, at which time three additional TABLE 2. — Mortality of test fish and insects during 2,4-D study in Nakwasina watershed, June 1968 Days of Insect Observation Number of Fish Fish MoRTAtrrY Number of Insects MoRTALrrY Station After Spraying i Start Finish (Percent) Start Finish (Percent) Noxon Creek 1 3 24 24 0 14 14 0 Noxon Creek 2 3 24 24 0 12 12 0 L-0 22 20 18 10 19 2 2 90 LI = 6-22 24 22 8 6 6 0 L-2 5 16 16 0 6 5 17 L-3 5 19 19 0 12 11 8 L^ 5 29 29 0 14 10 16 1^5 4 24 24 0 12 9 25 L< 5 16 16 0 0 — — L-7 4 32 32 0 16 16 0 L-8 5 32 32 0 16 16 0 L-9 4 16 15 6 6 6 0 L-10 4 22 22 0 6 6 0 U-I 4 13 13 0 0 — — U-2 4 13 13 0 13 7 46 U-3 4 12 12 0 10 8 20 U^ 4 13 13 0 0 — — U-5 4 12 12 0 12 9 25 U-6 4 12 7 42 14 13 7 U-7 4 14 14 0 12 7 42 U-8 4 16 16 0 10 7 30 U-9 4 12 12 0 15 13 13 U-10 4 10 8 20 0 — — Totals Control — 48 48 0 26 26 0 Lower section — 250 245 2 113 87 23 Llpper section - 127 120 6 86 64 26 ^ Spraying began June 6 in lower area and was completed in the upper area in the late afternoon of June 7. ' Some loss from natural emergence and predation. 'One box washed out 6 days after installation; these 15 fish not included in mortality determinations. Vol. 5, No. 2, September 1971 215 fish were dead, bringing total death of test fish to five for the lower area. In experiments with insects in the lower area, 119 im- mature Plecoptera and Ephemeroptera were distributed among 18 of the metal cylinders submerged in the live- boxes. Six insects were lost when a box washed out and are not included as mortalities in Table 2. In addition, some immature forms were lost because of emergence, and some were lost through predation. Eighty-seven of the 1 1 3 survived and were released when the experiment ended (Table 2). In the upper area, 7 containers with 86 inimature Plecop- tera and Ephemeroptera were placed in live-boxes. Some mortality resulted from emergence and predation; how- ever, at the end of the observation period 64 insects had survived and were released. In the upper area, 10 live-boxes containing 127 juvenile coho salmon and Dolly Varden were placed in the streams. These boxes remained in place from June 6 to 9. No time was available to allow the test fish to adjust to confinement in the boxes or to recover from effects of handling or transport. During 3 days of observation 10 fish died; of these, one had been injured previously, and two were killed by rough handling. Most of the live-box sites in the upper area were observed to have been hit by drifting spray. CONTROL AREA Forty-eight young salmonids, mostly coho salmon fry, were placed in four live-boxes in Noxon Creek to serve as control animals. The fish were held in boxes for 3 days after the spraying. None died during that period. No mortalities occurred among the insects held in Noxon Creek as controls. Twenty-six immature Plecop- tera and Ephemeroptera were used in the experiment. Concentrations of 2,4-D in Water and Fish Four samples of water and one sample of test fish, consisting of six coho salmon fry, were taken from the live-boxes 3 days after spraying was completed. Water samples were collected in 500-cc glass jars (thoroughly cleansed to remove possible contamination), transferred later to plastic bottles, and frozen. The sample of fish was frozen in a plastic bag. All samples were shipped by air to the Wisconsin Alumni Research Foundation for analysis of 2,4-D content. Gas chromatography was used for the determination of 2,4-D residues (Dow Chemical Company, Midland, Mich. 1968. Residue determination method, ACR. 12. Unpublished). Preliminary extrac- tions are modifications by the Wisconsin Alumni Re- search Foundation. The detection limits of this method are 0.0005 ppm for water and 0.05 ppm for fish tissue. The analytical results are not corrected for recovery, but rather are shown as instrument values. At the time of analysis, recovery rates ranged from 85 to 102% (Francis B. Coon, Wisconsin Alumni Research Founda- tion, Madison, Wis. 1970. Personal communication). Results were as follows: Type of SAMPLE Station L-0 L-0 L-2 Toad pond L-2 Date June 7 June 8 June 9 June 8 June 10 2,4-D con- tent (PPM) Water Water Water Water Fish <0.0005 <.0005 .2 .0002 .5 Evaluation of Effects of Spraying on Fish and Insects Emigrating pink and chum salmon were caught in nets at some stations in the Nakwasina River. Some of these fish were dead when collected possibly as a result of having been in the cod end of the net for as long as 18 or 20 hours. Moreover, water velocities at some stations were quite fast and could have accounted for some mortality. Catches of insects in drift nets varied between upper and lower areas. Only a few adult Diptera were captured at stations U-2 and U-3. In the lower area at stations L-1 (four nets in the main river). L-7 (two nets), and L-8 (two nets), the numbers of organisms in drift nets were considerably greater than at other stations; catches ranged from no insects to 1,546 in less than 24 hours. With the exception of some adult and terrestrial forms, all insects taken in drift nets were alive and active. Although there was no apparent damage to aquatic organisms which could be attributed to spray, the study results were inconclusive because only limited data could be obtained. Sufficient time was not available to obtain adequate pretreatment information, and test animals were not conditioned long enough before the spraying to eliminate effects of handling. Possible long- term effects of spray were not assessed, and only a few samples of water and animals were analyzed for 2,4-D content. The Oregon Fish Commission monitored a similar spraying operation in Oregon and stated that no harmful effects were observed on resident salmonid fishes or aquatic insects. (Louis C. Fredd and Thomas E. Kruze. 1963. Chemical treatment of alder stands in Wilson River watershed, April 1963. Res. Div., Oreg. Fish. Comm.. 9 pp. Unpublished.) As in our study, the Oregon observations were confined to immediate effects, and any long-term effects were not evaluated. Summary and Conclusions Treatment of the Nakwasina River watershed with 2,4-D caused no significant immediate mortality to aquatic organisms. Some mortality occurred in test fish and insects, but sufficient time was not allowed before spray- 216 Pesticides Monitoring Journal ing for effects of handling and confinement of test ani- mals to be fully determined. Some mortalities in fish undoubtedly resulted from rough handling, and some in insects resulted from emergence and predation. The spray drifted outside marked boundaries of spray areas in many cases; the extent of this drift was quite variable because of wind velocity and direction and altitude of the helicopter at spray release. In some cases, spray fell directly onto tributary streams. At least one small stream which received direct spray held fish and insects in containers for observation. There was no apparent diflference in survival or behavior between these animals and others held throughout the treatment area. Analysis of four water samples and one sample of fish tissue for 2,4-D content showed concentration levels well below those generally considered to be lethal to fish. In general, our study emphasized need for further, more detailed research on effects of pesticides on aquatic populations in southeastern Alaska. LITERATURE CITED (/) Applegate, Vernon C, John H. Howell, and A. E. Hall, Jr. 1957. Toxicity of 4,346 chemicals to larval lampreys and fishes. U.S. Fish Wildl. Serv., Spec. Sci. Rep. Fish. 207, 157 p. (2) DeVaney, Thomas E. 1968. Chemical vegetation control manual for fish and wildlife management programs. U.S. Bur. Sport Fish. Wildl. Resour. Publ. 48, 42 p. (3) Harrisson, Jos. W. E., and Edward W. Rees. 1946. 2,4-D toxicity-I, toxicity towards certain species of fish. Amer. J. Pharm. 118:422-425. (4) McKee, Jack Edward, and Harold W. Wolf. 1963. Water quality criteria: Resour. Agric. Calif., State Water Qual. Control Board, Publ. 3-A, 2nd ed., 548 p. (5) Norris, L. A. 1967. Chemical brush control and herbicide residues in the forest environment. In Symposium Pro- ceedings: Herbicides and vegetation management in forest, ranges, and noncrop lands, 1967, p. 103-123, Oreg. State Univ., School For. Corvallis, Oreg. Vol. 5, No. 2, September 1971 PESTICIDES IN SOIL Effects of a Cover Crop Versus Soil Cultivation on the Fate and Vertical Distribution of Insecticide Residues in Soil 7 to 11 years After Soil Treatment^'^ E. P. Lichtenstein, K. R. Schulz, and T. W. Fuhremann ABSTRACT The effects of a dense cover crop (alfalfa) and of repeated soil cultivations on the fate and vertical distribution of aldrin and heptachlor residues in soils were investigated. Eleven years after the application of the insecticides to the upper 4- to 5-inch soil layer, large differences in the amounts of aldrin, heptachlor, and their metabolites or formulation im- purities were noticed between cultivated and alfalfa-covered soils. Soil cultivation — in comparison to noncultivation — resulted in a 76 to 82% reduction of residues derived from the originally applied insecticides. Of the totally recovered aldrin-dieldrin residues from alfalfa-covered soils, 52% were located in the upper 2 inches of soil, and 32% in the 2- to 4-inch soil layer. In heptachlor-treated soils, however, 26% of the totally recovered residues were in the upper 2-inch soil layer, while 52% were located in the 2- to 4-inch soil layer. In addition, 5 to 6.5% of the totally recovered residues from aldrin- and heptachlor-treated soils, respectively, were located in the 6- to 9-inch soil layer, primarily in the forms of dieldrin or heptachlor epoxide. Introduction The persistence and fate of insecticides in soil have been the subject of many investigations. Some of the reported results are based on laboratory experiments and others on tests that were conducted under actual field condi- tions. In the latter case, mixed residues of various pesticides are often encountered, since in actual agri- cultural practices various insecticides and herbicides have been used over a period of years. In other cases, specially designed experiments were conducted under controlled field conditions. Results of one of these resi- due studies were recently published (/) describing the fate and "half-lives" of DDT, lindane, and aldrin after Department of Entomology, University of Wisconsin, Madison, Wis. 53706. ' Contribution from the Wisconsin Agricultural Experiment Station as a collaborator under North Central Cooperative Research Project 96, "Environmental Implications of Pesticide Usage." a single application to soils in 1954. Use of the term "half-life," however, has its limitations. Originally used to measure the rate of radioactive decay, the term "half-life" can be misleading when applied generally to pesticides in the environment. Since the persistence and fate of all these compounds is dependent on a variety of environmental factors (2), the half-life of any of these chemicals is a function of their chemical nature and the environmental conditions to which they are exposed. It is for these reasons that this term should only be used if strictly qualified with a specific description of the environmental conditions. After the application of insecticidal chemicals to soil, it is important to obtain information relative to their location within the soil, esf>ecially if the chemicals persist over a relatively long period of time. Questions pertaining to the potential movement of these chemicals in soils with water and their translocation into crops have frequently been raised. Studies conducted so far have shown that insecticides of an extremely low water solubility, such as the chlorinated hydrocarbon com- pounds, do not move with water to an appreciable ex- tent in soils (5). It has also been demonstrated that 1 to 3 years after insecticidal soil applications, aldrin and heptachlor residues were located primarily in the upper 2-inch soil layer (4). In another study, it was found that 10 years after soil application, 82% of the totally re- covered aldrin-dieldrin residues and 68 to 75% of all DDT residues were located in the upper 6-inch soil layer, while 18% and 25 to 32%, respectively, were in the 6- to 9-inch deep soil layer (7). In this study the eff'ects of a dense cover crop and re- peated soil cultivation on the fate and vertical distribu- tion of aldrin and heptachlor residues in soils were investigated. Since not many long term experiments of 218 Pesticides Monitoring Journal this kind have been conducted, it was felt desirable to reinvestigate some of the field plots that had been treated once with an insecticide in 1958 (5) or 1960 (4), or repeatedly with the same chemical during the 5-year period of 1958-62 (6). Procedures SOIL TREATMENT In May 1958, duplicate 30- by 16-foot Piano silt loam (formerly Carrington silt loam) plots near Madison, Wis., were treated with emulsions of aldrin and hep- tachlor at 5 or 25 lb/ acre (5). The commercial hep- tachlor formulation contained an impurity of 0.3 lb of gamma-chlordane per pound of heptachlor. Two similar- sized field plots were treated in 1960 with aldrin or heptachlor at 1 lb/ acre. After the insecticidal applica- tions, all soils were rototilled to a depth of 4 to 5 inches and seeded to alfalfa. This resulted in a dense cover crop in the following decade during which time the plots were left undisturbed, except for regular alfalfa harvesting. To investigate the effects of soil cultivation, two addi- tional plots (30 X 24 feet) were treated in 1958 with aldrin or heptachlor at 5 or 25 lb/ acre as described (5). Soils that were treated at 5 lb/ acre were again treated each May from 1959 through 1962. At the end of the 5 years, all plots had been treated with either one or five yearly applications with a total of 25 lb of in- secticide per 4- to 5-inch acre (5x5 or 25 lb). Various crops were grown each year on these plots (6), and regular soil cultivation practices were performed during the 12 growing seasons from 1958 through 1969. The abnormally high treatment rates of 5 and 25 lb/ acre were chosen, because at the time of the first insecticidal application (1958) less sensitive colorimetric methods had to be used for analyses. It was also felt that for the reliable detection of potential metabolites, higher in- secticidal application rates would be desirable. SOIL SAMPLING Residues in the upper 6-inch soil layer Cultivated soils, treated at 5 and 25 lb/ acre, were sampled in 1969 to a depth of 6 inches as described (5). Alfalfa-covered soils, treated in 1960 at 1 lb/ acre, were also sampled to a depth of 6 inches in 1970. Vertical distribution of insecticide residues in soil To determine the vertical distribution of the insecticidal residues, alfalfa-covered soils, treated at 5 and 25 lb/ acre in 1958 as described, were sampled 11 years later '^1969) to a depth of 9 inches. Thirty cores, % inch in diameter were collected from each plot, and each core was divided into three 2-inch layers (0-2 inch, 2-4 inch, and 4-6 inch) and one 3-inch layer (6-9 inch). The comparable soil layers of each plot were combined and frozen until analyzed. ANALYTICAL PROCEDURES All soil samples were extracted with acetonitrile, parti- tioned into hexane, and analyzed by electron capture gas- liquid chromatography as described (6). Results were ex- pressed in parts per million, based on the oven-dry weight of the soil under investigation. From these data, recoveries in pound-per-acre were calculated, after the dry weight of 1 acre of a Piano silt loam, 6 inches deep, had been determined as 1.630.000 lb. In addition, con- firmatory tests were conducted by employing thin layer chromatography (6). Extracts were also examined for the presence of any metabolites that might have been produced in addition to dieldrin or heptachlor epoxide. Tests were also conducted to ascertain the presence of impurities in the original insecticide formulation that could have remained in the soil after application. Soil extracts from aldrin-treated soils were compared with analytical grade aldrin, dieldrin, the photo isomer of aldrin (1, 1,2,3, 3a,7a-hexachloro-2, 3,3a, 3b,4,6a,7,7a- octahydro-2,4,7-methano-l//-cyclopenta(a)-pentalene), the photo isomer of dieldrin (1, 1,2,3, 3a,7a-hexachloro- 5,6- epoxydecahydro- 2, 4, 7 - metheno- \H - cyclopenta(a) - pentalene), "aldrin-OH" (6.7-r/-arz5-dihydroxy-dihydro- aldrin or trans-a\dnn diol), a metabolite obtained by Korte and Arent (7) from rabbit urine after oral admin- istration of dieldrin, and dicarboxyl aldrin (1,2,3,4.10, 10-hexachloro-6.7-dicarboxyl-l,4-enrf<7-5.8-ejro-dime- thano-1 ,4,4a, 5, 6.7,8. 8a-octahydronaphthalene). These chemicals were obtained through the courtesy of the Shell Chemical Company. Soil extracts from heptachlor-treated soils were com- pared with analytical grade heptachlor, heptachlor epoxide, chlordene (4,5,6,7.8,8-hexachloro-3a,4,7,7a- tetrahydro-4,7-en(/o-methanoindene), alpha and gamma- chlordane (1,2, 3,4,5, 6,7,8, 8-octachloro-2,3, 3a,4,7,7a- hexahydro-4,7-e«rfo-methanoindene), nonachlor (delta- trichloro-chlordene) (1,2,3,4,5,6,7, 8, 8-nonachloro-2, 3,3a, 4,7,7a-hexahydro-4,7-e/irfo-methanoindene), and "1-OH chlordene" (l-hydroxy-4, 5, 6,7,8, 8-hexachloro-3a,4, 7,7a- tetrahydro-4,7-e«rfo-methanoindene). All these com- pounds were obtained through the courtesy of the Vel- sicol Chemical Corporation. Results and Discussion THE EFFECTS OF A COVER CROP VERSUS SOIL CULTIVATION ON THE PERSISTENCE OF INSECTICIDE RESIDUES IN SOIL Large differences in the amounts of aldrin, heptachlor, and their metabolites or formulation impurities re- covered from cultivated and alfalfa-covered soils were noticed 1 1 years after the insecticidal soil treatment (Table 1). Only 3.0 and 3.8% of the aldrin applied at Vol. 5, No. 2, September 1971 219 25 and 5x5 lb/ acre were recovered from cultivated soils. However, 18.2% or five to six times more was still in the soil that had remained undisturbed. Similar results were obtained with soils that had been treated with heptachlor at 25 lb/ acre. Gamma-chlordane, an im- purity in the commercial heptachlor formulation, had been applied at 7.5 lb/acre (Table 1). When expressed in percent of this applied dosage, it was evident that this compound was more persistent than heptachlor plus heptachlor epoxide. Also, its persistence was not as af- fected by soil cultivation as that of heptachlor and hep- tachlor epoxide, since only 1.4 times more gamma- chlordane (17% of applied) was recovered from the alfalfa-covered soil (treated at 25 lb/ acre) than from the cultivated soils (treated at 25 and 5x5 lb/ acre). This smaller difference might be related to the lower vapor pressure of chlordane (2x10'= at 25 °C, Velsicol Corp.. private communication) as opposed to that of heptachlor (4x10* at 25°C, Velsicol Corp., private communication). Based on data in Table 1. soil cultivation — in compari- son to noncultivation of the alfalfa-covered plots — caused an average (25 and 5x5 lb) reduction of 81.5 and 76% of the residues that were derived from aldrin or heptachlor, respectively. Applying these figures to the soil treated with aldrin at 1 and 5 lb/ acre (Table 1), it would appear that with cultivation, residues of aldrin in soils would amount to 0.02 lb/ acre (2% of applied) and 0.16 lb/acre (3.3% of applied), respectively, after 10 years. In heptachlor-treated soils (Table 1) the residues of heptachlor plus heptachlor epoxide would amount to 0.026 lb/acre (2.6% of applied) and 0.182 lb/acre (3.6% of applied). The average reduction in the decline of gamma-chlor- dane residues due to soil cultivation was only 29.5%. Based on this figure, the content of gamma-chlordane in soils (Table 1) would after 10 to 11 years amount to 0.013 lb/ acre (4.3% of the 0.3 lb applied) and 0.127 lb/acre (8.5% of the 1.5 lb applied). In aldrin-treated soils the major metabolite was dieldrin which constituted over 90% of the total residue re- covered. The amount of photo-dieldrin ranged from 1.2 to 3.2% of the recovered dieldrin. No photo-aldrin could be detected. Heptachlor epoxide was the major metabolite in the heptachlor-treated soils and represented 94 to 100% of the total of these two insecticides re- covered. In addition, alpha-chlordane and nonachlor were found in these soils, and their persistence was also affected by soil cultivation. The presence of chlordene or "1-OH chlordene" could not be verified. When the recovery of insecticide residues is discussed in percent of the originally applied dosage one wonders, of course, what has happened to the amounts that were not recovered and have "disappeared." As far as residues derived from aldrin and heptachlor are concerned, vari- ous factors contribute to their dissipation from soils. TABLE 1. — Residues of aldrin and lieptacl^lor and tlieir metabolites in alfalfa-covered and cultivated soils 7 to 11 years after soil treatnient [T = TRACE; ND = NOT DETECTABLE] Lb/Acre Applied to Upper 5-Inch Soil Layer (1958) Alfalfa-Covered Soil = 5x51 (1958-1962) Cultivated Soil ^ Lb/Acre Recovered From Upper 6-Inch Soil Layer < ALDRIN-TREATED HEPTACHLOR-TREATED ■ Heptachlor Heptachlor epoxide Total Percent of applied Gamma-chlordane Percent of applied Alpha-chlordane Nonachlor .107 (10.7) .013 .745 .758 (15.2) .125 2.175 2.300 (9.2) .019 (6.3) .180 (12.0) 1.277 (17.0) T ND .046 .035 .387 .212 .459 (1.8) .064 .621 .685 (2.7) .837 (11.2) .946 (12.6) .094 .046 .114 .054 1 Total of 25 lb/acre in 5 yearly dosages of 5 lb each. 2 After the insecticide application, soils were seeded in alfalfa and allowed to remain covered. ' Soils were cultivated regulr.rly during each summer season. • Results for the soils treated at 5 and 25 lb/acre are averages of duplicated field plots. = A11 residue determinations were made on samples collected in 1969 except for analyses of alfalfa-covered soils treated at 1 lb/acre; these collected in 1970. » Heptachlor formulation contained 0.3 lb of gamma-chlordane per 1 lb of heptachlor. 220 Pesticides Monitoring Journal FIGURE 1. — Vertical distribution in 1969 of residues in 4 layers of a 9-inch deep loam soil which was treated 11 years previously to a depth of 4 to 5 inches with aldrin or hep- tachlor plus gamma-chlordane . Results are averages from plots treated with insecticide formulations at 5 or 25 lbs/acre. One of these is the metabolic breakdown into more polar substances which, with the exception of dieldrin and heptachlor epoxide, are more difficult to detect by the available analytical methods, and are also less toxic to insects or nontoxic (6). The other major factor is prob- ably volatilization into the atmosphere (8,9). VERTICAL DISTRIBUTION OF INSECTICIDAL RESIDUES IN ALFALFA-COVERED SOILS The total of aldrin-dieldrin residues recovered in 1969 from the upper 9-inch layer of alfalfa-covered soils amounted to 19% of the aldrin dosages applied in 1958 (Table 2). In these soils, 52% (average of results from plots treated at 5 and 25 lb/ acre) of the totally re- covered residue were located in the upper 2 inches of soil, 32% in the 2- to 4-inch soil layer, and 1 1 % in the 4- to 6-inch layer. Heptachlor plus gamma-chlordane had been applied in 1958 at 6.5 lb/ acre (5 lb of heptachlor and 1.5 lb of gamma-chlordane — Table 3) and 32.5 lb/ acre (25 lb of heptachlor plus 7.5 lb of gamma-chlordane — Table 3). Of these amounts, 16.4 and 14.1% were recovered after 1 1 years from the total 9-inch deep soil layer. Contrary to the aldrin-treated soils, an average of only 25.5% of the totally recovered residues were in the upper 2-inch soil layer, while 52% were located in the 2- to 4-inch soil layer (Fig. 1). T.'KBLE 2. — Vertical distribution of residues of aldrin and its metabolites in alfalfa-covered soils 11 years after insecticidal soil treatment [ND = NOT DETECTABLE; T = TRACE] RESIDUES DERIVED FROM 60 - ■ ALDRIN ^i n HEPTACHLOR + Jf-CL -.^ Z^ 50 COO lijcr Di^ .^ 9q40 (OUJ iuq: tElLl ^^^ 1 O^ 2.0 I RIBUTI TOTAL O 1 ■ 1- 1 1 (nu. ^^1 ^^1 mm qO ■ ■ ■ 0-2" Z-4" 4-6" 6-9" SOIL LAYERS Aldrin Dieldrin Photo-Dieldrin Total „ „ ^ z Z z z Soil I.AYERS «" o ^s o ^g o h5 «S hB z 2 £S z 2 z 2 z 2 < o U H < 0 s e < 0 3 H u g Z iS Sq U K £q .4 1^ S.a 3S £q SOIL TREATMENT AT 5 LB/ACRE 0- to 2-inch .008 80 .447 49 .013 62 .468 50 2- to 4-inch .001 10 .285 31 .006 28 .292 31 4- to 6-inch .001 10 .118 13 .002 10 .121 13 6- to 9-inch T 0 .064 7 ND 0 .064 6 Total (0- to 9-inch) .010 — .914 — .021 — .945 — Percent of Applied Aldrin = (0.2) (18.3) (0.4) 3 (18.9) SOIL TREATMENT AT 25 LB/ACRE 0- to 2-inch 2- to 4-inch 4- to 6-inch 6- to 9-inch .030 .006 .001 .001 80 16 2 2 2.500 1.540 .423 .200 54 33 9 4 .043 .011 .003 .004 70 18 5 7 2.573 1.557 .427 .205 54 33 9 4 Total (0- to 9-inch) .038 — 4.663 — .061 — 4.762 — Percent of Applied Aldrin = (0.2) (18.7) (0.2) »(19.1) ^ Distribution of a particuLr chemical in a specific soil layer in percent of the residue found in the totrl 0- to 9-inch soil layer. - Total of aldrin. dieldrin, or photo-dieldrin recovered from the 0- to 9-inch soil l.iyer in percent of applied aldrin. ' Sum of all compounds in the total 0- to 9-inch soil layer in percent of appUed aldrin. Vol. 5, No. 2, September 1971 221 Although the insecticides had been worked into the soil to a depth of 4 to 5 inches, an average of 5 and 6.5% of the totally recovered residues from aldrin- and hepta- chlor-treated soils, respectively, were located in the 6- to 9-inch soil layer, primarily in the form of dieldrin or heptachlor epoxide. During the 11 -year period, the insecticides moved somewhat in the soil, and differences observed between total aldrin and heptachlor residues were probably the result of different physical character- istics of the various chemicals, such as vapor pressures, water solubilities, etc. The amounts of each chemical and the total found in each of the four soil layers are also shown in Tables 2 and 3. Acknowledgment The authors would like to thank T. T. Liang for his See Appendix for chemical names of compounds discussed in this paper. Research supported by the College of Agricultural and Life Sciences, University of Wisconsin, Madison, Wis., and by P.H S Erant FD- 00258. LITERATURE CITED (/) Lichlenslein, E. P., T. W. Fuhremann, and K. R. Schulz. 1971. Persistence and vertical distribution of DDT, lin- dane and aldrin residues, 10 and 15 years after a single soil application. J. Agric. Food Chem. 19(4) :7I8-721. (2) Lichtenstein, E. P. 1969. Fate and movement of insec- ticides in and from soils. Mich. State Univ. Symp. on Pestic. in Soils, p. 101-106. (3) Lichlenslein, E. P.. T. W. Fuhremann, K. R. Schulz, and R. F. Skreniny. 1967. Effect of detergents and inorganic salts in water on the persistence and movement of in- secticides in soils. J. Econ. Entomol. 60(6): 1714-21. {4) Lichtenstein, E. P., C. H. Mueller, G. R. Myrdal, and K. R. Schulz. 1962. Vertical distribution and persistence of insecticidal residues in soils as influenced by mode of application and a cover crop. J. Econ. Entomol. 55(2):2I5-19. (J) Lichtenstein, E. P. 1960. Insecticidal residues in various crops grown in soils treated with abnormal rates of aldrin and heptachlor. J. Agric. Food Chem. 8(6):448-51. (6) Lichlenslein, E. P., K. R. Schulz, T. W. Fuhremann, and T. T. Liang. 1970. Degradation of insecticides in field soils during a ten-year period. Translocation into crops. J. Agric. Food Chem. 18(/) : 100-106. (7) Korle, F., and H. A rent. 1965. Isolation and identifica- tion of dieldrin metabolites from urine of rabbits after oral administration of dieldrin-"C. Life Sci. 4:2017-26. (5) Harris, C. R., and E. P. Lichlenslein. 1961. Factors af- fecting volatilization of insecticidal residues from soils. J. Econ. Entomol. 54(5):I038-45. (9) Lichtenstein, E. P., and K. R. Schulz. 1970. Volatilization of insecticides from various substrates. J. Agric. Food Chem. 18(5):814-18. TABLE 3. —Vertical distribution of heptachlor residues, its metabolites and formulation impurities in alfalfa-covered soils 11 years after soil treatment with heptachlor Hepi ACHLOR Heptachlor Epoxide Gamma- Chlordane Alpha- Chlordane NONACHLOR Total Soil Layers < o 1 z £ 8S <5 z o ll < o z 0 -I z 2 < = z o H Is z o z 5 < o z o H 5S £a 5S £q 2S £5 5S 0. Q 2x aQ 2S S.0 SOIL TREATMENT AT 5 LB/ACR E2 0- to 2-inch .004 31 .312 41 .047 25 .013 27 .007 18 .383 36 2- to 4-inch .007 49 .304 39 .107 57 .026 53 .020 54 .464 44 4- to 6-inch .002 15 .129 17 .027 14 .008 15 .008 20 .174 16 6- to 9-inch .001 5 .026 3 .008 4 .002 5 .003 8 .040 4 Total (0- to 9-inch) .014 - .771 — .189 _ .049 _ .038 _ 1.061 Percent of Applied s (0.28) (15.41) (12.54) - - - * (16.40) SOIL TREATMENT AT 25 LB/ACR £2 0- to 2-inch .011 9 .230 10 .174 13 .199 50 .095 44 .709 15 2- to 4-inch .097 73 1.375 54 .986 73 .167 42 .105 48 2.730 60 4- to 6-inch .017 13 .570 24 .117 9 .021 5 .012 5 .737 16 6- to 9-inch .007 5 .295 12 .076 5 .014 3 .007 3 .399 9 Total (0-to 9-inch) .132 - 2.470 - 1.353 - .401 — .219 — 4.575 _ Percent of Applied ' (0.55) (9.85) (18.10) - - * (14.10) • TT,. 1, . u, 7 r — ----.- ... „ op,.^...^ auii i„yct III pcicciii oi uic rcsiuue louna m tne u- to 9-inch soil layer. - rhe heptachlor formul.-.tion contained 0.3 lb of gamma-chlordane per 1 lb of heptachlor. MoT^L^7n''^elcL^',.T^Ty^7 epoxide recovered from the 0- to 9- inch soil layer in percent of applied heptachlor or total of gamma- cniordjne m percent of applied gamma-chlordrne. ' Sum of all compounds in the total 0- to 9-inch soil layer in percent of applied heptachlor plus gamma-chlordane. Pesticides Monitoring Journal National Soils Monitoring Program — Six States, 1967 G. B. Wiersma', P. F. Sand", and R. L. Schutzmann' ABSTRACT Six States were sampled in 1967 as a preliminary study of the National Soils Monitoring Program. The most com- monly occurring pesticides were members of the DDT group, followed in turn by dietdrin and chlordane. Elemental arsenic was found on almost all of the sample sites. DDT, TDE, and combined members of the DDT group (DDTR) were distributed equally over both cropland and noncrop- land sites, but DDE was more widely distributed on crop- land areas. No difference could be detected between the proportion of sites with DDT, TDE, and combined mem- bers of the DDT group (DDTR) on cropland from those on noncropland. But there was a significant difference between the proportions of sites with DDE on cropland and non- cropland sites. Introduction The National Soils Monitoring Program was initiated in response to the 1963 report of the President's Science Advisory Committee. Large-scale study areas were selected in Mississippi, North Dakota, Arizona, and Alabama, and investigation of these areas was made in 1964. In 1966, it was decided that sampling sites should be chosen randomly over the conterminous United States. The allocation for Maryland was made first, and a pilot run was conducted in the same year. When it became impossible to carry out the complete project as designed, the samples from certain States were taken. This paper is based on the information from samples taken in Georgia, Idaho, Maine. Nebraska, Virginia, and Washington. A description of the National Soils Monitoring Program is published in a previous issue of this Journal (7). ^ Environmental Quality Branch. Pesticides Regulation Division, Pesti- cides Programs, Environmental Protection Agency, Washington, D.C. - Plant Protection Division, Agricultural Research Service, U.S. De- partment of Agriculture, Hyattsville, Md. 20782. 2 Plant Protection Division. Agricultural Research Service, U.S. De- partment of Agriculture. Gulfport, Miss. Sampling Methods As previously described (/) sample sites were selected from the probability sample made some years earlier for the Soil Conservation Service and used for their Conservation Needs Inventory (CNI)*. Information from the CNI was used to establish two categories — cropland and noncropland. Cropland included land in corn, wheat and other grain, soybeans, hay, vegetables, orchards, sugar beets and sugarcane, tobacco, cotton, and other crops. Noncropland included woodlands, pas- tures, grazing land, and generally all lands not classified as cropland. All land not sampled for the CNI was classified as noncropland. This included urban land. Bureau of Land Management lands, national forests, and park lands. Cropland was sampled at 0.025% or one 10-acre block for every 40,000 acres of cropland. On a nationwide basis, this provided 9,468 sample sites from cropland. Noncropland was sampled at a rate of 0.0025% or one- tenth of that for cropland. This provided 3,832 sample sites from noncropland. The number of sites sampled and analyzed for each State in this study is given below: State Cropland Noncropland Georgia 30 19 Idaho 33 29 Maine 8 12 Nebraska 107 20 Virginia 19 14 Washington 45 23 242 117 The sample allocation procedure was worked out by Dr. E. L. Cox of the Biometrical Services Staff of the Agricultural Research Serv- ice, USDA. Vol. 5, No. 2, September 1971 223 A sample consisted of 50 soil cores, 2 inches in diam- eter and 3 inches deep taken in a grid pattern from each 10-acre site. These cores were composited, air-dried to a friable state, screened to remove rocks and large gravel, and thoroughly mixed. A 2-quart sample was then sent to the analytical laboratory (2). A nalytical Procedures A subsample of 300 g wet weight of soil was placed in a 2-quart 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. The isopropanol was removed by two washings with distilled water. The hexane was then filtered through a funnel containing glass wool and anhydrous sodium sulfate. No further cleanup was normally required before analysis (i). Analyses for chlorinated pesticides were performed on standard gas chromatographs equipped with tritium foil electron affinity detectors. A dual-column system em- ploying polar and nonpolar columns was utilized to identify and confirm pesticides. Columns and param- eters were as follows: Columns: glass, 6 mm o.d. x 4 mm i.d., 183 cm long, packed with one of the following: 3% DC-200 on 100/120 mesh Gas Chrom Q 9% QF-I on 100/120 mesh Gas Chrom Q 5% XE-60 on 100/120 mesh Chromosorb W 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 DC-200 180°C XE-60 180°C Low level sulfur interference was eliminated by using the XE-60 column. Further confirmation of problem residues was made by thin layer chromatography, p- values or chemical derivatization. The lower limit of detection is 0.01 ppm. The data are corrected for re- covery. The recovery rate for all pesticides was lOO'^r plus or minus 10%, Arsenic analysis was done by atomic absorption follow- ing HCl extraction, reduction to the plus three valence form, partitioning into benzene and back partitioning into water. Results and Discussion Pesticide residue data vary over a wide range. For example, within Nebraska, estimates of detectable resi- dues obtained from our sampling and assaying proce- 224 dures ranged from as low as 0.01 ppm to as high as 89 ppm. These high values are the principal contributors to the mean when the majority of the data are less than 1 ppm. The data presented in the following tables are estimates of the arithmetic means; they are not geometric means. Table 1 shows the mean pesticide residues and percent of sites with residues for cropland in all six States. With the exception of arsenic, all are chlorinated hydrocar- bons. DDT and its residues were found in all six States. Dieldrin residues were found in five States, chlordane in four States, and toxaphene in only two States. In addition to the pesticides shown, small amounts of aldrin were detected in Nebraska, Virginia, and Washington. These aldrin residues averaged .02 ppm or less for each State. Also, trace amounts of atrazine and heptachlor were found in Nebraska. Table 2 shows the mean pesticide residues and percent of sites with residues for noncropland in all six States. All are DDT or DDT isomers with the exception of arsenic. In each State there were soil samples which had a detectable level of DDT or its isomers. In Ne- braska only one noncropland site had a detectable DDT residue, but this residue was rather high. In addition to the pesticides shown, small amounts of dieldrin were detected in Idaho and Virginia. Because detectable levels of arsenic were found at almost every site in all six states, the arithmetic mean of arsenic is a mean estimate of the actual population mean. The pooled mean for arsenic could be an estimate of the baseline level except that the six States involved in this study are not all ecologically similar. In certain types of research, it is valuable to know the amounts of each of the members of the DDT group. These data have been summarized for the six States and are presented in Table 3 for cropland and noncropland. Between 65 and 75% of the sites analyzed for chlori- nated hydrocarbons had residues below the level of analytical sensitivity. With this high a percentage of qualitative observations, a logarithmic transformation followed by a statistical test for significance was not warranted at this time. However, a chi-square analysis was used to examine relative proportions of sites in crop- land and noncropland that showed pesticide residues. The cropland data for all six States were pooled and the proportion of sites with residues determined. The process was repeated for noncropland. The following formula was used to calculate the chi-square values {4): N X- r= / N \- ( !/?„ S„ - R,, S.,\ - - j N„ R N,, S R = Total number of sites with residues S r= Total number of sites with no residues Pesticides Monitoring Journal N := Total number of sites (cropland and noncropland) Rg := Number of cropland sites with residues R,, = Number of noncropland sites with residues 5„ = Number of cropland sites with no residues 5j =z Number of noncropland sites with no residues N„ := Total number of cropland sites N,, = Total number of noncropland sites In all cases except DDE, no significant difference could be detected between the proportion of sites with residues in cropland and the proportion of sites with residues in noncropland. This seems to imply that DDT, TDE, and the combined residues of DDT (DDTR) are as wide- spread in noncrop areas as they are in crop areas, but DDE appears to be more widespread in cropland areas. Other pesticides were not tested. TABLE 1. — Mean pesticide residues and percent of sites with residues for cropland areas [blank = not delected] State Residues N PPMi Arsenic Chlordane DiELDRIN DDTR = DDT TDE DDE TOXAPHENE Georgia 3.99 <0.01 <0.0I 0.81 0.62 0.03 0.16 0.55 Idaho 6.40 <0.01 0.01 1.63 1.15 0.11 0.37 0.44 Maine 16.98 0.38 0.27 0.08 0.03 Nebraska 5.33 0.02 0.02 0.02 0.01 <0.01 0.01 Virginia 6.05 0.01 0.02 0.05 0.03 0.01 O.OI Washington 3.05 <0.01 0.21 0.15 0.03 0.03 Overall 5.30 0.01 0.02 0.38 0.28 0.03 0.08 0.13 Percent Sites With Residues Georgia 100.0 3.3 3.3 70.0 66.7 46.7 70.0 33.3 Idaho 97.0 3.1 18.7 34.4 31.3 28.1 34.4 3.1 Maine 100.0 0.0 0.0 50.0 37.5 37.5 50.0 0.0 Nebraska 100.0 8.4 43,0 10.3 7,5 2.8 9.3 0,0 Virginia 100.0 11.8 17.6 35.3 23.5 23.5 23.5 0.0 Washington 100.0 0.0 13.3 26.7 15.5 4.4 26.7 0.0 Overall 99.6 5.4 25.5 27.2 21.7 14.6 25.9 4.6 ■ Values represent mean residues, calcubted from the results of analyses of composite ■ Includes o.p'-DDT, p.p'-DDT, o.p'-TDE, p,p'-TDE, o.p'-DDE, and p.p-DDE. nples taken at each sampling site within a State. TABLE 2. — Mean pesticide residues and percent of sites with residues for noncropland areas Residues in PPM » State Arsenic DDTRi DDT TDE DDE Georgia 2.56 0.11 0.08 <0.01 0.03 Idaho 7.00 0.03 0.02 0.01 <0.01 Maine 4.01 0.15 0.10 0,02 0.02 Nebraska 4.42 4.46 3.64 0.54 0.30 Virginia 3.79 <0.01 <0.01 <0.01 <0.01 Washington 2.54 0.01 <0.01 <0.01 <0.01 Overall 4.24 0.81 0.65 0.10 0.06 Percent Sites With Residues Georgia 100.0 36.8 36,8 10.5 36.8 Idaho 100.0 13.8 10,3 10,3 10.3 Maine 100.0 25.0 25,0 8,3 25.0 Nebraska 100.0 5.0 5,0 5,0 5.0 Virginia 100.0 28.6 14.3 14.3 14.3 Washington 100.0 13.0 13.0 8.7 8.7 Overall 100.0 18.8 16.2 9.4 15.4 ■ Values represent mean residues, calculated from the results of analyses of composite samples taken at each sampling site within a State. ■Includes o.p'-DDT, p,p'-DDT, o.p-TDE, p,p'-TDE. o.p'-DDE. and p,p '-DDE, Vol. 5, No. 2, September 1971 225 Very little can be inferred at this time about the relative amounts of DDT and its fractions in cropland and non- cropland areas. As stated before, the arithmetic means as presented in Tables 1 through 4 do not represent efficient, unbiased estimates, which would probably be somewhat less than those shown in the tables. We can state that DDT, TDE, and DDTR seem to be consistent with the hypothesis that they occur with equal frequency on both crop and noncrop areas, but the levels of these pesticides were found to be usually well under 0.5 ppm. DDE seems more widely dispersed on cropland than on noncropland, but the average amount present on both areas is less than 0.1 ppm. Table 4 gives the pesticides used in 1967 on each of the sampling areas. The figures are the percent of sample sites using the particular pesticide. These figures were obtained by questioning the landowners. Many more pesticides were reported than were detected by the chemical analyses, but chemical analyses were made only for arsenic compounds, chlorinated hydrocarbons, phenoxy herbicides, and phosphate compounds. DDT was reported on 5% of the sites in 1967, yet DDT residues were detected on 27.5% of the sites. Similar findings occurred for dieldrin, which was reported as being used on only 5% of the sample sites but was detected on 25.5% of the sites. TABLE 3. — Summary of residues for tlie DDT group [blank = not detected] CROPLAND GEORGIA Mean (PPM) Percent of Sites ■ Range (PPM) IDAHO Me.in (PPM) Percent of Sites Range (PPM) MAINE Mean (PPM) Percent of Sites Range (PPM) NEBRASKA Mean (PPM) Percent of Sites Range (PPM) VIRGINIA Mean (PPM) Percent of Sites Range (PPM) WASHINGTON Mean (PPM) Percent of Sites Range (PPM) ith Residues 0.09 50.0 0.01—0.56 0.07 25.0 0.01—2.04 0.04 37.5 0.01—0.25 <0.01 4.7 0.01—0.04 <0.01 11.8 0.02—0.03 0.03 8.9 0.01—1.35 0.53 66.7 0.02—3.40 1.08 31.3 0.02—33.15 37.5 0.06—1.62 0.03 23.5 0.02—0.20 0.11 15.5 0.02- 0.07 37.5 0.02—0.^ 0.03 46.7 0.01—0.21 O.Il 28.1 0.03—3.06 10.01 12.5 <0.01 2.8 0.01 — 0.05 0.01 23.5 0.01-0.06 0.03 4.4 0.03—1.10 0.16 70.0 0.01—1.53 0.36 34.4 0.02—10.23 0.03 50.0 0,01—0.19 0.01 23.5 0.01—0.07 0.03 26.7 0.01- NONCROPLAND GEORGIA Mean (PPM) Percent of Sites with Residues Range (PPM) 0.01 15.8 0.01—0,14 0.07 36.8 0.03—0.72 <0.01 10,5 0,03—0,05 0.03 36.8 0.01—0.28 IDAHO Mean (PPM) Percent of Sites with Residues Range (PPM) 1 <0.01 3.4 0.02 10.3 0,05—0,34 0.01 10.3 0.05—0.17 <0.01 10.3 0.01—0.05 MAINE Mean (PPM) Percent of Sites with Residues Range (PPM) 10.01 8.3 0.09 25.0 0.01 — 1.06 ' 0.02 8.3 1 <0.01 8.3 0.02 25.0 0.01—0.24 NEBRASKA Mean (PPM) Percent of Sites with Residues Range (PPM) 10,39 5.0 13.25 5.0 10.54 5.0 1 0.01 5.0 10.29 5.0 VIRGINIA Mean (PPM) Percent of Sites with Residues Range (PPM) <0.01 14.3 0.01—0.03 <0.01 14.3 0.01—0.02 <0.01 14.3 0.01—0.02 WASHINGTON Mean (PPM) Percent of Sites with Residues Range (PPM) 1 <0.0I 4.3 <0.01 13.0 0.01—0.05 <0,01 8.7 -0.01 <0.01 8.7 0.01— 0.02 1 Represents one value. 2 Both values equal to O.OI. 226 Pesticides Monitoring Journal The only pesticides reported used on noncropland areas were Ceresan L and 2,4-D in Virginia, and mirex in Georgia. Although DDT was not reportedly used on noncropland areas in 1967, its residues were detected on 18.8% of the sample sites. The residues of DDT on the noncropland areas either came from earlier applica- tions of DDT or from DDT used on cropland areas, which in turn were moved through the environment to the noncropland areas. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (/) Wiersma. C. 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(/):63-66. (2) Shepherd. D. R. 1969. Guidelines for collecting samples for the National Soil Monitoring Program. U.S. Dep. of Agric. Agric. Res. Serv., Plant Pest Control Division Memo. 804.3. 22 p. (3) Anon. 1969. Monitoring agricultural pesticide residues in 1965-1967. a final report on soil, crops, water, sedi- ment, and wildlife in six study areas. U.S. Dep. of Agric, ARS, ARS 81-32, 97 p. (4) Army Material Command. 1965. E.xperimental statistics. Section 2. Analysis of enumerative and classificatory data. Headquarters. Armv Material Command. AMCP 706-111. TABLE 4. — Percent of cropland sample sites treated with indicated pesticide for each Slate Percent of Sample Sites Treated Pesticide Georgia Idaho Maine Nebraska Virginia Washington *Aldrin 3.8 2.2 Amiben 1.0 *Atra2ine 3.3 3.0 12.5 11.5 5.3 Bcrban 2.2 Benzene hexachloride 1.0 8.9 ^Calcium arsenate 25.0 Captan 20.0 9.1 8.6 6.7 C.-rb ryl 13.3 2.0 10.5 Ceresan L 3.3 6.1 1.0 13.3 Ceres.".n M 6.1 2.2 Ceresjn red 10.0 2.0 2.2 Chevron 5353 2.0 *Chlordane 3.3 Copper cjrb^male 5.3 Copper sulphate 3.3 2,4-D 3.3 15.0 8.6 5.3 44.4 *DDT 23.3 9.1 1.0 5.3 Di-AIIate 3.0 Diazinon 3.0 12.5 5.3 Dicamba 3.0 Dichloropropane 5.3 Dicofol 2.2 'Dieldrin 3.0 9.6 2.2 Dinitrobuty! phenol 3.3 5.3 2.2 Dinitrocresol 25.0 Diphenamid 5.3 Disulfoton 3.0 1.0 10.5 2.2 Ethion 3.0 F; lone 6.7 Guthion 3.3 ^Heptachlor 1.0 Hexachlorobenzene 4.4 Isopestox 1.0 Lindane 5.3 M.^lathion 10.0 3.0 1.0 2.2 MCPA 3.0 Mercury 2.2 Mcthoxychlor 13.3 Methyl nitrile mercury 3.0 Methyl parathion 13.0 2.2 Mevinphos 2.2 Mirex 3.3 Panogen 3.0 1.0 2.2 Parathion 10.0 3.0 1.0 5.3 Phorate 1.0 Polyram 3.3 Propazine 1.0 Ro-Neet 3.0 Sulphur 10.0 5.3 TEPP 2.2 Tetradifon 2.2 Thiram 3.3 3.0 5.3 *Toxaphene 13.3 5.3 Trifluralin 6.7 Vernolate 6.7 * Residue detected. Vol. 5, No. 2, September 1971 227 BRIEFS Chlorinated Hydrocarbons in Livers of Fishes From the Northeastern Pacific Ocean ^ Thomas W. Duke- and Alfred J. Wilson, Jr.- Occurrences of pesticides in seafood, such as Jack mackerel from California, prompted the Bureau of Commercial Fisheries (BCF), now the National Marine Fisheries Service (NMFS), to conduct a preliminary survey of the pesticide content of some coastal fish from the Northeastern Pacific. The purpose of the survey was to determine if these fish had recently accumulated or were in the process of accumulating commonly used chlorinated hydrocarbon pesticides and to point out some specific problem areas; a comprehensive monitor- ing program could be established later on the basis of these and other results. Investigators at Gulf Breeze coordinated the survey as planned by BCF and analyzed the samples. Samples were collected and prepared for analysis by personnel from NMFS Laboratories at La Jolla, Calif., Seattle, Wash., and Auke Bay, Alaska. This note presents the levels of pesticides found in the fish livers. Methods Pesticide contract studies conducted previously at Gulf Breeze (Unpublished data, P. A. Butler, Environmental Protection Agency, Gulf Breeze Laboratory, Sabine Island, Gulf Breeze, Fla. 32561) indicated that (1) fish containing pesticide residues usually had highest levels in prespawning gonad and (2) in fish that contained residues, liver tissue contained relatively high amounts of pesticides — although usually less than the ripe gonads. ' Contribution No. 127, Gulf Breeze Laboratory. = Gulf Breeze Laboratory, Environmental Protecti< Island, Gulf Breeze, Fla. 32561. 228 Thus, for this preliminary study, liver samples were collected and analyzed. The fish were obtained either iced or frozen from the vessel. Ten fish of each species were collected when possible. Approximately 10 g of liver or the entire liver in small fish were collected from each of 10 fish to give a composite of 50 to 100 g of liver tissue. The composite sample was placed in a clean Mason jar and homogen- ized with an Osterizer. A 30-g aliquot of the homogenate was transferred to a second clean Mason jar and mixed with 90 g of a desiccant mix composed of 9 parts anhydrous sodium sulfate and 1 part Quso (a micro fine precipitated silica). The mixture was alternately frozen and blended with an Osterizer until a free-flowing powder was obtained. The resulting sample was stored in a freezer until shipped to Gulf Breeze. Because of the addition of the desiccant, it was not necessary to keep the samples frozen during shipment. All samples were analyzed within 30 days after addition of the desiccant. The samples were analyzed for the following chlorinated hydrocarbons: BHC, heptachlor, aldrin, heptachlor epox- ide, toxaphene, chlordane, methoxychlor, dieldrin, en- drin, o.p'- and p,p'-isomers of DDE, DDD, and DDT. Thirty grams of tissue were extracted for 4 hours with petroleum ether in a Soxhiet apparatus. Extracts were concentrated and partitioned with acetonitrile. The ace- tonitrile was evaporated to dryness at room temperature and the residue eluted from a Florisil column (7). Sample extracts were identified and quantified by gas chromatographs equipped with electron capture detec- tors and 5' x ''«" o.d. glass columns. Operating condi- tions are outlined in Table 1. Pesticides Monitoring Journal TABLE 1. — Operating conditions of gas cliromatographs Accumulation of Pesticides Liquid phase SCb DC 200 5 To QF-I 1:1 3% DC 200/ 5% QF-1 2% DECS Solid support 60/80 G;is Chrom Q 60/80 Gas Chrom Q 80/100 Gas Chrom Q 80/90 Anakrom ABS Oven temperjturc 190°C 185°C 185°C 190°C Injector and detector temper.iturc 210°C 210 C 210°C 210-C N„ flow rate (ml/minute) 20 25 25 25 Recovery rates were greater than 85% for chlorinated hydrocarbons found in the livers. Data in this report do not include a correction factor for percentage recovery. The lower limit of sensitivity is 0.01 ppm (mg/kg). All residues reported are on a wet-weight basis. In samples containing polychlorinatcd biphenyl com- pounds (PCB's), levels did not significantly interfere with the quantitation of DDT and its metabolites. PCB's were reported but not quantified. In a few samples, thin- layer chromatography was employed to separate and confirm the presence of all of these organochlorine com- pounds. Residues in fish livers from the three collection areas are shown in Table 2. It is apparent that the bottom- dwelling coastal fish from Santa Monica Bay contained much higher residues than did pelagic fish from the open ocean. The salmon that showed no detectable residues were in their fifth year of life and the second or third year away from their "home" stream. Lack of residues in liver, however, does not preclude the pres- ence of stored residues in fat or muscle. This lack sug- gests only that the fish had not recently accumulated the pesticides. A comparison of levels of residues in livers with other tissue in selected fish is shown in Table 3. The data are another indication of the extent to which man is encroaching on a vital natural resource. See Appendix for chen paper. cs of compounds discussed in this LITERATURE CITED (/) Mills. P. A.. J. H. Onlcy. and R. A. Gailher. 1963. Rapid method for chlorinated pesticide residues in non- fatty foods. J. Assoc. Off. Agric. Chem. 46(2):186-19L TABLE 2. — Organocliloridcs in livers from fish collected in tlie Pacific Ocean near the west coast of the United States I — = Not detectable (<0.01 ppm)] Concentrations op Organochlorides Date Number in Composite Sample MC/KG (PPM) Wet Weight Species Collected Location DDT and DDE DDD DDT Metabolites Other COLLECTED BY NMFS, LA JOLLA. CALIF.' Bonito (Sanla cliiliensis) 1-10-70 25''44'N: 113 08'W 10 0.050 0.012 0.038 0.10 1-13-70 5 mi. W Natividad L. Baja. Calif. 6 1.10 .054 0.13 1.28 PCB English sole 5-14-70 Point Loma — San 14 12.00 1.10 .83 13.93 PCB (Parophrys reluUis) Diego Bay. Calif. Hake (Merluccius produclus) 12-31-69 North of San Diego 52 4.50 0.71 1.40 6.61 PCB 1-11-70 26°06.7'N: I13°07.3'W 90 0.36 0.18 0.048 0.59 4-70 40--44.3'N: 124°30.3-W 13 1.40 0.29 0.43 2.12 4-18-70 43°24'7"N: 124'36'8"\V 13 2.30 0.39 0.65 3.34 Jack mackerel 5-7-69 31°25'N: I2r59-W 2 0.092 0.019 0.11 iTracliurus syminetricus} 5-25-70 Cortez Bank 17 1.00 0.12 0.30 1.42 5-27-70 6 mi W. of mission Beach Jetty. San Diego. Calif. 10 2.50 0.16 0.14 2.80 Lingcod iOphtodon eton^atus) 5-14-70 Del Mar, Calif. 1 15.00 0.90 1.90 17.80 Lizardfish iSynodus lucioceps) 1-14-70 28°47'N: 1I4°58.5'W 13 1.60 0.18 0.35 2.13 Vol. 5, No. 2, September 1971 229 1. — Organochloriclcs in livers from fish collected in the Pacific Ocean near the west coast of the United States — Continued [— = Not detectable (<0.01 pprti)] Concentrations of Organochlorides Species Date Collected Location Number in Composite Sample mg/kc (PPM) Wet Weight DDT AND DDE DDD DDT Metabolites Other Ocean white fish 1-8-70 Magdalena Bay, 10 0.22 _ _ 0.22 (Caulolatilus princeps) Baja, Calif. 1-12-70 San Hipolito Bay 10 0.088 - - 0.088 1-19-70 Cortez Bank, 40 naut. mi. W. San Diego 2 0.78 0.060 0.099 0.94 1-15-70 Cedros Island 10 0.14 0.031 0.056 0.23 Pacific mackerel 1-11-70 25"'44'N: 113'08'W 12 0.041 _ 0.014 0.055 (Pneumatophoriis diego) 1-11-70 25°44'N: n3°08'W 7 0.039 - - 0.039 Rockfish: Blue rockfish 5-12-70 Farnsworth Bank 5 9.4 0.79 1.30 11.49 (Sebastes mystinus) Bocaccio (Sebastes paucispinis) 5-13-70 Santa Monica Bay 9 510.00 33.00 48.00 591.00 Olive rockfish 5-12-70 Cortez Bank 5 21.00 1.00 2.60 24.60 Dieldrin (Sebastes serranoides) 0.076, PCB Rosy rockfish 5-12-70 Cortez Bank 7 27.00 1.20 1.60 29.80 Dieldrin (Sebastes rosaceus) 0.059, PCB 5-12-70 Farnsworth Bank 16 8.50 0.54 1.00 10.04 PCB Starry rockfish 5-12-70 Farnsworth Bank 13 16.00 0.71 1.4 18.11 PCB (Sebastes constellatus) 5-13-70 Santa Monica Bay 5 900.00 56.00 70.00 1026.00 Dieldrin 0.089, PCB Treefish (Sebastes serriceps) 1-19-70 Cortez Bank 10 1.60 0.080 0.16 1.84 5-12-70 Farnsworth Bank 7 6.40 0.31 0.56 7.27 Vermilion rockfish 5-13-70 Santa Monica Bay 10 141.00 9.00 12.00 162.00 (Sebastes miniatus) Sable fish 5-13-70 Santa Monica Bay 10 90.0 6.00 7.10 103.10 (Anoptopoma fimbria) Sand bass 1-8-70 Magdalena Bay, 10 0.038 0.038 (Paralabrax nebulifer) Baja, Calif. 1-12-70 San Hipolito Bay 10 0.15 - - 0.15 Sardines iSardinops caerutea} 4-70 San Diego Bay 32 0.96 - - 0.96 California scorpionfish 5-12-70 Farnsworth Bank 10 7.00 0.55 0.58 8.13 (Scorpaena guttata] Spiny dogfish 5-13-70 Santa Monica Bay 12 300.00 20.00 32.00 352.00 Dieldrin (Squalus acanthias) 0.14 5-13-70 Santa Monica Bay 5 200.00 15.00 13.00 228.00 PCB 5-13-70 Santa Monica Bay 1 406.00 24.00 32.00 473.00 Dieldrin 0.13, PCB White croaker 5-14-70 Oceanside, Calif. 16 16.00 0.28 0.35 16.63 (Genyomemus lineatus) YcUowfin tuna 3-8-70 Near Manzanillo, Mex. 11 0.046 0.084 0.028 0.16 (Thunnus albacares) 3-8-70 (Replicate sample) 11 0.048 0.097 0.024 0.17 COLLECTED BY NMFS, SEATTLE, WASH. Albacore tuna 1-7-70 Mid-Cilifomia to 10 0.044 0.014 0.028 0.086 (Thunnus alalunga) mid-Oregon coasts 230 Pesticides Monitoring Journal TABLE 2. — Organochlorides in livers from fish collected in the Pacific Ocean near the west coast of the United States — Continued [— = Not detectable (<0.01 ppm)J Date Collected Number in Composite Sample Concentrations of Organochlorides mc/kg (PPM) Wet Weight DDT AND DDT Metabolites Other Chinook salmon iOncorhynchtts tshawytschaj Sablefish (Anoplopoma fimbria) ilver salmon (Oncorliynclius kisutch) Sockeye salmon (Oncorhynckus nerfca) - COLLECTED BY NMFS. AUKE BAY, ALASKA Chum salmon fOncorhynchus kela) Coho salmon (Oncorliynclius kisutch) King Salmon (Oncorliynchus tshawylscha) 5-11-70 to 5-15-70 6-1-70 to 8-1-70 5-8-69 to 5-18-69 5-22-69 to 5-23-69 5-22-69 to 5-25-69 5-23-69 to 5-24-69 8^-69 8^-69 8-6-69 8-7-69 8-7-69 8-8-69 8-9-69 8-9-69 9-8-69 9-8-69 9-10-69 9-11-69 8-29-70 9-1-70 9-21-70 10-1-70 8-31-70 9-21-70 10-27-70 6-1-70 7-10-70 Mouth of Columbia River 47°30-N: 125'00'W Cowlitz River Hatchery 49=00'— 52' 30'N: 165°00'W 50-00'— 52°30'N: 164°45'— I65°00'W 50'>45'— 50°00'N: leS-OO'W SCOO'- 52°15'N: 165°00'W 50'45'— 5r30'N: 165°00'W 51°15'N: 176°22'W 5riO'N: I76''22'W SriO'N: 176°22'W 50°43'N: 176°22'W 50°43'N: 176''22'W 51''00'N: 176°22'W 49°30'N: 176°22'W 49°30'N: 176°22'W 5r30' to 52°30'N: 160=00'W 5r30'N: 160°00'W 52 30'N: 160°00'N 53''00'N: 160°00'W Noatak River, 20 mi. up- river from Noatak Village Yukon River. Rampart Village Taku River. Juneau Klehini River, Chilkat drainage Unalakleet River. 50 mi. upriver from village Taku River. Juneau T.iku River, Juneau T.iku River, Juneau Naknek Ri' Bay Vol, 5, No. 2, September 1971 231 TABLE 2. — Organoclilorides in livers from fish collected in the Pacific Ocean near the west coast of the United States — Continued [— = Not detectable (<0.01 ppm)] Species Date Collected Location Number in Composite Sample Concentrations of Oroanochlorides MG/KG (PPM) Wet Weight DDE DDD DDT Metabolites DDT and Other Pink salmon (Oncorhyrichus gorbuscha) Rainbow trout (Salnto gairdneri) Sockeye salmon (Oncorhynchus nerka) 9-16-70 9-16-70 9-21-70 7-13-70 Auke Creek, Juneau Lover's Cove, Barunof L Taku River, Juneau Auke Creek, Juneau 10 10 10 10 - - - - ^ Fish from C lifornia were collected and processed for rnplysis by personnel from NMFS Laboratory, La Jolla, Calif.; those from Washington, by NMFS Laboratory, Seattle, Wash.; those from Al. ska, by NMFS Laboratory, Auke Bay, Alaska, = Twenty-nine additional samples collected from 9-11-69 to 3-1-70 in the general area did not contain me.^.surable levels of these pesticides. TABLE 3. — Comparison of clilorinatcd hydrocarbon pesticides in various tissues of three species of fish [ — = Not detectable (<0.01 ppm)] Species and Location Tissue Number of Fish IN Composite Sample DDE DDD DDT Total DDT and Metabolites Other Pacific mackerel (Pneumatophorus diego) 25°44'N: 1I3°08'W Liver Ovary 7 7 0.039 0.029 — — 0.039 0.029 Testes 7 0.016 - - 0.016 Starry rockfish (Sebasles constellalus) Santa Monica Bay Liver 5 900.00 56.00 70.00 1026.00 Dieldrin 0.089, PCB Flesh 4 28.00 1.40 1.70 31.10 Fat 4 2200.00 181.00 207.00 2588.00 Dieldrin 0.23, PCB Whitefish (Caulolalicus princeps) Baja California, Mexico Liver Ovary 10 4 0.22 0.034 — — 0.22 0.034 Testes 6 0.098 0.013 - 0.11 232 Pesticides Monitoring Journal APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN ATRAZINE BHC CALCIUM ARSENATE CARBARYL CARBOPHENOTHION (TRITHION®) CHLORBENSIDE (MITOX®) CHLORDANE 2,4-D DCPA (DACTHAL®) DDE DDT (including its isomers and dehydrochlorination products) DIAZINON DICHLORVOS DICOFOL (KELTHANE®) DIELDRIN ENDOSULFAN (THIODAN®) ENDRIN ETHION HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE MCP MALATHION METHOXYCHLOR METHYL PARATHION POLYCHLORINATED BIPHENYLS (PCB's) PCNB PCP PARATHION PERTHANE® TDE (DDD) (including its isomers and dehydrochlorina- tion products) TETRADIFON (TEDION®) TOXAPHHNE Not less than 95% of l,2,3,4,10,10-hexachloro-l,4,4a,5,8.8a-hexahydro-l,4-cnrfo-exo-5,8-dimethanonaphthalene 2-chIoro-4-ethyIamino-6-isopropylamino-5-lriazine 1,2,3,4, 5, 6-hexachlorocyclohexane, mixed isomers tricakium arsenate 1-naphthyl methylcarbamate 5-[(p-chlorophenylthio) methyl] 0,0-diethyl phosphorodithioate p-chlorobenzyl p-chlorophenyl sulfide l,2,4,5.6.7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-melhanoindane 2,4-dichlorophenoxyacetic acid dimethyl ester of tetrachloroterephthalic acid I, 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 the o.p'-isomer (in a ratio of about 3 or 4 to 1 ) 0,0-diethyl 0-( 2-isopropyl-4-methyI-5-pyrimidyl ) phosphorothioate 2,2-dichlorovinyl dimethyl phosphate 4,4'-dichloro-a-(trichloromethyl)benzhydrol Not less than 85% of 1.2,3.4, l0.10-hex3chIoro(6.7-epoxy-l,4,4a,5,6.7.8,8a-octahydro-l,4,fnrfo-fXo-5,8-dimethano= naphthalene 6.7,8,9,10.10-hexachloro-l.5.5a,6.9.9a-hcxahydro-6.9-methano-2.4.3-benzodioxathiepin 3-oxide 1,2,3,4, 10. 10-hexachloro-6,7-cpoxy- 1.4,4a, 5,6,7,8, 8a-octahydro-l,4-fndo-cHdo-5,8-dimethanonaphthalene 0,0,0',0'-tetraethyl .y.5'-methylenebisphosphorodithioate 1.4,5,6,7,8,8-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 1,2, 3,4,5, 6-hexachlorocyclohexane, 99% or more gamma isomer 2-methyI-4-chlorophenoxyacetic acid diethyl mercaptosuccinate, S-estei with 0,0-dimethyI phosphorodithioate l,l,l-trichloro-2,2-bis(p-melhoxy phenyl) ethane O.O-dimelhyl 0-p-nitrophenyl phosphorothioate Mixtures of chlorinated biphenyl compounds having various percentages of chlorination pentachloronitrobenzene pentachlorophenol 0,0-diethyl 0-p-nitrophenyl phosphorothioate l,l-dichloro-2,2-bis(p-ethylphenyl) ethane I,l-dichloro-2,2-bis(p-chlorophenyl)ethane; technical TDE contains some o.p'-isomer also p-chlorophenyl 2,4,5-trichlorophenyl sulfone chlorinated camphene containing 67% to 69% chlorine Vol. 5, No. 2, September 1971 233 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 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 8'/2 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. 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. 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Environmental Protection Agency, 4770 Buford Highway, Bldg. 29, Chamblee, Ga. 30341. 234 Pesticides Monitoring Journal The Pesticides Monitoring Journal is published quarterly under the auspices of the WORKING GROUP ON PESTICIDES (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 iif 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 Science Foundation, and Xennessee 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 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 com- munity monitoring programs, universities, hospitals, and nongovernmental research institutions. both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research in\estigation 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 Andrew W. Breidenbach, 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 5 December 1971 Number 3 RESIDUES IN FISH, WILDLIFE. AND ESTUARIES Correlation of DDT and lipid levels for certain San Francisco Boy fish Russell D. Earnest and Pete E. Benvillc, Jr. Chlorinated hydrocarbon residues in shellfish (Pelecypoda) from estuaries of Lony Island. New York Jack Foehrenbach, Ghulam Mahmood, and Dennis Sullivan Ori^anochlon'ne pesticide residues in woodcock, soils, and earthworms in Louisiana. 1965 M. Anne Ross McLane, Lucille F. Stickel, and John D. Newsom Chlorinated insecticide residues in wildlife and soil as a function of distance from application^ J. A. Laubscher, G. R. Dutt, and C. C. Roan PESTICIDES IN SOIL Insecticide residues in soil on 16 farms in southwestern Ontario — 1964. 1966. and 1969 C. R. Harris and W. W. Sans Persistence of ort^anochlorine insecticide residues in ui^ricultural soils of Colorado Donald E. Mullins, Richard E. Johnsen, and Robert I. Starr DDT moratorium in Arizona — agricultural residues after 2 years G. W. Ware, B. J. Estesen, and W. P. Cahill PESTICIDES IN WATER Organochlorine insecticide residues in Everglades National Park and Loxahatchee National Wildlife Refuge. Florida Milton C. Kolipinski, Aaron L. Higer, and Marvin L. Yates Insecticide residues in a stream and a controlled drainage system in agricultural areas of southwestern Ontario, 1970 J. R. W. Miles and C. R. Harris Residue levels of dieldrin in aquatic invertebrates and effect of prolonged exposure on populations J. B. Wallace and U. Eugene Brady Efjfect of urban and agricultural pesticide use on residue levels in the Red Cedar River Matthevk' J. Zabik. Brien E. Pape, and James W. Bedford APPENDIX Chemical names of compounds discussed in this issue_ ERRATA RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Correlation of DDT and Lipid Levels for Certain San Francisco Bay Fish' Russell D. Earnest and Pete E. Benville, Jr.- ABSTRACT ring 1969, residue levels of DDT and its metabolites were crmined monthly for eight species of fisit and one species "rab collected from two sites in San Francisco Bay. Total 'due levels were highest in dwarf and shiner percli and est in flatfisli and crabs. Lipid concentrations were deter- led in all animals. Correlation coefficients were calculated percent lipid versus concentrations of DDE, DDD, DDT, ' total DDT (DDE + DDD + DDT). There was a sig- cant correlation (P ^.05) between percent lipid and DDT ' its nictaholiles for white perch, pile perch, and staghorn Ipiii: dwarf perch had a negative correlation. Introduction fht species of fish and one species of crab from San incisco Bay were collected and analyzed during luary through December 1969 for whole body res- es of p.p'-DDE. DDD (TDE). and DDT. The ani- ls sampled were dwarf perch (Microinetrus minimus): ner perch (CymatO!>aster aggregata): pile perch ocochilus vacca): white perch (Phanerodon furcalus): "ry flounder (Platiclithys stellatus); English sole irophrys velidus); speckled sanddabs (Citharichthys '.maeus); staghorn sculpin (Leptocottus armatit.'i): and market crab (Cancer magister). These species can be wied near our laboratory most of the year, and they important animals in our testing program. •h and crab collection stations were located at Para- e Beach, a shallow bay 6 miles north of San Fran- co, and Keil Cove, a rocky cove adjacent to Racoon ait 4 miles north of the citv. Our laboratory is Torn the Division of River Basin Studies. Bureau of Sport Fisheries tnd Wildlife, Fish and Wildlife Service, U. S. Department of the nterior. Sacramento, Calif. 95826. resent address: Fish Pesticide Research Laboratory, Bureau of Sport "isheries and Wildlife, Fish and Wildlife Service, U. S. Department f the Interior, La Crosse, Wis. 54601. situated on the Tiburon Peninsula midway between these sites. In collections made in this area, Modin (DE 46 18 170 32 27 32 39 22 11 12 41 IDD 54 14 130 14 13 26 34 13 8 14 32 )DT 32 25 110 35 23 32 34 16 14 18 34 otal 132 57 410 81 63 90 107 51 33 44 107 STARRY FLOUNDER (o. of fish in sample 1 1 1 ' 1 I 1 1 1 )DE 23 31 23 29 37 20 24 39 28 DD 51 50 39 31 39 34 38 38 40 IDT 13 46 25 30 50 19 25 40 31 otal 87 127 87 90 126 73 87 117 99 WHITE PERCH lo. of fish in sample 1 1 2 2 4 12 4 12 11 2 1 5 DE 46 43 35 36 30 26 37 33 28 29 13 32 DD 34 14 35 31 24 18 45 42 34 32 7 29 DT 81 27 53 42 22 21 39 40 31 32 12 33 otal 161 84 123 109 76 65 121 115 93 93 32 89 ENGLISH SOLE lo. of fish in sample 7 1 4 5 5 5 9 11 10 12 10 9 7 )DE 32 29 10 30 24 25 13 75 28 33 22 28 29 iDD 42 15 7 32 22 21 17 30 34 38 25 24 26 »DT II 37 11 55 25 27 13 19 26 30 23 28 25 otal 85 81 28 117 71 73 43 124 88 101 70 80 80 STAGHORN SCULPIN lo. of fish in sample 1 3 2 2 3 5 4 3 4 3 1 3 )DE 15 24 29 21 15 24 45 27 27 34 11 25 IDD 5 23 14 11 11 26 34 34 26 33 7 20 IDT 14 23 26 30 19 17 32 19 26 33 9 23 otal 34 70 69 62 45 67 111 80 79 100 27 68 ^OL. 5, No. 3, December 1971 237 TABLE 1. — Concentrations of DDE, ODD, DDT, and total DDT in fish from Paradise Beach during 1969 — Continued Residues in /io/Ko (wet weight)' Jan. Feb. Mar. Apr. May June July Aug. Sept. Oct. Nov. Dec. Mean SPECKLED SANDDAB No, of fish in sample 30 9 17 16 40 28 20 29 15 26 24 19 . 23 DDE 24 11 17 21 30 31 25 14 25 23 21 21 22 DDD 25 5 9 13 31 30 28 17 29 19 18 15 20 DDT 11 13 22 21 29 29 21 14 23 20 2 21 19 Total 60 29 48 55 90 90 74 45 77 62 41 58 61 MARKET CRAB No. of fish in sample 5 1 2 2 2 1 1 5 5 2 3 3 DDE 45 6 20 32 26 27 49 30 30 59 11 32 DDD 42 3 10 9 11 11 18 7 13 34 10 15 DDT 1 2 6 9 33 10 17 5 8 31 7 12 Total 88 11 36 50 70 48 84 42 51 124 28 57 ' Concentrations not c orrected fc r percent ecovery (see Methods). TA BLE 2.— Residues of DDE. DDD. DDT, and total DDT in fish from Keil Co ve during 1969 Residues in nc/Ka (wet weioht)i Jan. Feb. Mar. Apr. May June uly Aug. Sept. Oct. Nov. Dec. MEA^ DWARF PERCH No. of fish in sample 6 18 2 3 8 4 4 5 6 6 DDE 37 138 51 45 61 72 31 32 38 56 DDD 52 43 65 52 48 91 46 41 69 56 DDT 27 79 63 47 43 58 36 36 37 47 Total 116 160 179 144 152 221 110 109 144 148 SHINER PERCH No, of fish in sample 6 12 4 9 5 24 17 12 7 16 15 11 DDE 4 68 79 31 81 34 27 67 45 48 27 46 DDD 7 54 47 17 71 31 15 67 52 53 32 41 DDT 1 110 94 31 88 30 23 46 52 64 34 52 Total 12 232 220 79 240 95 65 180 152 165 93 139 PILE PERCH No. of fish in sample 1111 1 DDE 30 32 70 25 39 DDD 40 32 64 33 42 DDT 22 59 62 49 48 Total 92 123 196 107 130 238 Pesticides Monitoring Journai TABLE 2.— Residues of DDE. DDD, DDT, and total DDT in fish from Keil Cove during / 969— Continued Residues in #g/ko (wet weight)' May June Dec. Mean WHITE PERCH No. of fish in sample ' 2 2 2 4 4 14 5 2 2 2 4 DDE 52 46 67 33 34 13 28 27 14 80 34 39 DDD 57 33 58 35 34 4 23 24 6 69 39 35 DDT 33 79 97 48 47 11 20 19 10 78 37 44 Total 142 158 222 116 115 28 71 70 30 227 110 117 STARRY FLOUNDER No. of fish insa mple 1 1 1 1 1 1 1 1 1 DDE 35 37 25 15 24 35 32 36 30 DDD 50 40 15 4 30 50 54 41 36 DDT 17 45 26 20 28 41 33 26 30 Total 102/ 122 66 39 82 126 119 103 95 STAGHORN SCULPIN No of fish in sample 5 2 1 2 2 1 3 2 1 1 2 DDE 22 25 28 34 14 26 38 53 29 41 31 DDD 26 15 36 32 7 II 32 40 21 61 28 DDT 7 21 28 41 18 26 33 47 35 38 29 Total 55 61 92 107 39 63 103 140 85 140 89 ENGLISH SOLE No. of fish in sample 7 11 3 5 7 5 11 9 10 15 13 10 9 DDE 28 37 23 24 22 8 13 8 13 14 10 7 18 DDD 44 9 21 29 24 7 14 10 14 19 13 7 18 DDT 12 33 26 41 28 8 10 9 9 10 10 6 17 Total 84 79 70 94 74 23 37 27 36 43 33 20 52 SPECKLED SANDDAB No. of fish in sample 32 29 18 18 20 26 25 23 17 18 23 21 22 DDE 19 24 32 25 20 17 21 II 14 8 13 11 18 DDD 23 15 19 20 16 13 13 10 13 9 14 1 1 15 DDT 8 24 33 31 25 19 11 9 10 8 12 II 17 Total 50 63 84 76 61 49 45 30 37 25 39 33 49 MARKET CRAB No. of fish in sample 2 2 1 2 DDE 12 12 6 10 DDD 8 6 3 6 DDT 1 5 3 3 Total 21 23 12 19 ' Concentrations not corrected for percent recovery ( see Methods ) . Vol. 5, No. 3 Di XEMBER 1971 239 We observed a general concentration correlation of DDT (Table 3) with lipid content (Table 4) of fish and market crabs from Keil Cove and Paradise Beach. Lipid content for fish of the same species from both stations were added and averaged together because there ap- peared to be little variation with regard to collection site. Dwarf perch contained 6.4% lipid, the highest for all species analyzed, whereas other perch and the starry flounder had higher lipid levels than the sole, sanddab, and crab. Concentrations of DDT and metabolites were positively correlated with the lipid contents of white perch, pile perch, and sculpin at the .05 level of signifi- cance. There was a positive correlation in shiner perch. English sole, speckled sanddab, and market crab; how- ever, in some instances, the correlation was not signif- icant. Residues found in the starry flounder showed a significant positive correlation except between DDT and lipid which had a nonsignificant negative correlation. The dwarf perch had a significant negative correlation; however, the reason for this is unknown. Brandes and Dietrich (/) found differences as high as 11% in the fat of herring from the same catch although the fish were the same sex and had similar length and weight. We did not determine age or sex, and these factors may contribute to variations in lipid levels. Market crabs had the highest percent ash followed by the perch, flatfish, and sculpins (Table 4). Percent water ranged from 80% for sculpin to 70% for dwarf perch. Animals from Paradise Beach generally had higher con- centrations of DDT and metabolites than those collected at Keil Cove. However, we believe that Paradise Beach, being a shallow bay upstream from Keil Cove, is a more likely area for pesticides to concentrate. Monthly an- alysis of our laboratory's effluent and water samples from the immediate vicinity indicated that DDT residues were about the same as average residues at Paradise Beach and Keil Cove. The water residues of DDT at all locations (Table 5) are less by a factor of 100 than the 5 |Lig/ liter limit set by the California Water Quality Control Board (9). The annual mean concentration of DDT in bay water from both collecting stations was 4 ng/liter (Table 5). Although concentrations appeared to vary from month to month, particularly high values were found in March. These data coincide with the tremendous runoff in the Sacramento River during March which resulted from one of California's record snow-packs. Turbidity in- creased greatly in the river and bay and may account for the higher organochlorine content. DDT concentrations in water from the Great Lakes and San Francisco Bay are approximately the same, yet DDT in Great Lakes forage fish is in parts per million, while none of the fish sampled from San Francisco Bay e.xceeded 410 ppb (5,7.11). Other research at our laboratory indicates that TABLE 3. — Correlation of DDT concentration (/ig/kg) ai percent lipid in animals collected from Paradise Beach ai Keil Cove in 1969 Correlation Coefficient Number FOR Lipid with : Species OF Groups Analyzed DDE ODD DDT Tot ai DDT Dwarf perch 13 -0.74 -0.33 -0.39 -0.53 Shiner perch 19 0.28 0.45 '0.29 10.36 Starry flounder 16 0.49 0.63 1-0.02 0.46 White perch 17 0.61 0.51 0.44 0.53 Pile perch 14 0.83 0.89 0.67 0.79 Staghorn sculpin 19 0.67 0.50 0.55 0.59 English sole 24 0.58 '0.30 10.23 0.41 Speckled sanddab 23 10.07 0.39 10.005 10.17 Market crab 13 •0.03 10.02 10.02 ■0.03 1 Not significantly different from zero (P < .05). TABLE 4. — Percent composition of fish and market era collected from Paradise Beach and Keil Cove No. OF Fish Percent Composition (X ± SD) Animal Ash Water Lipid Other Com- ponent Dwarf perch 141 5.53 ±0.40 70.7 ±3.9 6.41 ± 2.50 17.3f Pile perch 28 4.84 ± 1.11 75.3 ± 2.6 4.36 ± 1.69 17. i: Shiner perch 256 4.20 ± 0.24 75.5 ± 2.9 3.44 ± 1.72 15.9' White perch 101 4.03 ± 0.20 76.8 ± 2.2 2.83 ± 1.33 16.3. Speckled sanddab 588 3.75 ±0.41 77.9 ± 1.1 2.74 ± 1.98 16.4. Starry flounder 18 3.67 ± 0.49 76.5 ± 2.6 2.48 ± 1.95 16.3' English sole 208 3.60 ± 0.25 79.6 ±2.1 2.03 ± 0.86 14.T Staghorn sculpin 56 3.30 ±0.41 80.0 ± 2.0 1.87 ±0.33 14.2; Crab 39 10.0 ± 1.5 76.7 ± 4.3 1.28 ±0.57 12.0: TABLE 5.— DDE, DDD, DDT and total DDT in mont • samples of bay water collected in 1969 at Paradise Bee i and Keil Cove Com- pound Residues in No/trrER PARADISE BEACH 240 Pesticides Monitoring Journ I suspended sediments in the bay strongly adsorb organo- chlorine pesticides and, thus, may reduce the amount of pesticides available to fish from bay water. In summary, DDT residues in the waters of San Fran- cisco Bay are similar to those found in Lake Michigan. Residues in most bay fishes, like those in Lake Michigan lake trout, are correlated with their lipid content. How- ever, the magnitude of the residues in bay fish is lower by a factor of 10 than those in Lake Michigan fish. We feel this inconsistency may be related, at least in part, to the high turbidity frequently observed in San Fran- cisco Bay. Persistent pesticides may be adsorbing to silt particles and are thus less available to the biota. A cknowledgments This study would not have been possible without the technical assistance of Mrs. Margie Gepner and Mrs. Vivian Cartwright. The manuscript was constructively reviewed by Dr. Richard Schoettger and other members of the Fish-Pesticide Research Laboratory. Columbia, Mo. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED {1) Brandes, C. H., and R. Dietrich. 1953. A review of the problem of tat and water content in the edible part of the herring. Fette and Seifen 55:533-54L (2) Carr, John. 1970. Insecticides and Great Lakes lake trout and echo salmon. Prog. Rep. No. 4. Annu. Meet. Great Lakes Fish. Comm., Minneapolis, Minn. 9 p. (3) Folch, ].. 1. Ascoli, M. Lees, J. A. Meath, and F. N. Lebaron. 1951. Preparation of lipid extracts from brain tissue. J. Biol. Chem. 191:833-841. (4) Gakstatler, J. H. 1967. The uptake from water by sev- eral species of fresh-water fish of p.p'-DDT, dieldrin and lindane; their tissue distribution and elimination rate. Diss. Abstr. B27:3820-B. (5) Henderson. C, W. L. Johnson, and A. Inglis. 1969. Organochlorine insecticide residues in fish (National Pesticide Monitoring Program). Pestic. Monit. J. 3(3): 145-171. (6) Herman, S. G., R. L. Garrett, and R. L. Rudd. 1969. Pesticides and the Western Grebe, p. 24-53. In Morton W. Miller and G. C. Berg, Chemical Fallout. Chas. C. Thomas. Springfield, III. (7) Macek, K. J., and S. Korn. 1970. Significance of the food chain in DDT accumulation by fish. I. Fish. Res. Board Can. 27:1496-1498. (8) Modin, J. C. 1969. Chlorinated hydrocarbon pesticides in California bays and estuaries. Pestic. Monit. J. 3(1): 1-7. (9) Regional Water Quality Control Board. 1967. State of California — San Francisco Bay Region. Resolut. No. 67-66. (10) Reinert, R. E. 1969. Insecticides and the Great Lakes. Limnos 2(3):4-9. (//) . 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4):233-240. (12) Spiegel, M. R. 1961. Statistics. Schaum Publishing Com- pany. New York. 359 p. Vol. 5, No. 3, December 1971 241 Chlorinated Hydrocarbon Residues in Shellfish (Pelecypoda) From Estuaries of Long Island, New York Jack Foehrenbach, Ghulam Mahmood, and Dennis Sullivan ABSTRACT Since October 1968, shellfish from 10 estuaries in Long Is- land, N.Y., have been collected on a monthly basis and exam- ined for chlorinated hydrocarbons. This study covers the period up to July 1970. The residues found were DDT, ODD, DDE, and dieldrin; concentrations were low, the highest being 0.146 mg/kg, wet weight. The distribution of residues could at times be correlated with agricultural use or type of community in the watershed surrounding the various stations. Introduction Since October 1968, the New York State Department of Environmental Conservation has been monitoring chlori- nated hydrocarbon residues in shellfish. The species examined are the hard clam (Mercenaria inercenaria), blue mussel (Mytihis edulis), oyster (Crassosirea vir- ginica), soft clam (Mya arenaria). ribbed mussel (Brachi- dontes deinissus plicatulus). and the bay scallop (Aeqiti- pecten irradians). This is part of a continuing nationwide survey conducted by the National Marine Fisheries Service, U. S. Department of Commerce (formerly the Bureau of Commercial Fisheries. U. S. Department of the Interior). Ten sites have been chosen (Fig. 1 ) and are sampled on a monthly basis. The areas were selected because of the amount of shellfish produced, the size and use of their drainage basins, and the hydrography of the estuary. The study reported here covers the period up to July 1970. The samples were collected in the field by the authors or by personnel from other governmental agencies. Analyses were carried out for the following compounds: DDT, DDD, DDE, aldrin, heptachlor, heptachlor epoxide, lindane, dieldrin, and endrin. FIGURE I. — Pesticide monitoring stations in. Long Island, New York Contribution No. 71-2 from the New York State Department of En- vironmental Conservation, Division of Marine and Coastal Resources, Ronkonlioma. N. Y. 11779. A nalytical Methods At least 12 shellfish of a single species were shucked an the excess water removed before grinding to homogeniz the samples. A 30-g subsample was mixed with 90 g of 9 to I mixture of anhydrous NajS04 and QUSO an then alternately frozen and ground until a flowing dr powder was obtained. The sample was then extracted i a Soxhlet apparatus for 4 hours with petroleum ethe The extract was concentrated and then partitioned wit acetonitrile saturated with petroleum ether. The aceton trile was evaporated just to dryness and the residue set through a Florisil column. The column was eluted wit a 6% and 15% solution of ethyl ether in petroleui ether. All pesticides mentioned above are eluted wit the 6% solution, except dieldrin and endrin which elui with the 15% eluant. The 15% eluate was furthi cleaned by sending it through a MgO-Celite column. Tl samples then were identified and quantified using a g: chromatograph equipped with an electron capture d' tector. The operating parameters were as follows: 242 Pesticides Monitoring Journa Columns: 5' x 1/8" glass, packed with 3% DC-200 on 80/100 mesh Gas Chrom Q Temperatures: Detector 191° C Injector 210° C Oven 191° C Carrier gas: Prepurified nitrogen at a flow rate of 40 ml/min. Thin layer chromatography was used on some of the samples to confirm results obtained by gas chromatog- raphy. The percent recovery was 85% or greater. The results were not corrected for the losses during analysis. Under the conditions of analysis (size of sample and extract, attenuation of chromatography, etc.). Lie sen- sitivity limit was determined as 0.010 mg/kg; values less than this but greater than 0.007 mg/kg are reported as "trace." Results and Discussion Although analyses were made for a total of nine com- pounds, only four were found — DDT. DDD, DDE. and dieldrin. The concentrations and stations where they were detected are given in Tables 1-4. The levels re- ported for DDT ranged from nondetectable to 0.12 mg/kg (wet weight), DDD from nondetectable to 0.146 mg/kg. DDE from nondetectable to 0.102 mg/kg. and dieldrin from nondetectable to 0.132 mg/kg. In a similar study of marine organisms from estuaries in California. Modin (/) found the same residues but in somewhat higher concentrations. He correlated the higher con- centrations with runoff from large agricultural and urban areas. The distribution and concentrations of residues found in this study at times appear to be related to the type of land use of pesticides in the drainage basin and also to the hydrography of the estuary. However, the fact that different species of shellfish were sampled in some areas must also be taken into account. From the DDT. DDE. and DDD data, it appears that the north shore (Stations 7, 8. 9. and 10) samples have higher residues than the south shore samples (Stations 1. 2. 3. and 4). The north shore samples, however, consisted of blue mussels, oysters, and soft clams while the south shore samples consisted mostly of hard clams. Results obtained from a station where different species were collected show that residue levels vary between species with blue mussels having the highest levels and hard clams the lowest. The samples from Station 6. regardless of species, have relatively high concentrations as do samples from Sta- tion 5. The area around Station 6 is fed by a large river {which is about 8.5 miles long and has a watershed area Vol. 5, No. 3, December 1971 of about 75 square miles; much of this watershed is used for agriculture. Similarly. Station 5 is surrounded by potato and other produce farms. The watershed also has several large creeks flowing through it that feed the bay. In addition, the bay in which Station 5 is located is closed off from the Atlantic Ocean for a large part of the year causing runoff to accumulate. It is interesting to note that neither DDT nor DDD are on the recom- mended list (2) which is given out by the County Exten- sion Service to control insects on farms. In contrast to DDT and its metabolites, hard clams have about the same concentration factor for dieldrin as other species of shellfish. The results from Station 10 indicate that all species of shellfish have about equal concentrations. It is evident that agricultural use contributed little to the dieldrin residues in shellfish. Dieldrin residues were more frequent and generally higher in samples from Stations 1. 7. 8, 9. and 10: the areas around these sites are occupied by country clubs, estates, and large residences. On the other hand. Station 5. which is surrounded by an agricultural area, had few samples that contained diel- drin residues, and these were in very low concentrations. A cknowledgments Special thanks is given to Philip Butler and Al Wilson of the National Marine Fisheries Service for their help and advice in starting this project and to Albert C. Jensen for reviewing the manuscript. Thanks is also given to personnel from various governmental agencies for help in collecting samples: namely, the Division of Law Enforcement of the NYS Department of Environ- mental Conservation. Town of Hempstead Department of Conservation and Waterways, and the Huntington Town Department of Harbors and Waterways. See Appendix for chemical names of compounds discussed in this paper. Financial support from the National Marine Fisheries Service under contracts 14-17-0002-268, 14-17-0002-345. and 14-17-0002-455 is grate- fully acknowledged. LITERATURE CITED (1) Modin, John C. 1969. Chlorinated hydrocarbon pesti- cides in California bays and estuaries. Pestic. Monit. J. 3(n:l-7. (2) Suffolk County Extension Service. 1968, 1969, 1970. Po- tato recommendations and production records; vegetable produce recommendations, n.p. 243 TABLE 1. — DDT concentrations in shell fisli, October 1968-July 1970 1- - = <0,007 ir g/kg; T = trace = >0.007 mg/kg but <0.010 mg/kg] Residues in mg/ko (wet weight) Date Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 Station 7 Station 8 Station 9 Station 10 Oct. 1968 0.012 - - - (Oys.) - - - - - Nov. 1968 - - - — (Oys.) — — — — — Dec, 1968 - - - - (Oys.) - — T — — Jan. 1969 T - - - T (Oys.) - - — — — Feb. 1969 0.012 - - - T (Oys.) - - T - 0.014 Mar. 1969 T - - - (Oys.) - 0.019 0.010 - 0.043 (B.mus.) Apr. 1969 0.038 - - - T (Oys.) 0.045 (R.mus.) 0.060 (B.mus.) 0.034 (B.mus.) 0.026 (B.mus.) 0.043 (B.mus.) May 1969 0.033 - - 0.021 (B.mus.) 0.024 (S.clam) - 0.032 (B.mus.) 0.021 0.032 (B.mus.) 0.012 June 1969 T - - - 0.010 (S.clam) - 0.048 (R.mus.) 0.046 (R.mus.) - T July 1969 - - - - (S.clam) - 0.020 (S.clam) 0.050 (B.mus.) T T Aug. 1969 - - - 0.12 (B.mus.) (S.clam) - (S.clam) - - - Sept. 1969 - - - T (B.mus.) (S.clam) 0.075 (R.mus.) T (S.clam) 0.047 (B.mus.) - 0.074 (B.mus.) Oct. 1969 0.012 - 0.024 T (B.mus.) (S.clam) - 0.015 (B.mus.) 0.028 (B.mus.) 0.017 (Oys.) 0.049 (S.clam) Nov. 1969 (Oys.) (B.sc.l (S.clam) (S.clam) (B.sc.) 0.026 (B.mus.) 0.055 (B.mus.) - 0.047 (S.clam) Dec. 1969 0.043 - - 0.022 (B.mus.) - 0.017 (B.mus.) 0.050 (B.mus.) - 0.046 (S.clam) Jan. 1970 - - (B.mus.) 0.061 (B.mus.) 0.076 (S.clam) Feb. 1970 - - (S.clam) 0.052 (S.clam) 0.025 (B.mus.) 0.040 (B.mus.) 0.020 (Oys.) 0.015 Mar. 1970 0.011 - T (S.clam) 0.049 (S.clam) - 0.036 (B.mus.) 0.049 (B.mus.) 0.011 (S.clam) 0.062 (S.clam) Apr. 1970 0.040 - - (S.clam) 0.010 (Oys.) 0.012 (R.mus.) (B.mus.) 0.012 (B.mus.) - 0.029 (S.clam) May 1970 - - T (S.clam) (Oys.) - 0.036 (B.mus.) 0.040 (B.mus.) 0.034 (B.mus.) 0.054 (S.clam) June 1970 T - 0.021 (B.mus.) 0.032 (B.mus.) (S.clam) 0.029 (B.mus.) 0.040 (B.mus.) T 0.070 (B.mus.) July 1970 0.01 0.011 (S.clam) 0.024 (B.mus.) T (Oys.) T (S.clam) 0.028 (B.mus.) 0.055 (B.mus.) 0.024 (B.mus.) 0.017 • NOTE: All sp ecies are the hard clam ex cept those ind icated in parentheses as follows: 01 B. m as. = Blue mussel Oys. S. cla = Oyster m = Soft clam R. m is. = Ribbed mussel B. sc = Bay scallop 244 Pe STICIDES M ONITORING JOURNAI ': TABLE 2.—DDD concentrations in shellfish. October 1968-July 1970 [ — = <0.007 mg/kg; T = trace = >0.007 mg/kg but <0.010 mg/kg] Residues in mo/kg (WET weight) Date Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 Station 7 Station 8 Station 9 Station 10 Oct. 1968 0.018 - - T 0.031 (Oys.) 0.033 - 0.036 0.011 0.029 Nov. 1968 0.016 0.017 - - 0.026 (Oys.) 0.039 - 0.022 - - Dec. 1968 0.014 0.012 0.011 T 0.023 (Oys.) 0.033 T 0.044 - 0.024 Jan. 1969 0.021 T 0.010 T 0.031 ( Oys. ) 0.027 T - - 0.018 Feb. 1969 0.030 0.013 0.024 0.017 0.047 (Oys.) 0.044 0.012 0.037 0.016 0.036 (B.mus.) Mar. 1969 0.018 - 0.013 - 0.021 (Oys.) 0.040 - 0.038 0.012 0.035 Apr. 1969 0.0 IS T 0.013 0.016 0.043 ( Oys. > 0.067 (R.mus) 0.025 (B.mus. 1 0.039 (B.mus.) 0.027 (B.mus.) 0.033 (B.mus.) May 1969 0.028 - 0.013 0.038 (B.mus.) 0.031 (S.clam) 0.033 0.024 (B.mus) 0.024 0.028 (B.mus.) 0.018 June 1969 0.013 - - T 0.029 (S.clam) 0.028 0.036 (R.mus.) 0.104 0.011 (R.mus.) 0,019 July 1969 0.018 - T T 0.021 (S.clam) 0.019 0.022 (S.clam) 0.100 (B.mus.) 0,015 0.022 Aug. 1969 0.019 - T 0.021 (B.mus.) 0.010 (S.clam) 0.023 0.020 (S.clam) 0.023 - 0.010 Sept. 1969 0.014 T - 0.020 (B.mus.) 0.010 (S.clam) 0.049 (R.mus.) 0.014 1 S. clam ) 0.127 (B.mus.) - 0.093 (B.mus.) Oct. 1969 0.021 T - 0.016 (B.mus.) (S.clam) T 0.029 (B.mus.) 0.073 (B.mus.) 0.055 (Oys.) 0.062 (S.clam) Nov. 1969 - 0.024 (Oys.) 0.012 (B.sc.) (S.clam) 0.023 (S.clam) 0.020 ( B. sc. ) 0.039 (B.mus.) 0,084 0.013 0.057 (S.clam) Dec. 1969 0.021 0.013 T 0.024 (B.mus.) 0.028 0.036 (B.mus.) 0.080 (B.mus.) T 0.057 (S.clam) Ian. 1970 0.013 T 0.018 (B.mus.) 0,090 0.071 (S.clam) Feb. 1970 0.013 T 0.013 (S.clam) 0.027 (S.clam) 0.037 (B.mus.) 0.0.58 (B.mus.) 0.052 (Oys.) 0.033 Mar. 1970 0.020 0.011 0.013 T (S.clam) 0.027 (S.clam) 0.026 0,037 (B.mus.) 0.060 (B.mus.) 0.019 (S.clam) 0.051 (S.clam) \pr. 1970 0.019 - - (S.clam) 0.014 (Oys.) 0.022 (R.mus.) 0.011 (B.mus.) 0.022 (B.mus.l - 0.028 (S.clam) May 1970 T 0.014 0.019 (S.clam) 0.045 (Oys.) 0.030 0.049 (B.mus.) 0.050 (B.mus.) 0.044 (B.mus.) 0.033 (S.clam) une 1970 0.016 0.020 0.034 (B.mus.) 0.036 ( B.mus.) 0.029 (S.clam) 0.045 (B.mus.) 0.059 (B.mus.) 0.016 0.048 (B.mus.) uly 1970 T 0.021 (S.clam) 0.018 (B.mus.) 0.025 (Oys.) 0.029 (S.clam) 0.059 (B.mus.) 0.146 (B.mus.) 0.037 (B.mus.) 0.022 MOTE: All sp ecies are the hard clam ex ept those inc cated in parer theses as foil ,ws: B. mu s. = Blue mussel Oys. = = Oyster S. cla Ti = Soft clam R. mu s. = Ribbed mussel B. sc. = Bay seal op v'oL. 5, No. 3, December 1971 245 TABLE i.—DDE concenlralions in shcllfisit, Oclobci 1 968-] lily 1970 t- - = <0.007 mg/kg; T = trace = >0.007 mg/kg but <0.010 mg/kgl Residues in mg/kg (wet weight) 1 Date Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 Station 7 Station 8 Station 9 Station 10 Oct. 1968 0.102 - - - 0.036 (Oys.) 0.015 0.015 0.013 - - Nov. 1968 - T - - 0.033 (Oys.) 0.015 - T - - Dec. 1968 T - T - 0.033 (Oys.) 0.014 - 0.015 - - Jan. 1969 T - - - 0.032 (Oys.) 0.012 - - - - Feb. 1969 0.010 0.010 T 0.027 (Oys.) 0.018 - 0.013 T 0.010 (S.clam) Mar. 1969 - - - - 0.019 (Oys.) 0.016 - 0.014 T 0.014 Apr. 1969 - - T 0.011 0.037 (Oys.) 0.029 (R.mus.) 0.012 0.018 (B.mus.) 0.013 (B.mus.) 0.013 (B.mus.) May 1969 0.011 - - 0.020 (B.mus.) 0.020 (S.clam) 0.015 0.015 (B.mus) T 0.024 (B.mus.) 0.018 June 1969 - - - - 0.021 (S.clam) 0.014 0.016 (R.mus.) 0.030 (R.mus.) 0.015 July 1969 - - - - 0.019 (S.clam) 0.010 0.018 (S. clam) 0.029 (B.mus.) - T Aug. 1969 - - - 0.012 (B.mus.) T (S.clam) 0.021 0.014 (S.cl.im) 0.015 - - Sept. 1969 - - 0.014 (B.mus.) 0.010 (S.clam) 0.020 (R.mus) 0.013 (S.clam) 0.034 - 0.034 (B.mus. Oct. 1969 - - - 0.010 (B.mus.) (S.clam) - 0.017 (B.mus.) 0.024 (B.mus.) 0.027 (Oys.) 0.030 (S.clam Nov. 1969 0.011 (Oys.) T (B.sc.) (S. clam) 0.012 (S.clam) 0.013 (B.sc.) 0.023 (B.mus.) 0.028 (B.mus.) T 0.023 (S.clam Dec. 1969 0.010 T - 0.013 (B.mus.) 0.013 0.021 (B.mus.) 0.030 (B.mus.) - 0.026 (S. claiti' Jan. 1970 - - 0.011 (B.mus.) 0.038 (B.mus.) 0.041 (S.clam Feb. 1970 - - (S. clam) 0.019 (S.clam) 0.017 (B.mus.) 0.015 (B.mus.) 0.027 (Oys.) 0.01 1 Mar. 1970 T - T (S. clam) 0.021 (S.clam) 0.014 0.0?! (B.mus.) 0.023 (B.mus.) 0.010 (S.clam) 0.024 (S.clam. Apr. 1970 - - - (S.clam) 0.016 (Oys.) T (R.mus) (B.mus.) (B.mus.) (B.mus.) 0.013 (S.clam' May 1970 - T 0.010 (S.clam) 0.032 (Oys.) 0.013 0.025 (B.mus.) 0.020 (B.mus.) 0.024 (B.mus.) 0.012 (S.clam' June 1970 T T 0.018 (B.mus.) 0.016 (B.mus.) 0.014 (S.clam) 0.021 (B.mus.) 0.013 (B.mus.) T 0.018 (B.mus. July 1970 - T (S. clam) 0.010 (B.mus.) 0.021 (Oys.) 0.014 (S.clam) 0.024 (B.mus.) 0.021 (B.mus.) 0.016 (B.mus.) O.OIO NOTE: All species are the hard clam ext ept those ind cated in parentheses as follows: B. mus. = Blue mussel Oys. = Oyster S. clam = Soft clam R. mus. = Ribbed mussel B. sc. = Bay scallop 246 Pes TICIDES M ONITORING JOURNAl TABLE 4. — Dicldrin coiwmrations in shellfish, October I96S-July I— = <0.007 mg/kg; T = trace = >0.007 mg/kg but <0.010 mg/kg] Residltes in mo/kg (WET WEIGHT) Date Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 Station 7 Station 8 Station 9 Station 10 Oct. 1968 - - - - 0.053 - - - - 0.020 (B.sc.) Nov. 1968 Dec. 1968 - - - ~ (Oys.) - - T - 0.048 Jan. 1969 - - - - 1 Oys. ) - - - - 0.037 Feb. 1969 - - - - ( Oys. ) - T - T 0.028 Mar. 1969 - 0.012 T 0.010 (Oys.) - 0.019 0.033 0.015 0.022 (B.mus.) Apr. 1969 0.014 - 0.020 T T ( Oys. ) 0.032 (R.mus. 1 0.024 (B.mus.) 0.024 (B.mus.) 0.030 (B.mus.) 0.054 (B.mus.) May 1969 T - - 0.014 (B.mus.) 0.012 (S.clam) 0.017 0.015 1 B.mus.) 0.014 0.024 (B.mus.l 0.085 June 1969 T - - T (S.clam) 0.107 (R.mus.) 0.104 (R.mus.) 0.086 0.013 July 1969 0.018 - - - (S.clam) 0.011 T (S.clam) 0.026 (B.mus.) 0.016 0.033 Aug. 1969 0017 - - (B.mus.) 0.022 (S. clam) - (S.clam) T _ 0.038 Sept. 1969 0.020 0.059 - T (B.mus.) (S.clam) 0.014 (R.mus.) 0.015 (S.clam) 0.018 (B.mus.) 0.017 0.132 (B.mus.) Oct. 1969 0.012 - - 0.046 (B.mus.) (S. clam) 0.093 0.026 (B.mus.) (B.mus.) (B.mus., 0.028 (S.clam) Mov. 1969 - 0.019 (Oys.) 0.026 (B.sc.) (S. clam) (S.clam) (S.clam) 0.018 (B.mus.) 0.023 (B.mus.) 0.015 0.040 (S.clam) Dec. 1969 0.017 0.012 - — (B.mus.) - 0.013 (B.mus.) 0.03 1 (B.mus.) 0.018 0.031 (S.clam) Ian. 1970 - - 0.014 (B.mus.) O.OIX (B.mus.) 0.029 (S.clam) reb. 1970 T - (S.clam) (S.clam) 0.016 (B.mus.) 0.016 (B.mus.) 0.031 (Oys.) 0.030 >Vlar. 1970 0.014 - - 0.012 (S.clam) ( S. clam ) 0.011 0.019 (B.mus.) 0.017 (B.mus.) 0.012 (S.clam) 0.030 (S.clam) 'Apr. 1970 T - - (S.clam) (Oys.) (R.mus.) 0.020 (B.mus.) 0.038 (B.mus.) 0.037 0.025 (S.clam) May 1970 - - (S.clam) T (Oys.) - 0.026 (B.mus.) 0.022 (B.mus.) 0.023 (B.mus.) 0.030 (S.clam) June 1970 T T 0.012 (B.mus.) 0.010 (B.mus.) (S.clam) 0.020 (B.mus.) 0.021 (B.mus.) 0.011 0.033 (B.mus.) fuly 1970 - (S. clam) T (B.mus.) (Oys.) T (S.clam) 0.023 (B.mus.) 0.026 (B.mus.) 0.019 (B.mus.) 0.020 NTOTE: All species are the hard clam except tho B. mus. = Blue mussel Oys. = Oyster S.clam = Soft clam R. mus. = Ribbed mussel B. sc. — Bay scallop ^^OL. 5, No. 3, December 1971 ed in p:irenthescs as folio 247 Organochlorine Pesticide Residues in Woodcock, Soils, and Earthworms in Louisiana, 1965 M. Anne Ross McLane', Lucille F. Stickel', and John D. Newsom" ABSTRACT Woodcock (Philohela minor), eartliworms, and soil samples were collected from January-March 1965, from fields in southeastern Louisiana approximately 3 years after discon- tinuance of areal treatments with heptachlor in this region. Heptachlor epoxide residues in woodcock averaged 0.42 ppm (dry weight], conspicuously lower than in 1961 and 1962. Residues of DDE in woodcock averaged 3.62 ppm, higher than in birds taken in the same area in 1961-62. Earthworms and soils contained traces of several organochlorine pesti- cides. Introduction Between 1956 and 1962, heptachlor was broadcast over considerable acreages of the southeastern United States in a program designed to eradicate the imported fire ant (Solenopsis saevissima). Areas scheduled for treatment thus included the major wintering range of North American woodcock. The occurrence and effects of heptachlor in woodcock and their foods were the sub- ject of a series of studies summarized by Stickel et al. (/). Approximately 3 years after discontinuance of the areal treatments, woodcock {Philohela minor), earthworms (Lumbricidae), and soils were sampled in areas near Baton Rouge, La. where earlier studies had been made. This paper reports the results of analyses of these samples for organochlorine pesticide residues. Increased interest in residues in edible tissues of woodcock as well as the possibility of a new fire ant eradication program made it appear appropriate to prepare this summariza- tion at this time. ' Patuxent Wildlife Research Center, Bureau of Sport Fisheries and Wildlife, Fish and Wildlife Service, U. S. Department of the Interior, Laurel, Md. 20810. = Louisiana Cooperative Wildlife Research Unit, Bureau of Sport Fish- eries and Wildlife, Fish and Wildlife Service, U. S. Department of the Interior, Baton Rouge, La. 70800. 248 Materials and Methods Woodcock were headlighted and caught in hand nets o the night of January 4, 1965, in the pastures and field where they were feeding. Ten were collected from Wil bert's fields, 3 miles west of Port Allen, West Bato Rouge Parish, in fields treated with heptachlor in 196 and 1962. Twenty-three others were collected in fields i St. Landry, Pointe Coupee, and Iberville Parishes, wher owners indicated that no heptachlor had been appliec There were 22 immature males, 2 adult males, 8 immc ture females, and 1 adult female. Twenty-two analyse were made of single birds or of pools of two birds, eac of the same age, sex, and locality. Worm samples were dug in February and March 1965 from wet areas in woodcock-feeding fields in the sani parishes where woodcock were collected and in Ascen sion Parish. Samples were from 15 fields, includin; Wilbert's 2 treated fields, 2 fields where fire ant mound had been treated in 1963 or later, and from 11 fields no believed to have been treated. Soil samples consisted of approximately 1 quart of sol composited from six sites in each field and consisting o the top inch of soil with the vegetation pared off. Soil were sampled from 20 fields, including all of the field from which earthworms were taken, plus 5 others. Woodcock, worms, and soils were kept frozen unti preparation for analysis. Analyses for organochlorim pesticide residues were performed by the Wisconsir Alumni Research Foundation (now WARF Institute Inc.). Woodcock were skinned; and beaks, legs, and gastroin- testinal tracts were removed and discarded. Brains wert removed for separate analysis. Carcasses were grounc Pesticides Monitoring Journal and homogenized, and a 20-g aliquot was taken for analysis. Brains were analyzed in their entirety. Samples were dried at 40°C for 72-96 hours, weighed, then ' ground with sodium sulfate, and extracted with petro- leum etheriethyl ether (96:4) in Soxhlet apparatus for 8 hours, cleaned and separated into two fractions by passage through a Florisil column (petroleum etheriethyl ether, 95:5, 85:15). Analysis was by Barber Coleman Pesticide Analyzer Model 5360 with an electron capture detector (Sr-90). TTie column was glass, 4 foot x 4 mm, packed with 5% DC-200 on Chromport xxx 70/90 mesh: temperatures were 230-C (injector). 200°C (col- umn), and 240°C (detector); carrier gas was nitrogen, with a flow rate of 70-90 ml per minute. Lipid was deter- mined by evaporating and weighing an aliquot of the tis- sue extract. Worms were homogenized and a 10-g aliquot was taken for analysis. The sample was dried at 40^C for 48-72 hours and weighed. Cleanup, extraction, and analysis were as described for woodcock. Soils were sifted through a 1/8-inch mesh screen, mixed, and a 20-g sample was taken for analysis. Water (50 ml) was added, and the sample was allowed to stand for 1 hour and then was extracted with acetonitrile by agita- tion for 3 minutes in a Waring Blendor, filtered through glass wool, separated by petroleum ether, dried with sodium sulfate, and cleaned and separated into two frac- :ions by passage through a Florisil column. Analysis was as described for woodcock. The quantity of organic matter was determined by weighing a sample before md after heating in a muffle furnace at 550 C for 4 hours; pH was read to the nearest 0.1 pH unit on a Beckman Zeromatic II pH meter. Recoveries of organochlorines from spiked samples were ■!5'~? or greater. Analytical readings were not corrected :"or recovery. Thin layer analyses confirmed the identity 3f DDT and metabolites, but quantities of other residues A-ere too small to be confirmed by this method. The limit of sensitivity for woodcock brains was 0.05 o 0.10 ppm for DDE, DDD, and DDT; and 0.02 to 105 ppm for dieldrin. The range is dependent on the sample size. The limit of sensitivity for carcass samples A-as 0.01 ppm for DDE, DDD, and DDT; and 0.02 3pm for dieldrin. For soils the sensitivity limit was 3.005 ppm for all chlorinated insecticides, and for earthworms 0.010 ppm was the sensitivity limit for all Jrganochlorine insecticides. Results and Discussion Woodcock carcasses contained heptachlor epoxide. DDE. DDD. DDT, and dieldrin (Table 1), all in rela- ;ively low concentrations. In discussion, residues will be expressed as ppm dry weight unless otherwise specified; Vol. 5, No. 3, December 1971 values in ppm wet weight and ppm lipid weight are given in Table 1 for comparison. Residues in birds of different age and sex were not distinguishably different, and all will be considered together; neither were there any clearcut differences in residues in birds from treated and untreated fields, which was to be expected in view of the wide-ranging feeding habits of woodcock. Wood- cock, however, return to the same wintering areas from year to year and have been recaptured in the same field (2). Heptachlor epoxide was found in 19 of 22 samples, in concentrations ranging from 0.06 to 1.79 ppm. The average was 0.42 ppm. and the median was 0.18 ppm. In contrast, seven woodcock taken from the same area in January 1961. contained an average of 2.4 ppm (0.4 to 6.1 ppm) of heptachlor epoxide (/). Fifty-two wood- cock taken from the same area in January and February 1962 also contained an average of 2.4 ppm of heptachlor epoxide (0.3 to 6.0 ppm) (Paliixent Wildlife Research Center files. Unpublished.) The 1962 woodcock were collected by Leslie L. Glasgow and were analyzed at Patuxent by colorimetric methods, as were the 1961 woodcock. Direct comparisons of the two methods of analysis are not available, but the 1965 residues were so very much lower than those of 1961-1962 that a true decline seems likely to have occurred. Residues of DDE in the 1965 woodcock ranged from 0.46 to 7.05 ppm. with a mean of 3.62 ppm. DDE in the 52 woodcock sampled in 1962 ranged from none detected to 7.7 ppm. with a mean of 0.97 ppm. Since TABLE 1. — Organoclilorine pesticides in Louisiana wood- cock, January 1965 Residues in Woodcock (ppm)' Chemical Dry Wet Lipid Weight Weight Weight Heptachlor epoxide Mean 0.42 0.149 1.87 Median 0.18 0.065 0.88 Range (3ND) = 0.06-1.79 0.022-0.62 0.17-6.33 Dieldrin Mean 0.27 0.090 1.65 Median 0.09 0.031 0.48 Range (8T) = 0.06-3.35 0.023-1.09 0.27-22.24 DDE Mean 3.62 1.26 17.90 Median 3.66 1.33 16.15 Range 0.46-7.05 0.18-2.49 1.41-44.28 DDD ' Mean 0.33 0.113 1.69 Median 0.20 0.076 0.83 Range 0.04-1.37 0.012-0.47 0.31-6.44 DDT1 Mean 0.08 0.028 0.36 Median 0.07 0.024 0.34 Range(2T) = 0.03-0.20 0.013-0.077 0.10-3.72 1 Analyses of 33 woodcock singly or in pools of two, a total of 22 analyses. - ND = not detected; T = trace; ranges exclude ND and T readings. which occurred in the number of samples shown in parentheses. However, all values were used in computing means and medians. For means, trace readings were used at one-half the stated "less than" values, and ND was used as zero. ^ Not separated from PCB's, as discussed in text. 249 colorimetric readings for DDE tend to be somewhat higher than those made by electron capture gas chroma- tography (J), it appears probable that the apparent in- crease is valid. Re-examinations of the chromatograms in 1970 by chemists at WARF Innstitue indicated that there was no PCB interference. As computed at the time of analysis, DDD residues in 1965 woodcock averaged 0.33 ppm, and those of DDT averaged 0.08 ppm. Thin layer confirmations in- dicated that these chemicals were in fact present. When the gas chromatograms were re-examined, they indicated the probable presence of polychlorinated biphenyls also, in trace amounts, and the likelihood that PCB's ac- counted for a proportion of the DDD and very nearly all of the DDT. TTie measurements are given to show the very small amounts of these chemicals that occurred together or separately (Table 1 ). Dieldrin was present in trace amounts in all birds. Residues of all chemicals in brains paralleled those in carcasses, but the samples were so small that only quantities of DDE were regularly measurable. These ranged from 0.58 to 1.98 ppm, with a mean of 1.26 and a median of 1.34 ppm. Residues in earthworms and soils are shown in Table 2. Heptachlor epoxide occurred in worms from the two fields that were treated in their entirety in 1961 or 1962; it also occurred in worms from the two fields that had received mound treatments since then, and from three fields with no known treatment. Chlordane, which usu- ally is present in technical grade heptachlor, also was detected in all hut one of these same fields. Soil an- alyses showed heptachlor epoxide and chlordane in the 2 treated fields, in 1 of 3 fields where there had been mound treatments, and in 3 of 15 fields thought not to have been treated; DDT and its metabolites were present in all earthworm and soil samples. Trace amounts of dieldrin were present in 10 earthworm samples and 1 soil sample. TABLE 2. — Organochlorine pesticides in Louisiana earth- worms and soils, February-March 1965 Number of Samples 5 S" 12 9 I- f- 7, is. §1 I "> s Concentrations (ppm dry weight) EARTHWORMS Heptachlor epoxide 15 8 2 5 ND ND-0.133 Dieldrin 15 5 10 0 T ND-T DDE 15 0 9 6 T T-0.307 DDD 15 0 6 9 0.06 T-0.456 DDT 15 0 13 2 T T-0.083 a-Chlordane 15 9 5 1 ND ND-0.09: Heptachlor epoxide Dieldrin DDE DDD DDT a-Chlordane ND ND 0.010 ND ND-0.118 ND-T T-0.028 T-O.OU T-0.033 ND-0.07f See Appendix for chemical names of compounds discussed in this paper. NOTE: ND = no detectable residues; T = trace = <0.06 ppm foi earthworms and <0.007 ppm for soils. Average moisture content of worms was 74%. Soil moisturt averaged 32%, organic matter 10%, and pH 6.6. LITERATURE CITED (1) Sticl^el, William H.. Don W. Hayne, and Lucille F Stickel. 1965. Effects of heptachlor-contaminated earth worms on Woodcocks. J. Wildl. Manage. 29(1):132-146 (2) Glasgow. L. L. 1958. Contributions to the knowledge o the ecology of the American Woodcock, Philohela mine (Gmelin), on the wintering range in Louisiana. Ph.D Thesis, Tex. Agric. Mech. Univ. xii + 158 pp. (3) Dale. William E.. and Griffith E. Quinby. 1963. Chlori nated insecticides in the body fat of people in the Unitei States. Science 142(3592):593-595. 250 Pesticides Monitoring Journal Chlorinated Insecticide Residues in Wildlife and Soil as a Function of Distance From Application' J. A. Laubscherr ' ' G. R. Dutt," and C. C. Roan= ABSTRACT DDT and its metabolites were studied in a diverse ecosystem downwind from an area of insecticide application. Results showed that the distance from agriculture determines the relative quantities of residues present in animals, birds, and soils. Residues of DDT plus its metabolites were detected at levels from 6 to 929 ppb in Whitefooted mice and from 2.9 to 2770 ppb in various other animals. Samples of quail liver from the study area contained residues ranging from 500 to 2800 ppb, and soil residues ranged from 3.6 to 6700 ppb. Results also showed that DDT residue levels in biological specimens decline as the soil insecticide concentrations decline. Introduction Since the introduction of synthetic pesticides, millions of tons have been applied to agricultural crops. A major portion of these pesticides have been organochlorine compounds. The persistence of these compounds mani- fested by their accumulation in the environment has been a subject of much concern in recent years. The relative levels of pesticides in ecosystems predomi- nantly downwind from application areas have been of interest to researchers. For example, Gerhardt and Witt (7) found that pesticides can and do drift for long ' Contribution No. 1508, Arizona Agricultural Experiinent Station. - Community Studies Project, Department of Entomology, College of Agriculture, University of Arizona, Tucson, Ariz. 85721. ■ Department of Agricultural Chemistry and Soils, College of Agricul- ture. University of Arizona, Tucson, Ariz. 85721. ' Present address: Woodson-Tenent Laboratories, 345 Adams, P. O. Box 2135, Memphis, Tenn. 38102. ■ Submitted in partial fulfillment of the requirements for the degree. Master of Science in Agricultural Chemistry and Soils, Graduate Col- lege, University of Arizona. distances and that their movement is regulated by particle size, wind velocity, and turbulence. Cohen and Pinkerton (3) showed that widespread distribution of pesticides can be due to translocation of soil particles with subsequent fallout or rainout in distant areas. Al- though chlorinated pesticides are subject to volatilization {16) and degradation by ultraviolet light (5) and soil microorganisms (10). it is well established that these pesticides are persistent in soil, Lichtenstein (9) showed that translocation within the plant is possible with some compounds such as aldrin and dieldrin, although DDT was not observed to be translocated. It is evident that animals are exposed to pesticides in their environment, and numerous investigators (4,8.12, 13) have found various concentrations of pesticides in wildlife. Ware et al. (17) have shown within the environ- ment there is a continuous buildup to equilibrium within some animal species. The following study was conducted to determine the functional relationships between chlori- nated hydrocarbon residues in wildlife and soils and distance from application areas. Chosen for study was an ecosystem in Arizona (Fig. 1) bordered on the upwind side by intensive agriculture where large quantities of DDT had been used in the recent past. The agricultural area is located essentially along the line from Tucson, Sahuarita, Amado, and Nogales. Sampling locations ntimbered on Fig. 1 are listed in Table 1; chemical and physical properties of the soils analyzed are listed in Table 2. The prevailing winds in this area are westerly and northwesterly. Wind velocities at the time of application were not considered in this study. Vol. 5, No. 3, December 1971 251 FIGURE 1 . — Map of study area Sonoita atonia Nogales SCALE IN MILES 10 20 30 In studying this ecosystem, it was postulated that pesti- cide deposition levels at various distances from applica- tion areas could be determined by the chemical an- alysis of representative soil samples, and that soil insecticide levels might then be related to the distance from application areas and to the pesticide levels in different types of mammal and bird species. Samples from 19 soils (0-1 cm in depth. 20 cm sq), 8 deer, 18 rodents, and 14 quail were collected from the study area. Composition of samples is outlined in Table 1. 252 A nalytical Procedures SOIL SAMPLES A sample of 100 g screen-sieved (minus 2 mm, to re- move stones) soil, as received in the laboratory was ex- tracted in a Soxhlet thimble for 24 hours with 300 ml of 1:1 (v/v) hexane and acetone (15). The extract was washed three times with distilled water to remove the acetone and polar contaminants. The volume of washed extract was then eluted through a 60/100 mesh Florisil column that had been partially deactivated by the addi- tion of 10% (w/v) distilled water (//). The effluent was concentrated to 5 ml in a beaker and quantitatively transferred to a graduated centrifuge tube. An aliquot of the extract was then injected into a gas chromato- graph and the chlorinated hydrocarbons determined. DEER SAMPLES A 5-g sample of fat was extracted in a Lourdes hom- ogenizer with a 50-ml microcup with 35 ml 1:1 hexane and ethanol. The extract was washed three times with distilled water to remove the ethanol, chilled, and filtered through pre-rinsed #1 Whatman paper (/). The extract was partitioned with hexane-saturated acetonitrile (14). The partitioned extract was eluted through a Florisil column using the same procedure as with the soil sam- ples. The lipid content was determined by the Folch method (6). OTHER ANIMAL SAMPLES These samples were extracted with the same technique as the deer samples, except that 1:1:1 (v/v/v) hexane ether-ethanol was used. The chilled filtration step wa^ deleted as was the acetonitrile partitioning on nonfa samples. An aliquot of the extract was evaporated in ; tared vessel and the remaining lipid determined gravi metrically. EQUIPMENT All the analyses for chlorinated hydrocarbons were made using a MicroTek 220 gas chromatograph. The column used was 1/4" by 6' and packed with 5% QF-1 on 80/100 Gas Chrom Q. A tritium foil electror capture detector was used. The column temperature was maintained at 180°C, and the nitrogen flow rate was 100 ml/min. Several confirmatory analyses for chlorinated hydro- carbons were made using a MicroTek 220 with a Dohrmann C-200 microcoulometer to measure halogen specifically. All solvents used were redistilled in glass prior to use. Recovery standards and reagent blanks coinciding with each group of samples were simultaneously processed. Recoveries of DDT, DDE, dieldrin, and DDD in forti- fied samples averaged 947c for all products analyzed with a high of 100% in soils and a low of 84% in deei fat. Pesticides Monitoring Journal TABLE 1. — Location and identification of samples Site No. Sample Composition Location Soil Type Tissue Type 1 Soil Cottonrat tiV/ Vi Sec 33 T 15S R14E do. Sand Liver 2 SoU Snake Cottonrat Rabbit Quail SW 1/4 Sec 8 T 17S RUE NW Vi Sec 18 T 17S RUE NE 1/4 Sec 23 T 18S RUE do. do. Loam Liver and fat Liver and fat Liver Liver 3 Soil Sec 34 T 17S RUE Silt loam 4 Soil Pack rat Quail Mule deer Sec 4 T 19S RUE do. Sec 29 T 19S RUE do. Sand Liver Liver Fat 5 Soil NE 1/4 Sec 11 T20S RUE SUt loam 6 SoU Quail Mouse NW V4 Sec 7 T 20S R13E do. do. Sand Liver Liver 7 Soil NE 1/4 Sec 21 T 22S R13E Sandy loam 8 Soil NW 1/4 Sec 2 T 24S RUE Sandy loam 9 Soil Fish SE Cor Sec 15 T 22S RI6E do. Sandy loam Whole fish 10 Soil NW Cor Sec 21 T 21S R16E Sandy loam 11 Soil Deer Quail Mice Cent. Sec 36 T 19S R16E T 20S R15E Sec 10 T 19S R16E Sec 22 T 19S R16E Sandy loam Fat Liver Liver 12 Soil Mice Rabbit Deer Sec 14 T 18S R16E do. do. do. Sandy loam Liver Fat Fat 13 SoU Mice Sec 7T 17S R16E do. Sand Liver 14 Whitetail deer Sec 15 T 19S RISE Fat 15 WhiletaU deer Sec 27 T 20S RUE Fat 16 Mule deer Sec 18 T 20S RUE Fat 17 Mule deer Sec 35 T21S R13E Fat 18 Whitetail deer Sec 33 T 20S R15E Fat TABLE 2. — Chemical and physical properties of soil samples Site No. Soil Type pH Organic Matter (Percent) Conduc- tivity 1 Soluble Salts in Saturated Exthact (milliequivalents) Percent Composition Total Salts Na Ca Mo Sand Silt Clay 1 Sand 7.8 4.70 .77 .92 .2 .44 .28 90 9 1 2 Loam 7.4 1.25 2.7 7.16 4.8 1.76 .6 36 45 19 3 SUt loam 6.6 3.6 .14 .28 .2 .06 .02 25 61 14 4 Sand 6.6 .60 .2 .28 .1 .08 .1 98 1 1 5 Silt loam 8.1 5.02 .54 1.14 .6 .36 .18 17 72 11 6 Sand 7.7 .50 .31 .32 .1 .14 .08 97 2 1 7 Sandy loam 7.5 4.92 1.75 2.20 .3 1.58 .32 60 35 5 8 Loamy sand 6.9 5.98 .23 .68 .5 .06 .12 77 16 7 9 Sandy loam 7.8 5.43 .45 .60 2 .24 .16 61 32 7 10 Sandy loam 7.4 6.63 .56 .40 .1 .26 .04 64 28 8 11 Sandy loam 7.5 2.85 .93 1.16 .4 .54 .22 70 25 5 12 Loamy sand 7.9 1.01 .68 .84 .2 .52 .12 84 15 I 13 Sand 8.0 1.11 .47 .68 .4 .24 .04 96 3 1 1 Conductivity of paste — mmhos/cm. NOTE: All soil samples consisted of a samplin ; area 20 cm square and 1 cm deep, taken on Januar y 1, 1968. Vol. 5 No. 3, Dec EMBER 1 J71 253 Results SOIL INSECTICIDE LEVELS As can be seen from Fig. 2 and Table 3, the farther downwind a sample site is from an area of agricultural application, the lower the level of pesticide residue. The average level of total DDT in soil samples, exclud- ing agricultural areas was approximately 50 ppb. This level represents about 45,000 kg (100,000 lb) of DDT over the entire 1735 sq km (0.008 lb/ acre). In determining the distance from application, the first sample from Site 2 was assigned the distance of 1 meter, which is the approximate distance from the spray nozzle to the soil. Prior to and during the study, approximately 9,000 to 13,600 kg (20,000 to 30,000 lb) of insecticides (pre- dominately DDT) had been applied annually on the western edge of the study area. Therefore, it was likely that residues had accumulated in the soil from drift or deposition of translocated pesticides during rainfall and duststorms. Because very low concentrations were ob- served at 40 km (25 miles) from the application area, accumulation due to rainfall and duststorms would ap- pear to be minimal. DEER PERIRENAL FAT Seven deer fat samples were analyzed for chlorinated hydrocarbons as itemized in Table 4. Three samples were taken from male desert mule deer (Odocoileits hemiomis crooki) and four from male whitetail deer (Odocoileus virginianiis coiisei). FIGURE 2. — Soil DDTR levels vs. distance from agriculture Fig. 3 shows the DDTR (DDT -|- DDE -f DDD) in deer fat samples plotted against the DDTR levels in soils as determined from the theoretical curve found in Fig. 2. The equation from the least squares regression line shown in Fig. 3 is )> = 2.5997;i: -f 25.128, with y representing the deer fat residue levels and x represent- ing the soil residue levels. The linear correlation coeffi- cient between deer fat DDTR residues and DDTR residues in the soil is 0.9787. The correlation between deer fat levels and soil levels of insecticide residues is quite good even though deer are known to range several kilometers. TABLE 3. — Chlorinated insecticide levels in soil samples from study area Distance Residues in PPB From Cotton Organic Site Clay Matter No. Field (Km) o,p'-DDE p,p'-DDE DiELDRIN o,p'-DDT P,p'-DDD p,p'-DDT DDTR' pH (Percent) (Percent) 1 6.6 0.8 26 0.6 3.7 0.9 20 55.4 7.8 1 4.7 2 0.001 200 1300 _ 600 500 3800 6700 7.4 19 1.3 0.01 436 — 79 45 265 800 0.05 192 — 10.6 — 60.2 284 0.10 — 290 — 32 16.4 95 502 0.20 — 148 — 11 13 53 78.5 0.50 — 70 — 8 7 25 40.8 1.00 — 145 — 8 11 31 281 3 5 0.3 6 — 0.7 0.6 8.8 17.4 6.6 14 0.4 4 8 0.7 11.5 ~ 1.3 0.4 27 42.6 6.6 1 0.6 5 16 - 0.5 0.3 0.7 0.1 6.4 7.8 8.1 11 5.0 6 5 0.3 13 0.2 3.7 0.9 20 39.7 7.7 1 0.5 7 2 7 180 — 21 7 100 341 7.5 5 4.9 8 13 1.5 ^ 1.3 6 0.9 13 29.8 6.9 7 6.0 9 24 — 2.6 0.6 3.2 - 9.6 15.8 7.8 7 5.4 10 29 0.4 7.5 1.1 5 0.6 11 25.7 7.4 8 6.6 11 40 0.3 1.1 0.3 1.0 — 2.6 5.2 7.5 5 2.9 12 30 - 0.8 0.2 0.5 0.2 2.0 3.6 7.9 1 1.0 13 19 - 3.4 0.1 4.5 0.5 15 23.9 8.0 1 1.1 ' DDTR = DDT -f- 1.114 (DDE + NOTE: — = not detected; blank = DDD). not analyzed. 254 Pesticides Monitoring Journal p The two deer species sampled eat browse and grass, and apparently little concentration of insecticides occurs in these animals. QUAIL LIVER The majority of the 14 quail were collected in two nonagricultural areas. Arizona quail are nonmigratory. having a total range of only 1 km (0.6 mile) (Mitchell. G.C., University of Arizona. 1967. Personal Communica- tion.). With such a limited range, they should be repre- sentative of the local area. Two Gambel's quail (Lophortyx i;amhelii gambelii) col- lected in agricultural areas (.Sites 2 and 6) had the highest chlorinated insecticide residue levels of any of the ani- mals collected, Table 5. Their current diet, as determined from the contents of their crops, consisted mostly of weed seeds common to the site. The Gambel's quail collected at Site 4 had been eating primarily catclaw (Acacia greggii) seed. The Harlequin quail (Cyrtonyx nwuieznmae) from Site 11 had been eating mostly roots and bDlbs from the proximity and had slightly higher levels of chlorinated insecticide residues than would be expected from the soil level analyses. This could be explained by the fact that the roots and bulbs in their diet could have had soil particles adhering to the surface. Ware et al. (17) showed that residue levels were higher at root surfaces than general soil levels. FIGURE 3.— Deer perirenal fal DDTR levels vs. soil DDTR levels TABLE 4. — Chlorinated insecticide levels in deer perirenal fat from the study area Species Site No. Per- cent Lipid Residues in PPB (Lipid Basis) Residues in PPB (Wet-Weight Basis) p.p'- DDE o.p'- DDT p.p'- DDD P.P'- DDT DlEL- DDTR' p.p'- DDE o.p'- DDT P.P'- DDD P.P'- DDT DlEL- DRIN DDTR- Total DDT (PPB) Mule Whiietail 4 16 17 11 14 15 18 88 7: t] 100 93 99 99 19 13 15 4 7 3 6 ■; 5 1 4 3 4 8 9 7 4 12 9 6 70 44 25 41 68 29 5 4 3 3 4 3 122 103 62 29 63 89 43 19 13 15 4 7 3 6 5 5 1 4 3 4 8 9 7 4 11 9 6 70 44 25 38 67 29 5 4 3 3 4 3 107 74 56 29 59 88 43 39 28 10 5.5 14 25 7.4 DDTR = DDT -1- 1.114 (DDE + DDD). TABLE 5. — DDT levels in quail liver Site Percent Lipid Residues in PPB (Lipid Basis) Residues in PPB (Wet-Weight Basis) Soil Levels DDTR' No. p.p'-DDE p,p-DDD DDTRi p,p'-DDE P,p'-DDD DDTR' (PPB) 2 4,2 57,000 900 65,000 2,400 300 2,700 6,700 4 3.5 18.000 _ 20,000 500 — 700 23 3.5 14,000 — 16,000 500 — 600 23 3.5 14.000 — 16,000 500 — 600 23 3.9 17.000 — 19,000 700 — 700 23 3.4 20,000 _ 22,000 700 — 700 23 3.8 16.000 — 18,000 600 — 700 23 4.0 12,500 — 14,000 500 — 600 23 6 5.3 47,000 600 53,000 2.400 400 2,800 87 n 2.4 28,000 _ 31,000 700 _ 700 7.6 5.0 9.000 — 10.000 500 — 500 7.6 3.9 15,000 — 17,000 600 — 600 7.6 3.8 13,000 — 14,000 500 — 500 7.6 4.2 18,000 — 20,000 800 — 800 7.6 ' DDTR = DDT + 1.114 (DDE 4- DDI NOTE: — = not detected. Vol. 5, No. 3, December 1971 255 FIGURE 4.- -Quail and mouse liver DDTR levels vs. soil DDTR levels - - • X ^,,,^^^ ^^ /» • ^^^ Mill - a ^^ Fig. 4 shows levels of DDT in quail liver (lipid basis) plotted against soil DDT levels. The equation for the regression line shown in Fig. 4 is y = 0.426 !:«• + 11.391 with y being the liver residue levels and x the soil residue levels. In spite of the difference in species and diets, the quail liver levels had a correlation coefficient of 0.7588 with soil levels from areas sampled. WHITEFOOTED MICE LIVER Whitefooted mice iPeromyscus sp.) occur in most areas of North and Central America and are plentiful in the Santa Rita area. Twelve mice (P. eremicus and P. mani- culatus) were collected by trapping. Fig. 4 shows a plot of DDT residue levels in mouse liver (lipid basis) against DDT residue levels in soil. The equation for the regression line shown in Fig. 4 is y — 0.2403 a: + 0.461 with y representing the liver residue levels and x representing the soil residue levels. The linear correlation coefficient for the line is 0.9937. Table 6 itemizes the residue levels in individuals. The diet of whitefooted mice is varied and includesi seeds and insects as staples. The total range of the; animals is usually less than 100 meters (328 feet) radiusi TABLE 6. — Chlorinated insecticide levels in liver of whitefooted mice Percent Lipid Residues in PPB (Lipid Basis) Residues in PPB (Wet-Weight Basis) Soil Levels DDTRi (PPB) 140 1,7(X) 1,600 1.100 2,300 2,000 2,900 1,600 2,200 39.7 5.2 23.9 23.9 23.9 23.9 ' DDTR : NOTE: - DDT+ 1.114 (DDE + DDD). = not detected. TABLE 7. — Chlorinated insecticide levels in other animals collected from the study area Residues in PPB (Wet-Weight Basis) Soil Levels DDTRi (PPB) Sigmodon Liver Sigmodon Liver Fat Sylvilagus Liver Syhilagus Fat Pituopliis Pituophis Liver Fat Fat Neotoma Liver Rhinicthys Pantosteus Whole fish Whole fish 690 2,700 7,500 8,500 940 2,770 9,500 11,100 6,700 6,700 ' DDTR = DDT + 1.114 (DDE -|- DDD). NOTE: — = not detected. 256 Pesticides Monitoring Journal {Mitchell. G.C., University of Arizona. 1967. Personal Communication.), and the mice therefore should be good indiciilors of insecticide residue levels. OTHER ANIMALS Two cotton rats {Sigmodon hispidus) were collected (Table 7). One was found drowned the morning after a flood, and the other was trapped. The animal from Site 2 was much higher in total pesticides than the animal from Site 1, as expected from the soil levels. The diet of the cotton rat consists primarily of grass, weed leaves, and seeds. The levels were similar to those found in rabbits from similar areas. The difference between levels in liver (lipid basis) and fat samples in rats is not known at this time. Two cottontail rabbits (Sylvilagits audiihoni) were col- lected from vastly different areas. The animal collected near Site 12 had levels similar to the deer of the area. The animal collected near Site 2 was as high as the cot- ton rat from Site 2. Since this animal came from an agricultural area, it probably ate plants that had been spra\ed directly for insect control. Two bull snakes {Pituophis mclanolvmits) were collected anil analyzed. A packrat (Neotoma albigula) collected from Site 4 had insecticide levels approximately the same as deer. This is readily explained by the fact that packrats eat mostly succulent cactus and grass, a diet very similar to deer. They have a very limited travel range of about ."^O meicrs (100 feet) or less in their lifespan. Two adult fish, speckled dace (Rhiniclhys osculiif,) and Gila sucker (Pantosteiis clarki) were netted in Sonoiia Creek, Site 9. The insecticide levels in the two fish were quite different. The speckled dace is omnivorous and feeds on insects and algae. The Gila sucker is a bottom- feeding fish and subsists mostly on dead and decompos- ing organic matter. The site was downstream from the Patagonia sewage treatment plant, but the residue levels in fish do not indicate significant quantities of insecti- cides in the water from local use. Discussion Chlorinated insecticide residue levels in soils downwind from an application area decrease as the distance from the area of application increases. Levels of organochlo- rine residues in the surface soil from the agricultural area studied were about 7000 ppb. The levels decreased to about 8 ppb at 40 km (25 miles). Chlorinated insecticide residue lc\els in animals v\ithin the area vary widely but are directly proportional to the soil residue levels. The residue levels in deer fat averaged 73 ppb. with a range of 29 to 122 ppb. The mean residue levels in quail livers were 21.300 ppb (lipid basis) with a range of 10.000 to 65.000 ppb. Livers of whitefooted mice contained an average of 3100 ppb chlorinated insecticides, with a range of 140 to 20.500 ppb. also on a lipid basis. Tissues from other animal species within the area may follow the same trend of linearity with respect to soil levels as do the deer, quail, and mice sampled. This would depend upon the relative storage or metabolic capabilities and the dietary habits of the indiivduals. The presence of o.p'-DDT was reported in several samples; positive identification was not made, but tech- nical DDT can contain significant concentrations of o.p'-DDT thus retention time data and chlorine presence were the only specific tests made. See Appendix for chemical names of compounds discussed in this paper. The Arizona Community Studies Pesticide Project is supported by Contract No. PH 86-65-84 with the Division of Pesticide Community Studies, Pesticides Programs. Environmental Protection At'cncy, Chamblee, Georgia. LITERATURE CITED (1) Anglin. C. and W. P. McKinlcy. 1960. Procedure for cleanup of plant extracts prior to analysis for DDT and related pesticides, J. Agric. Food Chem, 8:186. 12) Biggar. J. W.. G. R. Dull, and R. L. Riggs. 1967. Pre- dicting and measuring the solubility of pp'-DDT in water. Bull. Environ. Contam. Toxicol. 2(2):90-l()0. (ii Cohen, J. M.. and Cecil Pinkerlon. 1966. Widespread translocation of pesticides by air transport and rainout. Am. Chem. Soc. Series. 60:163-176. (4l Cole. H.. D. Barry. D. E. H. Frear, and A. Bradford. 1967. DDT levels in fish, streams, stream sediments, and soil before and after DDT aerial spray application for fall cankerworm in northern Pennsylvania, Bull. Fnviron. Comtam. Toxicol. 2(3):127-146. l5) Fleck. E. E. 1949. The action of ultraviolet light on DDT. J. Am. Chem. Soc. 71:1034. (6) Folch. J.. M. Less, and G. H. S. Slanley. 1957. A simple method for the isolatinn and purification of total lipids from animal tissues. J. Biol. Chem. 226:497-509. (7) Gerhardl. P. D., and J. M. Witt. 1963. Summary of downwind drift limits, comparison of dust vs. spray. Pestic. Residue Study, Univ. of Ariz. 18) Greenwood. R. J.. Y. A. Greichus. and E. J. Hiigghins. 1967. Insecticide residues in big game mammals of South Dakota. J. Wildl. Manage. 31(2):288-292. 19) Licluenslein, E. P. 1959. Absorption of some chlori- nated hydrocarbon insecticides from soils into crops. J. Agric. Food Chem., 7:430-433. ilO) Licluenslein, E. P. 1965. Research in pesticides. Aca- demic Press. New York and London. Part V. p. 199. (ll)Moubry. R. J.. G. R. Myrdal. and J. A. Jensen. 1966. Rapid screening method for detecting chlorinated hydro- carbon pesticide residues in the fat of milk, cheese and butter. Paper presented at Meeting of Assoc, of Off. Anal. Chem. Vol. 5, No. 3, December 1971 257 (12) Pillinoir. R. £.. J. E. Peterson. R. A. Wihon. M. A. f/5) Primate Research Laboratories, EPA. Manual of an- Mohn. G. H. he. ami C. W. Hall. 1963. Residues in alylical methods. Jan. 1971. , , . , . vr X, r. .■ J iiriiif c. A- (16) I'an Middcleii). C. H. 1966. Fate and persistence of forest birds m New Mexico. Pesticide-Wildlife Studies. "" //n-ci,. » a /-u c ,,„ _ , r. , , ,„.i 11 r~- inn orcanic pesticides in the environment. Am. Chem. Soc. U.S. Dep. Inter. Fish and Wild). Circ. 199. '. f^n.-rio 149 (13} Turner, N. 1965. DDT in Connecticut wildlife. Conn. ^^y^ ^^"J.^" ^^^ '^ j ^slesen. and W. P. Calull. 1968. An Agric. Exp. Stn. Bull. 62. ecological study of DDT residues in Arizona soils and (14) Biirchfield, H. P.. and D. E. Johnson. 1965. Guide to alfalfa. Pestic. Monit. J. 2(3): 129-132. the analysis of pesticide residues. Vol. 1, Sec. II. B.L. (IS) IVcir, I. 1966. Biological effects of pesticides in the en- ad). U.S. Dep. Health, Educ, Welfare. vironmcnt. Am. Chem. Soc. Series 60:38-53. 258 Pesticides Monitoring JouRNAi PESTICIDES IN SOIL Insecticide Residues in Soils on 16 Farms in Southwestern Ontario — 1964, 1966, and 1969^ C. R. Harris and W. W. Sans ABSTRACT A study was conducted on 16 farms in southwestern Ontario during 1964, 1966, and 1969 to determine the extent to which residues of insecticides were accumulating in agricul- tural soils as a result of current insect control practices. Residues of organochlorine insecticides were determined by ^as-liquid chromatography (GLC), while those of the organo- vbosphorus insecticides were determined qualitatively by non- specific enzymatic analysis and quantitatively by GLC where oossible. Residues of the organochlorine insecticides were •jresent in soils on all 16 farms in 1964, 1966, and 1969. DDT/DDE/DDD occurred on all farms, aldrin/dieldrin on 14 of 16, and heptachlor/heptachlor epoxide y-chlordane on 5 farms. Other organochlorine insecticides delected included licofot in orchards, endrin, trace amounts of lindane, and 'ndosulfan. Highest average residue levels of the organo- chlorine insecticides were present in orchard > vegetable > obaaco > field crop soils. The use pattern indicated that the organochlorine insecticides were used almost exclusively he- ween 1961 and 1964, but that the organophosphorus insecti- cides received increased use from 1965-1969. Residues of the irganochlorine insecticides in soil appeared to be consistent vith the use pattern in that they were highest in 1966 and ieclined by 1969 to levels similar to those found in 1964. °reliminary data indicated that the trend to extensive use of he organophosphorus insecticides is resulting in the presence j/ residues of some of these materials in vegetable soils. Introduction For over 2 decades, the organochlorine insecticides have lean used extensively to control insects attacking agri- -ultural crops. While these materials have proved to he Contribution No. 474, Research Institute, Canada Department of Agriculture, University Sub Post Office, London 72, Ontario. highly effective against both soil and foliar insects, some are persistent, and residues of these compounds or their metabolites are known to accumulate in soils (/). In Canada, DDT has been used extensively since it became available, and since soil insects have been a particularly serious problem, the cyclodiene insecticides were also used extensively between 1954 and 1960 but at a de- creasing rate since that time. Some areas of the country, e.g., the Prairie Provinces, have received large scale applications of pesticides, but at irregular intervals and at relatively low rates of ap- plication. By contrast, in southwestern Ontario, an area of intensive agriculture with a broad spectrum of soil types and high value cash crops, pesticides are applied regularly in concentrated areas at relatively high rates. A study in 1964 (7) on 31 farms in southwestern Ontario indicated that residues of the organochlorine insecticides were present in nearly all soils, with the most common being technical DDT and its metabolites DDE and DDD>aldrin/dieldrin> heptachlor/heptachlor epoxide/ y-chlordane>endrin. The highest residues were found in orchard > vegetable > tobacco > other field crop soils. The study was continued through 1969 on 16 of the original 31 farms to determine to what extent insecticide residues were accumulating in agricultural soils as a re- sult of the insect control practices during that time. This report summarizes the data obtained on the per- sistence of organochlorine insecticides in soils on these 16 farms for 1964, 1966, and 1969 and also provides some preliminary data on the occurrence in soils of some organophosphorus insecticides used as replace- ments for DDT and the cyclodiene insecticides. v'oL. 5, No. 3, December 1971 259 Methods and Materials The 16 farms selected tor the study were in areas of very intensive agriculture requiring extensive use of insecticides. Care was taken to select cooperators who would adhere closely to the registered or recommended uses of insecticides. Crops included fruit, tobacco, and a wide range of vegetable and field crops. Soil type varied considerably, with orchards on sandy to clay loam, tobacco on sand to sandy loam, vegetables on sandy loam or muck, and field crops on sandy loam or heavier mineral soils (Table 1). Each cooperator was inter- viewed, and as much as possible, a 10-year history of cropping practices and insecticide treatments was ob- tained (Table 1). While such data serve as a useful guide- line, experience has shown that information obtained in this manner is often erroneous, particularly with re- gard to insecticide use. After initiation of the study in 1964, the cooperators were asked to keep more accurate records of insecticide use. and thus the 1965-69 data are more representative of use patterns than the pre- 1964 data. SAMPLING PROCEDURES Soil samples were collected in 1964. 1966, and 1969. Each sampling site, comprising an area of approximately 5 acres within a field, was mapped out by measurement from permanent landmarks in order to assure returning to the exact site in ensuing years. Five subareas were sampled within the 5-acre site. The subareas, which were 4 feet square, were placed diagonally to the perim- eter of the field. Twenty-five 6- by 1- inch cores were taken from each subarea; the cores from all subareas were pooled in order to obtain a representative sample of the field. The pooled sample (approximately 10 lb of soil) was sealed in a plastic bag and refrigerated at 2°C. In orchards, samples were taken both between and under the trees and analyzed separately, but for the purposes of this study the results have been averaged. Samples were taken in October and November of each year. During the course of the study, two farms ceased to be used for agriculture (Table 1 ). Farm No. 9 be- came part of a housing development in 1967 and there- fore was not sampled in 1969. Farm No. 15 was con- verted to a municipal park in 1968, however, samples were collected from the park in 1969. ANALYTICAL PROCEDURES The procedures for extraction, fractionation, and an- alysis were designed primarily for the organochlorine insecticides. Although data are also presented on or- ganophosphonis insecticide residues in soil, it should be noted that subsequent experience has indicated that these procedures are not adequate for some organo- phosphorus insecticides therefore, the data on these compounds should not be considered complete. Insecticide residues were extracted from the soil within a few days of sampling. Two hundred milliliters of dis- tilled acetone was added to 200 g of moist soil (water content adjusted to approximately 50% field moisture capacity) in 16-oz screw cap bottles. The bottles were swirled to obtain good distribution of the acetone:soil mixture, and 200 ml of distilled petroleum ether or hexane was added. The bottles were capped and tumbled on an end-over-end tumbler for 1 hour at approximately 29 rpm, then the supernatant liquid was transferred to 2-liter separatory funnels and the acetone removed by washing three times with distilled water. (Subsequent experience has shown that more polar organophosphorus insecticides such as fensulfothion (Dasanit) remain with the acetone: water mixture and are therefore discarded) The hexane phase was passed through anhydrous sodium sulfate and collected in 8-oz screw cap bottles. Th extracts were stored at — lO'C until analyzed. Recover}' values, obtained by adding known amounts of insecticide standards to residue-free sandy loam and muck soil! followed by evaporation of the solvent prior to extrac tion, indicated >90% recovery for all the organc chlorine insecticides and for some organophosphorui insecticides such as diazinon. Dursban, dichlofenthioi (Nemacide), and parathion. Recovery data using thi extraction procedure were not obtained for the less com mon organophosphorus and carbamate insecticides o the metabolites. Since the soil types used in the recover studies were not representative of the wide range c soils sampled in this study, nor of weathered sample: no corrections were made for percent recovery. Injection of crude extracts from soil into a gas chromt tograph can result in poor definition of peaks whe several insecticides are present, misinterpretation c other soil components or contaminants as insecticide and rapid degeneration of GLC column and detectc efficiency. Consequently, all samples were cleaned u and fractionated on Florisil columns. The technique ha been described in detail (12) and will be outlined onl briefly here. The column was eluted with four solveni as follows; 200 ml of petroleum ether (first fraction 200 ml of 5:1 benzene:petroleum ether (second fraction 200 ml of chloroform (third fraction); and 150 ml c acetone (fourth fraction). The first fraction containe residues of heptachlor, aldrin, o.p'-DDT, p.p'-DDT. an DDE. The second fraction contained lindane, heptachic epoxide, y-chlordane, dieldrin, endrin, DDD, methox^ chlor, dicofol, and endosulfan. The majority of the o ganophosphorus insecticides or their metabolites aj peared in the third and fourth fractions, but son^ chlorinated organophosphorus insecticides eluted in tf second fraction. The eluates were concentrated to aj proximately 2 ml in a rotary evaporator, the residi taken up in hexane, and transfrred to a 10-ml volume ric flask. 260 Pesticides Monitoring Journa TABLE 1. — Crop history and insecticide usage for the 16 farms studied, 1960-69 Farm General Classifi- cation (Crops) Soil Type Crop History and Insecticide Usage No. 1960 1961 1962 1963 1964 1965 1966 1967 1968 1969 1 Field Clay loam Crops Insecticides alfalfa alfalfa corn aldrin corn aldrin aldrin corn aldrin corn aldrin com wheat corn 2 Field Sandy loam Crops Insecticides no data no data corn Htseed tr.) oats alfalfa sugar beets corn oats, alfalfa alfalfa alfalfa soybeans 3 Field Loam Crops Insecticides fallow turnips aldrin corn turnips aldrin wheat oats oats, alfalfa potatoes DDT corn corn 4 Field Clay Crops Insecticides turnips aldrin clover fallow- oats turnips aldrin wheat aldrin wheat aldrin corn. cabbage mev rye, cabbage mev turnips, fen, C 5 Tobacco Sandy loam Crops Insecticides rye. tobacco no data potatoes no data rye no data tobacco no data rye no data tobacco aldrin pota- toes, wheat endrin, DDT potatoes C tobacco C potatoes C, endrin 6 Tobacco Sand Crops Insecticides rye tobacco DDT rye tobacco DDT wheat tobacco DDT wheat tobacco DDT wheat tobacco DDT 7 Tobacco Sand Crops Insecticides tobacco aldrin, DDT rye tobacco DDT wheat tobacco DDT wheat tobacco DDT rye tobacco DDT rye 8 Tobacco Sandy loam Crops Insecticides tobacco aldrin rye tobacco H, DDT "1 tobacco DDT, endrin rye, tobacco DDT, C rye, tobacco C rye, tobacco DDT, C rye, tobacco DDT, C rye, tobacco DDT, C, Dur 9 Vegetables Sandy loam Crops onions onions onions lettuce lettuce toma- lettuce no data no data no data Insecticides aldrin aldrin, aldrin DDT DDT - - no data no data no data 10 Vegetables Muck Crops Insecticides onions aldrin. H onions aldrin, H onions D, H onions D, H onions D, H onions Dz. dichlo onions dichlo, aldrin DDT, dichlo DDT onions DDT 11 Vegetables Muck Crops radishes radishes radishes radishes radishes sorghum cucum- bers. corn corn radishes Insecticides endrin, DDT endrin, DDT endrin, DDT endrin, DDT endrin, DDT - corn endo, aldrin - DDT, P 12 Vegetables Muck Crops Insecticides onions DDT celery DDT celery DDT DDT DDT celery DDT Dz celery, onions DDT, endo. celery, onions DDT, endo. celery. DDT, endo, mev 13 Vegetables Sandy loam Crops Insecticides radishes aldrin radishes aldrin radishes aldrin radishes aldrin radishes aldrin onions ethion beets radishes ethion, P, DDT radishes ethion, P radishes ethion, P 14 Vegetables Muck Crops Insecticides DDT carrots DDT lettuce DDT onions DDT carrots DDT carrots DDT, Dz, DDT, Dz. dichlo carrots DDT, Dz, dichlo DDT, Dz, dichlo lettuce, radishes C, mal 15 Fruit Sandy loam Crops Insecticides apples DDT apples DDT apples DDT apples DDT apples DDT apples no data apples no data apples none none 16 Fruit Sandy loam Crops Insecticides apples no data apples no data apples no data apples no data apples no data apples no data apples no data apples no data apples no data apples no data NOTE: C = carbaryl D = dieldrin Dz =r diazinon dichlo = dichlofenthion Dur = Dursban endo = endosulfan Vol. 5, No. 3, December 1971 fen = fensulfothion H = heptachlor mal — malathion mev = mevinphos P = parathion 261 Organochlorine insecticide residues were determined using GLC. Studies in 1964 were carried out using a Wilicins Aerograph Model 600C Hy-Fi gas chromato- graph and an additional oven. Model 550, equipped with electron capture detectors; subsequent studies used a Varian Aerograph Model 205B dual column GC and a Model 1200 single column GC equipped with electron capture detectors. Operating parameters have been described in detail elsewhere {12). In 1964, 2-column packings were used: DC- II (5% on Chromosorb W) for identification and quantitation and QF-1 (5% on Aeropak 30) for additional verification. In the following years a DC-200 (5% on Aeropack 30) column was used in place of the DC-1 1 column. In cases where identifica- tion was still in doubt, chemical conversion techniques prior to GLC were also utilized (12). The samples were analyzed for: heptachlor. heptachlor epoxide, y-chlor- dane, aldrin, dieldrin, endrin, o,p'-DDT, p,p'-DDT, DDE, DDD, dicofol, methoxychlor, endosulfan, and lindane. Results obtained for o.p'- and p,p'-DUT are reported as technical DDT. Sensitivity of the techniques was 0.01 ppm in 1964 and 0.001 ppm in 1966 and 1969. Results are reported in parts per million based on the oven-dry weight of the soil. Organophosphorus insecticide residues which had been extracted were detected qualitatively by enzymatic an- alysis and quantitatively, when possible, by GLC. Enzymatic analyses were done on fractions 3 and 4 of the Florisil eluate which were known to contain the majority of the organophosphorus insecticides or their metabolites. The technique used was a modification of the methods of Giang and Hall (2) and Hensel el al. (8). Two solutions were prepared: (a) a buffered pseudo- acetylcholinesterase solution utilizing outdated human blood plasma and (b) a 0.132 m acetylcholine bromide solution. One milliliter aliquots of fractions 3 and 4 of the eluates from the Florisil columns were placed in 5-ml beakers. Control samples and control samples plus known concentrations of an enzyme-inhibiting insecti- cide (diazinon) were also prepared. All samples were replicated. The samples were evaporated just to dryness and 2 ml of Solution (a) added to the beakers at pre- cisely timed 2-minute intervals. The beakers were in- cubated in a water bath at 37±0.5°C for 70 minutes, stirring at 15-minute intervals. The samples designated for the initial pH readings were read at that time. One milliliter of Solution (b) was added to the remaining beakers which were then incubated for another 2 hours. Final pH readings were taken and percent inhibition was calculated as follows: Percent inhibition = ii pH of control sample — A pH of treated sample A pH of control sample (ApH = pH |„,,,^, — pH ,,„„) When possible, the presence of organophosphorus in- secticide residues in the soil was determined quantita- tively by GLC utilizing the equipment and techniques outlined above. Verification was made using a Wilkins Hy-Fi Model 600C GC equipped with an alkali flame ionization detector using cesium bromide or rubidium sulfate salts. Results and Discussion Information obtained from those cooperators who could provide data on insecticide use indicated that, in nearly all cases, insecticides had been used extensively between 1960 and 1969 (Table 1). An exception was on Farm No. 2 where the only reported insecticide use had been a heptachlor seed treatment in 1961. Between 1961 and 1964, the organochlorine insecticides were used almost exclusively; from 1965-69, more emphasis was placed on use of organophosphorus insecticides. The greatest pesticide usage was on fruit, vegetable, and tobacco crops, with few insecticide requirements for field crops. The cyclodiene insecticides were used primarily for soil insect control — including the seed-corn maggot, Hylemya platura (Meigen); the cabbage maggot, H. brassicae (Bouche); the onion maggot, H. antiqua (Meigen); the black cutworm, Af^rotis ipsilon (Hufnagcl); the variegated cutworm, Peridroina saticia (Hubner); the northern corn rootworm, Diahrotica loni^icornis (Say); and several species of wireworms. Aldrin was the in- secticide most used, with heptachlor and endrin used to a lesser extent. DDT was used extensively for control of the dark-sided cutworm, Euxoa messoria (Harris) in tobacco, as well as the other cutworm species listed above. It was also used extensively for controlling a wide range of foliar insects on tobacco, vegetables, and fruit. In some cases, e.g., on tobacco, a single soil application was applied annually. In other cases, e.g., vegetables and orchards, numerous applications were made in a single year. Between 1958 and 1964, the seed-corn, onion, and cabbage maggots all developed resistance to the cyclo- diene insecticides {6,9.10) as did the dark-sided cut- worm attacking tobacco (6). As a result, use of the cyclodiene insecticides decreased significantly by 1965. The main use between 1965 and 1969 was for control of the northern corn rootworm. Aldrin, dieldrin, and heptachlor were banned from agricultural use in the Province of Ontario in May 1969. DDT received ex- tensive use up to 1969, particularly for cutworm control in tobacco and on vegetable crops; however, other recommended uses decreased markedly between 1965 and 1969, and it was banned, with two exceptions, from use in Ontario in January 1970. The data in Table 1 also indicate that insecticides receiving increased u.se in place of the organochlorine insecticides include mevinphos. fensulfothion, carbaryl, Dursban, diazinon, dichlofen- thion, endosulfan, parathion, malathion. and ethion. 262 Pesticides Monitoring Journal The results (Table 2) show that DDT plus metabolites were present in the soil on all 16 farms, with the smallest amounts on Farms 1 and 2 which had been devoted solely to field crops. The highest residues were found in the two orchards on Farms 15 and 16. On Farm 15. residues of technical DDT reached a peak of 97 ppm in 1966. Aldrin and dieldrin were found in 14 of 16 soils in amounts ranging from a trace (<0.001 ppm) to as high as 2.3 ppm of aldrin and 2.5 ppm dieldrin on Farm 11 in 1969. Heptachlor/heptachlor epoxide/y-chlordane were present in significant amounts on six of the farms. Endrin was found on only two farms in 1964; by 1969, TABLE 2. — Residues of organochlorine insecticides found in agricultural soils on 16 farms in southwestern Ontario in 1964, 1966, and 1969 Residues in Soil (PPM)> No. Year Hepta- Heptachlor 7-Chlor- CHLOR EPOXIDE DANE Aldrin Dieldrin Endrin DDT = DDE DDD DlCOFOL 1 1964 _ _ _ 0.51 0.40 _ _ _ _ _ 1966 T T T 0.22 0.23 0.01 0.02 T T — 1969 T T T 0.29 0.31 0.01 0.02 T T — 2 1964 _ _ — T T — — _ — _ 1966 — — — 0.03 0.29 — 0.03 0.01 T — 1969 — — — T 0.11 0.10 0.03 0.21 T — 3 1964 _ _ _ 0.51 0.85 _ 0.32 — _ _ 1966 0.29 1.29 — 0.38 0.15 T — 1969 — — — 0.10 1.16 — 0.93 0.15 T — 4 1964 _ _ _ 0.17 1.05 _ 2.64 T — _ 1966 — — — 0.09 1.10 — 0.40 0.12 T — 1969 — — — 0.04 1.13 — 0.30 0.06 0.01 — 5 1964 _ _ — 0.23 0.57 0.11 0.95 — — — 1966 — — — 0.14 0.64 0.10 0.95 0.09 T — 1969 — — — 0.01 0.30 0.06 0.26 0.09 0.02 — 6 1964 T T T T 0.31 — 3.80 0.25 — — 1966 0.03 0.16 0.06 0.02 0.33 0.10 4.97 0.48 0.16 — 1969 T 0.04 0.03 0.02 0.17 0.07 4.57 0.88 0.05 — 7 1964 T T 0.10 T 0.32 — 4.58 0.05 0.06 — 1966 0.40 0.10 0.13 0.01 0.51 0.03 4.85 1.00 0.03 — 1969 0.01 0.08 0.08 0.01 0.48 0.03 1.88 0.79 0.10 — 8 1964 T 0.15 0.17 T 0.21 _ 2.11 0.32 0.10 _ 1966 0.02 0.14 0.13 T 0.17 0.05 4.63 1.01 0.06 — 1969 T 0.07 0.07 T 0.10 0.04 4.03 0.77 0.08 — 9 1964 T T 0.19 T 1.26 _ 3.44 0.15 T — 1966 0.02 0.14 0.13 0.48 1.52 — 2.34 0.33 0.06 — 1969 10 1964 0.24 T 0.63 T 1.11 — 4.60 0.42 — — 1966 0.23 0.19 0.55 0.08 3.33 0.38 10.89 1.14 0.17 — 1969 0.07 0.05 0.22 0.07 1.19 0.08 5.75 0.25 0.14 — 11 1964 _ _ _ 2.13 1.58 3.76 13.80 0.75 0.38 — 1966 _ 1.23 2.52 6.55 15.23 0.74 0.95 — 1969 — — — 2.33 2.54 3.54 7.82 0.81 0.77 — 12 1964 _ T _ _ 22.64 1.09 0.27 — 1966 _ 0.73 0.19 — 34.69 1.41 0.21 — 1969 — — — 0.19 0.21 — 38.18 2.29 0.29 — 13 1964 T T _ 0.79 0.67 _ 0.59 O.II — — 1966 0.04 0.24 0.18 0.11 0.54 — 0.22 0.14 T — 1969 0.04 0.16 0.13 0.08 0.67 — 0.21 0.05 — — 14 1964 _ _ _ T 0.78 — 45.36 1.65 0.58 — 1966 — 0.17 1.29 — 96.20 4.00 1.22 — 1969 — — — 0.04 0.87 1.06 43.42 3.07 1.30 — 15 1964 _ _ _ _ 93.35 8.40 2.70 4.95 1966 _ _ _ _ _ _ 97.07 9.94 1.78 2.97 1969 _ _ _ — — — 75.94 8.39 2.04 4.93 16 1964 _ _ _ _ _ 66.70 12.65 3.30 3.10 1966 _ 62.50 7.84 1.48 2.44 1969 - - - - - — 23.11 7.65 1.41 1.75 1 0.64 ppm endosulfan was detected on Farm No. 12 in 1969 Trace amounts of lindance were detected on F found in any of the soils. = o,p'-DDT + p,p'-DDT. NOTE: T = trace = <0.1 ppm in 1964 and <0.01 ppm in 1966 and 1969. — = no residue detected; limit of sensitivity 0.01 ppm in 1964; 0.001 ppm No. i in 1966 and 1969 and on Farm No. 13 in 1966. No residues of methoxychlor were 1966 and 1969. Vol. 5, No. 3, December 1971 263 residues were present on nine farms, indicating increased use of this compound as some of the other insecticides were phased out. Trace amounts of lindane were de- tected on two farms, but no residues of methoxychlor were found. Dicofol was present in relatively high con- centrations in the two orchard soils while endosulfan was detected on Farm 12 in 1969. For the purpose of this discussion, the results obtained on 15 of the farms have been averaged in order to point out general trends. Farm 9 was e.xcluded since a 1969 sample was not obtainable. It should be noted, however, that due to the limited number of samples the results may not be statistically significant. As mentioned above, between 1961 and 1964 the organochlorine insecticides were used almost exclusively, but from 1965-69 in- creased emphasis was placed on use of the organophos- phorus insecticides (Table 1). The average residue levels for the cyclodiene insecticides in soil tended to be con- sistent with the use pattern. In all cases, with the excep- tion of aldrin, cyclodiene insecticide residues were high- est in 1966 and appear to have declined slightly since then (Fig. 1). The highest concentration of aldrin oc- curred in 1964, and it was present at slightly lower levels in both 1966 and 1969. The most pronounced decline between 1966 and 1969 occurred with hepta- chlor. Dieldrin, endrin, y-chlordane. and heptachlor epoxide appear to have decreased at slower, parallel FIGURE 1. — Average residue levels (ppm) of the cyclodiene insecticides jound in soil on 15 farms in_ southwestern Ontario in 1964, 1966, and 1969 200- 100 •80 _,-60 CO -40 Q-20 I— 2 08 E 06 o. ■"04 ■02 ■0! I"'-- .•-J2^L CYCLODIENES ^. ^DIELDRIN ^•->|NDRIN — • ALDRIN -• • • y-CHLORDANE c >I.EPOXI0E HEPTACHLOR^ 1964 1966 YEAR 1969 rates. The average total cyclodiene insecticide residue levels of 1.24. 1.82, and 1.32 ppm for 1964, 1966, and 1969, respectively, indicate that the residue levels in the soil in 1969 were similar to those found in 1964. Residues of technical DDT also reflected the changing use pattern; they were highest in 1966 (Fig. 2) and by 1969 had declined to an average value of 13.7 ppm, as compared to the 1964 level of 17.4 ppm. Residues of DDE and DDD remained relatively stable, presumably reflecting the microbial degradation of DDT to these compounds. Residues of dicofol in the two orchards sampled also showed little decrease. The aver- age total residue levels for DDT and the related com- pounds were 20.17, 24.74, and 16.32 ppm for 1964, 1966, and 1969, respectively, thus indicating that resi- dues of DDT and the related materials in 1969 had decreased to a level lower than that found in 1964. Of the 15 farms sampled in 1964, 1966, and 1969, 4 fitted the category of field crops, 4 were tobacco farms, 5 were vegetable farms, and 2 were orchards (Table 1 ). When the data obtained on the cyclodiene insecticides were summarized on the basis of these four general categories (Table 3), it was apparent that vegetable soils, on the average, contained the highest levels of these compounds. Tobacco soils also contained residues of most of the commn cyclodiene insecticides, but at considerably lower levels. Residues of aldrin, dieldrin, and endrin were present in the field crop soils. The average cyclodiene insecticide residues for the four field crop soils were greater than those found in tobacco soils. However, this was due primarily to the fact that on Farms 3 and 4, turnips had been included in the rotation prior to 1965, and aldrin was used for cabbage TABLE 3. — Average residue levels for common cyclodiene insecticides found in agricultural soils on 15 farms in south- western Ontario in 1964, 1966, and 1969 in relation to cropping practice S Average Residue Levels in PPM » £ D ^ z z d S < £ 0 u IS 1 1- u u Zt^ >- I I £ < Q u (-U Field 4 1964 _ 0.30 0.58 0.88 1966 — — — 0.16 0.73 T 0.89 1969 — — — 0.11 0.68 0.03 0.82 Tobacco 4 1964 T 0.04 0.07 0.06 0.35 0.03 0.55 1966 0.11 0.10 0.08 0.04 0.41 0.07 0.81 1969 T 0.05 0.05 0.01 0.26 0.05 0.42 Vegetable 5 1964 0.05 T 0.13 0.58 0.83 0.75 2.34 1966 0.05 0.09 0.17 0.46 1.57 1.39 3.73 1969 0.02 0.04 0.10 0.54 1.10 0.94 2.74 Fruit 2 1964 1966 1969 I - E E I ■ trace = <0.I ppm in 1964 and <0.01 in 1966 and 1969. = no residue detected. 264 Pesticides Monitoring Journal -Average residue levels of DDT, and its metabolites and dicofol found in agricultural soils on 15 farms in southwestern Ontario in 1964, 1966, and 1969 in relation to cropping practices No. OF Farms Sampled Average Residue Levels in PPM Crops Year DDTi DDE DDD Dicofol Total DDT Related Compounds Field 4 1964 1966 1969 0.74 0.21 0.32 T 0.07 0.11 T T — 0.74 0.28 0.43 Tobacco 4 1964 1966 1969 2.86 3.85 2.69 0.16 0.65 0.63 0.04 0.06 0.06 - 3.06 4.56 3.38 Vegetable 5 1964 1966 1969 17.40 31.45 19.08 0.80 1.49 1.29 0.25 0.51 0.50 - 18.45 33.45 20.87 Fruit 2 1964 1966 1969 80.02 79.79 49.53 10.53 8.89 8.02 3.00 1.63 1.73 4.03 2.71 3.34 97.58 93.02 62.62 1 o.p'-DDT + p.p'-DDT. NOTE: T = trace = <0.I ppm in 1964 and <0.01 ppm in 1966 and 1969. — = no residue detected. maggot control. The data obtained on Farms 1 and 2 are more typical of farms devoted to field crops. No residues of the cyclodiene insecticides were found in the orchards. When the data for DDT were summarized in relation to cropping practices (Table 4), it was apparent that or- chards contained high residues of DDT and related ma- terials followed by vegetable, tobacco, and field crops in that order. FIGURE 2. — Average residue levels (ppm) of DDT and related materials found in soil on 15 farms in southwestern Ontario in 1964, 1966, and 1969 20 •— rjilll^ «. DDT+reloted moteriols DDT -^^J 10 8 =! fi o to 4 z UJ e2 . DDE • - • , 1— o UJ W1 1 - z ' - -8 • |6 4 : •^--^,... DICOFOL>^ DDD-' 2 1964 1966 1969 YEAR Average residue levels for all the organochlorine in- secticides detected in relation to cropping practices (Fig. 3) indicated that the highest residues were present in orchards > vegetable > tobacco> field crop soils. In orchards, the residue levels were highest in 1964, and decreased in both 1966 and 1969. In vegetable and tobacco soils, residues reached a peak in 1966 and de- creased in 1969 to a point only slightly higher than levels found in 1964. In field crop soils, total organochlorine insecticide residues were highest in 1964 and have dropped since then. FIGURE 3. — Average residue levels (ppm) of the organo- chlorine insecticides found in soil on 15 farms in southwestern Ontario in 1964, 1966, and 1969 in relation to cropping practices 100 - • •■•- • _ ORCHARD 80 60 # -J 40 ■ „'••■•——._ VEGETABLE to ^-'^ — • ? 20 m-" LlJ O ^'0 - '-> 8 . i 6 ■ _^^« TOBACCO 1 ^ •■ — '" — • a. 2 ■ _ FIELD CROP. 1 1964 1966 1969 YEAR Vol. 5, No. 3, December 1971 265 The residue levels found in agricultural soils in relation to cropping practices are based on a very small number of samples. Nevertheless, the data for orchard, vegetable, and tobacco soils are probably quite representative of the situation in southwestern Ontario. However, the data on field crops are unquestionably biased. Of the four farms in this general category, two contained relatively high residues of the cyclodiene insecticides as a result of turnip production: the other two contained residues resulting from corn rootworm and seed maggot control measures. The corn rootworm is a problem only in the southermost counties of the Province, and the acreage of turnips is limited. Consequently, the data given arc not representative of the large acreage of agricultural land devoted to field crops which receive little or no insecticide treatment. The total land area of the Province of Ontario com- prises over two hundred million acres (//) (Table 5). Of this, only 6% is devoted to commercial farming operations, and over one-half of this acreage is planted in field crops where little insecticide is required. Soils containing high residue levels, i.e., tobacco, vegetable, and orchard soils, comprise 0.13% of the total land area of the Province and 2.4% of the land devoted to commercial farming. Thus, although relatively high residue levels are present in these particular soils, they are concentrated in relatively small pockets. In addition, particularly in vegetable soils, the highest residue levels were found in muck soils where they are adsorbed and their insecticidal properties inactivated; under these con- ditions, residues cannot be absorbed by crops and are subject to very little vertical movement {3.4.5). Never- theless, residues of the organochlorine insecticides can move from these contaminated soils by either wind or surface water erosion to contaminate adjacent areas as well as streams and lakes. TABLE 5. — Total acreage of land in the Province of Ontario and acreage devoted to agricultural production, 1969 Acreage Percent of Total Total land area of Province 220,218.880 100.0 Commercial farms 13,229,561 6.0 Field crops (other than tobacco) 7,559,000 3.4 Tobacco 120,000 0.05 Vegetables 121,489 0.05 Fruit 77,869 0.03 The enzyme inhibition tests in 1969 indicated that in- hibitory substances were generally below significant levels in field crop, tobacco, and orchard soils (Table 6). However, both the third and fourth fractions from the extracts of vegetable soils generally showed significant inhibition, thus indicating the presence of organophos- phorus insecticides or their metabolites. It should be pointed out that some of the metabolites of organophos- phorus insecticides have a much greater inhibitory effect than the parent materials, and therefore the data 266 obtained on the fourth fraction may be indicative of only minute quantities of highly inhibitive compounds. GLC analyses confirmed the presence of dichlofenthion in soils on Farms 10 and 14 in 1964, Farms 10 and 12 in 1966, and Farms 10 and 14 in 1969. Ethion was detected in the soil on Farm 13 in 1966 and 1969, diazinon on Farm 14 in 1966 and 1969, diazoxon on Farm 13 in 1969, and parathion and paraoxon on Farm 11 in 1969. Federal and provincial government regula- tions and recommendations have placed considerable emphasis since 1966 on decreased use of the organo- chlorine insecticides and increased use of the organo- phosphorus and carbamate insecticides. These results reflect the trend toward increased use of the organo- phosphorus insecticides (Table 1) in that they were detected in soils on only 2 of 5 vegetable farms in 1964, in 4 of 5 in 1969. These particular organophos- phorus insecticides are generally considered to be of limited persistence in soil. However, they are often applied at higher rates and over shorter intervals during the growing season, and their limited persistence may be offset to some extent by the greater total amounts applied. A ckrtowledgments The technical assistance of H. Simmons and Miss Lucille Ho is gratefully acknowledged. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (1) Edwards, C. A. 1966. Insecticide residues in soils. Resi- due Rev. 13:83-132. (2) Giang, P. A., and S. A. Hall. 1951. Enzymatic determi- nation of organic phosphorus insecticides. Anal. Chem 23:1830-1834. (3) Harris. C. R.. and W. W. Sans. 1970. Vertical distribu- tion of residues of organochlorine insecticides coUectei from six farms in southwestern Ontario. Proc. Entomol Soc. Ont. 100:156-164. (4) Harris, C. R., and W. W. Sans. Behaviour of dieldrin in soil: microplot field studies on the influence of soil typ« on biological activity and absorption by carrots. J. Econ, Entomol. In press. (5) Harris. C. R.. and W. W. Sans. Behaviour of heptachloi epoxide in soil. J. Econ. Entomol. In press. « (6) Harris. C. R.. G. F. Manson. and J. H. Mazurek. 1962. Development of insecticidal resistance by soil insects. J. Econ. Entomol. 55:777-780. (7) Harris. C. R.. W. W. Sans, and J. R. W. Miles. 1966. Exploratory studies on the occurrence of organochlorine insecticide residues in agricultural soils in southwestern Ontario. J. Agric. Food Chem. 14:398-403. (S) Hcnscl. J.. A. E. Hewitt. J. M. Sheets, and R. C. Scott 1956. Microestimation of Demeton residues by the cholinesterase technique. Chemagro Rep. No. 3427. (9) McClanahan. R. J.. C. R. Harris, and L. A. Miller. 1958 Resistance to aldrin, dieldrin, and heptachlor in the onion maggot, Hyleniya antiqua (Meig.) in Ontario Annu. Rep. Entomol. Soc. Ont. 89:55-58. Pesticides Monitoring Journal (10) Niemczyk, H. D. 1965. Cabbage maggot resistance to aldrin in Ontario. J. Econ. Entomol. 58:163-164. (11) Ontario Department of Agriculture. 1969. Agricultural statistics for agriculture for Ontario. Publ. No. 20, 105 p. (12) Sans, W. W. 1967. Multiple insecticide residue determi- nation using column chromatography, chemical con- version, and gas-liquid chromatography. J. Agric. Food Chem. 15:192-198. -Enzymatic inhibition by extracts of agricultural soils from 16 farms in southwestern Ontario in 1969. and residues of organophosphorus insecticides detected by GLC in 1964, 1966, and 1969 Farm No. Extract Fraction Percent Inhibition ' from Extracts Equivalent to Soil Samples of: Organophosphorus Insecticides Determined by GLC (PPM) 0.04 0 0.4 G 1.6 0 1964 1966 1969 I 3 4 1.7 5.1 3.4 14.0 7.2 40.7 _ - — 2 3 4 2.5 3.0 2.1 4.2 2.5 5.5 _ _ _ 3 3 4 5.4 7.8 5.4 12.2 5.4 18.1 — — _ 4 3 4 0.4 0.6 2.1 8.9 5.5 30.6 — — — 5 3 4 2.1 3.0 1.7 2.2 9.4 9.8 _ — — 6 3 4 2.6 4.3 2.6 8.1 2.1 23.8 _ — — 7 3 4 4.3 4.7 4.7 8.1 — _ — 8 3 4 2.4 4.4 3.4 6.3 8.2 17.9 — — — 9 3 4 - — 10 3 4 10.8 11.7 67.9 72.5 81.7 82.5 dichlo(0.85) dichlo(l.lO) dichlo(0.32) 11 3 4 16.3 74.1 80.6 82.0 82.0 83.3 — _ P(1.71) Po(O.Ol) 12 3 4 2.2 8.3 7.9 42.9 14.9 74.6 — dichlo(0.03) _ 13 3 4 1.7 35.7 6.0 80.9 20.0 88.9 - ethion(0.29) elhion(0.24) Dzo(0.03) 14 3 4 3.4 4.2 11.0 26.3 55.1 66.9 dichlo(0.45) Dz(0.09) dichlo(0.07). Dz(0.07) 15 3 4 3.5 3.5 7.5 18.0 18.4 26.3 — _ — 16 3 4 1.8 2.2 16.1 18.8 16.3 24.6 - — — ^ Significant only if percent inhibition is >20. NOTE: — — No residues detected. Blanks = No sample available. Limit of sensitivity: 1964 = 0.1 ppm, 1966 = 0.01 ppm, 1969 dichlo = dichlofenthion P = parathion Dz = diazinon Po = paraoxon Dzo = diazoxon Vol. 5, No. 3, December 1971 267 Persistence of Organochlorine Insecticide Residues in Agricultural Soils of Colorado' Donald E. MuUins", Richard E. Johnsen, and Robert I. Starr' ABSTRACT An exploratory study of the presence and persistence of organochlorine insecticide residues in soils of Colorado was conducted. Fifty samples of orchard and cultivated soils were collected during the summer of 1967 and analyzed in 1968. A new ultrasonic extraction technique was utilized, and analyses were done using electron-capture gas chromatog- raphy and thin layer chromatography. DDT was detected in 27 of the 50 soils sampled and ranged in concentrations from 0.06 to 41.10 ppm. Aldrin and/or dieldrin residues were detected in 14 of 50 samples, ranging from less than 0.02 to 0.91 ppm. Heptachlor and/or its epoxide were found in 1 1 of the soils sampled at concentra- tions of less than 0.02 to 0.07 ppm. Gamma-chlordane was found in 8 of these 50 samples at concentrations of less than 0.02 to 0.05 ppm. Other materials detected in these 50 soils were: lindane, in 8 samples, dicofol in 7, endrin in 2, endo- sulfan in 1, tetradifon in 1, and toxaphene in 1. Residues of organochlorine insecticides were not detected in nine of the samples analyzed. The overall organochlorine concentrations in the soils sampled were lower than those reported by workers in other regions. Introduction The accumulation of organochlorine insecticide residues in agricultural soils has been the subject of increasing concern. Many experiments have been conducted to determine the persistence of insecticides in the soil under controlled conditions. Studies are needed now to de- termine the extent of organochlorine residue buildup in agricultural soils, resulting from general applications by both commercial applicators and individual farmers. A number of general studies of this type have been con- ' From the Department of Entomology, Colorado State University, Fort Collins, Colo. 80521. Published with the approval of the Director of the Colorado Agricultural Experiment Station as Scientific Series Paper No. 1635. - Present address: Department of Entomology, Virginia Polytechnic Institute. Blacksburg. Va. 24060. 3 Present address: Wildlife Research Center, Bureau of Sport Fisheries and Wildlife, Denver Federal Center. Denver, Colo. 80225. ducted in recent years {J-3, 6-9). A few of these in- cluded some soils from the western United States (7,8), but only one represents an in-depth study concerned exclusively with western soils (9). Since Colorado contains a diverse agriculture and a variety of soils, a limited statewide survey of its soils was initiated in the summer of 1967. The overall purpose was to study the retention of organochlorine insecticide residues in agricultural soils where application histories and cropping practices were known to determine if any correlations between application rates, crops grown, and soil types with residue levels could be made. Methods and Materials SAMPLING PROCEDURES To obtain soil samples, contacts were made initially with county agents, chemical suppliers, and applicators. The growers whose names were supplied by these sources were interviewed, and if accurate records on pesticide application, cropping, and cultivation histories were available, soil samples were collected. Fifty soil samples were collected from the major agri- cultural areas of Colorado (Fig. 1). When sampling a field, the approximate center was determined and a grid system established. The grid consisted of 6 rows, 10 paces apart, with 5 core samples taken per row 10 paces apart for a total of 30 cores. A core sample was obtained by inserting a 53.3- by 1.9-cm steel core- sampler to a depth of 15 cm. The cores were collected in a 4-liter glass jar and sealed with a Teflon-lined lid. Upon receipt at the laboratory, the samples were air-dried, pulverized, passed through a 16-mesh soil sieve and stored at 4° C in 2-liter jars with Teflon-lined lids. Orchard samples, included in the total, consisted of a composite of core samples from under and between trees. The samples from under trees were taken about 1 meter from the trunk. 268 Pesticides Monitoring Journal FIGURE 1. — A map of Colorado indicating soil sampling sites Aliquots of each composite sample soil (ca. 150 g) were analyzed for pH, organic matter, and physical prop- erties by the Soil Testing Laboratory, Colorado State University. For soil moisture determinations 100-g aliquots of the air-dried samples were oven-dried for 48 hours at 120°C. All calculations were based on this oven-dry weight. ANALYTICAL PROCEDURES Two 50-g air-dried subsamples (oven-dry basis) were removed from each of the 50 samples for analysis. Each soil subsample was placed in a 16-oz (473-ml) French square bottle, wet to field capacity with distilled water, and allowed to equillibrate for at least 1 hour before extraction. All solvents used were reagent grade chemi- cals glass-distilled prior to use. Each soil sample was extracted in duplicate with acetone for 30 seconds using the ultrasonic technique of Johnsen and Starr (4) which greatly reduces the time required for extraction with recovery values as good or better than conventional extraction procedures. The Polytron Ultrasonic Gen- erator (Model PT20ST, Brinkmann Instruments. IVest- bury, N. Y.) used was equipped with a saw-toothed cutting head (probe). After extraction, the generator probe was rinsed several times with acetone, and the combined extract, rinsings, and soil were transferred to a Buchner funnel containing Whatman No. 42 filter paper and filtered under partial vacuum. The clear filtrate was transferred quantitatively to a 1 -liter separatory funnel containing 100 ml of ben- zene and 250 ml of water containing 10% saturated NaMS04 solution. The funnel was shaken for 1 minute. and after the layers had separated, the lower aqueous layer was drawn off into a second funnel and extracted two times with 50 ml of benzene. The benzene extracts were combined, washed three times with 200 ml of water as used above, and the extract dried by passage through a column of anhydrous Na2S04. The extract was reduced in volume to about 5 ml with a flash evaporator and chromatographed on an activated Florisil (60/100 mesh) column (20 mm i.d.). The Florisil was stored at 130" C in glass bottles until used. The column consisted of 10 g of Florisil preceded and followed by 3 cm of anhydrous Na2S04 and was pre-rinsed with 50 ml of petroleum ether. After the extract and rinsings had reached the top of the column, the column was eluted with 200 ml of 15% diethyl ether in petroleum ether (v/v). The eluate was reduced in volume to near dryness as described above and made up to volume with benzene. Two gas chromatographs with different columns were employed in qualitative and quantitative analyses of the extracts. In addition, spiking aliquots of the extracts with known chemicals and thin layer chromatography of the extracts were used to confirm the results obtained by gas chromatography. The two chromatographs used were Varian Aerograph Hy-Fi Models 600-B and 550, each equipped with a 250-mc tritium source electron capture detector and a Model 328 isothermal temperature controller. The re- corder employed was a 1-mv Leeds and Northrup Model H equipped with a disc integrator. The operating conditions for the gas chromatographic procedures were as follows: I. Instrument: Model 600 Column: 1/16" i.d. x 3' pyrex glass packed with 5% Dow-ll silicone grease on 60/80 mesh Chromosorb W Temperatures: Column: 185°C Injector: 210^C Detector: 187°C Carrier Gas: Prepurified N^ at 20 ml/min II. Instrument: Model 550 Column: 1/16" i.d. x 5' pyrex glass packed with 6.2% QF-1 plus 4.8% OV-17 on 80/100 mesh Gas Chrom Q Temperatures: Column: 205 °C Injector: 205 °C Detector: 205 °C Carrier Gas: Prepurified N . at 20 ml/min An attempt was made to identify all chromatographic peaks, except when extraneous peaks were encountered which did not correspond with those of the standards having similar retention times, or when the sample his- tory did not indicate a probable identity. Vol. 5, No. 3, December 1971 269 Thin layer chromatography (TLC) was used as a final attempt in resolving some analytical problems. Chroma- tographic plates were prepared by mixing 50 g of Silica Gel G (Adsorbosil-1) containing 10% CaSOj binder with 35 ml distilled water. The slurry was applied at a thickness of 250 mjj. with a Desaga applicator, the plates air-dried and activated at 110°C for 2 hours. Samples to be studied were concentrated by flash evaporation down to 0.5 to 2 ml and spotted onto the plates along with appropriate standard solutions. The plates were developed with 8% acetone in «-heptane, sprayed with a chromogenic agent (10 mg AgNO;, in H.jO, added to 10 ml 2-phenoxyethanol. and the mixture diluted to 200 ml with acetone), and the spots developed by ex- posure to low wavelength ultraviolet radiation for about 15 minutes. Since toxaphene is a complex mixture, quantitation was estimated by TLC in the one sample found to contain its residues. Analytical reagent blanks and recovery standards were carried through the extraction and cleanup procedures, and in all cases recovery exceeded 95%; therefore, no corrections were applied to the data. The minimum sensitivity of the method for quantitation was 0.003 ppm with values detected below 0.002 ppm reported as traces. Results and Discussion The overall results of the survey are presented in Table 1. The insecticide history indicates which insecticides were applied, the years of application, and the total amount applied expressed in parts per million (ppm). This calculation is based on the accepted standard that an acre of land 6 inches deep weighs 2 x 10'"' lb (a hectare of land 15.24 cm deep weighs 2.24 x 10" kg); therefore, an application of 2 lb/ 6-inch acre (2.24 kg/ hectare) would be equivalent to 1 ppm. The residues detected are tabulated in such a manner that the parent compound, metabolites, and contaminants in commer- cial preparations are indicated. For example, it is known that technical chlordane contains small amounts of heptachlor and also that technical heptachlor contains traces of chlordane isomers. It should be pointed out that most of the insecticides were used as foliar applications; only aldrin and hep- tachlor were used primarily as soil insecticides. A question mark follows the lindane residues detected (Table 1), because these residues were not confirmed by TLC. In addition, none of these samples had a recorded history of lindane or benzene hexachloride use. How- ever, since these soils were from vegetable-growing areas, they may have been treated earlier with benzene hexachloride, or lindane-treated seed may have been used. It is evident from Table 1 that a considerable number of samples contained residues of certain insecticides even though the prior history indicated that none were ap- plied for up to 10 years or more. For example, DDT was found in Sample 42 at a level of 41.1 ppm although there was no recorded use of DDT at that site for 10 years. Table 2 shows the number of soils to which specific compounds were applied and the number of samples in which residues were detected. The percent positive sam- ples was calculated in relation to the 50 samples an- alyzed. The average amounts applied over the recorded periods (Table 1) and the average amount detected per sample are included. For both DDT and tetradifon, higher levels were detected than were applied. Possible explanations for these discrepancies are (1) a 10-year history is inadequate, (2) records of pesticide use were inaccurate, (3) insecticides were concentrated in certain soil layers, and/or (4) errors were made in sampling. Because of these discrepancies, no correlations, aside from rather general conclusions, can be made. The data pertaining to DDT are presented separately in Table 3. The distribution of residues of the two isomers of DDT and their metabolites DDE and TDE and the percent of residues detected in relation to the known amount of material applied are included to indicate the extent of DDT retention in the soil samples studied. It is obvious that there were heavy applications of DDT prior to the history obtained for a number of the samples; also, in the case of Sample 6, DDT was applied in 1959, but the rate was not recorded. An indication of an aged residue might be obtained by comparing the relative amounts of p.p'-DDT and p.p'-DDE. Similar levels as in Sample 12, could indicate an older deposit, while a higher ratio of DDT to DDE as in Sample 29. is indicative of a more recent application. Results show that the level of TDE in the soil is very low in com- parison to DDE, possibly denoting a more active aerobic rather than anaerobic metabolism. Soil Samples 29, 30, and 31 illustrate the complexity involved in comparing persistence of residues in differ- ent samples. All three samples came from fields farmed by the same individual for 10 years, and all had re- ceived varied applications of DDT. The higher levels of DDT in Sample 30 as compared to Sample 31 could be attributed to the higher organic matter and clay con- tent in Sample 30; however, it is evident that the history for Sample 30 is incomplete, because more residues were detected than were applied. Samples 29 and 31 had different cropping patterns, and both retained low percentages of their DDT applications, although Sample 29 had a high clay content. 270 Pesticides Monitoring Journal Table 4 presents the average organochlorine insecticide residues found in the soil samples in relation to the types of crops grown. As expected, the soils from or- chards contained the highest levels of residues detected, with soils from vegetable-growing areas a distant second. These data seem reasonable since fruits and vegetables usually receive the heaviest insecticide applications. Re- sults show that DDT and related compounds contribute most heavily overall to the residue content of the soils studied. Only with samples from grain-growing areas were cyclo- diene insecticide residues more prevalent than DDT residues. This is possibly a result of the past use of cyclodienes in soil insect and grasshopper control pro- grams. Mullins (5) gives additional information on the soils, cultivation, and fertilization practices and more com- plete details on this study. Summary and Conclusions Although this study was somewhat exploratory in nature, the results may serve as an indication of the general oc- currence and persistence of organochlorine insecticides in agricultural soils of Colorado. Because of limitations in obtaining complete insecticide histories, correlations of the soil type and various other properties with actual residue content of the soils could not be made. Residues of DDT were detected in all of the major agricultural areas of Colorado (54% of the soils sam- pled). Low levels of aldrin and/or dieldrin were de- tected in 28% of the samples. Heptachlor and/or its epoxide were found in 22% of the samples studied. The other insecticides were found at lower frequencies. Two samples with records of no insecticide treatment were found to contain no residues, and seven other samples with known insecticide applications had no detectable residues. ■ These results indicate that significant amounts of DDT residues persist in soils where they have been applied frequently. Overall, the residue levels of the organo- chlorine insecticides in the Colorado agricultural soils sampled generally were lower than those reported by workers in different areas of the United States and Canada. See Appendix for chemical names of compounds discussed in tiiis paper. Supported in part by Regional Project W-45, "Residues of Selected Pesticides — Their Nature, Distribution, and Persistence in Plants, Animals and the Physical Environment." LITERATURE CITED (1) Duffy, J. /?., and N. Wong. 1967. Residues of organo- chlorine insecticides and their metabolites in soils in the Atlantic Provinces of Canada. J. Agric. Food Chem. 15(3);457-464. (2) Gish, C. D. 1970. Organochlorine insecticide residues in soils and soil invertebrates from agricultural lands. Pestic. Monit. J. 3(4):241-252. (3) Harris. C. R., W. W. Sans, and J. R. W . Miles. 1966. Exploratory studies on occurrence of organochlorine in- secticide residues in agricultural soils in southwestern Ontario. J. Agric. Food Chem. 14(4):398-403. 14) Johnscn. R. E., and R. I. Starr. 1971. Ultrarapid extrac- tiiin iif insecticides from soil using a new ultrasonic tech- nique. J. Agric. Food Chem. In press. (5) Mullins, D. E. 1968. The presence and persistence of organochlorine residues from insecticides applied to cul- tivated soils of Colorado. M.S. Thesis, Colorado State University. (6) Seal. W. L.. L. H. Dawsey. and G. E. Cavin. 1969. Moni- toring for chlorinated hydrocarbon pesticides in soil and root crops in the eastern states in 1965. Pestic. Monit. J. l(3):22-25. (7) Stevens. L. ].. C. W. Collier, and D. W. Woodham. 1970. Monitoring pesticides in soils from areas of regular, lim- ited, and no pesticide use. Pestic. Monit. J. 4(3): 145-166. (S) Traiilmann, W. L., G. Cheslcrs. and H. B. Pionkc. 1968. Organochlorine insecticide composition of randomly se- lected soils from nine states — 1967. Pestic. Monit. J. 2(2): 93-96. (9) Ware. G. W.. B. ]. Estesen. and W. P. Caliill. 1968. An ecological study of DDT residues in Arizona soils and alfalfa. Pestic. Monit. I. 2(3): 129-1 32. Vol. 5, No. 3, December 1971 271 TABLE 1. — General injormation on soils sam [T = trace = <0 pled, cropping, insecticides applied, and residues found ,02 ppm — — nol detected j Crops ' Soil History Insecticides Applied Residues Found Sample Percent Total No. Texture Organic Matter pH Percent Clay (YEARS) Compound Years Applied Applied (PPM) Compound Amount (PPM) 1 Grain Loam 1.3 7.9 23 10 None — — 2 Grain Loam 1.5 7.8 23 11 Aldrin 1957, 1959-67 6.75 Aldrin Dieldrin 0.20 0.33 3 Grain Loam 2.1 7.9 24 10 Aldrin 1958-62 2.50 Aldrin Dieldrin 0.03 0.30 4 Grain Clay loam 1.4 7.9 28 11 Aldrin 1957-58 0.13 - — 5 Grain Loam 4.3 7.6 22 11 Aldrin 1960-67 3.00 Aldrin Dieldrin 0,29 0,17 6 Grain Clay loam 1.9 7.7 34 11 Dieldrin DDT Heptachlor 1960. 1967 1959 1961 0.63 0.13 Dieldrin 0.30 7 Grain Clay loam 1.7 7.7 34 9 Dieldrin 1959 0.13 Dieldrin DDT 0.08 0.06 g Grain Clay loam 1.8 7.8 36 10 DDT 1960, 1964 2.25 DDT 0,31 9 Forage Sandy clay loam 2.9 7.7 34 10 None - - 10 Grain Loam 1.5 6.5 18 10 Aldrin Heptachlor 1965 I960, 1967 0.50 0.50 Aldrin Dieldrin H. epoxide 0.61 0.30 0.02 11 Vegetable Sandy 1.5 7.7 28 10 DDT I960, 1967 2.00 DDT 0.98 clay loam Endosulfan Endrin Heptachlor Toxaphene 1964 1958 1962-63 1964 1.00 0.20 0.25 1.50 H. epoxide T 12 Mixed Sandy clay loam 2.1 7.5 28 10 Dieldrin Endosulfan Heptachlor I960 1961, 1964 1959 0.19 1.50 0.25 DDT 1.35 13 Mixed Sandy 1.7 7.6 24 10 Dieldrin 1964 0.13 _ _ clay loam DDT Endosulfan Endrin Toxaphene 1958, I960, 1966 1966 1959 1966 5.25 1.25 0.20 1.50 DDT 1.72 14 Mixed Sandy 1.9 7.5 28 10 DDT I960, 1967 2.50 DDT 1.69 clay loam Endosulfan Endrin Heptachlor 1964 1958 1962-63 0.25 0.20 0.25 H. epoxide T 15 Mixed Sandy 1.0 7.8 23 10 Dieldrin I960 0.19 _ clay loam DDT Endosulfan Endrin Heptachlor 1965 1962, 1965 1963 1959, 1961 1.00 1.25 0.20 0.25 DDT H. epoxide 0.76 T 16 Vegetable Loam 2.2 7.5 23 10 DDT Endosulfan Endrin Toxaphene 1967 1964 I960 1959. 1960 0.50 0.38 0.15 6.26 DDT Endosulfan 1.02 0.04 17 Vegetable Sandy 1.7 7.6 21 II DDT 1957, 1959 1.50 DDT 1.49 clay loam Endrin 1957, 1959 0.30 — — 18 Vegetable Sandy loam 1.5 7.6 13 11 DDT Endrin 1957, 1959 1957, 1959 1.50 0.30 DDT 1.52 19 Vegetable Sandy loam 2.0 7.8 18 10 Perthane Toxaphene 1964, 1967 1958-59, 1961. 1962, 1964-67 1.00 6.00 DDT Toxaphene 0.15 1.00 20 Grain Sandy loam 1.8 7.6 13 ?0 Aldrin 1965-67 1.5 Aldrin Dieldrin 0.16 0.44 21 Forage Sandy clay loam 2.2 7.6 24 10 Aldrin 1957 0.06 - - 272 Pesticides Monitoring Journal TABLE 1.- -General information on soils sampled, c ropping. insecticides c pplicd, and res dues found — Continued Crops 1 Soil History Insecticides Applied Residues Found Sample Percent Total No. Texture Organic Matter pH Percent Clay (YEARS) Compound Years Applied Applied (PPM) Compound Amount (PPM) 22 Vegetable Sandy loam 2.1 7.0 15 5 DDT Endrin Perthane Toxaphene 1963-64 1963-67 1965-67 1963, 1965-67 2.25 0.63 1.50 4.50 DDT Lindane(?)= 3.88 0.05 23 Vegetable Sandy loam I.I 6.8 11 5 DDT Endrin Perthane Toxaphene 1963-64 1964-67 1965-67 1964-67 3.50 0.50 1.50 4.50 DDT Endrin Lindane(?)-' 1.34 T 0.02 24 Vegetable Sandy loam 0.8 6.3 II 5 Chlordane DDT Endrin Toxaphene 1963 1964 1965 1965-67 0.50 0.25 0.13 2.00 DDT Lindane(7)- 0.24 T Vegetable Sandy loam 1.3 7.4 13 5 DDT Endrin Toxaphene 1966 1964, 1967 1965-67 0.25 0.25 0.75 DDT Endrin Lindane(?)= 0.93 T T 26 Vegetable Sandy clay loam 1.1 6.8 21 5 DDT Toxaphene 1964-66 1965-67 3.75 1,25 DDT Dicofol Lindane (?)= 0.97 0.81 0.04 27 Vegetable Sandy loam 1.5 6.9 11 5 DDT 1963 1.50 DDT Dicofol Lindane(?)= 2.08 0.45 0.17 28 Forage Sandy clay loam 0.8 8.7 32 12 None — — 29 Mixed Clay loam 2.4 7.5 31 10 DDT 1966-67 4.50 DDT 0.80 30 Vegetable Clay loam 3.9 7.5 39 10 DDT 1959-61. 1963-65. 1967 15.75 DDT 22.27 31 Vegetable Sandy loam 2.3 7.2 20 10 DDT 1958-67 22.50 DDT 1.68 32 Grain Sandy loam 2.7 7.7 13 13 Aldrin 1956-66 6.00 Aldrin Dieldrin 0.41 0.23 33 Grain Sandy clay loam 2.6 7.2 28 10 Aldrin 1966 0.50 Aldrin Dieldrin Chlordane H. epoxide 0.05 0.16 T T 34 Grain Clay loam 2.7 6.8 37 10 Aldrin 1966 0.50 Aldrin Dieldrin Chlordane H. epoxide 0.05 0.11 T T 35 Forage Clay loam 3.2 7.5 39 10 Heptachlor 1963 0.13 — — 36 Mixed Clay loam 2.2 7.7 31 10 Heptachlor 1961 0.13 — — 37 Forage Sandy clay loam 1.9 7.4 26 8 Heptachlor 1962-64 0.39 - - 38 Forage Sandy clay loam 1.9 7.4 26 10 Heptachlor 1960-62 0.39 - - 39 Forage Clay loam 3.6 7.2 28 10 Aldrin Dieldrin Heptachlor 1964 1963 1958-61 0.25 0.13 0.50 Chlordane H. epoxide T 0.03 40 Orchard Silty clay 3.6 7.4 40 6 BHC Endosulfan 1964-65 1966-67 0.50 0.50 DDT Lindane 5.04 0.06 41 Orchard Silty clay 4.9 7.4 42 6 Dicofol BHC Tetradifon 1963, 1965-66 1964, 1967 1963-64. 2.15 0.43 1.68 DDT Dicofol Lindane 17.10 1.01 0.05 1966 42 Orchard Loam 3.1 7.4 26 10 Dicofol Tetradifon 1958-64, 1967 1964-67 10.45 1.25 DDT Dicofol Tetradifon 41.10 0.93 1.01 Vol. 5, No. 3, December 1971 273 TABLE 1 — General information on soils sampled, c roppint;, 'nscclicides c pplied, and res dues found — Continued Crops ' Soil History (YEARS) Insecticides Applied Residues Found Sample No. Texture Percent Organic Matter pH Percent Clay Compound Years Applied Total Applied (PPM) Compound Amount (PPM) 43 Orchard Loam 3.4 7.4 26 10 Dicofol Endosulfan Tetradifon 1961, 1964, 1966 1962-63 1964 4.20 1.00 0.50 DDT 6.64 Dicofol 1.21 44 Orchard Silty clay loam 3.0 7.5 28 5 DDT Dicofol Tetradifon 1967 1963, 1965-66 1964 1.00 4.00 1.00 DDT 18.76 Dicofol 0.10 45 Orchard Clay loam 4.4 7.7 28 5 DDT Dicofol Endosulfan Tetradifon 1963-64 1963-64, 1967 1966 1967 8.00 1.00 0.25 0.25 DDT 16.27 Dicofol 0.84 46 Forage Clay loam 5.3 7.4 31 10 Chlordane Heptachlor 1966-67 1958-65 1.50 1.48 Chlordane 0.05 DDT 0.23 H. epoxide 0.07 47 Forage Sandy loam 2.8 7.0 13 10 Chlordane Dieldrin Heptachlor 1965-67 1964 1958-63 2.25 0.13 0.75 Chlordane 0.02 Dieldrin T Heptachlor T H. epoxide T 48 Forage Clay loam 3.5 6.9 29 10 Chlordane Dieldrin Heptachlor 1965-66 1964 1958-61, 1963 1.50 0.13 0.61 Chlordane T Dieldrin T 49 Forage Silty clay 1.4 7.4 40 10 Chlordane Dieldrin Heptachlor 1966-67 1964 1958-63 1.50 0.13 0.75 Chlordane 0.03 Dieldrin T H. epoxide T 50 Forage Clay loam 3.8 7.2 34 10 Chlordane Heptachlor 1965-67 1958-63 2.25 0.75 Chlordane 0.05 Dieldrin 0.02 H. epoxide T Grain includes crops such as: wheat, oats, barley, sorghum, and corn. Forage includes crops such as: alfalfa and eludes crops such as: beans, onions, watermelons, cucumbers, cabbage, lettuce, peas, and celery. Mixed includes crops in a manner in which no one group was predominant. These residues were not confirmed by TLC, and none of these samples had a recorded history of lindane or BHC soils were from vegetable-growing areas, they may have been treated earlier with BHC, or lindane-treated seed may rangeland. Vegetable in- 1 mixture of the above use; however, since these have been used. TABLE 2. — Distribution of organochlorine residues applied and detected in the Colorado soils sampled [T = trace = <0.02 ppm; — = not detected] Average Amount No. OF Soils Positive Percent Positive Average Amount Detected in Compounds Treated Samples Samples ' Applied (ppm) Samples (ppm) DDT 20 27 54 4.20 5.57 Aldrin = 11 8 16 1.97 0.48 Dieldrin •' 9 14 28 1.79 0.07 Heptachlor ■ 16 11 22 0.47 0.01 Chlordane = 6 8 16 1.50 0.02 Dicofol 5 7 14 4.36 0.83 Benzene hexachloride " 2 8 16 0.47 0.15 Endrin 11 2 4 0.28 T Perthane 3 _ _ 1.33 — Tetradifon 5 1 2 0.94 1.01 Endosulfan 9 1 2 0.82 0.04 Toxaphene 9 1 2 3.14 1.00 ^ Calculated in relation to the 50 samples analyzed. - Aldrin plus dieldrin. ■■' Dieldrin and aldrin were applied to soil sample no. 39. ' Heptachlor plus heptachlor epoxide. Only sample no. 47 contained heptachlor; all other sample residues •■■ Found residues of heptachlor epoxide in samples 33, 34, 39, 46, 47, 49, 50. " Six of eight samples (22-27) had a peak quite similar to that of lindane (the gamma isomer of benzen matography, but concentrations were not high enough for confirmation with thin layer chromatography. ere in heptachlor epoxide form, hexachloride) on gas-liquid chro- 274 Pesticides Monitoring Journal TABLE 3. — Residues of DDT detected in the soils sampled [ — = not detected] Amount Applied (PPM) Residues in PPM Percent of Amount Applied No. o,p'-DDE p,p'-DDE p,p'-TDE o,p'-DDT p,p'-DDT Total Detected 6 7 _ _ _ _ _ _ 7 - — — — - 0.06 0.06 8 2.25 O.OI 0.14 - 0.04 0.12 0.31 13.7 11 2.00 0.01 0.28 — 0.03 0.66 0.98 48.5 12 — - 0.60 - 0.17 0.58 1.35 13 5.25 - 0.50 - 0.19 1.03 1.72 32.8 14 2.50 0.05 0.55 - 0.19 0.90 1.69 67.6 15 1.00 0.01 0.11 - 0.06 0.58 0.76 76.0 16 0.50 - 0.15 — 0.06 0.81 1.02 204.0 17 1.50 0.01 0.71 — 0.05 0.72 1.49 99.3 18 1.50 0.01 0.60 - 0.02 0.89 1.52 101.3 19 - - 0.03 - - 0.12 0.15 22 2.25 0.01 0.68 - 0.25 2.94 3.88 172.4 23 3.50 — 0.28 - 0.22 0.84 1.34 38.2 24 0.25 - 0.05 - - 0.19 0.24 96.0 25 0.25 - 0.12 — 0.09 0.72 0.93 372.0 26 3.75 — 0.11 — 0.15 0.71 0.97 25.9 27 1.50 — 0.67 — 0.15 1.26 2.08 138.7 29 4.50 — 0.05 — 0.07 0.68 0.80 17.8 30 15.75 0.34 4.51 0.36 6.58 10.48 22.27 141.5 31 22.50 0.02 0.44 - 0.51 0.71 1.68 7.5 40 - 0.04 2.04 0.04 0.69 2.23 5.04 41 - - 6.88 0.10 2.07 8.05 17.10 42 - - 11.52 0.24 5.52 23.82 41.10 43 - - 2.17 0.09 0.58 3.80 6.64 44 1.0 - 9.83 0.04 1.18 7.71 18.76 1876.0 45 8.0 0.04 5.41 0.06 1.57 9.19 16.27 203.4 46 — - 0.08 - 0.06 0.09 0.23 TABLE 4. — Average organochlorine insecticide residues {ppm) in soil in relation to types of crops grown [ — = not detected] DDT and Other Total Type of Soil Samples Related Cyclo- Organo- Organo- Crop ' Compounds = DIENES 3 chlorines • chlorines Grain 1.2, 3, 4,5, 6, 7,8, 10, 20, 32,33,34 0.03 0.33 — 0.36 Forage 9, 21, 28, 35, 37, 38, 39, 46, 47, 48, 49, 50 0.02 0.03 - 0.05 Mixed 12, 13, 14, 15, 29, 36 1.26 0.01 - 1.26 Vegetable U. 16, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 31 3.06 O.OI 0.10 3.16 Orchard 40,41,42,43,44,45 18.12 - 0.32 18.44 ^ See footnote for Table 1. - DDT and related compounds: DDT, TDE, DDE. and dicofol. " Cyclodienes: heptachlor, heptachlor epoxide, 7-chlordane, aldrin, dieldrin, endrin, and endosulfan. * Other organochlorines: tetradifon, toxaphene, and lindane. Vol. 5, No. 3. December 1971 275 DDT Moratorium in Arizona — Agricultural Residues After 2 Years' G. W. Ware, B. J. Estesen, and W. P. Cahill ABSTRACT The 1969 and 1970 moratorium on agricultural use of DDT in Arizona has been very effective. Green alfalfa residues declined significantly in these 2 years, to a probable plateau of 0.05 ppm. Beef fat residues also dropped correspondingly in 1970 to one-half the level found in 1969. DDTR soil residues have changed almost negligibly, suggesting a half- life in excess of 10-12 years. These residues are now pri- marily DDE, indicating that any future problems during the DDT moratorium will be attributable to this "universal con- taminant," rather than to the parent DDT. Introduction The DDT moratorium in Arizona initiated in January 1969, has successfully completed its second year and is well into the third (1). This is the second report on the decline of DDT residues and related degradation prod- ucts (DDTR) following more than 20 years of agricul- tural use. For the best indicators of DDTR decline, we have con- tinued to annually monitor green alfalfa and soil from the same fields and beef fat from the same feed lots. Sampling Methods As in the previous report (1) soil and alfalfa samples were collected from the three major irrigated areas — the Salt River Valley near Phoenix, Pinal County, and the Yuma mesa and valley. Desert soil samples adjacent to these areas were also collected. In addition, an earlier study was continued to provide a reference standard and continuity to the moratorium monitoring back to 1967 (2); the sampling site for this study was located on the 60-mile Maricopa County east-west transect known as Baseline Road. The sampling techniques used here were identical to those previously reported. From the Department of Entomology, The University of Arizona, Tucson, Ariz. 85721. Analytical Methods Alfalfa and soil samples were carried through the same extraction and cleanup procedures as previously de- scribed (/.2). Beef fat samples were carried through the rapid, on-column extraction cleanup method for animal fat [3). Analysis was by electron capture gas-liquid chromatog- raphy (ECGC). Recovery standards and analytical re- agent blanks were carried through the extraction and cleanup procedures for each day's analyses. Recoveries were consistently above 90%: however, these correc- tions were not, applied to the data presented. The mini- mum sensitivity of the analytical method was arbitrarily set at 0.02 ng for p.p'- and o,/)'-DDT, DDE, and DDD. Standard curves extended from 0.03 to 0.10 ng. The relative sensitivities were 0.001 ppm for alfalfa. 0.003 ppm for soil, and 0.06 ppm for beef fat, based on a minimum sample size and 6 /xl extract injected into the chromatograph. Analytical ECGC confirmatory tests were conducted on a random basis, using a double length GC column at a slightly higher temperature, as well as p-value de- terminations using acetonitrile and hexane (4). Because of the very low levels of DDTR and the interfering peaks from toxaphene used on cotton, all alfalfa ex- tracts were dehydrohalogenated after Florisil cleanup and measured only as o,p'- and p,p'-DDE described by Cahill et al. (5). Results and Discussion The analytical results of alfalfa, soil, and beef fat samplings during the past 2 years are presented in Tables 1-8, as total DDTR. The statistical analyses in- dicated in Tables 1 through 7 were the Student-Newman Keul's test for differences among residue means for dif- ferent sampling dates. In Tables 1 and 4 these com- 276 Pesticides Monitoring Journal parisons were made on least squares means due to in- adequate samples in one or more columns. Data in Table 8 were not analyzed statistically due to lack of samples for 1970. The alfalfa residues from all four areas shown in Tables 1-4 appear to have leveled off at about 0.05 ppm or the inherent level which will probably be present for the next several years. For alfalfa residues, there were significant differences among sampling date means in all four areas. Yuma being the most notable, following the apparent mora- torium violations reflected in the September 1969 resi- duces (I). Residues in the alfalfa soils all declined slightly on an average from the last sampling period (Tables 5-7) but none significantly. Since the decline is almost negligible, the suggested time required for these residues to reach one-half their present level is probably in excess of 10-12 years. The desert soils appear to have changed least of the two categories. Because the desert soil collections involve only the top 0.25 inch of soil, they are the most subject to wind-blown contaminants, thus may change rapidly in DDTR values. Residues blown by wind may in turn become part of the unexplained changes in DDTR values found in green alfalfa. The beef-fat DDTR residues in Table S have shown a prominent drop from the 1968 level, 0.49 vs. 0.97 ppm. We believe that visceral beef fat is probably the best indicator of DDT use in agriculture, when all feed consumed by the animals is grown locally, as in Arizona. The DDTR residues now found in Arizona alfalfa, soils, and beef fat are primarily DDE. This indicates that any problems arising from our inherent DDTR residues in the future will be attributable to the "universal contam- inant," DDE, rather than the parent compound. See Appendix for chemical names of compounds discussed in thi« paper. This study is a contribution to Regional Project W-45. "Residues of Selected Pesticides — Their Nature. Distribution, and Persistence in Plants. Animals and the Physical Environment." University of Arizona Agricultural Experiment Station Journal Series No. 1779. LITERATURE CITED (/) Ware. G. W.. B. J. Eslcscn. C. D. John, and W . P. Cahill. 1970. DDT moratorium in Arizona — agricultural residues after 1 year. Pestic. Monit. J. 4(1 ):2 1-24. {2\ Ware. G. W.. B. J. Eslcsen. and W. P. Cahill. 1968. Pesti- cides in soil — an ecological study of DDT residues in Arizona soils and alfalfa. Pestic. Monit. J. 2(3):129-132. (3) Cahill. W. P.. B. J. Estesen. and G. W. Ware. 1970. A rapid on-column extraction-cleanup method for animal fat. Bull. Environ. Contam. Toxicol. 5(1):70-71. (4) Bowman, M. C and Morton Beroza. 1965. Extraction p-values of pesticides and related compounds in six binary solvent systems. J. Assoc. Off. Agric. Chem. 48(5): 943-952. (5) Cahill. W. P.. B. J. Esiesen. and G. W. Ware. 1970. De- terminantion of DDT in the presence of toxaphene resi- dues. Bull. Environ. Contam. Toxicol. 5(3):260-262. TABLE 1. — DDTR residues in green alfalfa. Baseline Rd., Maricopa County, Arizona REsrouES IN PPM Field No. 1967 August 1968 September 1969 September 1970 September Total DDE o,p-DDT p,p'-DDT Total o.p'-DDE p,p'-DDE Total o.p'-DDE p,p'-DDE Total 2 .034 .030 .160 .220 .004 .034 .038 .007 .043 .050 3 .283 .003 .024 .027 .003 .027 .030 4 .170 .017 .018 .080 .120 .004 .034 .038 .003 .034 .037 5 .Oil .012 .040 .060 .002 .018 .020 .003 .021 .024 6 .277 .003 .032 .035 .002 .020 .022 8 .794 .003 .024 .027 9 .019 Oil .040 .070 .007 .027 .034 .004 .038 .042 10 .350 .032 .012 .040 .084 .006 .048 ,054 .008 .154 .162 11 .453 .018 .080 .450 .548 .008 .056 .064 .005 .042 ,047 12 .299 .012 .008 .050 .070 .003 .022 .025 .005 .033 .038 13 .606 .004 .017 .021 Average .404 .020 .024 .123 .167 .004 .033 .037 .004 .041 .045 Least Squares Means ^ .388 ' .201 '■ .069" .045' NOTE: Blank = no samples analyzed. ^ Means with same letter are not significantly different at the 0.05 level. Vol. 5, No. 3, December 1971 277 TABLE 2.- -DDTR residues in green alfalfa during 1969-1970 DDT moratorium, Maricopa County, Arizona Residues in PPM FlELD 1969 January 1969 September 1970 September DDE o.p'-DDT P,p'-DDT Total o,p -DDE P,p'-DDE Total o,p'-DDE P,p'-DDE Total 1 .065 <.011 .022 Ml 005 .037 .042 .006 .051 .057 2 .189 .022 .073 .303 008 .054 .062 .004 .046 .050 3 .066 .007 .024 .102 008 .070 .078 .008 .085 .093 4 .079 <.026 .028 .107 006 .041 .047 .005 .071 .076 5 .038 <.006 .012 .049 004 .026 .030 .003 .022 .025 6 .076 ,011 .019 .113 008 .056 .064 .006 .054 .060 7 .047 .010 .018 .082 005 .029 .034 .001 .022 .023 8 .092 .010 .020 .125 009 .047 .056 (.068) 9 .057 .009 .020 .085 005 .039 .044 .011 .090 .101 Average ^ .079 .012 .026 .117" 006 .044 .051 ' .005 .056 .061 ■ •JOTE: Blanks = no samples analyzed. Figures in parentheses represent missing values calculated by randomized blocl 1.0 |Ug/kg. were rounded to two significant figures; 0.0 /xg/kg represents values less than the sensitivity of the method. No correction when added to moist soils. Residue values for for percent recovery was included in the data. TABLE 1.— Description of pesticide-sampling stations in Everglades National Park and Loxahatchee National Wildlife Refuge Map Location Geological Number Survey Name and Location (Fig. 1) Station Number of Sampling Point Remarks 1 Number Levee 67 canal above In Water Conservation Area 3 at the northeast boundary of Ever- unassigned S-12E near Homestead. Fla.. Lat. 25° 45' 50" Long. 80° 40' 30" glades National Park near water control structure 12E. 2 2-2908.15 Everglades P-3i near In Shark River Slough, the largest slough in Everglades National Homestead. Fla., Park. Stage is affected by local rainfall and by flow through Lat. 25° 36' 30" several gated control structures along southern rim of Water Long. 80° 41' 30" Conservation Area 3. 3 2-2908.28 Everglades P-36 near Everglades P-36, is also located in Shark River Slough in Ever- Homestead, Fla.. glades National Park and its stage is affected by local rainfall Lat. 25° 32- 30" and by flow from Water Conservation Area 3. Long. 80° 47' 00" 4 2-2908.30 Everglades P-35 near In Everglades National Park at the downstream end of the Shark Homestead, Fla., River Slough, a drainage area that covers approximately 200 Lat. 25° 27' 20" square miles. Tributary affected by tide. Long. 80° 52- 30" 5 2-2908.58 Shark River at Ponce de I^on At channel marker 68 at the entrance to Ponce de Leon Bay within Bay near Homestead, Fla., Everglades National Park. A brackish bay. Lat. 25° 20' 07" Long. 81° 06' 44" 6 2-2908. Taylor Slough near At Taylor Slough bridge on State Highway 27 in Everglades Na- Homestead, Fla., tional Park. Taylor Slough is the second largest slough in the Lat. 25° 24' 05" Park, draining approximately 40 square miles of Everglades-type Long. 80° 36' 25" habitat. The sampling station borders a large truck-farming re- gion. 7 Number Taylor Slough at alligator Alligator hole approximately 100 feet north of Taylor Slough unassigned hole near Homestead, Fla., Lat. 25° 24' 05" Long. 80° 36' 25" bridge. 8 2-2907.98 Taylor River near A small stream in Everglades National Park entering Little Madeira Florida City, Fla.. Bay of Florida Bay. A seasonally fresh-water stream which Lat. 25° 50' 10" drains from the Taylor Slough and a coastal mangrove swamp. Long. 80° 36' 25" It becomes fresh in the rainy season. 9 2-2907.96 Little Madeira Bay n ar A small coastal bay adjoining Florida Bay in Everglades National Key Largo. Fla., Park. Lat. 25° 11' 25" Long. 80° 41' 45" 10 2-2785. Everglades below S-5A near At the northern end of Water Conservation Area 1. This area is Delray Beach. Fla., a national wildlife refuge called Loxahatchee. The conservation Lat. 26° 41' 00" area is bordered by a large truck-farming region. Long. 80° 22' 10" 11 2-2812.95 Everglades 1-15 near Delray Beach. Fla.. Lat. 26° 23' 45" At the southern end of Water Conservation Area 1. Long. 80° 17' 40" TABLE 2. — Sutnmary of sampling procedures Material Sampled Sampling Container Quant rrv Sampled Procedure for Collection Water Teflon bottle 1 liter Collected just below surface in teflon bottles Submerged soils Aluminum can 100 g Ekman dredge used in deep water and aluminum can used in sha'low marsh waters Algal mat Aluminum foil 100 g Picked by hand and wrapped in foil Aquatic plants Aluminum foil Whole plants 100 g Picked by hand and wrapped in foil Aquatic animals Glass mason jar with aluminum foil under lid or aluminum can Minimum of 10 g per species Collected by seine or dip net Vol. 5, No. 3, December 1971 283 PLANT MATERIALS (VASCULAR PLANTS AND ALGAL MATS) A sample of approximately 100 g of hand-chopped plant material was placed in a blender and then ex- tracted with acetonitriie following the procedure de- veloped by Mills et al. (15). This technique involves an acetonitriie extraction followed by partitioning between hexane and an acetonitrile-water mixture. The extracts were concentrated and cleanup accomplished by the standard activated Florisil procedure. A recent in- vestigation (16) indicated that this procedure is the most effective of several methods tested for determination of pesticide residues in vegetables. Recovery studies are planned for typical examples of algal mats and vascular plants from the Everglades. Plant residue data were reported on a dry-weight basis, and no correction for percent recovery was included. AQUATIC ANIMALS The procedure of Onley and Bertuzzi (17) was employed for extraction of insecticides from aquatic animals (mostly small fishes). Generally 40 g of animal tissue was used for determining the organochlorine insecticide residues. The method employed a mixture of acetone- methyl cellosolve and formamide to extract the pesticide residues with the use of calcium stearate to hold fatty constituents. Extracts were cleaned up by the standard activated Florisil procedure. The frozen aquatic animals were thawed, hand-chopped, and then placed in a blender. After extraction, concentration, and cleanup, dual column electron-capture gas chromatography provided the final qualitative and quantitative analysis. Recoveries ranged from 80 to 108%. Data were reported on a whole-weight basis with no correction for moisture. No correction for percent recovery was included. Results and Discussion Tables 3 through 7 summarize the findings from the analysis of organochlorine residues in water, submerged soils, and aquatic plants and animals, December 1966 to October 1968. Water in Everglades National Park and Loxahatchee National Wildlife Refuge contained DDT, DDD, and DDE in the range 0.00 to 0.03 fig/ liter. Some samples of soilr. underlying marshes in these areas had concentrations of the DDT family (i.e., DDT, DDD, and DDE) as much as three orders of magnitude greater than the concentrations found in water. Since the analyses of samples for the data reported in Tables 3-7 were performed, the problem of PCB interference in the identification of the "DDT family" has received widespread attention. A careful re-evaluation of the chromatograms revealed no characteristic PCB patterns. Various articles (18-20) document the fact that adsorp- tive forces of the inorganic and organic fractions in submerged soils and soil particles play an important role in the acquisition and retention of organochlorine residues. Accumulation of DDT and its metabolites by marsh plants and animals is shown by the samples obtained from the park and refuge. Algal mats (Table 5) at the base of Everglades food chains, and omnivorous marsh- dwelling crustaceans (Table 7) showed accumulations of the DDT family in some cases, as much as three orders of magnitude greater than the trace concentrations found in water. Marsh fishes (Table 7), intermediate in Ever- glades food chains, concentrated these compounds as much as four orders of magnitude greater than the residues found in water. The highest concentrations of the DDT family were found in the higher carnivores and omnivores. Table 8 presents a generalized scheme of biological concentration of the DDT family from resi- due data obtained in south Florida. GAS CHROMATOGRAPHY The insecticides were analyzed on either a Varian Aero- graph Model 600 chromatograph with a concentric tube tritium electron-capture detector or a MicroTek 220 gas chromatograph equipped with high temperature Ni-63 detectors. Electron-capture detector columns used were 1/8" o.d. (5' or 10' length) pyrex glass on the Varian 600 and 6' long x 1/4" o.d. pyrex glass on the Micro- Tek 200. Columns were packed with 60/80 mesh Gas Chrom Q coated with either 3 to 5% DC-200 or 3 to 5% QF-1. Aliquots of 5 /^l were injected onto both columns, and the presence of an insecticide was reported only when definitely confirmed on both columns. In- strumental conditions (column temperature, gas flow rate, etc.) were similar to those already reported (4). Adjustments were made to yield optimum performance and sensitivity. 284 The data on organochlorine pesticide residues shown on Tables 3 through 7 indicate a variation in total amount of residues observed at different times at one location; whereas, persistency or trends in levels would be ex- pected. Stickel has observed (21) that "extreme vari- ability is typical of residues, even in samples taken at one time and place." It may be that pesticides are being introduced to the Everglades through a series of time- variable events such as precipitation or dustfall, rathei than any constant low level buildup through surface- watei transport. Therefore, the introduction of pesticides may be related to seasonal pesticide usage near the park and refuge or perhaps at even longer distances. Pesticide residue data on samples of rainfall in south Florida have been obtained since 1968 and will be published in another report. Pesticides Monitoring Journal These data indicate that the average amount of DDT and its metabolites in rainfall is an order of magnitude greater than the amount in surface water in the park and refuge. For example, the surface water at Taylor Slough (Station 6, Fig. 1) contained 0.03 /xg/ liter of DDT+DDD + DDE on October 7, 1968; the value for rainfall at the same station was 0.46 ^ug/ liter. Accumulation of pesticide residues in aquatic plants may be due to fallout and adherence to the surfaces of plants and/or internal buildup through metabolic up- take. Mosquitofish data in 1968 (Table 7) at all locations are consistent in that the February concentrations arc always higher than samples in October. This probably reflects a seasonal variance and shows that mosquitofish, which are pesticide concentrators and tend to become resistant to pesticides (22), concentrate more DDT and metabolites in the "dry" season than in the "wet" season. The basic contribution of the data given in Tables 3 through 7 is in showing that organochlorine insecticide residues are present in all trophic levels of the Everglades aquatic environment. Future studies in the park and refuge will be aimed at determining pesticide sources, defining the distribution and assessing the fate of or- ganochlorine and other types of pesticides, and detailing seasonal and long-term fluctuations in the aquatic and biological distribution of pesticide residues. Acknowledgments The authors thank Fred M. Hoover, Jr.. of the Miami office of the U.S. Geological Survey for his efforts in developing techniques for the collection of hydrobio- logical materials, and are especially indebted to Wendell Holswade for the development and application of tech- niques for the materials processed in the U.S. Geological Survey's laboratory in Washington, D.C. Herman Feltz deserves credit for initiating the program of environ- mental studies on pesticides in south Florida. This report was prepared by the Geological Survey in cooperation with the National Park Service and Fish and Wildlife Service. See Appendix for chemical names of compounds discussed in this paper. LITERATURE CITED (/) Feltz, H. R., W. T. Sayers, and H. P. Nicholson. 1971. National monitoring program for the assessment of pesticide residues in water. Pestic. Monit. J. 5(l):54-62. (2) Lamar, W. L., D. F. Goerlilz, and L. M. Law. 1965. Identification and measurement of chlorinated organic pesticides in water by electron-capture gas chromatog- raphy. U. S. Geol. Surv. Water-Supply Pap. 1817-B. 19 p. Vol. 5, No. 3, December 1971 (3) Goerlilz D. F. Techniques of water resources investiga- tions of the U. S. Geological Survey. Book 5, Chap. 42. Methods for analysis of organic substances in water. In press. (4) Brown, E., and A. Y. Nishioka. 1967. Pesticides in selected western streams — a contribution to the national program. Pestic. Monit. J. l(2):38-46. (5) Manigold, Douglas B., and Jean A. Schulze. 1969. Pesti- cides in selected western streams — a progress report. Pestic. Monit. J. 3(2):124-135. (6) Yales, Marvin L., Wendell Holswade, and Aaron L. Higer. 1970. Pesticide residues in hydrobiological en- vironments: problems relating to analysis and sampling. Abstracts of Papers. Symposium on Environmental Sampling, Concentration, and Sample Preservation. Am. Chem. Soc, 159th Annual Meeting, Houston, Tex. (7) Higer, Aaron L., and Milton C. Kolipinski. 1970. Sources of pesticides in Florida waters. U. S. Geol. Surv. Open-File Rep., Tallahassee, Ela. 20 p. (8) Kolipinski. Millon C. and Aaron L. Higer. 1969. Some aspects of the effects of the quantity and quality of water on biological communities in Everglades National Park, U. S. Geol. Surv. Open-File Rep., Tallahassee, Fla. 97 p. (9) Woodwell, George M. 1967. Toxic substances and eco- logical cycles. Sci. Am. 216(3);24-31. (10) tVoodwell, George M., Charles F. Wurster, Jr., and Peter A. Isaacson. 1967. DDT residues in an east coast estuary: a case of biological concentration of a per- sistent insecticide. Science: 156:821-823. (11) Spitzer, Philip R., Millon C. Kolipinski, and Aaron L. Higer. 1969. Pesticides in Florida, an annotated selected bibliography, January 1965-April 1968. U. S. Geol. Surv. Open-File Rep., Tallahassee, Fla. 79 p. (12) U. S. Geological Survey. 1967. Water resources for Florida. Water Qual. Rec, Water Resour. Div., Talla- hassee, Fla. Part 2, 313 p. (13) U. S. Geological Survey. 1968. Water resources for Flor- ida. Surface Water Rec, Water Resour. Div., Tallahas- see, Fla. Part 1, Vol. 2, 204 p. (14) Barry. H. C, J. G. Hundley, and L. Y. Johnson. 1968. Pesticide analytical manual. Food and Drug Adm., Vols. I and II. U.S. Dep. Health, Educ, and Welfare, Wash- ington. D.C. (15) Mills. P. A., J. Onley, and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Anal. Chem. 46(2):I86-191. (16) Burke. J. A., and M. L. Porter. 1966. A study of the effectiveness of some extraction procedures for pesti- cide residues in vegetables. J. Assoc. Off. Anal. Chem. 49(2):370-374. (17) Onley. J. H.. and B. F. Berluzzi- 1966. Rapid extrac- tion procedure for chlorinated pesticide residues in raw animal tissues and fat and meat products. J. Assoc. Off. Anal. Chem. 49(2):370-374. (18) Lichlenslein, E. P., B. S. Schulz, M. S. Skrcntny. and Y. Tsukano. 1966. Toxicity and fate of insecticide resi- dues in water. Arch. Environ. Health 12:199-212. (19) Bailey, G. W., and J. L. While. 1964. Review of adsorp- tion and desorption of organic pesticides by soil colloids, with implications concerning pesticide bioactivity. J. Agric. Food Chem. 12(4):324-332. (20) Edwards, C. A. 1970. Persistent pesticides in the en- vironment. CRC-Crit. Rev. Environ. Control l(l):n-51. (21)Slickel, W. H. 1969. What should we publish? Pestic. Monit. J. 2(4):139. {22} Culley. D. D., Jr.. and D. E. Ferguson. 1969 Patterns of insecticide resistance in the mosquitofish, Gambusia affinis. J. Fish. Res. Board Can. 26(9):2395-2401. 285 TABLE 3. — Organochlorine insecticides in surface waters of Everglades National Park and Loxahatchee National Wildlife Refuge Sampling Point (Map Location Number, Fig. I, Table 1) Date Sampled Residues in /iO/LiTER EVERGLADES NATIONAL PARK 1 10-3-68 0.01 0.01 0.01 0.00 2 2-28-68 0.03 0.00 0.00 0.00 10-3-68 0.01 0.00 0.00 0.00 3 2-28-68 0.00 0.00 0.00 0.00 10-3-68 0.00 0.00 0.00 0.00 4 12-1-66 0.00 0.01 0.00 0.00 3-4-68 0.00 0.00 0.00 0.00 10-1-68 0.02 0.00 0.01 0.00 5 3-4-68 0.01 0.00 0.00 0.00 10-3-68 0.01 0.00 0.00 0.00 6 12-1-66 0.02 0.01 0.01 0.00 7-6-67 0.00 0.01 0.01 0.00 2-27-68 0.00 0.00 0.00 0.00 10-7-68 0.02 0.00 0.01 0.00 9 3-8-68 0.02 0.00 0.00 0.00 LOXAHATCHEE NATIONAL WILDLIFE REFUGE 10 10-8-68 0.02 0.01 0.01 0.00 11 10-8-68 O.OI 0.00 0.00 0.00 Aldrin, dieldrin, endrin, heptachlor. heptachlor epoxide, and lindane. TABLE 4. — Organochlorine insecticides in submerged soils of Everglades National Park and Loxahatchee National Wild- life Refuge Sampling Point Date Sampled Residues in ;hg/kg (Map Location Number, Fig. 1, Table 1) DDT DDD DDE Others ' EVERGLADES NATIONAL PARK 1 7-6-67 10.0 20.0 10.0 0.0 2-28-68 0.0 30.0 7.8 0.0 10-3-68 0.0 0.0 0.0 0.0 2 2-28-68 0.0 19.0 6.1 0.0 10-3-68 0.0 3.9 0.0 0.0 3 2-28-68 0.0 8.5 2.8 0.0 10-3-68 45.0 0.0 3.8 0.0 4 3-4-68 0.0 2.3 1.8 0.0 10-1-68 3.0 0.0 0.0 0.0 5 3-4-68 0.0 2.8 0.6 0.0 10-1-68 0.0 2.8 0.0 0.0 6 7-6-67 1.0 2.0 2.0 0.0 2-27-68 3.3 20.0 21.0 0.0 10-7-68 3.1 0.0 1.0 0.0 7 2-27-68 3.1 4.7 6.3 0.0 10-7-68 1.0 1.2 I.O 0.0 9 3-8-68 0.0 0.0 0.0 0.0 LOXAHATCHEE NATIONAL WILDLIFE REFUGE 10 10-8-68 15.0 23.0 8.8 0.0 u 10-9-68 0.0 8.6 0.0 0.0 ' Aldrin, dieldrin, endrin, heptachlor, heptachlor epoxide, and lindane. 286 Pesticides Monitoring Journal TABLE 5. — Organochlorine insecticides in algal mats of Everglades National Park Point Residues in I1.G/Y.Q (Map Location- Date Table 1) DDT DDD DDE Others i Algal Mat — composed of filaments 2 12-15-67 30.0 3.0 0.6 0.0 and cells of blue-green and green 2-27-68 2.6 0.3 0.5 0.0 algae, diatoms, desmids. micro- 10-3-68 3.0 0.0 0.0 0.0 scopic animals and calcite. forming a thick felt-like mat on the ground 3 2-27-68 1.5 1.3 1.3 0.0 and around plant stems in aquatic 10-3-68 1.0 0.5 0.0 0.0 6 2.0 3.0 2.0 0.0 2-27-68 2.8 0.7 0.8 0.0 8 2-27-68 1.5 2.3 1.0 0.0 10-3-68 0.3 0.0 0.3 0.0 Aldrin, dieldrin, endrin, heptachlor, heptachlor epoxide, and lindane. TABLE 6.- -Organochlorine insecticides in aquatic vascular plants in Everglades National Park and Loxahatchee National Wildlife Refuge Material Sampling Point (Map Location Number, Fig. 1, Table 1) Date Sampled Residues in /u;/kg (Whole Plants) DDT DDD DDE Others 1 2 12-15-67 12-15-67 12-15-67 2-27-68 10-3-68 4.0 4.0 0.0 14.0 2.0 2.0 2.0 0.0 0.0 0.0 0.5 0.5 0.0 0.9 0.0 0.0 0.0 0.0 0.0 0.0 Sawgrass (Cladium jamaicensis) 3 4 2-27-68 10-5-68 2-27-68 15.0 2.0 2.0 0.0 1.0 0.0 0.9 0.0 0.1 0.0 0.0 0.0 6 2-27-68 10-3-68 9.0 20.0 0.0 1.0 0.6 0.0 0.0 0.0 8 10-3-68 10-5-68 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 10 10-8-68 3.0 4.0 2.0 0.0 11 10-9-68 24.0 2.5 1.0 0.0 2 12-15-67 5.0 2.0 1.0 0.0 Needle grass (Eleocharis cellulosa) 3 4 2-27-68 10-3-68 2-27-68 0.0 3.5 6.8 0.6 0.0 1.0 8.4 0.0 0.8 0.0 0.0 0.0 6 2-27-68 8.5 2.0 I.I 0.0 8 2-27-68 10-3-68 8.4 1.5 1.7 1.5 1.6 0.7 0.0 0.0 Pickerel weed iPontederia lanceolata) 10 11 10-8-68 10-9-68 2.5 4.5 2.5 1.5 1.5 0.0 0.0 0.0 Aldrin, dieldrin, endrin, heptachlor, heptachlor epoxide, and lindane. Vol. 5, No. 3, December 1971 287 TABLE 7. — Organochlorine insecticides in aquatic animals in Everglades National Park and Loxahatchee National Wildlife Refuge Material Sampled (Whole Animals) Sampling Point (Map Location Number, Fig. 1. Table 1 ) Date Sampled Residues IN ag/ko DDT DDD DDE Dieldrin Lindane Others ' Pond snail egg (Pomacea paludosa) 11 10-9-68 0.0 0.0 14.0 0.0 0.0 0.0 Oyster (Crassoslrea virginica) 5 8 3-4-68 3-8-68 0.0 0.0 0.0 0.0 0.0 27.0 0.0 0.0 0.0 0.0 0.0 0.0 Gastropod mollusk (Brachiodontis sp.) 8 3-8-68 0.0 0.0 0.0 0.0 0.0 0.0 Crab (Rhithropanopeus barrisii) 8 3-8-68 0.0 0.0 0.0 0.0 0.0 0.0 Fresh-water prawn ( Palaemonetes paludosus) 4 10 3-4-68 10-8-68 0.0 0.0 41.0 0.0 92.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Crayfish iProcambarus allenij 10 2-28-68 10-8-68 0.0 0.0 0.0 0.0 0.0 37.0 0.0 0.0 0.0 0.0 0.0 0.0 Flagfish (Jordanella ftoridiae) 6 10 10-4-68 10-8-68 124.0 176.0 17.0 93.0 43.0 99.0 0.0 0.0 0.0 0.0 0.0 0.0 Mosquitofish (Gambusia affinis atftnis) 2 2-28-68 10-3-68 330.0 22.0 48.0 4.3 160.0 31.0 0.0 0.0 0.0 0.0 0.0 0.0 3 2-28-68 10-3-68 380.0 40.0 120.0 103.0 230.0 45.0 0.0 0.0 0.0 0.0 0.0 0.0 4 3-28-68 460.0 78.0 270.0 0.0 0.0 0.0 6 2-27-68 10-4-68 470.0 140.0 78.0 18.0 300.0 114.0 1.1 0.0 0.9 0.0 0.0 0.0 8 10-3-68 0.0 16.0 0.0 0.0 0.0 0.0 11 10-11-68 65.0 0.0 139.0 0.0 0.0 0.0 Aldrin, endrin, heptachlor, and heptachlor epoxide. TABLE 8. — Generalized scheme of biological accumulation of the DDT family in south Florida [X = digit! Environmental Component Concentration of DDT + DDD + DDE. ^g/liter or ^c/kg (Approx. ppb) Source of Data Water Surface Ground (in Biscayne aquifer) Rain Everglades submerged soils Everglades algal mats or periphyton (producer) Everglades vascular plants (producer) Everglades crustaceans (omnivores) Everglades marsh fishes (omnivores and primary carnivores) Everglades alligators (higher carnivore) Eagle and Everglade Kite (higher carnivore) Man (higher omnivore) ^ .ox .ox X XO. xo. X. xo. xoo. xoo. xooo. xooo. This report Unpublished data ^ Unpublished data ^ This report This report This report This report This report Unpublished data ' 18). William B. Robertson, oral communication. (14) 1 Collected by the authors of this report. 288 I 'ESTiciDEs Monitoring Journal Insecticide Residues in a Stream and a Controlled Drainage System in Agricultural Areas of Southwestern Ontario, 1970 ' J. R. W. Miles and C. R. Harris ABSTRACT A creek flowing into Lake Erie and a controlled drainage system (the water of which is pumped into Lake Erie) were monitored for insecticide residues during 1970. Big Creek, located in Norfolk County. Ontario, drains an area of 280 square miles, chiefly tobacco farms. P,p'-DDE, o.p'-DDT, p.p'-DDD. p.p'-DDT, and dieldrin were determined in water, bottom mud, and fish. The greatest concentration of total DDT was 67 parts per 10" (American trillion) in the water, 441 pp 10' (American billion) in the mud. and 1.0 ppm in the fish. There appeared to be a correlation between rainfall and the concentration of insecticide in the creek water. In 1970, the total amount of organochlorine insecticides that passed from this creek into Lake Erie per week averaged 0.11 lb. The drainage system, near Erieau, Ontario, drained about 1,500 acres of muck land used for growing vegetables. Concentrations of insecticides in the drainage system were greater than those in Big Creek, but the transfer of insecti- cides into Lake Erie was much less from the drainage system. Introduction The erosion of agricultural soils into creeks and thence into lake systems is a possible source of insecticide con- tamination. In 1964, this laboratory initiated studies on the accumulation of residues of the organochlorine in- secticides in farm soils in southwestern Ontario (4). Later work included investigation of translocation into crops from the most contaminated soils (5,7) and profile Contribution No. 484, from the Research Institute, Canada Depart- ment of Agriculture, University Sub Post Office, London 72, Ontario. Studies to check on possible leaching into ground water (6). A natural extension of these soil studies was to examine the insecticide content of water systems drain- ing areas containing contaminated farms. Big Creek in Norfolk County, Ontario, drains 280 square miles (13). chiefly tobacco farms in its upper reaches and tobacco, corn, and mixed farming in its lower area. DDT has been used extensively in this area for many years, primarily for cutworm and hornworm control. Since January 1, 1970, DDT use has been re- stricted to cutworm control and requires a provincial government permit. A recent study (8) has shown that residues of DDT and its metabolites in soil on tobacco farms in this area averaged 3.1, 4.6, and 3.4 ppm in 1964, 1966, and 1969. respectively. Residues of dieldrin in soil on the same farms averaged 0.6, 0.8, and 0.4 ppm in 1964, 1966. and 1969, respectively. Near Erieau, Ontario, a drainage ditch collects the water draining from 1500 acres of muck land used in growing radishes, spinach, onion, celery, etc. This muck land is below the level of Lake Erie water and is con- tained by dykes. Most of the farms in the area have automatic pumps which pump water from their tile drains into the ditch. The ditch water is about 6 to 8 feet below the level of Lake Erie, and is periodically pumped (not automatic) into the lake by a diesel- powered pump which handles between 35,000 and 40,000 gallons of water per minute. Residues of DDT in the soil of one farm in this area were 22.6, 34.7, and 38.2 ppm, respectively, in 1964, 1966, and 1969, while residues of dieldrin were 0.19 and 0.21 ppm in 1966 and 1969 (8). Endosulfan was also detected in the soil on this farm in 1969 (0.64 ppm). Vol, 5, No. 3, December 1971 289 Materials and Methods Water was sampled weekly, and bottom mud was sampled monthly, from mid-April to mid-October 1970. Sampling from Big Creek was at two points — the upper creek (third order — Strahler's system) (W) a few miles north of Delhi, Ontario, and the lower creek (fourth order) (10) just before it empties into Lake Erie. The two sampling points were approximately 20 miles apart. Samples from the Erieau ditch were collected at the pump house and also at a point 1 mile upstream. Water samples were collected using a 1-pint steel container attached by nylon masons line to a bamboo pole. Samples were taken from just below the surface. The water samples were poured into 2-quart glass sealers (calibrated at 1500 ml) having an aluminum foil liner under the cap. At the laboratory each sample was trans- ferred to a 2-liter separatory funnel by means of a glass filter funnel. Before the transfer, the samples were shaken to ensure sediment transfer. After the initial transfer, the jars were laid on their side for several minutes to collect the remaining portion of sample for transfer. Ten milliliters of distilled acetone was added to the jar, and the jar was rotated so that all surfaces were rinsed by the acetone. This rinse was then trans- ferred to the separatory funnel. Seventy ml of hexane was then added to the jar, the jar rotated as with the acetone, and the hexane transferred to the separatory funnel. The separatory funnel was stoppered, shaken vigorously for 2 minutes, and then allowed to stand 15 to 20 minutes for separation of the hexane layer. The aqueous layer was then drained off, and 15 g of an- hydrous sodium sulfate was added to the separatory funnel. After a 5- to 10-minute period, the dried hexane extract was poured from the top of the separatory funnel into a glass-stoppered reagent bottle, using a filter funnel with a plug of glass wool. Mud samples were collected using a homemade sampler consisting of a steel container, 3'/4 inches in diameter and 1% inches deep, attached to the end of an aluminum pole 24 feet long. Five samples of mud were taken from near the bank of the creek or ditch to mid-stream and combined into a composite sample in a plastic bag. Mud samples, weighing 300 g each, were extracted by tumbling for 1 hour in glass bottles with 100 ml acetone and 400 ml hexane. The acetone was washed out in separatory funnels, and the hexane extract dried with sodium sulfate. Portions of the mud samples were dried to determine the moisture content, and the insecticide residues were calculated on the dry weight. Recoveries of the reported insecticides, added to mud at 0.2 ppm, were 91 to 103%. Whole fish were macerated for 2 minutes with acetone- hexane, anhydrous sodium sulfate added, and the mix- ture tumbled for 1 hour. The hexane extract was washed free of acetone, dried with anhydrous sodium sulfate, and fractionated on Florisil (12). Recoveries of the re- ported insecticides added directly to the fish flesh at 0.1 ppm before extraction ranged from 91 to 95%. FRACTIONATION AND CLEANUP OF WATER AND MUD EXTRACTS A chromatographic column 15 mm i.d. (coarse sintered disc) was packed with 1 cm anhydrous sodium sulfate, 8 g prewashed Florisil 60/100 mesh, and a second 1-cm layer of anhydrous sodium sulfate. A larger batch of the Florisil had been previously soaked in a beaker with distilled benzene for 1 hour. The benzene was filtered off, the Florisil soaked in hexane, and the hexane filtered off. The hexane wash was repeated, the hexane filtered off, and the solvent removed from the Florisil in a rotary evaporator. Ten milliliters of hexane was added to the column. Just before the upper hexane level entered the sodiurh sul- fate, the sample, previously concentrated to about 5 ml, was added. The sample flask was rinsed with 2 ml of hexane and the rinse added. The walls of the column were rinsed with a further 2 ml of hexane. When this rinse had entered the sodium sulfate, 75 ml of hexane was added, and 75 ml of the hexane eluate was collected in a T 24/40 125-ml Erienmeyer flask. A second flask' was placed under the column, 75 ml of 3:2 (v/v) benzene-hexane mixture added to the column, and 75' ml of eluate collected. The contents of each flask were concentrated almost to dryness in a rotary evapora- tor; the flasks were then removed and rotated at roonr temperature until the last of the solvent evaporated. The residue was taken up in 1.0 ml of hexane, and the extract was transferred to a screw-capped (tin-foil lined/ glass vial and stored in a freezer. In this fractionation aldrin, heptachlor, p.p'-DDE. o,p'-DDT, and p.p'-DDl elute with the hexane; lindane, dieldrin. p.p'-DDD endosulfan, and endrin elute with the benzene-hexane Recoveries of the insecticides from distilled water forti fied at 1 pp 10" (American billion) were 92 to 105'r for the combined extraction and fractionation. GAS-LIQUID CHROMATOGRAPHY Varian Aerograph gas chromatographs models 1200 and 600D were used. The model 1 200 was equipped with a pyrex glass column 2 m x 3 mm (1.5 mm i.d.) packed with 2% DC-200 + 3% QF-1 on Gas Chrom Q 100/120 mesh, operated at 175 'C. Retention time ot p,p'-DDT was 13.2 minutes. The model 600D had a similar column packed with 5% XE-60 on Aeropak 30 100/200 mesh and operated at 200°C. Retention time of p.p'-DDT was 15.2 minutes. Nitrogen was the carrier gas; flow rate 40 ml/ minute. Identities were also con- firmed on a third column (5% DC-200), but it was not used on a regular basis. 290 Pesticides Monitoring Journal Results and Discussion FIGURE 1 — Concentrations c / total DDT in water of BIG CREEK lower Big Creek and apparent correlation with rainfall The concentrations of p,//-DDE, o.p'-DDT, p.p'-BDD, p.p'-DDT, and dieldrin found in the water of Big Creek, Norfolk County, Ontario, are shown in Table 1. All ' »...r.u . concentrations were very low, the maximum DDT level : ' A (July 21) being 67 parts per 10^- (American trillion). Higher levels of DDT in the water in May coincided with the application of DDT to rye cover crop and soil for cutworm control. Total DDT and dieldrin in the creek water were less than the maximum reasonable stream allowances of 0.5 and 0.25 /xg/ liter (2). The ' /--\/\ ,/-./--/ W/~ -^ /\^ '""" ^A_A/-W^-\^- /V " j:.,' ':.'. " T ' ',..' " " ' ,1." " '.„;:„* 1 ' «'.,.'L. ' 7x',.!;' DDT concentrations in the creek water were similar to the concentrations [up to 0.12 ^g/liter (120 pp 10'^)] reported by Manigold and Schuize (9) as occurring in streams in the Western United States. In two instances ganochlorine insecticides per week. No attempt was (May 12 and August 18) there were higher than average made to determine if the insecticidal compounds were concentrations of dieldrin in upper Big Creek water. in solution, suspension, or adsorbed on silt particles and these were reflected in rises in dieldrin concentra- since this investigation was to determine the total con- tion on those dates in lower Big Creek water. Flow tamination entering Lake Erie from Big Creek. There measurements combined with average insecticide con- was an apparent correlation between the concentrations centration during April to October 1970 indicated an of insecticide in lower Big Creek water and th e weekly average transfer into Lake Erie of 0.11 lb total or- subtotals of rainfall (Fig. 1). TABLE 1. — Insecticide concentrations in water of Bif; Creek, Norfolk County, Ontario, Canada 1970 Date (1970) Residues in Parts per 10"= (American Trillion) tJppER Big Creek Lower Big Creek P.P'- DDE o.p'- DDT P,P'- DDD P,P'- DDT Diel- drin Total DDT P.p'- DDE o.p'- DDT P.P'- DDD p,p'- DDT Diel- drin Total DDT April 14 2 <1 3 13 2 18 <1 8 2 4 <1 14 28 1 <1 1 3 2 5 2 <1 4 24 3 30 May 5 8 <2 20 13 35 7 88 100 8 25 230 5 <1 14 23 3 2 42 20 47 18 94 88 41 133 247 5 3 13 30 79 4 51 27 19 6 9 59 7 25 93 15 9 27 37 12 21 88 Sept. 3 30 9 68 76 6 28 183 8 I 11 11 3 6 31 10 19 5 65 54 6 15 143 7 <1 11 8 2 9 26 17 25 4 75 37 6 20 141 5 <1 12 7 2 5 24 24 31 8 97 53 9 85 189 8 3 16 20 8 14 47 Oct. I 23 6 77 82 6 187 188 6 2 13 13 4 32 34 8 20 6 64 41 5 48 131 7 2 18 20 5 23 47 15 20 6 60 33 8 25 119 5 1 11 6 3 8 23 TABLE 4. — Insecticide concentrations in bottom mud, drainage ditch, Erieau, Kent County, Ontario, Canada, 1970 Residues in Parts per 10" (American Billion), Dry Weight p,p'-DDT Endosulfan UPSTREAM April 16 42 64 35 320 <1 4 461 May 15 109 109 353 842 <1 8 1413 June 10 180 190 670 690 30 17 1730 July 9 160 30 560 360 50 11 1110 Aug. 6 200 30 710 340 <1 62 1280 Sept. 10 140 30 600 210 <1 37 980 Oct. 15 170 <3 680 260 <1 37 1100 AT PUMP HOUSE May 15 7 13 13 27 <1 <1 60 June 10 70 40 240 120 10 <1 470 July 9 50 <3 160 50 20 <1 270 Aug. 6 90 <3 190 70 <1 1 350 Sept. 10 40 5 100 16 <1 1 160 Oct. 15 50 <3 160 40 <1 1 260 TABLE 5. — Insecticide concentrations in fish, 1970 Residues in Parts per 10" (American Billion), Fresh Weight. Whole Fish BIG CREEK, NORFOLK COUNTY, ONTARIO Suckers 2 239 <3 208 198 36 18 645 Suckers 2 340 92 114 409 23 10 955 Chub, large 9 800 <3 212 <3 189 11 1012 Chub, small 17 604 <3 165 <3 36 17 769 DRAINAGE DITCH, ERIEAU, ONTARIO NOTE: — = not detected. Vol. 5, No. 3. December 1971 293 TABLE 6. — DDT pumped into Lake Erie from Erieau Drainage Ditch, 1970 Total DDT ' Month Holms Transferred into Lakh Pumped (LB) April 95.5 0.120 May 13.0 0.020 June 12.5 0.010 July 16.5 0.009 Aug. 6.0 0.006 Sept. 8.0 0.005 Oct. nil nil 1 Total of p,p'-DDE, o,p'-DDT, p,p'-DDD and p,p'-DDT. Summary The results of this study indicate that residues of the organochlorine insecticides, primarily DDT and its metabolites, and to a lesser extent dieldrin, are present in streams and ditches draining agricultural areas whose soils contain residues of these insecticides. While the residue concentrations found in the water were ex- tremely small and were below maximum reasonable stream allowances (2), residues in the mud were 820 to 13,000 times the concentrations in the water. Residues found in the fish were 50.000 to 80,000 times the con- centrations found in the water, thus indicating magnifica- tion as the insecticides move up through the biological chain. Acknowledgments The authors wish to make the following acknowledg- ments: Water sampling — Mr. B. Shoemaker Mud analyses — Mrs. M. H. H. Thomson Fish analyses — Mr. W. W. Sans Creek flow measurements — Mr. G. Hietkamp Erieau pumping data supplied by Mr. Willie Impens, R. R. No. 3, Blenheim, Ontario. Fish supplied by Ontario Department of Lands and Forests. Rainfall data courtesy of Delhi Research Station, Can- ada Department of Agriculture. See Appendix for chemical names of compounds discussed paper. LITERATURE CITED (/) Bagley, G. £., W. L. Reichel, and E. Cromartie. 1970. Identification of polychlorinated biphenyls in two bald eagles by combined gas-liquid chromatography-mass spectrophotometry. J. Assoc. Off. Anal. Chem. 53:251- 261. (2) Ettinger, M. B., and D. I. Mount. 1967. A wild fish should be safe to eat. Environ. Sci. Technol. 1:203-205. (3) Guenzi, W. D., and W. E. Beard. 1967. Anaerobic bio- degradation of DDT to DDD in soil. Science 156:1116- 1117. (4) Harris. C. R.. W. W. Sans, and J. R. W. Miles. 1966. Exploratory studies on occurrence of organochlorine insecticide residues in agricultural soils in southwestern Ontario. J. Agric. Food Chem. 14:398-403. (5) Harris. C. R.. and W. W. Sans. 1967. Absorption of organochlorine insecticide residues from agricultural soils by root crops. J. Agric. Food Chem. 15:861-863. {6} Harris, C. R., and W. W. Sans. 1969. Vertical distribu- tion of residues of organochlorine insecticides in soils collected from six farms in southwestern Ontario. Proc. Entomol. Soc. Ont. 100:156-164. (7) Harris, C. R.. and W . W. Sans. 1969. Absorption oi organochlorine insecticide residues from agricultural soils by crops used for animal feed. Pestic. Monit. J 3:182-185. (8) Harris. C. R., and W. W. Sans. 1971. Insecticide resi- dues in soils on 16 farms in southwestern Ontario — 1964. 1966. and 1969. Pestic. Monit. J. (This issue). (9) Manigold. D. B.. and J. A. Schulze. 1969. Pesticides in selected Western streams — a progress report. Pestic Monit, I. 3:124-135. f/0) Morisawa. M. 1968. Streams — their dynamics and morphology. //; Earth and Planetary Science Series. Mc- Graw Hill Book Co.. New York. p. 152. (1 1) Reinerl, R. E. 1970. Pesticide concentrations in Greal Lakes fish. Pestic. Monit. J. 3:233-240. (12) Sans. W. W . 1967. Multiple insecticide residue determi- nation using column chromatography, chemical con- version, and gas-liquid chromatography. J. Agric. Food Chem. 15:192-198. (IB) Yakutchik. T. J., and W. hammers. 1970. Water re sources of the Big Creek drainage basin. Water Resour Rep. No. 2. Div. Water Resour. Ont. Water Resour Comm., Toronto, Ont., p. 1. 294 Pesticides Monitoring Journal Residue Levels of Dieldrin in Aquatic Invertebrates and Effect of Prolonged Exposure on Populations ' J. B. Wallace and U. Eugene Brady ABSTRACT A woolen mill that uses dieldrin as a moth-proofing agent releases 0.2 parts per million (ppm) in the plant's effluent, which in turn empties into a small Piedmont river in South Carolina. The number of species of aquatic invertebrates downstream in this river has been greatly reduced, and popu- lation complexes have been altered. In all cases, dieldrin levels in extracts of specimens were higher downstream from the plant's effluent outfall than upstream. In some cases dieldrin residues in the downstream fauna were higher by a thousandfold than levels in the upstream counterparts. Down- stream, the dieldrin residue, based on wet weights, was as high as 24 ppm in Simulium vittatum Zett. larvae (Diptera: Simuliidae); 23 ppm in Hydropsyche sp. and 103 ppm in Cheumatopsyche sp. larvae (Trichoptera: Hydropsychidae): and 62 ppm in snails fPhysa sp.). Introduction Contamination of many of our rivers and streams b\ pesticides is well documented. Lichtenberg et al. {12) in a 5-year survey over the United States reported that the last 2 years of their survey reflected a decreasing trend in the use of persistent chlorinated hydrocarbon compounds. In their survey, dieldrin continued to be the dominant pjesticide in streams across the United States although its occurrence also had dropped in the last 2 years of their survey (1967-1968). Dieldrin and other chlorinated hydrocarbon insecticides are known to be readily absorbed into fatty tissues (3). and many "nontarget" aquatic animals and even algae [17) accumulate residues of these pesticides. The amount of residue of any particular chlorinated hydrocarbon insecticide in animals varies greatly, depending upon the levels of exposure and the particular adaptations of the species. Ferguson (5) has reviewed many of these adaptations. Journal paper No. 981. University of Georgia. College of Agricul- culture, Experiment Station, Athens, Ga. 30601. Considerable information is available concerning chlori- nated hydrocarbon residues in aquatic invertebrates, but little or no data are available concerning residues in invertebrates collected at a specific location that has been subjected to continuous and prolonged exposure to a chlorinated hydrocarbon insecticide. In this paper dieldrin residues are compared in several species of aquatic invertebrates collected upstream and down- stream from a location at which dieldrin is regularly released. This study concerns the Rocky River in Abbeville Co., S. C. A woolen mill which has been in operation over 10 years near this river uses dieldrin as a moth-proofing agent during the dyeing process. Contents of the dyeing vats, rinse water from the yarn, and other process wastes are piped directly into a series of four oxidation lagoons. The effluent from these lagoons, about 1 million gallons per day, enters a small stream which in turn enters the Rocky River about 0.8 mile below the lagoons. The average discharge rate of the Rocky River is 307 ft'Vsec. TTie presence of dieldrin in the effluent from this mill has been documented by Dr. A. W. Garrison (personal coiitmunication) of the Environmental Protec- tion Agency's Southeastern Water Laboratory, Athens, Ga, Garrison found the concentration of dieldrin in the effluent stream as it entered the Rocky River to be 200 parts per billion (ppb); in the Rocky River just below its confluence with the outfall stream. 17 ppb; and in the Rocky River near its junction with the large Savannah River, about 5 miles below the plant outfall. 6 ppb. The above figures are based on averages obtained in water samples taken in March and October 1969. Lichtenberg et al. (12) have reported concentrations of dieldrin in the Savannah River at North Augusta, S. C. (some 50 miles downstream from this plant) averaging .085 ppb be- tween the years 1964-68. This river was constantly in the top three most dieldrin-polluted rivers in the United States during the 5-year period in the above report. Vol. 5, No. 3, December 1971 295 FIGURE 1. — Diagrammatic map of Rocky River near Calhoun Falls, S. C. The Invertebrate Fauna In an effort to make some quantitative estimation of the invertebrate fauna of the polluted area, a series of Surber square foot samples were taken on September 13, 1970. Station I (map) was a riffle area in Rocky River about Vi mile upstream from the junction with the small stream containing the dieldrin effluent. The bottom substrate at Station I was composed of large rocks on which a thick Podostemum ceratophyllum (Podostema- ceae) mat was growing. Station II was on the "clean" side of the Rocky River opposite the small stream containing the dieldrin effluent. Station III was only 3.3 meters from Station II and just below the junction with the small effluent stream on the same side of the river as the effluent. Stations II and III were not true riffle areas, but both stations had bottoms consisting of large rocks and a rather swift current (1.5 - 2.5 ft/ sec). the rocks on the Station II side of the stream had a rather thick Podostemum ceratophyllum mat: those on Station III side had little or no P. ceratophyllum. and a rather thick Sphaerotilus growth covered the rocks. Sta- tion IV was appro.ximately Vi mile downstream from Stations II and III. Station IV was a riffle area (the first riffle area below the outfall) consisting of rocks and small stones. There was some Sphaerotilus and fila- mentous algae growing on the rocks at this location. The hellgrammite, Corydalis cornuta L. (Megaloptera: Corydalidae), Hydropsyche sp. (Trichoptera: Hydro- psychidae), and Simulium vittatum Zett. (Diptera: Simuliidae) used for the April 18. 1970, downstream dieldrin analysis were removed from rocks in this riffle and from limbs and debris just upstream from this riffle. Station V was about 4 miles downstream from Station IV. The river was deeper and slower at this point. The steep banks were 10-20 feet high on either side of the river. The bottom was silty, and there were no rocks. The nature of the bottom and the substrate to which the organisms were attached prohibited the use of the Surber square foot sampler for quantitative sampling. The Cheumatopsyche sp. (Trichoptera: Hy- dropsychidae) and S. vittatum larvae obtained for diel- drin analysis on February 24, 1970, at this station were removed from treetops and debris that had fallen into the river. High water levels in April 1970 prevented acquiring enough Cheumatopsyche larvae for dieldrin analysis on April 18 at this location. The fauna list at the various stations in Table 1 is the result of five square-foot samples at Station I, three each at Stations II and III, and five at Station IV, taken on September 13, 1970. The invertebrates from all samples at each station were then converted to number per square meter. Station I contained by far the greatest number of species. The Ephemeroptera, Plecoptera, Megaloptera, and Trichoptera fauna was severely reduced at the stations downstream from the textile plant outfall (Table 1 ). It should be emphasized that most of the Ephemeroptera that were found downstream were very small, perhaps indicating recently hatched individuals. Also, the pos- sibility of downstream drift, such as that reported by Anderson (/) and Elliott (6), cannot be eliminated. Probably the most striking difference in the fauna oc- curred between Stations II and III. Although the sta- tions were only 3.3 meters apart, the aquatic insect fauna at Station III was almost nonexistent except for a few Chironomidae larvae. The only insects to show a downstream increase at Station IV were Chironomidae (Diptera) larvae and Empididae (Diptera) larvae. There were 8 Empididae larvae per square meter found in the upstream (Station I) samples, and 47 per square meter were found in the downstream (Station IV) samples. The Chironomidae larvae went from 14 per square meter upstream (Station I) to 4800 per square meter downstream (Station IV), a 340-fold increase in the downstream (Station IV) fauna. The composition of the Chironomidae fauna changed between the various stations — at Station I it consisted of Calospectra sp.; downstream at Station IV the fauna was composed largely of Polypedihtm nr. scalaemim (Schrank). Among the fauna other than insects, Oligochaeta increased down- stream at Station IV (1600+ versus 22 per square meter upstream at Station I). 296 Pesticides Monitoring Journal TABLE 1. — Bottom fauna in numbers per square meter in the Rocky Rivei at Calhoun Falls, S. C, on September 13, 1970 Number/Square Meter Organism Station I Station II Station III Station rv TurbeUaria 11 0 0 0 Oligochaeta 22 50 22 1600+ Insecta Ephemeroptera Ephemercllidae Baetidae Tricorylhodes sp. Isonychia sp. Pseudocloeon sp. Undetermined 41 92 32 0 25 0 40 0 0 0 0 0 3 1 0 5 Heptageniidae Slenonema sp. 5 7 0 1 Odonata Agrionidae Enallagma sp. 3 0 0 0 Plecoptera Pteronarcidae Pleronarcys dorsata 5 0 0 0 Megaloplera Corydalidae Corydalis cornula 27 0 0 1 Coleoptera Elmidae MacTOnychus sp. 5 14 0 3 Trichoptera Psychomyiidae 3 0 0 0 Hydropsychidae Hydropsyche sp. Cheumatopsyche sp. 527 57 65 40 0 0 12 0 Hydroptilidae Leptoceridae Athripsodes sp. 3 8 3 3 0 0 3 0 Diptera Chironomidae Simuliidae Empididae Simulium vittatum Nr. Hemerodromia sp. 14 84 8 47 58 0 15 5 0 4800+ 19 47 Materials and Methods Invertebrates used for dieldrin analysis were collected using standard aquatic dip nets. The specimens were placed in small plastic bags and frozen in dry ice in the field. The bags containing the specimens were trans- ferred to a freezer after returning to the laboratory. The number of individuals in each replicate for dieldrin analysis varied, depending upon the group involved. There were approximately 25-40 larvae of Cheuma- topsyche sp. and Hydropsyche sp. in each replicate in- volving these two genera, 50-100 larvae of Simulium, 1 larva in each replicate of Corydalis cornuta L., and 25-30 snails, Physa sp., in each of the downstream repli- cations. EXTRACTION OF DIELDRIN Frozen samples were washed twice with 5-ml portions of redistilled acetone for 30 seconds, air dried for several minutes, and then weighed. A preliminary test showed that no more weight loss occurred when acetone was used as a wash than occurred using water. The method of analysis was a modification of the procedures in the Pesticide Residue Analysis Manual (1969) of the Federal Water Pollution Control Administration. Samples were homogenized for 5 minutes in a Waring microblender containing 20 ml of methanolethyl ether (1:1) and 1 g of anhydrous sodium sulfate. Each homo- genate was evaporated to dryness with a rotary evapora- tor at 40°C, and the residue was extracted three times with redistilled Ai-hexane. Dieldrin was partitioned into acetonitrile (analytical reagent) by extracting the hexane fraction three times with acetonitrile saturated with n- hexane. Acetonitrile was removed by rotary evaporation; the residue was dissolved in petroleum ether (analytical reagent) and cleaned up on a Florisil column with 6% and 15% ethyl ether in p>etroleum ether as the solvent system. In almost all cases, dieldrin was in the 15% ethyl ether fraction. The column eluate was diluted to 5 ml with redistilled ethyl ether (petroleum ether inter- ferred with GLC analysis), evaporated to near dryness, and stored at 7°C until analyzed by gas-liquid chroma- tography (GLC). GAS-LIQUID CHROMATOGRAPHY Analyses were conducted with a Varian Aerograph gas chromatograph (Model 2100) equipped with a "'Ni elec- tron capture detector. Five microliter aliquots of all samples were injected in duplicate on each of two columns (glass, 6 mm i.d. x 6 feet) packed with 5% OV-210 on 60/80 mesh Chromosorb W (Carrier gas: No at 100 ml/min; column temperature: 200°C) and with 1.5% OV-17 and 1.95% QF-1 on 100/120 mesh Chro- mosorb W (Carrier gas: No at 120 ml/min; column tem- perature: 195°C). Dieldrin in appropriately diluted ex- perimental samples was quantitated by comparing peak heights from linear standard curves obtained by inject- ing known quantities of analytically pure dieldrin in- termittently with experimental samples. Vol. 5, No. 3, December 1971 297 Each of three groups of last-instar larvae of the Indian- meal moth, Ploclia interpunctella (Hubner) (50 larvae/ group), "spiked" with 1 yu.g of dieidrin was extracted and cleaned up as described above to determine percent recovery. Average recovery was 74% . Dieidrin was not detected in nonspiked Plodir. samples. Results and Discussion Known dieidrin from two suppliers co-chromatographed with a compound in each of several selected experi- mental samples. The extremely high levels of residues detected in insects collected downstream and the smaller amounts in insects upstream from the known source of release of dieidrin supports the conclusions that the residues reported are dieidrin. Also, Dr. A. W. Garrison (personal communication) has mass spectral evidence that dieidrin is present in the outfall stream. In all cases, dieidrin residue levels were higher in the downstream fauna than their upstream counterparts (Table 2). In Simuliiim viitatum, the average increase in the February collections was 1,178-fold downstream. In the April collections there was a 56-fold increase in the downstream S. vittatiun compared to those upstream. The lower residues in the April downstream collections of Simuliiim as compared to February collections were probably due to their shorter period of exposure to dieidrin. The April Simulium larvae were small and represented a second generation that had been exposed only a few weeks, whereas the February larvae were the overwintering forms which had been exposed to dieidrin much longer. The highest residue levels in any of the animals occurred in the C/ieumaiopsyche col- lected in February downstream at Station V. The dieidrin level in the two replications of Clwumatospsyclie at this point ranged from 90 to 103 ppm (Table 2). Unfortunately, no upstream Clieumatopsyche were an- alyzed, but in the closely related genus Hydropsyclie the dieidrin residue levels upstream were 0.171-0.685 ppm in the two replicates collected on the February date. On April 18 1970, larvae of Hydropsyclie were collected at Station IV and upstream at Station I. In two replicates there were 432- to 547-fold increases in dieidrin residues in the downstream Hydropsyclie fauna compared to that upstream. The hellgrammite, Corydalis cornuta L., had the smallest amount of dieidrin of any organism tested downstream. The two downstream specimens of C. cornuta contained 1.213 and 0.920 ppm dieidrin, re- spectively. Despite this low level, the downstream speci- mens had a 60-fold increase over the upstream C. cor- nuta. In both upstream and downstream specimens of C. cornuta, the larger 2-year-old larvae had higher levels than the smaller 1-year larvae. Downstream, where the snail fauna was composed almost solely of Pliysa sp., these snails contained 33 to 62 ppm dieidrin There were no snails collected at upstream stations where few Pliysa snails were present, but many Goniob- asis sp. were observed. TABLE 2. — Dieidrin residues in certain aquatic invertebrates from the Rocky River, Abbeville County, S. C. [T = trace = <.02 ppm; — = not detected] Datb (1970) Station Number OF Samples DiELDRiN Residues in PPM (Wet Weight)i 1 Upstheam = Downstream - OV-210 3 OV-17/QF-13 OV-210-' OV-17/QF-1- Blackfly larvae Simulium vittatum Simulium vittatum Caddisfly larvae Cheumatopsyche sp. Hydropsyclie sp. Hydropsyclie sp. Hellgrammite larvae Corydalis cornuta Snail Physa sp. Feb. 24 Apr. 18 Feb. 24 Feb. 24 Apr. 18 Apr. 18 Feb. 24 I. V 1, IV V 1 I. IV I. IV V 1 2 - 0.04 T 0.19 0.08 0.26 0.21 19.44 23.03 23.92 24.53 14.84 17.48 103.67 103.49 98.74 90.55 0.69 0.58 0.17 0.05 0.04 T 0.03 T 0.02 T No specimens 17.28 17.28 18.01 23.22 1.21 1.48 0.92 1.00 58.36 62.47 33.24 37.41 » These figures were not co - Upstream (Station I), do ■■■ Gas chromatograph colu * Compare with Hydropsyc 298 rected for percen wnstream (Statio ■nn (these figures le. recovery. 1 rv, V)— position were not corrected rom dieidrin sou for percent recc ce. very) Pesticidb s Monitoring Journa These data indicate that there is a great deal of varia- tion in dieldrin residue levels between various groups of organisms. Although the two genera of Trichoptera, ' Hydropsyche and Cheiimatopsyche, are in the same family (Hydropsychidae), in collections downstream there was approximately a four to five times higher dieldrin content in the Cheiimatopsyche than in the Hydropsyche larvae. This may be due to any one or a combination of the following factors: (1) Although both are reported to be omnivorous filter feeders, there may be subtle differences between feeding habits in these two genera. (2) There probably are physiological differ- ences in regard to ability to cope with dieldrin or store the dieldrin in the body. The amount of dieldrin in the \Cheumatopsyche larvae indicates that the Cheumatop- Uyche larvae are actually concentrating this insecticide I in fat tissue at much higher levels than Hydropsyche. Perhaps this explains the absence of Cheiimatopsyche larvae at Station IV. Possibly, they cannot cope with the higher dieldrin levels at this station as compared to Station V (levels based on water analyses. Garrison, versonal communication.) (3) There may be some dif- ferences attributable to the habitat. Many of the Cheii- matopsyche larvae at Station V were recovered from limbs, etc., at the silty bottom of the river where there were possibly higher residues of dieldrin in the sur- rounding sediments. Holden (9) reported that many ;hlorinated hydrocarbon insecticides such as dieldrin settle in such sediments. Holden also noted that levels of 15 ppm dieldrin in the mud may result in several fold increases of dieldrin in the invertebrate fauna living in such environments. (4) Another possibility that should not be overlooked is the possible seasonal effect on resi- due levels. The downstream Cheiimatopsyche were col- liected in February and the Hydropsyche in April. Kelso I?/ al. (11) recently found seasonal variations iii DDT residues in fish, the lowest levels of DDT occurring in spring and summer. 9ne rather surprising result was the relatively low levels of dieldrin found in the hellgrammite. Corydalis cor- niita. Gut analysis has revealed this animal to be a predator on other aquatic insects, including Trichoptera land Simuliidae larvae. With the reported increase in concentration of chlorinated hydrocarbons up the food chain, (13, 18), one would expect C. cornuta to have higher pesticide levels than its prey: instead, the Simiili- •im and hydropsychid larvae that represented probable Drey had 12 to 70 times more dieldrin than the hell- jgrammite. This may be due to one of two factors: either \Corydalis does not store dieldrin or has some efficient mechanism for eliminating it. These data would support jthe findings of Keith {10). Peterle {16), and Chadwick and Brocksen (5) that aquatic organisms may not neces- sarily show pesticide concentrations relative to their position in the food chain. Since Corydalis larvae were much less abundant downstream, they possibly repre- sented recent migrants into the downstream area. How- ever, the finding that both larvae collected downstream contained higher dieldrin residues than those upstream (Table 2) may discount this latter possibility. One point that should be emphasized is that most of the animals with higher dieldrin concentrations discussed in this study are near the bottom of the food chain and are either detritus or omnivorous filter feeders. Judging from the relatively high concentrations of diel- drin in the Hydropsychidae and Sinniliiim larvae and their exposure for several years, one may certainly surmise that they have developed some degree of resist- ance to this pesticide. Such resistant organisms that concentrate pesticides at these lower trophic levels could foreseeably represent real hazard to higher organisms that feed on them. This idea has been previously ex- pressed by Naqvi and Ferguson {14) and Ferguson (7). Since residues in the specimens examined in this study were several thousand times higher than residues found in the water, such organisms as Hydropsychidae and Simuliidae larvae may offer excellent possibilities as biological monitors for pesticides. For example, the Cheiimatopsyche larvae at Station V had 103 ppm diel- drin compared to the water sample which had only 6 ppb. This represents a 17,000-fold concentration of dieldrin in Cheiimatopsyche larvae compared to the water sample at Station V. The idea of using inverte- brates as pesticide monitors was also expressed by Butler {4) utilizing oysters and Bedford et al. {2) using the freshwater mussel. This area should certainly be explored in greater detail. Undoubtedly, much of the discrepancy between the amount of pesticide in the water and the organisms is due to the low solubility of dieldrin and the fact that it settles to the substrate (9) where most of the organisms discussed in this study are found. Also, the fact that aquatic organisms feed on particular organic matter increases their chances of coming into contact with higher concentrations of dieldrin than that normally present in the water. Nicholson {15) has pointed out that monitoring to detect the presence of chlorinated hydro- carbon pesticides in water alone will not suffice due to the ability of pesticides to concentrate in sediments and aquatic organisms. Determination of the source of pollution by a pesticide and a critical evaluation of the need for application are extremely important to the realistic control of pollution. Certainly, the abatement of all nonessential applications of persistent pesticides should be a common objective. Vol. 5, No. 3, December 1971 299 A cknowledgments The authors express their thanks to Dr. A. W. Garrison of the Southeastern Water Laboratory, U.S. Department of the Interior, (now Environmental Protection Agency) Athens, Ga. for generously providing the data on water analyses of dieldrin in the streams mentioned in this study. Thanks are also extended to Mr. Fred F. Sher- berger. Miss A. E. Gordon, and Miss Bobbie Griffin for assistance in gathering the data. See Appendix for chemical names of compounds discussed paper. This research was partially supported by USDI Federal Water Quality Administration Grant 18050 DFQ and NIH Grant 5 ROl ES00253. LITERATURE CITED f/) Anderson, N. H. 1967. Biology and downstream drift of some Oregon Trichoptera. Can. Entomol. 99:507-21. (2) Bedford. J. W.. E. W. Roelofs. and M. J. Zabik. 1968. The freshwater mussel as a biological monitor of pesti- cide concentrations in a lotic environment. Limnol. and Oceanogr. 13:118-26. (3) Bridges, W. R.. B. J. KaUrnan, and A. K. Andrews. 1963. Persistence of DDT and its metabolites in a farm pond. Trans. Am. Fish. Soc. 92:421-7. (4) Butler, P. A. 1966. The problem of pesticides in estu- aries. Am. Fish. Soc. Spec. Publ. No. 3, 154 p. (5) Chadwick, G. C. and R. W. Brocksen. 1969. Accumu- lation of dieldrin by selected fish-food organisms. J. Wildl. Manage. 33:693-700. (6) Elliott, J. M. 1967 . Invertebrate drift in a Dartmoor stream. Arch. Hydrobiol. 63:207-37. {7) Ferguson, D. E. 1967. The ecological consequences of pesticide resistant fishes. Trans. 32nd N. Am. Wildl. and Nat. Resour. ConL 103-107. (8) Ferguson, D. E. 1969. The compatible existence of non- target species to pesticides. Bull. Entomol. Soc. Am. 15: 363-66. (9) Holden, A. V. 1965. Contamination of fresh water by persistent insecticides and their effects on fish. Ann. Appl. Biol. 55:332-5. {10) Keith, J. O. 1966. Insecticide contamination in wetland habitats and their effects on fish-eating birds. J. Appl. Ecol. 3:71-85. (11) Kelso. J. R. M., H. R. MacCrimmon, and D. J. Ecobi- chon. 1970. Seasonal insecticide residue changes in tis- sues of fish from the Grand River, Ontario. Trans. Am. Fish. Soc. 99:423-6. (12) Lichlenberg, J. J., J. W. Eichelberger, R. C. Dressman, and J. E. Longbottom. 1970. Pesticides in surface waters of the United States — a 5-year summary, 1964- 1968. Pestic. Monit. J. 4(2):71-86. (13) Macek, K. ]., and S. Korn. 1970. Significance of the food chain in DDT accumulation by fish. J. Fish Res. Board Can. 27:1496-8. (14) Naqvi. S. M.. and D. E. Ferguson. 1968. Pesticide toler- ances of selected freshwater invertebrates. J. Miss. Acad. Sci. XIV: 1 20-6. (15) Nicholson. H. P. 1967. Pesticide pollution control. Science. 158:871-6. (16) Pelerle, T. J. 1966. The use of isotopes to study pesti- cide translocation in natural environments. J. Appl Ecol. 3:181-91. 1 17) Vance, B. D., and W. Drummond. 1969. Biological con centration of pesticides by algae. I. Am. Water Work; Assoc. 61:360-2. (IS) Woodwcll, G. M., C. F. Wurster, and P. A. Isaacson 1967. DDT residues in an east coast estuary: a case o biological concentration of a persistent insecticide Science. 156:821-4. 300 PEsnciDES Monitoring Journaii Effect of Urban and Agricultural Pesticide Use on Residue Levels in the Red Cedar River '-^ Matthew J. Zabik, Brien E. Pape, and James W. Bedford ABSTRACT Analyses on 1549 water and bottom samples have shown high levels of DDT and its metabolites ITDE and DDE) in the Red Cedar River. The river becomes progressively more contaminated in a downstream direction and shows seasonal variations. The concentrations of pesticides in bottom samples give a ^ood indication of long term contamination, whereas levels 'n the suspended matter (that retained by a 5-n filter) indi- cate the amount of pesticide being carried on a short term basis. Results of this study have shown that the largest amount of vesticide contamination entering the Red Cedar River comes from the waste water treatment plants. Introduction Pesticides may enter surface waters by direct applica- tion, by indirect drift into waters from adjacent spray ipplication, in runoflf from pesticide-treated areas con- tiguous to a watershed, or by discharge of industrial and or municipal waste effluents. The purpose of the present study was to quantify the :ontribution of these possible sources of pesticide con- tamination from a representative agricultural-urban stream. Study Area DESCRIPTION OF THE RIVER The Red Cedar River is located in south-central Michi- gan. It originates in Cedar Lake and flows northwesterly |through Livingston and Ingham Counties, joining the ' Michigan Agricultural Experiment Station Journal Article No. 4762. ■ Contribution from the Department of Entomology and Institute of Water Research, Michigan State tJniversity, East Lansing, Mich. 48823. Grand River in Lansing (approximately 80 km down- stream). Twelve major tributaries enter the stream, draining a total area of approximately 122,000 hectares. The stream varies from 2 to 30 meters in width, and the mean gradient through its entire course is about 0.45 m/km. The headwaters drain primarily marsh and wetland areas and have been extensively dredged and straightened. Upstream, the land is rolling with pasture and small grain predominating; farther downstream, there is extensive agricultural development, urbaniza- tion, and industrialization. The waters of the river now serve in irrigation and as a depository for domestic and industrial wastes, as well as for limited recreational purposes. In general, the river may be described as a warm-water, highly buffered alkaline stream, usually clear, but showing increased turbidity during periods of rapid runoff. The drainage system is representative of a midwestem agricultural and urban stream of moderate size with a low relief gradient. The decrease in discharge in recent years has brought the stream to a critical base flow level (1). SAMPLING STATIONS Twelve permanent sampling stations were established (Fig. 1 ) from just above the Williamston Waste Water Treatment Plant to the junction of the Red Cedar River and the Grand River. The stations were selected to represent relatively unpolluted levels, highly polluted conditions, and areas of the river showing water quality recovery below the Williamston and East Lansing treat- ment plants and their associated urban drainage systems. Station 1 is located 140 meters above the outlet of the Williamston Treatment Plant and 300 meters below the Williamston impoundment. The bottom material in this area consists of large stones and sand with silt pockets along the river's edge. The depths recorded in the proc- ess of sampling ranged between 0.5 and 1.5 meters. Vol. 5, No. 3, December 1971 301 FIGURE 1. — Map of Red Cedar River showing station locations ' ' ■ KILOMETERS This relatively "clean" station illustrates water quality conditions satisfactory to sustain a diverse lotic fauna, including several species of game fish. The land usage above this station is largely agricultural, with a few small communities contributing an urban storm-drainage runoff to the river. Sampling Station 2 is located 20 meters below the Williamston treatment outlet (160 meters downstream from Station 1). The bottom is similar to that of Station 1, except that the sludge deposits are large and in some areas extend halfway across the stream. The depth ranged from 0.5 to 1 .5 meters. The stream is rich in nutrients; and many of the benthic organisms found at Station 1, such as fresh water mussels, are not found here. Station 3 is located approximately 8 km downstream from Station 2, at the M-43 bridge, in a riffle area. The streambed is composed of sand and gravel. The average width is 12 meters and the depth ranged from 0.3 to 0.6 meters. The land usage in this area is predominately agricultural, with some sparse residential settlements. Station 4 is located at the Hagadorn Road Bridge, ap- proximately 12 km downstream from Station 3. The river is influenced by a small dam (the MSU dam) described below. Between Stations 3 and 4, the river runs by or through two residential communities (Has- lett and Okemos) and some agricultural land. The average depth was about 2 meters. The bottom consists of sand and silt, with deposits of decaying leaves and other detritus. 302 Station 5 is located on the Michigan State Universits (MSU) Campus, approximately 500 meters from Station 4. This portion of the river, between Stations 4 and 5. is bound by the City of East Lansing and by the MSL Campus. The East Lansing sanitary-storm overflow is located in this area. The river is 2 to 3 meters deep ai the sampling point and is located in the backwaters just above the MSU Dam (2 meters high). Station 6 is located below the MSU Dam and about 3(i meters below Station 5. The bottom at this location consists of large rocks and sand. Station 7 is located 300 meters below Station 6. at the Kalamazoo Street Bridge, on the MSU Campus. The bottom consists of sand, rocks, and silt. Stream depth was approximately 1 meter. Stations 8 and 9 were chosen as points above and belo\v the old East Lansing Sewage Treatment Plant. This plant was deactivated just before this study was initiated. The river bottom undergoes a drastic change between these two points. At Station 8, the bottom is mainly sand and gravel, with silt along the edges. Station 9 has a bottom consisting of large sludge deposits which extend across the entire river and are up to 1 meter in depth near the sampling point. Station 8 is 500 meters down stream from Station 7, and Station 9 is 300 meters downstream from Station 8. Station 10 is located 5 meters below the outlet of the East Lansing Waste Water Treatment Plant, about 15C meters from Station 9. The bottom at this site is largely Pesticides Monitoring Journal sand, due to the excavation involved in the placement of the outlet pipe in the river bottom. Extensive sludge beds are developing in this area. Station 1 1 is located several hundred meters from Sta- tion 10, and is just below the outlet of an experimental, tertiary treatment settling pond. The bottom is sand and silt, and the river depth varied from 1 to 2 meters. Station 12 is located at the junction of the Red Cedar River and the Grand River. It is characterized by deep beds of organic detritus. WASTE TREATMENT FACILITIES The Williamston Treatment Plant serves a population of about 3,000 people. It is a primary treatment facility with an average daily effluent of approximately 500,000 gallons. About one-half of the storm-sewer system in Williamston is constructed to deliver its collected waste water to the treatment plant. The East Lansing Waste Water Treatment Plant com- pleted in 1966, is a secondary treatment facility. The plants serves the City of East Lansing, the MSU Cam- pus, and the Okemos area. Because of the 38,000 student population at MSU, the amount of waste water handled by the plant changes considerably when the student population is lower during the summer months. The range in the volume of waste water effluent is about 6'/2 to 12 million gallons per day. During the summer months, the daily effluent averages around 7 million gallons per day. Since the handling capacity of the plant is 8 million gallons per day. It is often necessary to bypass treatment of some influent waters. Methods Samples were taken according to a bimonthly schedule I from April 1966 to November 1968. Water samples I were taken as 5-liter grab samples and held in brown glass bottles sealed with Teflon-lined screw caps; the bottles had been cleaned previously with dichromate cleaning solution and thoroughly rinsed with hexane, acetone, and distilled water. Bottom samples were taken with a modified soil core (6 cm in diameter and 12 cm jdeep) and held in water-tight cartons while in the field. A j total of 778 water and 771 bottom samples were col- ilected and analyzed during the course of this study. CHEMICAL AND PHYSICAL ANALYSES The following chemical and physical exammations ot water samples were made according to the procedures in Standard Methods (3): (I) chemical oxygen demand ICOD), expressed as mg O^/liter water, according to the dichromate reflux method; (2) phenolphthalein and tc'taj alkalinity, expressed as mg CaCO./ liter water, and measured at pH 8 and pH 4 using 0.02 n H:.S04; (3) conductivity, expressed as /j. mhos/cm, and measured Vol. 5, No. 3, December 1971 with a Serfass Conductivity Bridge; (4) orthophosphate and total phosphate, expressed as mg PO4/ liter water, and determined spectrophotometrically according to the Stannous Chloride method. Turbidity was determined by recording the percentage transmission of a water sample through a 40-mm quartz cell in a double-beam ultraviolet spectrophotometer at 690 nifi. This percentage transmission was then con- verted to Turbidity Units by comparison of the re- corded transmission with a standard curve obtained from reference solutions who.se turbidity was determined in a Jackson Turbidometer and then plotted versus their corresponding transmissions at 690 m/x. The percent moisture in the bottom samples was ob- tained by drying a 10-g sample, from which excess water had been decanted, in a vacuum oven at 60"C until a constant weight was obtained. The organic content of the bottom samples was obtained by ignition of a dry 10-g sample in a covered Vycor crucible at 600^C. (No correction was made for loss of carbonates). PESTICIDE RESIDUE ANALYSES Analyses were carried out to determine the level of the chlorinated hydrocarbon residues in the samples of water, suspended matter, and bottom soil from all sta- tions. Suspended matter was removed from the water sample (approx. I liter) by pressure filtration through a Metricel filter (142 mm diameter, 50.0 fj. pore size) using a Gel man Pressure Filtration System. The filters were air-dried, weighed, and stored in a culture tube with Teflon-lined screw caps. The volume of the water filtered and weight of the suspended matter collected (dry weight) were recorded. Residues were extracted with 5 ml of glass-distilled hexane (the filters were crushed, then shaken for 10 minutes). Water collected after microfiltration was used to de- termine the dissolved residue levels. A 1,000-ml volume of water was extracted with three successive 100-ml por- tions of glass-distilled hexane. The solvent was drawn off and dried over anhydrous sodium sulfate. The com- bined extract was concentrated with a Kaderna-Danish Concentrator to a volume of 5 ml. A lOO-g sample from the composite soil cores (1 kg) was used to determine residue levels in the soil samples. Enough water was added to bring the moisture content to approximately 25%; to this slurry 200 ml of hexane- acetone (1:1) mixture was added. The mixture was shaken for 10 minutes and allowed to stand for 12 to 14 hours, then shaken for 10 minutes more, and the 303 hexane layer decanted off. The mixture was then suc- cessively extracted with two additional 100-ml portions of hexane. The combined hexane extract was washed with two 100-mi portions of distilled water, dried over anhydrous sodium sulfate, reduced to 10 ml. placed on a 30- by 2-cm column of activated Florisil-Celite (5;1), and eluted with 300 ml of hexane. The 300 ml collected was reduced to 50 ml. Gas chromatography of pesticide residues was carried out with a Beckman model GC-4 gas chromatograph, equipped with a discharge electron capture detector and 70- by 'A -cm stainless steel columns. The packing material was either 5% DC-11 or 11% OV-17/QF-1 (l/l>/2) on 80/100 mesh Gas Chrom Q. The columns were conditioned until endrin and a p.p'-DDT standard each gave only one peak. General temperature para- meters used throughout this study were: inlet tempera- ture— 230°C; inlet line — 220°C; column compartment — 200°C: detector line — 230 -C: detector compartment — 280T. Quantitation was based on peak height. The residue concentrations were based on the weight of water samples, dry weight and organic content of bottom soil samples, and the volume of the water from which the suspended matter originated. The identity of the pesticides found was confirmed by FIGURE 2.- -Average concentrations of DDT and DDT metabolites in water by station ! 3 I S i ! 10 M I! thin layer chromatography and mass spectroscopy. Mass spectroscopy results also demonstrated the absence of any polychlorinated biphenyls (PCB). Recovery of DDT from water ranged from 80-90%, from bottom sediments 87-93%, and from suspended matter 97-103%. The lower limit of detectability for DDT in water was 0.02 ppb and was 0.5 ppb in sediments and suspended matter. Results and Discussion RESIDUES IN WATER The average residue levels of DDT in the 64 bimonthly water samples taken from each station were determined (Fig. 2). Levels of DDT at the 1 2 stations were generally lower than the DDT metabolites. Comparative analyses have shown the water-soluble residue to be a poor indicator of pesticide contamination in this stream. The soluble residues appeared to be close to the saturation point foi these pesticides at all stations, and therefore showec only limited fluctuation between stations. The highest levels of DDT were found in June of eacl year, with the highest levels of DDT metabolites ob served in April (Fig. 3). FIGURE 3. — Average concentrations of DDT and DO' metabolites in water b\ month jii III vti yn m m »\ m sip iti ii« iic mil 304 Pesticides Monitoring Journ/ One explanation is that DDT deposited in the previous year was metabolized or degraded over the winter and then dissolved by waters and flushed into the streams during the spring thaw. The DDT would not increase until after the spring spray applications and would be delayed by its slow dissolution into rain waters. Follow- ing the spring thaws, the metabolites of DDT accounted for the majority of the chlorinated hydrocarbon resi- dues. This relationship was reversed in May and June, a result consistent with an increase in the DDT applica- tions and spray programs for the control of the Dutch Elm Disease Bark Beetle and mosquito vector control programs. The higher levels of DDT and its metabolites late in the year reflected the greater discharge of the river (i.e., increased runoff and mobilization of pesticides in the bottom) (Table 1). TABLE 1. — Average water flow for the Red Cedar River on the sampling dales of this study FIGURE 4. — Average concentrations (dry weight) of DDT and DDT metabolites in bottom by station Month Jan. Feb. March April May June July Aug. Sept. Oct. Nov. Dec. ' Taken above Station 5. RESIDUES IN SOIL The level of the residues in the bottom soil increased farther downstream (Fig. 4). The residues based on the dry weight were significantly correlated [r.,^r.66 from (2)] with the percent organic matter in the soil (Fig. 5). Levels of pesticides residues (parts per million) per unit of organic matter changed little between stations; therefore, the total amount of pesticide present appeared to be dependent on the weight of organic matter. DDT and its metabolites showed a seasonal variation in the bottom samples (Fig. 6). DDT and DDT meta- bolites increased during April and May, reflecting in- creased spring runoff (increased erosion) and new spray applications in the study area. The gradual decrease in residues over the summer months was probably the result of a decrease in pesticide spray applications. A rapid partitioning occurred between the soil and water, indicated by monthly variation from a high of 6.48 ppm DDT in April to a low of 0.28 ppm DDT in September (Fig. 6). The rapid turnover of pesticides in this stream indicates that it possesses the potential to decontaminate itself if further pesticide introduction were limited. This also means that there would tend to be an accumulation of pesticides in the lower reaches of the stream and at the stream's eventual confluence with a lentic body of water. FIGURE 5.- -Average percent organic matter in bottom by station Vol. 5, No. 3, December 1971 305 FIGURE 6. — Average concentrations (dry weight} of DDT and DDT metabolites in bottom by month 001 MIIIO i_l! m m mi joi jvi lot sip oci now oic KOIIH FIGURE 7. — Average concentrations of DDT and DDT metabolites in suspended matter by station (based on volume of water from which suspended matter originated) -—001 — 00 1 M n«i 1 ? J « s W« 1 10* FIGURE 8. — Average turbidity by station / ! I i I I 1 10 M 1! FIGURE 9. — Average concentrations of DDT and DDT metabolites in suspended matter by month (based on volume of water from which suspended matter originated) I! l! I' !■ - Ml III Mio m MIT JOI Jill to( SIP on ii* i(c KOI I K 306 Pesticides Monitoring Journa RESIDUES IN SUSPENDED MATTER When considering the data for residue levels in su- spended matter, it is important to reaHze that the levels of residues are based on the unit weight of water from which the suspended matter was obtained. Results show substantial increases in DDT and its metabolites at Stations 2 and 10, as compared to the upstream Stations 1 and 9, respectively (Fig. 7). Calcula- tions based on the average flow of the river versus the flow of the Williamston and East Lansing plants and the levels of DDT residues at the upstream and effluent stations indicated that these two waste treatment facili- ties increased the pesticide contamination of the stream by 94% and 82%, respectively. Also, the pesticide con- tamination of the stream (Fig. 8) closely followed the increased turbidity at the sampling points. In general, the monthly variation in the DDT metabolites in the suspended matter (Fig. 9) followed the same pattern as the bottom samples. Again, the monthly varia- tion in turbidity (Fig. 10) closely followed that of pesti- cides in the suspended matter. Two 24-hour sampling studies (samples taken at 1-hour intervals) indicated that the pesticide contamination of the suspended matter was a much better indicator of daily variation in pesticide burden of the stream than FIGURE 10.- -A\ erage turbidity b V month 110' » n 31 j«i m m m \ui m m m s!p iti ii« m IIIIH 1 Vol. 5, ^ io. ?,D ECE MBE RlS 71 was the level in the bottom samples. In contrast, the bottom soil residues were better indicators of long term pesticide burden and history in the stream. CHEMICAL AND PESTICIDE CLEANUP Stations 1, 2, and 3 provided a good opportunity to look at the relationship of water quality and DDT resi- due levels in the aquatic environment. The purpose was to get a general picture of possible relationships be- tween water quality improvement occurring from Sta- tions 1 to 2 to 3, and the change in the levels of DDT residues between these stations. The following physical-chemical indicators of water quality at these stations were considered: chemical oxygen demand; total alkalinity; turbidity; and conduc- tivity (Fig. 11). As a result of the waste water effluent from the Williamston plant, each of these physical- chemical indicators showed a substantial increase at Station 2. In each case, the data at Station 3 showed that the high levels present upstream had decreased. All of this is quite expected, and illustrates the well-docu- mented occurrence of the physical and biological "clean- up" of polluted waters. When compared to the DDT residues at these stations (Fig. 12), Station 2 showed a higher residue level than Station 1 ; and Station 3 showed a decrease compared to Station 2. There are probably two basic dynamic mechanisms in operation that are responsible for the improvement in water quality and the decrease in residue levels below Station 2. These are: (1) settling of suspended matter, which was shown to be the major contribution to the buildup of pesticide residues; and (2) removal or metabolic degradation of the residues by biological systems. FIGURE 11. — Comparison of water quality parameters at Stations 1. 2, and 3 it IIS m ; n SI M 1 i '* 1 " 1 *' It m 1 1 m 1 1 1 IS ■ 1 ■ m II _ » III - IK 1 - m 1 ^ u ills 1 1 j = lis 1 ' 1 "" *■ I E ■" ill r " " j 1 - 1 j j — 1 " II ~ u 1 1 ! iu III ; 1 I LM —J 1 1 1 ill * SI 1 nil 1 I 1 ' Ml " 1 ! 1 1 M 307 FIGURE 12. — Comparison of DDT concentrations at Sta- tions I, 2, and 3 0I5- 090 080 010 0(0 }}lt ^ ^060' .OSO' ^IIO' * 100' 1 =005' M.l 11- 0, i ! ! 1 1 3 SMIIOK 1 ! 3 1^3 carried on a day-to-day basis. Results of this research have shown that the largest amount of pesticide con- tamination entering the Red Cedar River comes from the waste water treatment plants. These results point out the need for a constant surveil- lance of rivers and streams for pesticide contamination, with more emphasis on the amount of contamination from urban and suburban areas. It is equally important to stress the need for better waste facilities, since the majority of the DDT residues are adsorbed on the suspended matter and could (theoretically) be removed by improved waste water treatment. Acknowledgments The authors wish to express their thanks to Dr. Robert C. Ball, Director, Institute of Water Research, Michigan State University and Dr. Gordon Guyer. Chairman of the Department of Entomology, Michigan State Univer- sity, for their interest and assistance throughout this study. See Appendix for chemical names of compounds discussed in thisi paper. The work upon which this publication is based was supported by funds provided by the Office of Water Resources Research. Summary and Conclusions Results have shown high levels of DDT and its meta- bolites in the Red Cedar River. The river becomes progressively more contaminated in a downstream direc- tion. Results have shown that residue levels in water are poor indicators of pesticide contamination compared to levels in the suspended matter and bottom samples. The bottom samples give a good indication of long term contamination but are affected greatly by the organic level in the soil. The suspended matter gives a more immediate indication of the amount of pesticide being LITERATURE CITED (1) Ball. R. C. K. J. Linton, and N. R. Kevern. 1968. The Red Cedar River Report I. Chemistry and hydrology. Publ. Mus., Michigan State University, Biol. Ser. 4(2): 29-64. (2) Siegel, S. 1956. Nonparametric statistics for the behav- ioral sciences. McGraw-Hill Book Company, Inc., New York. (3) American Public Health Association. 1965. Standard methods for the examination of water and wastewater including bottom sediment and sludge. 12th Ed. New York, N. Y. 308 Pesticides Monitoring Journal APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN BHC CARBARYL CHLORDANE I a-CHLORDANE I 1 7-CHLORDANE DDE DDT (including its isomers and dehydrochlorination products) DIAZINON DIAZOXON DICHLOFENTHION (NEMACIDE®) DICOFOL (KELTHANE®) DIELDRIN DURSBAN® ENDOSULFAN (THIODAN®) ENDRIN ETHION FENSULFOTHION (DASANIT®) HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE MALATHION METHOXYCHLOR MEVINPHOS POLYCHLORINATED BIPHENYLS (PCBs) PARAOXON PARATHION PERTHANE® TDE (DDD) (including its isomers and dehydrochlorina- tion products) TETRADIFON (TEDION®) TOXAPHENE Not less than 95% of l,2,3.4,IO,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-e'n(io-exo-5,8-dimethanonaphthalene 1,2,3,4,5,6-hexachlorocyclohexane, mixed isomers 1-naphthyl methylcarbamate l,2,4,5,6,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4.7-methanoindane , alpha isomer , gamma isomer 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 thi o,p'-isomer (in a ratio of about 3 or 4 to I ) (?,0-diethyl 0-(2-isopropyI-4-methyl-6-pyrimidyl) phosphorothioate diethyl (2-isopropyl-4-methyl-6-pyrimidinyl) phosphate 0-2,4-dichlorophenyl 0,0-diethyl phosphorothioate 4,4'dichIoro-a-(trichloromethyl) benzhydrol 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,fndo-exo-5,8-dimethano= naphthalene (?,0-diethyl 0-(3,5,6-trichloro-2-pyridyI) phosphorothioate 6,7,8,9,10,10-hexachloro-l,5,5a,6,9,9a-hexahydro-6.9-methano-2.4,3-benzodioxathiepin 3-oxide l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-I,4-e/ido-endo-5.8-dimethanonaphthalene O,0,0',0'-tetraethyl 5,5'-methylenebisphorodithioate 0,(?-diethyl 0-[p-(methylsulfinyl)phenyl]phosphorothioate l,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro^,7-methanoindene l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 1,2,3,4, 5,6-hexachlorocyclohexane, 99% or more gamma isomer diethyl mercaptosuccinate, 5-ester with (5,(?-dimethyI phosphorodithioate 1,1, l-trichloro-2,2-bis ( p-me thoxyphenyl ) ethane methyl 3-hydroxy-a/p^a-crotonate. dimethyl phosphate Mixtures of chlorinated biphenyl compounds having various percentages of chlorination diethyl p-nitrophenyl phosphate 0,0-diethyl O-p-nitrophenyl phosphorothioate l,l-dichloro-2,2-bis(p-ethylphenyl) ethane l,l-dichloro-2,2-bis(p-chlorophenyl) ethane: technical TDE contains some o.p'-isomer also p-chlorophenyl 2,4,5-trichIorophenyl sulfone chlorinated camphene containing 67% to 69% chlorine Vol. 5, No. 3, December 1971 309 Errata PESTICIDES MONITORING JOURNAL. Volume 5. Number 1, p. 8, Table lA — Last three entries under Station No. 50, Kenai River, last column headed EST. PCB's: As Shown Should Be 1.53 <.10 2.64 .29 5.48 .27 PESTICIDES MONITORING JOURNAL. Volume 5. Number 2. p. 76 and 77: Under small fruits, the last two paragraphs, beginning with "The assumption of normality. . . ," should be placed at the end of the section entitled Siatisiical Treatment of Data on p. 74. 310 Pesticides Monitoring Journal 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 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 SVi 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 afliliations, 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. 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 tyfje 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, Pesticides Programs. Environmental Protection Agency, 4770 Buford Highway, Bldg. 29, Chamblee, Ga. 30341. Vol. 5, No. 3, December 1971 311 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 e-xpected 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 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, Chairtnan Anne R. Yobs, Environmental Protection Agency Andrew W. Breidenbach, Environmental Protection Agency Thomas W. Duke, Environmental Protection Agency William F. Stickel. Fislj and IVildlife Service Milton S. Schechter, Agricultural Research Service Paul F. Sand, Agricultural Rcsearcli 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 Volumes March 1972 Number 4 Page RESIDUES IN FOOD AND FEED Pesticide residues in total diet samples l\'l) 313 P. E. Corneliussen Dietary intake of pesticide chemicals in the United States (III), June l96S-April 1970 331 R. E. Duggan and P. E. Corneliussen Pesticide residues lit .\weet potatoes and soil — 1969 342 P. F. Sand, G. B. Wiersma, and J. L. Landry Pesticide residues in onions and soi! — 1969 345 G. B. Wiersma, W. G. Mitchell, and C. L. Stanford RESIDUES IN FISH, WILDLIFE, AND ESTUARIES A survey of the lead content of fish from 49 New York State waters 34X Irene S. Pakkala. Merrie N. White. George E. Burdick, Earl J. Harris, and Donald J. Lisk PESTICIDES IN WATER Residues in ponds treated witli two fornuilations of dicldobenil 356 A. G. Ogg, Jr. APPENDIX Clicniical nanus of einnpounds discussed in tliis issue 3b(l ACKNOWLEDGMENT 361 iiniiiiiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii!iiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiniiiiiiiiiiiiiiiiiiiiiiiiiiiiiiin^ CUMULATIVE INDEX (VOLUMES 1-5, JUNE 1967-MARCH 1972) Preface — 362 Subject index 363 Autlior index 374 RESIDUES IN FOOD AND FEED Pesticide Residues in Total Diet Samples (VI) p. K. Comeliussen ' ABSTRACT ?ticidc residue levels delected in ready-lo-eal foods re- .lined at relatively low levels during the sixth year of the tal Diet Study in its present form. Samples were collected \'ing combinations. Most common wei DDT, lindane, DDE. TDE. and dieldrin, with respecti^ maximum values of 0.077 ppm, 0.008 ppm, 0.002 ppn 0.004 ppm, and 0.014 ppm. Twenty-four compositi contained malathion, with a maximum value of 0.09 ppm. Also found were aldrin, diazinon. heptachlor epo; ide, parathion, and BHC. Arsenic (As^.O.j) was not foun in any of the 30 composites. Bromides were detected i 27 of the 30 composites (1.5 to 94 ppm). Cadmium w; detected in 27 composites (maximum 0.06 ppm). POTATOES: Ten organochlorine pesticides were foun in 26 of the 30 composites. The most common pesticide foimd v\ere DDE, DDT, and dieldrin, with maximui respective values of 0.025 ppm, 0.021 ppm, and 0.05 ppm. Also detected were endrin, BHC, parathion, CIPC 2,4-D, heptachlor epoxide, chlordane, TCNB, endc sulfan, diazinon, and TDE. Arsenic (As^.O..) was d( tected in two composites, each at 0.1 ppm. Bromide were found in I 3 of 30 composites (1 .5 to 52 ppm). Cac mium was found in 29 composites (0.01 to 0.08 ppm). 314 Pesticides Monitoring Journa AFY VEGETABLES: Eight organochlorine pesti- ;s were found in 28 of 30 composites. Most com- nly found were DDT. DDE. dieldrin. endosulfan mers I and II plus sulfate), and TDE. with maximum Dective levels of 0.031 ppm. 0.0 10 ppm. 0.009 ppm. 40 ppm, and 0.003 ppm. Eight composites contained athion with a maximum value of 0.009 ppnT six con- led methyl parathion with a maximum of 0.023 ppm. o detected were BHC, DCPA (Dacthal®), diazinon. aphene, and dicofol. Arsenic (AsoO;i) was not de- ;ed. Bromides were found 21 times (0.5 to 23 ppm). imiuni was found 28 times (0.01 to 0.14 ppm). One ividual sample of celery contained 3 ppm dithiocar- nates calculated as zineb. GUME VEGETABLES: Seven organochlorine pestl- es were found in 19 composites. DDT. DDE. and lE were found most frequently, with maximum values 0.032 ppm, 0.007 ppm, and 0.007 ppm, respectively. ;o detected were dieldrin. lindane, parathion. BHC, i dicofol. Bromides were detected in 17 composites ) to 18 ppm). Arsenic (AsoO-j) was not detected. Imium was detected 10 times (0.01 to 0.04 ppm). )OT VEGETABLES: Six organochlorine pesticides re found in 23 of 30 composites. DDE was found 1 S les at a maximum of 0.025 ppm. DDT was found 16 les at a maximum of 0.029 ppm, and dieldrin 5 times a maximum of 0.010 ppm. Also found were TDE, dane, and endrin. Bromides were detected in 19 of composites (1.0 to 19 ppm). Arsenic (As^O,,) was de- ted once at 0.2 ppm and cadmium 27 times (0.01 m to 0.08 ppm). Dithiocarbamates (calculated as eb) were detected three times in individual onion nples at a maximum of 1 .4 ppm. ^RDEN FRUITS: Eleven organochlorine pesticides re detected in all 30 composites in varying combina- ns. Most common were DDT, TDE, DDE, dieldrin, dane, and total endosulfan at maximum respective els of 0.102 ppm, 0.084 ppm, 0.019 ppm, 0.010 m, 0.003 ppm, and 0.005 ppm. Five composites con- ned parathion at a maximum level of 0.013 ppm. 50 found were BHC, endrin, toxaphene, diazinon, Irin, heptachlor epoxide, and malathion. Bromides :re detected 22 times (1.0 to 11 ppm) and cadmium times (O.OI to 0.10 ppm). Arsenic (As^.O.j) was de- :ted once at 0.2 ppm. lUITS: Eight organochlorine pesticides were found 24 of 30 composites. DDT, DDE. dicofol, dieldrin, d TDE were found most frequently at maximum ipective levels of 0.474 ppm. 0.020 ppm, 0.102 ppm, )03 ppm, and 0.018 ppm. Ethion was found in 15 30 composites at a maximum level of 0.129 ppm and ilathion 6 times at a maximum level of 0.053 ppm. Also found were endosulfan, diazinon, BHC, methoxy- chlor. parathion, and orthophenylphenol. Bromides were found in 19 of 30 composites (0.5 to 31 ppm) and cad- mium 10 times (0.01 to 0.07 ppm). Arsenic (As^Og) was found once at 0.2 ppm. OILS. FATS. AND SHORTENING: Nine organochlo- rine pesticides were found in 15 of 30 composites. Most common were DDE, DDT, ' ^E. dieldrin. and BHC at maximum respective levels of 0.019 ppm, 0.044 ppm, 0.027 ppm, 0.005 ppm, and 0.020 ppm. Malathion was found in seven composites at a maximum level of 0.166 ppm. Also found were HCB, lindane, 2,4-DB. diazinon, heptachlor epoxide, and endosulfan. Bromides were found in 21 composites (0.5 to 29 ppm) and cadmium 28 times (0.01 to 0.04 ppm). SUGARS AND ADJUNCTS: Seven organochlorine pesticides were found in 19 of 30 composites. DDT was found in 14 of 30 composites (maximum 0.008 ppm), DDE in 12 composites (maximum 0.003 ppm), lindane in 10 composites (maximum 0.003 ppm). and TDE in 7 composites (maximum 0.003 ppm). Also detected were dieldrin, aldrin, heptachlor epoxide, malathion, and PCB's. Bromides were found in 25 composites (1.0 to 154 ppm), cadmium in 18 composites (0.01 to 0.02 ppm), and arsenic was not detected. BEVERAGES: DDT and TDE were each found once at trace levels (below 0.001 ppm). Bromides were found in 17 of 30 composites (0.5 to 30 ppm) and cadmium in 9 composites (0.01 to 0.04 ppm). Arsenic was not detected. Bromide reportings include naturally occurring bromides as well as residues from pesticide treatment. Sixty-eight percent of the composites contained detectable bromides (above the 0.5 ppm limit of detection). The percentages back through the four previous reporting periods were 64.4^r. 76. 99^. 83.1%, and 76.8%. A total of 3.7% of the bromide residues exceeded 25 ppm compared with 8.6%, 5.8%, 4.2%, and 3.8% for the four earlier annual reporting periods. The detailed data in Tables 2a and 2b are reported in the same format used for earlier periods (3-6,12) for comparison. Trace amounts or non-quantitative positive findings are not included in the averages. Where no average value is given, the results on the individual com- posites are shown. In these tabulations, as in the earlier reports, the bromide and arsenic values are reported on an "as is" basis for three food classes: Dairy Products (I); Meat, Fish, and Poultry (II): and Oils. Fats, and Shortening (X): even though the earlier tabulations (6) indicated a "fat basis." Cadmium results are also reported on an "as is" basis. 3L. 5, No. 4, March 1972 315 Discussion Residues of organochlorine pesticides were found in 267 of the 360 composites examined (74.29?^) for this class of chemicals. Corresponding percentages for previous years were 64.7% for 1968-1969, 65.6% for 1967-1968, 62.3% for 1966-1967, and 53.8% for 1965-1966. Or- ganic phosphorus compounds were found in 74 com- posites. The four previous reporting periods showed 59, 26. 25, and 27 composites with findings of organophos- phorus residues, respectively. Chlorophenoxy acids (herbicides) were found four times during this reporting period. While this class of residues was detected 14 times during the 1968-1969 period, 10 of the 14 were PCP. Chlorophenoxy acid residues were found in 7 composites in 1967-1968, 8 in 1966-1967, and 13 in 1965-1966. Carbar>'l was not detected in any of the diet composites during this period. There were three, zero, and four re- portings in the three earlier reporting periods, respec- tively. Amitrole was not found during this period or in past periods of this program. Dithiocarbamates were detected in four individual food commodities at a maximum of 3 ppm (zineb) in celery. Unprepared fruits and vegetables were examined for dithiocarbamates before compositing in order to avoid decomposition by hydrolysis. Previous report periods, showed zero to four dithiocarbamate findings each time. Recovery studies were conducted through the entire year with all classes of pesticides in various food groups. Table 4 gives recovery data for seven of the more com- monly occurring organochlorine pesticides, as well as data for representative pesticides in the other residue categories. It should be pointed out that each recovery experiment consisted of a single determination for the blank and a single determination for the fortified sample. Generally, these determinations were made simultaneously and sometimes the fortification level was much less than the blank residue level. In other cases, not enough re- covery experiments were performed to be statistically significant. Such recovery data are not reported. Many recovery experiments were performed for each class of compounds, but Table 4 presents those which are representative of the pesticide classes and were per- formed most frequently. 316 Based on the recovery data, it is apparent that residu reportings may vary considerably from the "true" valm however, results thus far are useful in appraising the n; tional residue picture. At low fortification levels. reco\ eries from 0 to 200% may be encountered. Accurac generally increases with higher fortification levels sine the ratio of weight of pesticide to weight of sample more favorable. See Appendix for Table I. of compounds not Ackn(>wledi;nu'iU The author gratefully acknowledges the analytical wor from the FDA laboratories in Baltimore, Md.; Bostoi Mass.; Kansas City, Mo.; Los Angeles, Calif.: and Mir neapolis, Minn. LITERATURE CITED (1) Armour, J. A., anil J. A. Burke. 1970. Method for seji arating polychlorinated biphenyls from DDT and i analogs. J. Assoc. Off. Agric. Chem. 53:761. (2) Barry, H. C, J. G. Hundley, and L. Y. Johnson. 196' (Revised 1964. 1965, 1968, 1969, and 1970). Pesticic Analytical Manual, Vol. I and II, Food and Dn Admin., U.S. Dap. Health. Educ. and Welfare. (3) Corneliussen. P. E. 1969. Pesticide residues in tot diet samples (IV). Pestic. Monit. J. 2(4): 140-1 52. (4) Corneliussen, P. E. 1970. Pesticide residues in total di samples (V). Pestic. Monit. J. 4(3):89-105. (5) Duggan. R. £.. H. C. Barry, and L. Y. Johnson. 196i Pesticide residues in total diet samples. Science 15 101-104. (6) Duf;f>an, R. E.. H. C. Barry, and L. Y. Johnson. 196. Pesticide residues in total diet samples (II). Pesti Monit. J. 1(2):2-12. 17) Duggan, R. £., and P. E. Corneliussen. 1972. Dietai intake of pesticide chemicals in the United States (III June 1968-ApriI 1970. Pestic. Monit. J. this issue. (8) Duggan. R. E.. and G. Q. Lipscomb. 1969. Dietary ii take of pesticide chemicals in the United States (II June 1966-April 1968. Pestic. Monit. J. 2(4):I53-16: (9) Duggan. R. E.. and F. J. McFarland. 1967. Asses; ments include raw food and feed commodities, marks basket items prepared for consumption, meat sample taken at slaughter. Pestic. Monit. J. 1(1): 1-5. (10) Duggan. R. £.. and J. R. Wealhcrwax. 1967. Dietar intake of pesticide chemicals. Science 157:1006-1010. (//) Food and Agriculture Organization and World Healt Organization. 1967. Evaluation of some pesticide res dues in food. Report of a joint meeting of the FA( Working Party and the WHO Expert Committee o Pesticide Residues, 1966. PL:CP/I5: WHO/Foo Add./67.32. (12) Martin. R. J., and R. E. Duggan. 1968. Pesticide resi dues in total diet samples (III). Pestic. Monit. J. 1(4 11-20. Pesticides Monitoring Journai \BLE 1. — Number of composites where pesticide residues were found and ranges in the amounts (June 1969 — April 1970) No. OF Positive No. OF Composites with Ranges Pesticide Composites Residues Reported OF PPM WITH Residues As Traces > Reportings ^DMIUM 251 7 0.01-0.14 (OMIDES 245 0 0.5-154 3T l,l,l-Irichloro-2.2-bis(p-chlorophenyn ethane (isomers other than p.p' also included in reportings) 200 26 0.001-0.474 DE l,l-dichloro-2,2-bis(p-chlorophen>n ethylene (isomers other than p.p' also included in reportings) 182 46 0.001-0.459 )E l.l-dichloro-2.2-bis(p-chlorophenyl) ethane (isomers other than p.p' also included in reportings) 118 20 0.001-0.181 ELDRIN Not less than 85% of 1. 2.3.4.10, 10-hexachloro-6.7-epoxy-1, 4,4a, 5,6.7.8.8a- oclahydro-l,4-enrfo-exo-5,8-dimethanonaphthalene 112 9 0.001-0.092 NDANE I.2.3.4.5.6-hexachlorocyclohexane, 99*7^ or more gamma isomer 49 4 0.001-0.076 I.2.3.4,5,6-hexachlorocyclohexane. mixed isomers except gamma 49 6 0.001-0.187 EPTACHLOR EPOXIDE 1.4.5.6.7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4.7-methanojndan 40 3 0.001-0.089 ALATHION diethyl mercaptosuccinate. i-ester with 0.0-dimethyl phosphorodithioate 39 I 0.002-0.166 AZINON 0,0-diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioale 21 3 0.001-0.039 lDRrN 1,2.3,4. 10,10-hexachloro-6,7-epoxy-l,4,4a,5.6.7.8.8a-octahydro-1. 4- e/7(yo-eMrfo-5.8-dimethanonaphthalene 5 2 0.001-0.004 3XAPHENE chlorinated camphene containing 67% to 69% chlorine 4 I 0.080-0.132 ITHIOCARBAMATES Calculated at Zincb 4 1) 0.7-3.0 (onions and celery only) :nb 1.2.4.5-tetrachloro-3-nitroben2enc 3 0 0.001-0.004 LDRIN ot less than 95% of l.2,3,4.I0,10-hexachloro-1.4.4a.5.8.8a-hexahydro-1.4- e/j Residues In Parts Per Million DT Average Positive Composites Number Range 0.014 5 0.002-0.077 0.002 0.006-0.010 T 1 T 0.002 3 0.002-0.005 0.002 5 0.002-0.004 DE Average Positive Composites Number Range 0.001 5 T-0.002 T T T 1 T 0 T 2 0.001-0.002 DE Average Positive Composites Number Range 0.002 4 0.001-0.004 T 1 T T 1 T 0 0.001 4 0.001-0.002 'lELDRIN Average Positive Composites Number Range 0.001 2 0.002 0.001 1 0.006 0.003 2 0.005-0.014 0 0.001 2 0.003-0.004 INDANE Average Positive Composites Number Range T 2 T 0.001 3 0.001-0.002 0.002 0.0034).007 0.002 0.001-0.008 0.001 4 0.001-0.002 ^OL. 5, No. 4, March 19 72 319 TABLE 2a. — Levels of pesticide residues commonly found — by food class and region (June 1969— A pri 7970)— Continu. IT = Trace = <.001 ppm] Pesticide Boston Kansas Cinr Los Angeles Baltimore Minneapolis II 1. Grain and Cereal ' — Continued Residues In Parts Per Million MALATHION Average Positive Composites Number Range 0,013 3 0.014-0.034 0.038 5 0.024-0.096 0.029 6 0.014-0.048 0.029 5 0.013-0.060 0.032 5 0.020-0.070 DIAZINON Average Positive Composites Number Range 0.002 3 0.002-0.006 0.001 1 0.007 0.003 3 0.0O1-O.017 0 0.001 2 0.002 TOTAL BROMIDES Average Positive Composites Number Range 15.8 6 5.0-24 13.4 4 3.5-56 12.3 6 6.0-28 26.4 6 7.5-94 9.2 5 1.5-21 CADMIUM Average Positive Composites Number Range 0.04 5 0.01-0.06 0.02 4 0.02-0.06 0.02 6 0.01-0.02 0.02 6 0.02-0.03 0.03 6 0.02-0.03 IV. Potatoes ' Residues In Parts Per Million DDT Average Positive Composites Number Range 0.006 6 T-0.021 T 1 0.003 0.001 2 T-0.006 0.002 4 1-0.010 0.001 3 T-0.005 DDE Average Positive Composites Number Range 0.005 5 T-0.025 0.001 3 T-0.003 0.001 3 T-0.003 0.003 5 T-0.009 0.001 3 0.001-0.004 DIELDRIN Average Positive Composites Number Range T 1 T 0.002 1 0.009 0.001 3 0.001-0.006 0.010 2 0.001-0.057 0.006 3 0.002-0.020 TOTAL BROMIDES Average Positive Composites Number Range 2.6 3 1.5-in 0.2 1 1.5 0 14.2 4 4.0-52 4.6 5 4.0-7.0 CADMIUM Average Positive Composites Number Range 0.04 5 0.02-0.07 n.()4 6 0.02-0.07 0.04 6 0.03-0.07 0.04 6 0.01-0.06 0.05 6 0.03-0.08 V. Leafy Vegetables • Residues In Parts Per Million DDT Average Positive Composites Number Range 0.007 5 T-0.027 0.006 4 0.003-0.018 0.003 3 0.005-0.007 0.008 4 0.005-0.016 0.010 6 0.003-0.031 DDE Average Positive Composites Number Range T 1 T 0.002 1 0.010 0 0.002 2 T-O.OlO 0.003 4 0.001-0.010 ENDOSULFAN (I, II, plus Sulfate) Average Positive Composites Number Range T 1 0.001 T 1 T 0.001 2 0.002-0,004 0.002 1 0.009 0.008 2 0.005-0.040 320 Pesticides Mor JITORING JoURNi ABLE 2a. — Levels of pesticide residues commonly found — by food class and region (June 1969 — April 1970) — Continued [T = Trace = <.001 ppm] Kansas City Los Angeles Minneapolis V. Leafy Vegetables ' — Continued Residues In Parts Per Million DE Average Positive Composites Number Range 0 0 0 0.001 3 T-0.002 0.001 0.003 lELDRIN Average Positive Composites Number Range 0.001 2 0.002-0.005 0.002 1 0.009 0.001 2 0.002-0.006 T T-0.002 0.001 1 0.004 ETHYL PARATHION Average Positive Composites Number Range 0.003 2 0.003-0.013 0 0.001 1 0.005 0.001 1 0.007 0.004 2 0.002-0.023 VRATHION Average Positive Composites Number Range 0.002 2 T-0.009 0 0.002 2 0.004-0.008 0.001 2 T-0.004 0.002 0.004-0.007 )TAL BROMIDES Average Positive Composites Number Range 2.5 5 0.5-7.0 9.2 2 1.5-4.0 1.5 4 2.0-3.0 7.2 5 1.5-23 1.6 5 0.5-4.5 \DMIUM Average Positive Composites Number Range 0.07 5 0.03-0.14 0.03 5 0.02-0.06 0.05 6 0.03-0.10 0.02 6 0.01-0.04 0.06 6 0.02-0.14 VT. Legume Vegetables ' Residues In Parts Per Million DT Average Positive Composites Number Range 0.002 6 T-0.007 0.006 0.002-0.032 0.004 3 0.006-0.010 T T-o'o02 0.004 0.022 DE Average Positive Composites Number Range T 6 T-O.OOl T 1 0.002 0.001 1 0.007 T T-0?002 T 3 0.001 3E Average Positive Composites Number Range T T-0.002 0.001 1 0.007 0.002 0.005-0.007 T f 0.002 0.004-0.006 DTAL BROMIDES Average Positive Composites Number Range l.S 4 1.0-6.0 1.7 3 1.0-4.5 1.5 4 2.0-3.0 4.3 3 2.5-18 1.8 3 1.0-5.0 ADMIUM Average Positive Composites Number Range 0.01 5 0.01-O.03 <0.0I 1 0.02 <0.01 2 0.01 0.01 2 0.01-0.04 0 'OL. 5, No. 4, March 19 72 321 TABLE 2a. — Levels of pesticide residues commonly found — by food class and region fJune 1969— April 1970)— Continu [T = Trace = <.001 ppm] Pesticide Boston Kansas City Los Angeles Baltimore Minneapolis VII. Root Vegetables ^ Residues In Parts Per Million DDT Average Positive Composites Number Range O.OOi 5 T-O.OlO 0.002 2 T-0.014 O.OOI 3 T-0.003 T 2 T-0.002 0.008 4 0.005-0.029 DDE Average Positive Composites Number Range 0.003 5 T-0.025 T 3 T 0.001 3 T-0.003 T 2 T-0.002 0.003 5 0.001-0.008 DIELDRIN Average Positive Composites Number Range 0.002 3 0.002-0.008 0.002 2 T-O.OlO 0 0 0 TOTAL BROMIDES Average Positive Composites Number Range 1.8 3 1.0-8.0 1.0 2 1.0-1.1 3.0 4 1.0-12.0 7.6 5 2.5-19 2.8 5 1.5-5.5 CADMIUM Average Positive Composites Number Range 0.04 5 0,03-0.08 0.02 4 0.01-0.07 0.02 6 0.01-0.06 0.02 6 0.01-0.04 0.02 6 0.01-0.04 VIII. Garden Fruits' Residues In Parts Per Millie DDT Average Positive Composites Number Range DDE Average Positive Composites Number Range TDE Average Positive Composites Number Range DIELDRIN Average Positive Composites Number Range LINDANE Average Positive Composites Number Range ENDOSULFAN (I. IT, plus Sulfate) Average Positive Composites Number Range PARATHION Average Positive Composites Number Range T-0.003 0.019 6 0.002-0.084 0.007 6 0.006-0.008 0 0.002 1 0.013 0.031 6 0.013-0.052 0.001 322 Pesticides Monitoring Journ> ^LE 2a. — Levels of pesticide residues commonly found — by food class and region (June 1969 — April 1970) — Continued [T = Trace = <.001 ppm] Los Angeles VIII. Garden Fruits ' — Continued Residues In Parts Per Million )TAL BROMIDES Average 3.2 2.0 2.0 4.8 2.7 Positive Composites Number 5 3 5 5 4 Range 2.0-6.5 2.5-6.5 1.0-3.0 1.5-11 3.0-6.0 \DMIUM Average 0.02 0.02 0.02 0.01 0.03 Positive Composites Number 5 5 6 5 6 Range 0.01-0.07 0.01-0.03 0.01-0.02 0.01-0.02 0.01-0.10 IX. Fruits 1 Residues In Parts Per ! OT Average Positive Composites Number Range 0.001 3 T-0.004 0.084 3 0.010-0.474 0.005 5 0.003-0.011 0.011 3 0.003-0,054 0.004 3 0,004-0,011 DE Average Positive Composites Number Range 0.004 5 T-0.020 0.002 4 T-O.OIO T T-O.OOl T 2 T 0,001 4 0,001-0.002 )E Average Positive Composites Number Range T 2 T 0 0.003 1 0.018 T 2 T-0.003 0.004 2 0.010-0.012 ICOFOL Average Positive Composites Number Range 0.005 2 0.011-O.019 0.006 3 0.009-0.015 0.020 5 0.010-0.040 0 0.031 5 0.006-0.102 miON Average Positive Composites Number Range T 1 0.002 0,009 2 0.026-0.028 0.013 6 0.002-0.023 0.001 T-0.008 0.026 4 0.001-0.129 lELDRIN Average Positive Composites Number Range 0.001 4 T-0.003 T 2 T-0.003 0 T 1 T 0.001 4 0.001-0,003 ALATHION Average Positive Composites Number Range 0 0.005 0.002-0.027 0,015 0.039-0.053 0 0,005 2 0,011-0.019 DTAL BROMIDES Average Positive Composites Number Range 1.2 3 0.5-5.0 6.9 4 1.0-31 0.7 1.0-3.0 6,9 4 4.5-16 4,7 6 2.0-14 ADMIUM Average Positive Composites Number Range 0.02 5 0.01-0.07 <0.01 1 0.01 0.01 3 0.01-0.06 0 <0.01 1 0.01 'OL. 5, No. 4, March 197 2 323 TABLE 2a. — Levels of pesticide residues commonly found — by food class and region (June 1969 — April 1970) — Continu [T = Trace = <.001 ppm) Kansas City Los Angeles X. Oils, Fats, and Shortening (83-88% Fat)' Residues In Parts Per Million — Fat Basis DDT Average 0.014 0.003 0.002 Positive Composites Number 4 3 0 0 1 Range T-0.044 T-0.020 0.009 DDE Average 0.005 0.002 T 0.001 0.002 Positive Composites Number 4 4 1 1 2 Range T-0.019 T-0.009 T 0.006 0.004-0.005 TDE Average 0.009 T 0.001 Positive Composites Number 3 2 0 0 1 Range 0.014-0.027 T 0.004 DIELDRIN Average 0.001 o.oni T 0.001 Positive Composites Number 1 2 I 0 1 Range 0.005 0.002-0.005 T 0.005 BHC Average 0.001 0.005 T Positive Composites Number 1 0 2 0 2 Range 0.005 0.010-0.020 T MALATHION Average 0.038 0.011 0.016 Positive Composites Number 3 2 n 0 2 Range 0.015-0.166 0.009-0.055 0.017-0.079 TOTAL BROMIDES Average 6.0 6.2 8.5 11.0 6.8 Positive Composites Number 6 2 5 4 4 Range 0.5-14 16-21 3.0-24 8.0-29 5.0-22 CADMIUM Average 0.02 0.02 0.02 0.02 0.03 Positive Composites Number 5 5 6 6 6 Range 0.01-0.04 0.01-0.04 0.01-0.03 0.01-0.04 0.02-0.03 XI. Sugars and Adjuncts ^ Residues In Parts Per Million DDT Average Positive Composites Number Range 0.004 6 T-0.005 0.001 1 0.004 0.00 1 2 T-0.005 0.001 1 0.008 0.003 4 0.002-0.007 DDE Average Positive Composites Number Range 0.001 6 T-0.002 T 1 T T T-0.003 0 0.001 3 0.001-0.002 TDE Average Positive Composites Number Range o.oni 3 0.002 T 1 T 0 0 0.001 3 0.001-0.003 LINDANE Average Positive Composites Number Range 0.001 0.002-O.003 T 2 T-O.OOl 0.001 4 T-0.002 0 T 2 0.001-0.002 324 Pesticides Monitoring Journ .BLE 2a. — Levels of pesticide residues commonly found — by food class and region (June 1969 — April 1970) — Continued [T = Trace = <.001 ppm] Kansas City Los Angeles Minneapolis XI. Sugars and Adjuncts ' — Continued Residues In Parts Per Million [tal bromides kverage osilive Composites Number Range 10.3 6 4.0-18 11.4 4 1.0-39 5.0 5 2.0-9.0 5.5 5 5.0-8.0 29.8 5 5.0-154 DMIUM ivcr.ige 0.01 <0.01 0.01 0.01 <0.01 ositive Composites Number Range 5 0.01-0.02 1 0.02 5 0.01 4 0.01 3 0.01 XII. Beverages > Residues In Parts Per Million TAL BROMIDES iverage 3.2 0.7 0.3 1.3 5.7 ositive Composites Number 5 3 2 3 4 Range 1.0-7.0 1. 0-2.0 1.0 1.0-5.0 0.5-30 DMIUM average 0.01 ^0.01 <0.0I <0.01 'ositive Composites Number 4 1 2 2 0 Range 0.01-0.04 0.01 0.01 0.01 ix composite samples examined at each of five sampling districts: Boston. Kansas City, Los Angeles. Baltimore, and Minneapolis. Averages sted are averages of six composites of each site. iTE: Bromide, cadmium, and arsenic values are reported on an "as is" basis (no drying or isolation of fat) for Dairy Products; Meat, Fish, and Poultry; and Oils. Fats, and Shortening. TABLE 2b. — Peslicidcs found infrequently — by food class and region (June 1969 — April 1970) IT = Trace = <.0Ol ppm] No. Com- posites I. (a) Dairy Products (8-13% Fat)' Residues In Parts Per Million — Fat Basis idanc Baltimore Kansas City Minneapolis I 1 1 0.002 0.007 0.002 senic (As=0,,) Boston 2 •0.1, 0.1 B (Card as Aroclor 1254) Baltimore 1 0.05 'As is" basis (no drying or isolation of fat). II. (a) Meat, Fish, and Poultry (17-23% Fat)' Residues In Parts Per Million — Fat Basis :b Los Angeles 2 T, 0,01 -DB Minneapolis 1 0.012 azinon Minneapolis 1 0.005 B (Cal'd as \roclor 1254) Los Angeles 2 0.09, 0.13 B (Cal'd as Aroclor 1260) Minneapolis 1 0.12 No. Com- posites III. (a) Grain and Cereal ^ Residues In Parts Per Million Aldrin Kansas City 0.002 BHC Kansas City T Heptachlor epoxide Boston Kansas City Minneapolis 0.002 T, 0.001 0.002 Paralhion Los Angeles 0.002 IV. (a) Potatoes ' Residues In Parts Per Million BHC Baltimore 2 T, 0,004 Chlordanc Boston 0.002 CIPC Minneapolis 0.318 TDE Baltimore 0.002 Endrin Boston Boston Los Angeles T, T, 0.001 T 0.004 2,4-D Minneapolis 0.028 Diazinon Baltimore Los Angeles 0.002 T )L, 5. No. 4, March 1972 325 TABLE 2b. — Pesticides found infrequenlly — by food class and region (June 1969 — April 1970) — Continued No. Com- posites IV. (a) Potatoes "^Continued Residues In Parts Per Million Heptachlor epoxide Boston 0.003 Parathion Los Angeles 0.003 TCNB Boston 0.001-0.004 Endosulfan (Total) Boston Minneapolis 0.005 0.002. 0.008 Arsenic (AsiOs) Boston Minneapolis 0.1 0.1 V. (a) Leafy Vegetables ' Residues In Parts Per Million BHC Minneapolis O.OOI DCPA (Dacthal®) Baltimore 0.088 Diazinon Baltimore Boston Los Angeles T 0.039 0.009 Dicofol Minneapolis 0.006 Toxaphene Baltimore T. 0.040 Dithiocarbamates (Zineb) Kansas City 3.0 (Celery only— com- posites not examined) VI. (a) Legume Vegetables ' Residues In Parts Per Million BHC Los Angeles 1 0.006 Lindane Kansas City Los Angeles T 0.001 Dieldrin Boston T Dicofol Los Angeles 0.26 Parathion Baltimore Los Angeles T 0.001 VII. (a) Root Vegetables ' Residues In Paris Per Millio Lindane Boston Kansas City 2 0.017, 0.072 T TDE Baltimore Boston Minneapolis 2 T T, T 0.004 Endrin Boston 0.004 Arsenic (AsiOa) Kansas City 0.2 Dithiocarbamates (Zineb) Minneapolis 3 0.7-1.4 (Onions only — com- posites not examined) VIII. (a) Garden Fruits ' Residues In Parts Per Million Aldrin BHC Boston Kansas City Minneapolis 0.001, 0.003 0.003 No. Com- posites I. (a) Garden Fruits' — Continued Residues In Parts Per Million Endrin Baltimore Boston T 0.001 Diazihon Baltimore Los Angeles T 0.002 Heptachlor epoxide Kansas City T Malathion Los Angeles T Toxaphene Baltimore Los Angeles 0.132 0.15 Arsenic (AsuOj) Boston 1 0.2 IX. (a) Fruits" Residues In Parts Per Million BHC Kansas City 2 T, 0.003 Diazinon Baltimore T Los Angeles 0.001 Minneapohs 0.001 Methoxychlor Baltimore 0.023 Orthophenylphenol Kansas City 0.2 Parathion Baltimore T Endosulfan (I. II. Los Angeles 0.010 plus Sulfate) Minneapolis 0.008. 0.010 Arsenic (AS2O3) Boston 1 0.2 X. (a) Oils, Fats, and Shortening (83-88% Fat)" Residues In Parts Per Million — Fat Basis Lindane Boston Kansas City Minneapolis 0.046 0.010 0.021 HCB Los Angeles Minneapolis T-0.032 0.008 2,4-DB Minneapolis 0.123 Diazinon Minneapolis 0.003 Heptachlor epoxide Kansas City T Endosulfan (L 11, plus Sulfate) Minneapolis 0.185 XI. (a) Sugars and Adjuncts ^ Residues In Parts Per Million Aldrin Boston 1 0.002 Dieldrin Boston Minneapolis 0.001 0.001 Heptachlor epoxide Boston T Malathion Los Angeles 0.005 PCB (Card as Aroclor 1254) Los Angeles 0.08 XII. (a) Beverages " Residues In Parts Per Million DDT TDE Boston Boston Six composite samples examined at each of five sampling Districts Boston, Kansas City, Los Angeles. Baltimore, and Minneapolis. 326 Pesticides Monitoring Journai 'ABLE 3. — Comparison of residues before and after processing by dietician (average PPM levels for residues found six or more times per food group) Pesticide Potatoes IV Leafy Vegetables V Legume Vegetables VI Root Vegetables VII Garden Fruits VIH Fruits IX Average Retention of Residues ( "^ ) Before After Before After Before After Before After Before After Before After Residues After Prep'n. Residues Before Prep'n. DT 0.009 0.002 0.015 0.007 0.005 0.003 0.033 0.003 0.037 0.019 0.022 0.021 47 DE I).n06 0.002 0.001 0.001 0.001 0.001 0.021 0.002 0.002 0.002 0.002 0.001 66 DE - - - - 0.001 0.001 - 0.017 0.003 0.003 0.001 76 >ieldrin 0.003 0.004 0.001 0.001 - - - - 0.004 0.004 0.001 0.001 108 )icofol - - - - - - - - - 0.031 0.012 39 ndosulfan (I, n, plus Sulfate) — — 0.007 0.002 — — — — ■~ — ~ ~ 29 arathion - - 0.003 0.001 - - - - - - - - 33 lethyl parathion - - 0.004 0.002 - - - - - - - - 50 thion - - - - - 0.020 0.009 45 TABLE 4. — Recovery experiments June 1969 — April 1970 [( ) = Averages; T = Trace = <.001 ppm) Type of Food Composite Spike Level — PPM Blank Level — PPM Range Total Recovered — PPM Range Number of Recovery Experiments 4eptachlor epoxide Fatty Non-fatty Non-fatty Non-fatty Fatty Non-fatty Non-fatty Fatty Non-fatty Non-fatty Non-fatty Non-fatty Non-fatty Non-fatty Non-fatty Fatty Non-fatty Non-fatty Fatty Non-fatty 0.02 0.003 0.010 0.100 0.010 0.003 0.050 0.050 0.003 0.030 0.010 0.003 0.010 0.003 0.01 0.05 0.01 0.003 0.001-0.014 (0.009) 0.000-0.001 (0.001) 0.000-0.007 (0.002) 0.000 0.000-0.009 (0.004) 0.000-0.002 (0.000) 0.002-0.049 (0.014) 0.000-0.031 (0.015) 0.000 0.000 0.000-0.004 (0.002) 0.000-0.002 (0.000) 0.000 0.000-0.002 (0.001) 0.000 0.000 0.000 0.000 0.000-0.017 (0.003) 0.000-0.002 (0.001) 0.000 0.012-0.034 (0.025) 0.003-0.004 (0.004) 0.010-0.019 (0.014) 0.074-0.124 (0.099) 0.012-0.018 (0.015) 0.002-0.005 (0.003) 0.051-0.104 (0.068) 0.037-0.086 (0.062) 0.004 0.026 0.010-0.012 (0.011) 0.002-0.004 (0.003) 0.007-0.010 (0.009) 0.003-0.005 (0.004) 0.004 0.041-0.058 (0.049) 0.002-0.005 (0.003) 0.009-0.014 (0.012) 0.030-0.053 (0.040) 0.004-0.012 (0.009) 0.002-0.006 (0.003) Vol. 5, No. 4. March 1972 327 TABLE 4. — Recovery experiments June 1969 — April 1970 — Continued Type of Spike Blank Total Number of j| Pesticide Food Level — Level — Recovered — Recovery 1 Composite PPM PPM Range PPM Range Experiments 1 Ronnel Non-fatty 0.05 0.000 0.040-0.053 (0.044) 5 \ Non-fatty o.in 0.000 0.075-0.104 (0.089) 5 Malathion Fatty 0.05 0.000-0.047 (0.018) 0.053-0.078 (0.060) 5 Non-fatty 0.05 0.000 0.045-0.087 (0.072) 5 1 1 Non-fatty O.IO 0.000 0.061-0.118 (0.086) '7 1 Parathion Non-fatty 0.05 0.000-0.008 (0.002) 0.039-0.059 (0.050) 9 ! Non-fatty O.IO 0.000-0.0 10 (0.002) 0.066-0.160 (0.101) 4 Non-fatty 1.00 0.000 0.088-0.109 (0.962) 5 Methyl parathion Non-fatty 0.05 0.000 0.032-0.051 (0.042) 6 Non-fatty 0.1 0.000 0.045-0.131 (0.080) 6 Aldrin Fatty 0.003 0.000 T-0.004 (0.002) 5 Non-fatty 0.010 0.000 0.002-0.012 (0.010) 6 Non-fatty 0.050 0.000 0.048-0.052 (0.049) 5 Non-fatty 0.100 0.000 0.088 1 Endrin Fatty 0.003 0.000 T-0.002 (0.001) 4 Non-fatty 0.003 0.000 0.002-0.004 (0.003) 5 Non-fatty 0.010 0.000 0.007-0.012 (0.010) 5 2.4-D Fatty 0.050 0.000 0.014-0.040 (0.024) 5 Fatty 0.100 0.000 0.093 1 Non-fatty 0.100 0.000 0.063-0.101 (0.085) 6 2.4-DB Fatty 0.020 0.000 T-O.OU (0.003) 6 Fatty 0.050 0.000 0.010-0.030 (0.021) 3 Fatty 0.350 0.000 0.30-0.32 (0.31) 2 Non-fatty 0.020 0.000 0.01-0.02 (0.02) 2 Non-fatty 0.050 0.000 0.015-0.059 (0.040) 5 Non-fatty 0.200 0.000 0.05-0.24 (0.14) 7 Non-fatty 1.00 0.000 0.68-1.06 (0.84) 6 2,4,5-T Fatty 0.200 0.000 0.050-0.190 (0.13) 8 Non-fatty 0.020 0.000 T-0.02 (0.010) 4 Non-fatty 0.100 0.000 0.005-0.121 (0.052) 6 Non-fatty 0.200 0.000 0.20-0.22 (0.21) 2 2,4,5-TP Fatty 0.020 0.000 0-0.001 (T) 3 Fatty 0.500 0.000 0.37-0.73 (0.55) 2 Non-fatty 0.500 0.000 0.19-0.72 (0.42) 10 Non-fatty O.I 00 0.000 0.13-0.15 (0.14) 2 328 Pesticides Monitoring Journai TABLE 4.- — Recovery experiments June 1969 — April 1970 — Continued Tl PE OF Spike Blank Total Number of Pesticide Food Level— Level — Recovered — Recovery Composite PPM PPM Range PPM Range Experiments rsenic (As^Oa) Fatty 0.10 0.00 0.03-0.14 (0.09) 10 Fatty 0.50 0.00-0.40 (0.05) 0.19-0.80 (0.42) 14 Non-fatty 0.10 0.00-0.03 (0.00) 0.03-0.21 (0.095) 20 Non-fatty 0.50 0.00-0.20 (0.02) 0.12-0.60 (0.44) 29 Non-fatty 1.0 0.00 0.31-1.18 (0.76) 23 thion Non-fatty 0.05 0.000-0.008 (0.001) 0.038-0.136 (0.056) 10 Non-fatty 0.10 0.000 0.023-0.100 (0.074) 10 iazinon Non-fatty 0.05 0.000 0.036-0.068 (0.051) 6 Non-fatty 0.10 0.000 0.067-0.139 (0.103) 6 arbophcnothion Non-fatty 0.050 0.000 0.010-0.050 (0.025) 5 Non-fatty 0.10 0.000 0.054-0.095 (0.076) 5 cntachlorophcnol Fatly 0.02 0.000 0.000-0.010 (0.003) 4 Fatty 0.10 0.000 0.053-0.069 (0.061) 2 Non-fatty 0.05 0.000 0.000-0.001 (T) 4 Non-fatty 0.10 0.000 0.002-0.043 (0.018) 5 ICPA Fatty 0.50 0.000 0.36-0.47 (0.42) 2 Fatty 0.10 0.000 0.008-0.084 (0.031) 4 Non-fatty 0.02 0.000 0.010-0.040 (0.021) 4 Non-fatty 0.05 0.000 0.017-0.100 (0.044) 4 Non-fatty 0.50 0.000 0.46-0.49 (0.48) 2 AC? Non-fatty 0.10 0.000 0.018-0.081 (0.044) 6 Non-fatty 1.00 0.000 0.26-0.94 (0.56) 5 BA Fatly 0.02 0.000 0.000-0.020 10.011) 4 Fatty 0.10 0.000-0.100 (0.050) 0.010-0.100 (0.055) 2 Fatty 0.50 0.000 0.32-0.40 (0.37) 3 Non-fatty 0.02 0.000-0.020 (0.001) O.OO0-0.022 (0.009) 10 Non-fatty 0.05 0.000 0.010-0.066 (0.043) 6 Non-fatty 1.00 0.000 0.31-1.27 (0.86) 6 Amitrole Non-fatty 0.05 o.ooo 0.020-0.090 (0.045) 22 Non-fatty 0.1 0.000 0.040-0.108 (0.069) 19 Non-fatty 0.2 0.000 0.12-0.20 (0.16) 4 Carbaryl Non-fatty 0.20 0.000 0.15-0.25 (0.19) 22 Non-fatty 0.50 0.000 0.40-0.50 (0.47) 7 Non-fatty 1.00 0.000 0.70-1.30 (0.95) 21 Vol. 5, No. 4, March 1972 329 TABLE 4. — Recovery experiments Jur (' 1969— April / 9 70— Continued Type of Spike Blank Total Number of Pesticide Food Level — Level — Recovered — Recover 1 Composite PPM PPM Range PPM Range EXPERIMENTi Bromides Fatty 5.0 0.0-4.3 (0.2) 0.5-13.0 (6.3) 16 Fatty in.o 1.4-6.0 (4.0) 8.1-19.5 (15.2) 5 Fatty 50.0 0-18.7 (5.8) 14.7-46.0 (38.6) 5 Non-fatty 5.0 0-3.5 (1.5) 0.8-9.4 (5.5) 9 Non-fatty 10.0 0-7.0 (2,7) 3.0-14.7 (10.3) 22 Non-fatty 50.0 0-21.U (3.9) 24.5-60.0 (46.3) 19 Zineb 17 Individual fruits & vegs. 5.00 0.00 1.8-5.4 42 7 Individual (3.7) fruits & vcgs. 1.00 0.00 0.70-1.08 (0.85) 12 Cadmium Fatty 0.05 AA 0.00-0.01 (0.00) 0.04-0.06 (0.05) 6 0.05 P 0.00 0.00-0.04 (0.03) ■6 Fatty 0.1 AA 0.00-0.03 (0.01) 0.06-0.17 (0.10) 18 0.1 P 0.00-0.04 (0.02) 0.04-0.12 (0.091 9 Non-fatty 0.01 AA 0.00-0.01 (0.00) 0.01-0.02 (0.01) 11 0.01 P 0.00-0.01 (0.00) 0.01-0.02 (0.01) 7 Non-fatty 0.05 AA 0.00-0.05 (0.01) 0.00-O.OQ (0.06) 20 0.05 P 0.00-0.05 (0.02) 0.05-0.13 (0.07) 6 Non-fatty 0.1 AA 0.00-0.05 (0.02) 0.06-0.17 (0.10) 11 0.1 P 0.00-0.04 0.00-0.12 8 (0.02) (0.08) NOTE: AA = atomic absorption; P = polarography. 330 Pesticides NfoNiTORiNG Journ.' Dietary Intake of Pesticide Chemicals in the United States (III), June 1968-April 1970 R. E. Duggan ' and P. E. Corneliussen - ABSTRACT •suits are presented of the continuing study of dietary intake pesticide chemicals on samples collected in 1969 and 1970. ■esc results are cotnpared with those obtained dtirinf; the rt 4 years of the study. Comparison showed that daily ake of DDT analogs declined significantly while aldrin- 'Idrin levels were unchanged. Geographical differences were 'iiificant. The pesticide residue levels found were lower in the established acceptable daily intakes. on the results of analyses of subjective and/ or objective sampling, including total diet studies. The purpose of this article is to report the average daily intake of pesticide chemicals from 60 samples collected from June 1968 through April 1970 in 37 cities. Residue levels in ppm in these samples have been reported by Corneliussen {3.4) in accord with earlier publications on this continuing study. The results will be compared with the earlier findings. Introduction n earlier report {S) discussed the average daily intake pesticide residues from food ready for consumption am 46 "total diet" samples collected in retail food ares in 25 different cities during the period June 1964 rough April 1966. Results were reported in summary rm on 30 additional samples collected from June 1966 rough April 1967 in 29 different cities (9) and 30 mar- ■ts in 27 different cities from June 1967 through April 168 (10). McGill and Robinson (16) reported the daily take of DDT compounds and dieldrin in complete epared meals and representative milk samples during 1-year period in S. E. England. I recommendations included in the 1967 report of the int meeting of the FAO Working Party of Experts id the WHO Expert Committee on Pesticide Residues -) it was noted that further information was needed Office of Associate Commisioner for Compliance, Food and Drug Administration, U. S. Department of Health, Education, and Welfare. Rockville, Md. 20852. Sciences Branch, Office of Executive Director of Regional Operation. Food and Drug Administration, U. S. Department of Health. Educa- tion, and Welfare, Rockville. Md. 20852. 'OL. 5, No. 4, March 1972 Source of Data Although details of the investigation have been described fully in earlier reports (2-7,15). a brief review of the major elements may be desirable. A market basket of 1 1 7 food items is obtained from retail food stores in the same manner a customer selects his food. Each market basket represents a 2-week diet, constructed with the advice and assistance of the U. S. Department of Agriculture, for a 16- to 19-year-old male. This age group consumes greater quantities and kinds of food than any other age group. The market baskets are pur- chased bimonthly in different cities within five geo- graphic regions of the United States. A total of 30 such baskets are obtained during each yearly period. Cities of different population size are represented in each region. The foods are prepared for consumption in diet kitchens. Each sample is divided into 12 classes of similar foods; and each class of food, containing the proper amount of the individual food items, is composited and slurried for analysis. Each composite is analyzed separately at sensitivity levels substantially below those normally used on samples of raw agricultural products to determine compliance with tolerances. Multiresidue methods (/) valid for more than 60 common chlorinated organic and 331 organic phosphate chemicals are used. These methods employ electron capture and thermionic gas-liquid chromatography (GLC). Results are confirmed by thin layer and/or microcoulometric GLC. Recoveries are generally quantitative but are dependent upon individual compounds and levels employed (4). No correction is made for recovery. Each sample is also examined for selected herbicides, carbamates, and inorganic residues. Organic Residues Tables 1 and 2 summarize the annual findings in tern of the calculated daily intake of specific chemicals four in each of the 12 separate food classes. The daily intal is calculated in milligrams from the concentration parts per million found in the food class and the amoui of food prescribed for consumption during the 14-ds period. Table 1 represents the samples collected fro TABLE 1. — Calculated daily intake of pesticide residues by food class expressed in niilligrams per day from June 1968 to April 1969 [T = <0.001 MG] I 11 III IV V VI VII VIII IX X XI XI Chemical Detected >■ 2 -J t-o. i 5 z in J 0 0 J > is < 5 2 <« 5< a CHLORINATED CHEMICALS DDT 0.002 0.005 0.002 T 0.001 0.001 T 0.002 0.002 T T ^ DDE 0.004 0.005 T T T T T T T T T - IDE 0.001 0.002 T T T T T 0.001 0.001 T T - Dicldrin 0.002 0.001 0.002 T T T T T T T T - Lindane T T 0.001 T T T — T T T T — BHC 0.001 T T T _ — _ T — - Heptachlor cpo.xide 0.001 0.001 T T T — T T T — - Dicofol (Kelthane®) — — — — — — 0.007 — — - Aldrin — T T — — — T — — — — - Endrin — T T T T — — — — Methoxychlor — — T — — — — — — — — - Toxaphene — T — — 0.001 T T 0.002 — — — — Chlordane — T — — — - Heptachlor T T T T — — — — - Endosulfan — — — T 0.001 — T T — — - TCNB — T T T — — _ Perthane Ovex Chlorbenside — — 0.001 — 0.003 — — T — — - - - - - T - - - - - ORGANIC PHOSPHATES Malathion _ T 0.007 T T 0.005 _ Parathion T T T T — — Methyl parathion — — T — T — — — — — — — Diazinon T T T T T — T — T — — Disulfoton (Di-Syston®) — — ^ T — — _ — — Ethion — — — — 0.003 — — — Ronnel — — T — - — — — — — — — HERBICIDES 2,4-D _ T _ _ _ _ DCPA (Dacthal®) — _ — T T _ T — — — — MCPA 0.001 T — — — — — — T — PCP 0.001 0.001 0.001 — — — — T — T T — CARBAMATES Carbaryl - - - - - T - - 0.003 - - - INORGANIC RESIDUES Bromides 1.81 1.24 7.19 1.27 0.33 0.32 0.11 0.32 1.39 0.50 0.54 ^1.5; Arsenic (AsiOa) 0.005 0.034 0.011 0.002 0.001 0.001 T 0.001 0.004 T 0.001 0.01 Cadmium 0.005 0.004 0.014 0.007 0.005 0.001 0.001 0.002 0.005 0.002 0.001 0.0( 1 Total bromide (Br) and total arse nic (As.Oa present inc ludes naturally occurring amoi nts. 332 Pe iTICIDES MONITC JRING Jo URNA me 1968 through April 1969. Table 2 represents the ;riod June 1969 through April 1970. These periods ill be referred to as 1969 and 1970, respectively, in e following text. During the 1969 period, residues of 19 chlorinated chemicals, 7 organic phosphates, 4 herbicides, and 1 carbamate were detected. Similarly, in 1970, residues of 17 chlorinated chemicals. 5 organic phosphates, 3 herbicides, and 2 carbamates were found. TABLE 2. — Calculated daily intake of pesticide residues by food class expressed in milligrams per day from June 1969 to April 1970 [T = <0.00I MGl I n in IV V VI VII VIII IX X XI XII .^ ^ ^ (rt S -1 z V) J J 2 (rt 2 y "■g •r, 2 < is < z ■« 1 5 * s o HiS &!= §t H 5 H as. 55 ou D- J> j> S^ Ou. u. 555 d>< n CHLORINATED CHEMICALS DT 0.001 0.004 0.002 T T T T 0.002 0.005 T T T DE 0,003 0.006 T T T T T T T T T DE 0.001 0.001 T T T T T 0.001 T T T T eldrin 0.002 0.001 T 0.001 T T T T T T T ndane T T T — _ T T T — T T T epiachlor epoxide 0.001 0.001 T T — — — T — T T — iC 0.001 O.OOI T T T T — T T T — — cofol (Kellhanew) — — — — T 0.001 — — 0.003 — — — drin CB idrin — T T — — — — T — T T — _ T _ _ T T _ _ _ ethoxvchlor 0.001 — — — — — — — T — — — 3xaphene — — — — T — — 0.001 — — — — nlordane — — T — — idosulfan — — — T T — — T T T — — eptachlor — — — — — — T — — — — — CNB — — — T — ~ — ~ ~ ~ ~ ~" ORGANIC PHOSPHATES alathion _ 0.01 1 T 0.001 0.001 T _ 1 rath ion — — T T T T — T T — — — eihvl paraihion — — — — T — — — — — — — lazinon — T 0.001 T T — — T T T — — hion — — — — — — — 0.004 HERBICIDES CARBAMATES INORGANIC RESIDUES' romides 3.60 1.27 6.00 0.75 0.19 0.18 0.12 0.26 0.92 0.38 0.63 2.53 rsenic (AsiOa) 0.006 0.048 — 0.001 — — T 0.001 0.001 — — — admium 0.002 0.003 0.010 0.008 0.003 T 0.001 0.002 0.002 0.001 0.001 0.005 MISCELLANEOUS 0.001 Total bromide (Br) and total arsenic (As^Os) present includes naturally 'OL. 5, No. 4, March 1972 333 Fig. 1 shows the distribution of the total daily intake of pesticides among the organic chemical classes. Al- though there are differences in each year of the study, a major part of the dietary intake of pesticides is chlori- nated organic compounds, with lesser amounts of or- ganic phosphate compounds, herbicides, and carba- mates. This high proportion of chlorinated organic residues is expected because of their greater persistance and wide use patterns. CHLORINATED PESTICIDE CHEMICALS Residues of chlorinated organic pesticide chemicals were found in each of the 60 diet samples examined. Residues were found in each of the food classes although not in all composites of each class. The incidence ranged from 1 positive composite of 60 examined in the Beverage class to positive findings in 58 composites of the Meat, Fish, and Poultry class. Although tabular data on specific compounds are not presented on a regional or seasonal basis, Fig. 2 and 3 show the daily intake of total chlorinated residues by geographical area and by seasons for 1969 and 1970, respectively. Table 3 presents the average daily intake, and ranges, of total chlorinated organic chemicals, by region and year. The average daily intake of total chlori- nated pesticide chemicals calculated from the 30 diet samples was 0.056 mg in 1969. Individual diet samples ranged from a low of 0.003 mg to a high of 0.158 mg. FIGURE 1. — Distribution of residues by chemical class, 1967-1970 Similarly, the average intake was 0.044 mg/day witl a range for individual diet samples from 0.002 mg/da to 0.146 mg/day in 1970. These values are lower than those reported in th previous 2 years of the investigation. The decline is il lustrafed in Fig. 1. The decline in chlorinated residue resulted in an increase in the relative percentage o organic phosphorus residues to an all-time high o 26.9%. Because of the great differences in toxicity among th individual chlorinated pesticide chemicals, the specifi chemicals comprising the total chlorinated residues ar most significant. The data presented in Tables 1 and show a generally qualitative consistency of intake wit the findings (10) for the first 4 years, June 1964 throug April 1968, of the total diet study. The levels, howeve; have decreased over the 6-year period. The frequenc with which TDE and DDE are found is probably du to metabolism and/ or conversion of their parent con FIGURE 2. — Tola! chlorinated pesticide residues by locatio and season. June 1968 — April 1969 334 Pesticides Monitoring Journa )Ound DDT. TTnere is only limited use of TDE and no lirect use of DDE as pesticide chemicals. DDT and its inalogs composed approximately two-thirds of the total ihlorinated organic residues found during the current !-year period. They were found in all food classes ex- :ept Beverages. DDT alone accounts for approximately )ne-third of the total intake of chlorinated organic resi- lues. The distribution of total chlorinated residues and 3DT and its analogs among the different food classes 'or each year of the study is shown in Fig. 4; the percent )f the total diet each food class represents is also shown n Fig. 4 for comparison. It can be seen that the distribu- ion of the chlorinated residues has remained quite :onstant during the 6 years of this study. The major lOurces of both total chlorinated organic residues and 3DT and analogs are those food classes representing iroducts of animal origin, namely. Dairy Products and he Meat, Fish, and Poultry classes. These two classes ire the source of approximately half of the intake of otal chlorinated residues and DDT and its analogs. This s significant in view of the fact that these products re- :eive little direct application of pesticide chemicals and, herefore, their presence must be due to indirect and FIGURE 3. — Total chlorinated pesticide residues by location and season, June 1969 — April 1970 environmental sources. Grains, Fruits, and Garden Fruits combined account for about 40% of the total intake of this class of chemicals. This is to be expected since direct applications are made to these types of raw agricultural products. The dietary intake from the remaining seven food classes: Potatoes; Leafy Vegeta- bles; Legume Vegetables; Root Vegetables; Oils, Fats, and Shortening; Sugars and Adjuncts; and Beverages is about 10% of the total chlorinated organic pesticide residues. Residues of dieldrin, lindane, and heptachlor epoxide continue to follow DDT and its analogs in order of fre- quency of occurrence. Dieldrin, lindane, and heptachlor epoxide combined account for 14.3% and 13.6% of the total chlorinated pesticide residue found in these sam- ples in 1969 and 1970. respectively. The incidence and amount of the remaining 14 chlori- nated organic pesticide chemicals detected during this 2-year period are too low to be of any significance as individual residues. The average daily intake of these 14 pesticide chemicals combined is less than 0.020 mg/ day with more than half of the individual chemicals present in amounts below 0.001 mg/day. Statistical A nalysis Simple observation of the findings over the 6 years of this study suggest an overall decline in the daily intake of chlorinated pesticide residues. Findings for only the 4-year period 1967 through 1970 were analyzed statis- tically since the full 360 composites per year were not examined in the first years of this study. DDT analogs, aldrin-dieldrin combined, and other chlo- rinated pesticide residues were considered as three sep- arate items in the statistical analysis. A preliminary analysis showed that standard deviations of the daily intake in a district in a year were proportional to the means of the observations (Table 3). Consequently, the analysis was conducted using the logarithms of the observations. There is a clear exponential decline in the annual in- takes of DDT analogs (linear when the logarithm of the intake is plotted versus time). The difference between years is significant at the 0.999 level. There is no con- sistent pattern of seasonal variation. There is no significant change from year to year in the intake of aldrin and dieldrin. Average levels between dis- tricts differ significantly at the 0.999 level and are as follows: Baltimore 0.0008 mg/day, Boston 0.0026 mg/ day, Kansas City 0.0054 mg/day, Los Angeles 0.0034 mg/day, and Minneapolis 0.0026 mg/day. Seasonal pat- tern could not be confirmed statistically. Vol. 5, No. 4, March 1972 335 rM***^^*^MJ'^w^^^uj^^^^^^^-F-^7-r D :s o ------ Oc = = = .-=.-= ^ < < < < < so so ^ ^ ^ "^^ i-> CT\ (7\ Ov CTs OS ON 1* > I > J aj O fr. O c/) CQ r 1= 1= >< >< d s > > ^ - ^ x winz^cumjk r r r r MW-r 336 }U33J3(] Pesticides Monitoring Journa TABLE 3. — Average daily intake of cirlorinated organic chemicals by region and year expressed in milligrams per day Los Angeles Minneapolis TOTAL CHLORINATED RESIDUES vverage tange .D. 0.01.1 0.003-0.020 0.007 0.020 0.002-0.055 0.020 0.062 0.017-0.095 0.029 0.056 0.U29-0.094 0.025 0.046 0.051 0.029-0.058 0.026-0.146 0.013 0.047 0.101 0.080-0.158 0.029 0.054 0.032-0.087 0.022 0.061 0.018-0.115 0.033 0.040 0.028-0.059 0.011 DDT. DDE. TDE COMBINED average .ange .D. 0.011 0.003-0.020 0.007 0.012 0.002-0.028 0.009 0.045 0.015-0.087 0.029 0.044 0.022-0.072 0.021 0.021 0.036 0.015-0.041 0.013-0.137 0.0 10 0.049 0.058 0.037-0.075 0.014 0.035 0.015-0.056 0.014 0.026 0.008-0.037 0.010 0.020 0.016-0.024 0.003 ALDRIN— DIELDRIN COMBINED vverage .ange D. 0.002 0-0.009 0.004 0.003 0-0.013 0.005 0.008 0-0.026 0.010 0.003 0.001-0.007 0.002 0.006 0.007 0.002-0.009 003-0.013 0.003 0.004 0.005 0.001-0.013 0.004 0.005 0.002-0.008 0.002 0.005 0.002-0.008 0.002 0.005 0.003-0.009 0.002 he yearly differences of the remaining chlorinated esticide residues taken as a group were significant at the .99 level. Districts were significantly different at the .999 level. No seasonal pattern could he confirmed ;atistically. 10NPE.STICIDAL CHLORINATED ORGANIC RESIDUES orneliussen (4) reported five occurrences of polychlori- ated hiphenyl (PCB's) residues during 1970. primarily 1 the Meat, Fish, and Poultry class. PCB's are a group f nonpesticidal industrial compounds which have been ;ported only recently because of improved analytical ichniques. While no comparisons can be made at this me. future reports will no doubt discuss any developing ends in residues of this kind. )RGANIC PHOSPHATE PESTICIDE CHEMICALS he incidence of organic phosphate pesticide residues icreased during this 2-year period. Residues in this lass were found 101 times in 1970 and 60 times in 969, compared to 24 in 1968 and 27 in 1967. The verage daily intake for this 2-year period was 0.012 ig/day compared with 0.009 mg/day for the previous -year period. Malathion accounted for 157c of the aily intake of this residue class over this 2-year period. "hirty-eight percent of the detections were malathion, nd 61% of the malathion detections were " the Grain nd Cereal class. Ethion averaged 0.003 ing/dav . itake ver this 2-year period with an average of ' ' ^ .ections ler year, all of which were in the Fruit class. The re- naining five organic phosphates detected were too low n incidence and intake to be considered regular com- •onents of the diet. HERBICIDE AND CARBAMATE CHEMICALS The incidence and quantity of herbicide chemicals un- derwent significant reductions during this 2-year period. The average daily intake of residues in this class was 0.004 mg during 1969, the same as the average of 1967 and 1968. This is equivalent to 4.7% of the total intake of organic pesticide residues. The intake dropped to less than 0.001 mg day in 1970, amounting to only 0.8% of total pesticide residue intake. The most significant reductions were in 2.4-D and PCP residues which were dominant in previous years. Tables 1 and 2 show a shift away from such residues in foods of animal origin, that is. the Dairy Products and the Meat, Fish, and Poultry classes. Since herbicides are not used directly on these products, there may have been changes in environmental sources which caused these residues to appear higher in earlier years. The incidence and amounts of carbamate chemicals were again very low, comprising 3.6% and 5.0% of the total organic pesticide residue intake for 1969 and 1970, re- spectively. Carbaryl was found in three composites dur- ing 1969 but was not found during 1970. CIPC was found once in 1970. Dithiocarbamate residues (calculated as zineb) were not found during 1969 but were found on three individual celery and onion samples during 1970. During 1969 and 1970, analysis for dithiocarbamate residues was performed on individual fresh fruits and vegetables be- fore compositing in order to prevent hydrolysis decom- position. Dithiocarbamaies are not considered as being regular components of the dietary intake of pesticide residues because of the continued low incidence and levels. foL. 5, No. 4, March 1972 337 Inorganic Residues An average of 67 'vr of all composites examined during the 2-year period covered by this report contained resi- dues of inorganic bromides. All food classes were found to contain some bromide residue. The analytical method used does not differentiate between naturally on ...ring bromides and those resulting from treatment with or- ganic bromide fumigants. Results show a daily intake of 16.8 mg in 1969 and 16.3 mg in 1970. As in the previous 2-year period, the highest total bromide resi- dues for this 2-year period were found in the Grain and Cereal food class. The calculated average daily intake for this 2-year period is 16.6 mg and corresponds to 5.4 ppm concentration. Under certain conditions, un- treated foods may contain as much as 25 ppm {13) of naturally occurring bromides. Table 4 shows the percentage of food class composites at various levels of bromide content. TABLE 4. — Perceiu of loltil composilcs coiilainini; hroinidc in different quantitative ranges. Range— PPM 1969 1970 0.1-5.0 5.1-25.0 >25.0 35.8 22.8 Residues of arsenic were detected in 16% of the com- posites examined in 1969 and in 67c of the composites during 1970. The analytical method used does not distinguish between naturally occurring arsenic and that resulting from arsenical pesticide chemicals. The daily intake of arsenic, calculated as AsoO^, was 0.075 mg for 1969 and 0.057 mg for 1970. The calculated average for this 2-year period corresponds to a 0.02 ppm level, the same as in the previous 2-year period. Although cadmium and its compounds have no pesti- cidal usage, all composites were examined for this ele- ment during both years of this reporting period. The methodology was sensitive to 0.01 ppm. Residues were detected in 68% of the composites examined in 1969 and in 70% of the composites during 1970. The cal- culated average for each year was 0.02 ppm. The daily intake of cadmium was 0.050 mg for 1969 and 0.038 mg for 1970. Murthy el al. {18) reported a mean intake of 0.092 mg/day in a study of institutional diets in the United States. That report referenced many other re- ports which showed wide variations, depending on the nature of the study. Daily Intake Levels The diet constructed for use in this investigation (61 represents a food intake almost twice the "average" intake of the "average" individual. Therefore, the c culated values shown in Tables 1 and 2 are considc' as maximum dietary intakes of pesticide cheniic from a well-balanced diet. Table 5 summarizes the incidence and calculated da- dietary intake of the 22 organic pesticide chemicals i served in more than 1 % of the composites in any of t 6 years of the investigation. The frequency of occi rence and sensitivity of the method must be consider in attaching significance to the calculated daily diet, intake of a specific pesticide chemical. A few occi rences of a chemical for which the method is relativi insensitive will result in a comparatively high calculat daily intake. In such instances, it would be illogical - conclude that the calculated daily intake was as \a as a similar value calculated from a greater number observations of a pesticide chemical where the anah ti method is more sensitive and accurate. The values obtained during this study have been cc verted to milligrams per kilogram of body weight, ba'- on the average weight (69.1 kg) of the 16- to 19-year-( male. Table 6 compares these values with the acceptable da intake proposed for some pesticide chemicals by Food and Agriculture Organization of the United > tions and the World Health Organization Expert Co mittee on Pesticide Residues (12). Acceptable daily take is defined as "the daily dosage of a chemical whi' during an entire lifetime, appears to be without : preciable risk on the basis of all facts known at t time. 'Without appreciable risk' is taken to mean i practical certainty that injury will not result even af a lifetime of exposure." It can be seen that no acceptable daily intake val has been exceeded during the 6 years of this study, a the calculated daily dietary intake for practically pesticide chemicals is one order of magnitude (1/1 or more below that considered safe by the FAO-WI- scientists. The FAO-WHO Expert Committees have set an accej able daily intake level for aldrin and dieldrin combint The average combined level of these two chemic. reported in the high consumption diet used in this vestigation are. in a practical sense, equivalent to t accepted value. Except for DDT and its analogs, eldrin is the pesticide chemical most frequently fou in food. Dietary intakes of DDT compounds during the 6 ye£ of this study have shown a general decline to the poi where they are now well below the 6-year average ai only half as great as the first 4-year average. Aldri dieldrin intakes have remained relatively constant di ing the 6 years of this study. 338 Pesticides Monitoring Journ/ p TABLE 5. — Average incidenee and daily intake of 22 pesticide chemicals IT = <0.001 MG] 1965 1966 1967 1968 1969 1970 Percent Percent Percent Percent Percent Percent Compound Positive Daily Positive Daily Positive Daily Positive Dmlv Positive Dmly Positive Daily Compos- Intake— Compos- 1 nt^ke— COMPOS- NTAKE — Compos- 1 NTAKE — Compos- 1 NTAKE— Compos- 1 NTAKE — ites* Mg ites** Mc ITES*** Mg ITES*** Mg ITES'*» Mg ITES*** Mg DT 37.5 (1.031 37.3 0.041 38.6 0.026 49.2 0.019 48.9 0.016 55.6 0.015 DE 31.5 0.018 33.0 0.028 31.1 0.017 37.5 0.015 39.4 0.011 50.6 O.OIO DE 19.4 0.013 25.7 0.018 28.9 0.013 31.1 0.0 11 28.1 0.005 32.8 0.004 ieldrin 18.5 0.005 21.3 0.007 15.3 0.004 15.6 0.004 25.3 0.005 31.3 0.005 indanc 15.8 0.004 12.3 0.004 10.6 0.005 15.3 0.003 13.3 O.OOI 13.3 0.001 eptachlor epoxide 13.4 0.002 12.0 0.003 8.9 O.OOI 13.1 0.002 12.2 0.002 II. I 0.001 HC 6.5 0.002 6.0 0.004 8.9 0.002 9.7 0.003 10.6 0.001 13.6 0.001 lalathion — — 5.3 0.009 3.6 0.010 1.9 0.003 5.8 0.012 11.1 0.013 arbaryl 7.4 0.15 2.7 0.026 I.l 0.007 — — 0.8 0.003 _ _ Idrin 5.6 0.001 3.7 0.002 3.3 O.OOI 3.9 T 1.4 T 0.8 T 4-D 4.2 0.005 3.0 0.002 1.7 O.OOI 0.6 O.OOI 0.3 T 0.3 T >iazinon — — 3.0 O.OOI 0.3 T 0.3 T 3.9 T 5.8 0.001 icofol (Kelthanc) 0.5 0.003 3.7 0.002 5.6 0.012 4.7 0.010 3.6 0.007 4.4 0.004 CP 1.4 T 3.3 0.006 2.2 O.OOI 1.9 O.OOI 2.8 0.002 — — ndrin 2.8 T 2.0 T 1.7 T I.l 0.001 3.3 T 1.4 T [eihoxychlor — — 1.6 T 0.8 0.001 1.1 0.001 0.3 T 1.9 0.001 eptachlor 1.9 T — — 0.3 T 0.3 T 1.7 T 0.3 T oxaphenc — — 1.0 0.002 — — l.I 0.002 3.6 0.004 1.1 0.001 erlhanc 0.5 T 1.3 O.OOI — — 0.6 0.001 I.l 0.004 — — aralhion — — 1.0 T 1.4 0.001 0.6 T 3.3 T 5.0 T ndosulfan — — 1.6 T 0.3 T 0.8 T 4.2 0.001 5.3 0.001 Ihion - - 0.3 T 1.1 0.002 1.7 O.OOI 1.7 0.003 4.4 0.004 ' 216 composiles examined. ' 312 composites examined. ' 360 composites examined. TABLE 6. — Dietary intake of pesticide chemicals Mg/Kg of Body Weight/Day WHO-FAO Accept. Daily Intake Total Diet Studies 6-Year Average .Idrin 'ieldrin Total arbar>I >DT 9DE IDE Total lichlorvos 'iphenyl lamma BHC (Lindane) romidc leptachlor leptachlor epoxide Total lalaihion )ia?inon 'aralhion IIHC )icofol (Kcllhane) indrin "otal Chlorinated Pesticides 'olal Orpanophosphates otal Herbicides 0.005 0.004 0.02 0.002 0.005 0.00001 0.00008 0.00009 0.002 0.0004 0.0003 0.0002 0.0009 0.00004 0.00009 0.000 1 0.0005 0.0005 0.0003 0.0002 0,001 0.00001 0.00005 0.00006 0.0001 0.0004 0.0002 0.0002 0.0008 0.0000 1 0.00005 0.00006 0.0003 0.0002 0.0002 0.0007 0.0000001 0.00007 0.00007 0.00004 0.0002 0.0002 0.0001 0.0005 0.0000006 0.00007 0.00007 0.0002 O.OOOI 0.0001 0.0004 0.00001 0.00007 0.00008 0.0005 0.0003 0.0002 0.0002 0.0007 NOT DETERMINED- NOT determined- 0.00007 ' 0.39 0.000003 0.00003 0.00003 0.00003 0.00004 0.000009 0.0012 0.00012 0.0001 0.00002 0.00001 0.00004 O.OOOI 0.000004 0.0016 0.00014 0.00022 0.000001 0.00002 0.00002 0.0002 0.000001 0.00001 0.00003 0.0002 0.000004 0.0012 0.00025 0.00005 0.000001 0.00003 0.00003 0.00004 0.000001 0.000001 0.00004 0.0001 0.00001 0.0010 0.00007 0.00006 0.000001 0.00003 0.00003 0.0002 0.000004 0.00001 0.00002 0.0001 0.000004 0.0008 0.00023 0.00005 0.0000001 0.00002 0.00002 0.0002 0.00001 0.000003 0.00002 0.00005 0.0000005 0.0006 0.00026 0.000008 0.000001 0.00003 0.00003 0.0001 0.00001 0.00001 0.00003 0.0001 0.000005 0.0011 0.00019 0.00008 Total bromides present — includes naturally occurring bromides. ''OL. 5, No. 4, March 1972 339 From complete prepared meals in England, McGill, Robinson, and Stein (17) calculated an average intake for DDT of approximately 0.0009 mg/kg/day over a 3-year study period (1965-1967). This is essentially the same as the average DDT analog intake of 0.0007 mg/ kg/day in the U.S. diet over the 6 years of the total diet study. Their calculated intake for HEOD, the major constituent of technical dieldrin was 0.0003 mg/kg/day for 1965-66 and 0.0002 mg/kg/day for 1967. These intakes of dieldrin are several times higher than the 6-year average of 0.00007 mg/kg/day_ in the U.S. total diet study. Summary and Conclusions The kinds and frequency of chlorinated organic pesticide chemicals found in the total diet samples during the period June 1969 through April 1970 do not differ significantly from those found during the period June 1964 through April 1968. Levels of DDT analogs de- clined, but aldrin-dieldrin levels were unchanged. Resi- dues of chlorinated organic pesticides were commonly found in all diet samples and all food classes within samples except Beverages. One beverage sample con- tained a small amount of lindane. The 6-year average daily intake of all chlorinated organic pesticide residues was 0.0011 mg/kg of body weight. The incidence of organic phosphate pesticide chemicals has increased during each of the years. Malathion, most frequently found in grain and cereal foods, was a major factor in the dietary intake of organic phosphate pesti- cides. The dietary intake of this class of compounds has shown an irregular but general increase, particularly in 1969 and 1970. Based on the first 3 years for which there are reliable analytical results for organic phos- phorus pesticide chemicals, 1966-1968, the average diet- ary intake of all chemicals in this class was 0.0001 mg/ kg of body weight. This figure increased to 0.0002 in 1969 and 0.00025 in 1970. The incidence and levels of herbicide chemicals have remained low throughout the 6 years of the study and show dramatic declines in 1970. Herbicides have been found in 9 of the 12 food classes during the 6-year period. No herbicide residues have been reported in Legume Vegetables, Root Vegetables, and Garden Fruits. The average daily intake of all herbicides for the period 1965-1968 was 0.0001 mg/kg of body weight. This intake decreased to 0.00006 in 1969 and to an insignificant trace in 1970. The findings for carbaryl and carbamate chemicals were too limited to consider these pesticide residues as regular constituents of the diet. The incidence and levels of AsoO-, have remained lo\ during the 6 years of this study. While there is a wid variation in the actual annual range, the differences gcr crally are due to higher values for a few samples ex amined during a particular year. There is a natural low level background of arsenic (14) in foods, and th values reported during this period are within or slightl above the natural background. The dietary intake c arsenic from pesticide use does not appear to be sig nificant. The incidence and amount of bromides in the total die samples have remained fairly uniform during the 6 year of this investigation. The amount found, representin naturally occurring bromides and that resulting fror pesticide use, is less than half the FAO-WHO accepi able daily intake. The FAO-WHO acceptable daily ir take is based on the residues resulting from the use c ethylene dibromide and methyl bromide. There seen- to be no reason to be concerned about differentiatin between the bromides resulting from fumigation an those of natural origin as long as the total does nc approach the acceptable value. During the 6->ear period. June 1964 through Apr 1970, the residues of most pesticide chemicals preser in a high consumption well-balanced diet have been bt low and in most cases substantially below the limi established for acceptable daily intakes by the Worl Health Organization and the United Nations Commi tees and in no case above the safe levels anticipate when legal tolerances were established for food. Th low level findings on foods ready for consumption ai consistent with the somewhat higher levels found o the raw agricultural products because of reductions i residues associated with food processing. Reduction i residue levels were reported by Corneliussen (4) fc fruits and vegetables. These levels on raw agricultural products are in tur much lower than the safe tolerances established fo raw agricultural products under Section 408 of th Food. Drug, and Cosmetic Act. Tolerances are estab lished in the United States so that pesticide chemical can be used effectively, and when needed, in the pre duction of food without harm to the consumer. A toler ance does not mean that all foods will contain residue at the tolerance limit when harvested and shipped. Dat (9.11) on thousands of shipments of food examined fo compliance with tolerances show that although a ma jority of the shipments contained one or more pesticid residues, no residues were detected in many lots of fooc A majority of the residues reported were at very lo\ levels, and relatively few, about 3%, exceeded toler ances or administrative guidelines. 340 Pesticides Monitoring Journ.m Pesticide levels in foods are not static. There have been number of occurrences which could have resulted in significant increases in the dietary intalve of pesticides if prompt corrective measures had not been taken be- fore the problem became a national concern. Foods of animal origin continue to be the major source of chlo- rinated organic pesticide residues in the diet. These foods represent about one-fourth of the diet used in this study. They were the source of about half of the intake of total chlorinated pesticide residues and DDT ;ompounds. They were the source of an even greater jroportion of the dietary intake of heptachlor epoxide, 3HC. and dicldrin. The residues of aldrin and dieldrin ire. for practical purposes, equivalent to the acceptable laih' intake. The significance of this observation is the lossibility that the acceptable daily intake may be ex- reeded under certain dietary patterns. There is equal ignificance in the observation that reductions in residue evels in foods of animal origin would be the most ef- ective means of lowering the dietary intake of pesticide hemicals and, in particular, the more toxic pesticides laving low acceptable daily intakes. The dietary intake of pesticides, as measured by this investigation, is a final check which shows that the toler- ance and control system for pesticides in the United States is effective in assuring safe foods. This situation exists because of the joint efforts of the agricultural and chemical industries, universities, and regulatory agencies, both Federal and State. These findings lead us to con- clude that continuous broad surveillance and monitoring programs are required: (a) to determine the extent and trends of pesticide residues in the national food supply; (b) to insure that sufficient voluntary and regulatory ac- tivity be taken to maintain current levels of control of pesticide residues in foods, including the immediate removal of any hazardous foods from the channels of commerce: and (c) to adjust tolerances as necessary in consideration of current toxicology data and current good agricultural practices. See Appendi: paper. les of compounds discussed in UTKRATURK CITED (1) Barry. H. C, J. G. Hundley, and L. Y. Johnson. 1963. (Revised Annually). Pesticide analytical manual. Vol. 1. Food and Dnig Admin.. U.S. Dep. Health, Educ, and Welfare. Washington. D.C. 20204. (2) Cornelii/sscn. P. E. 1969. Pesticide residues in total diet samples (IV). Pestic. Monit. J. 2(4): 140-152. {3) CorncUussen. P. E. 1970. Pesticide residues in total diet samples (V). Pestic. Monit. J. 4(3):89-105. (4) Corneliussen. P. E. 1972. Pesticide residues in total diet samples (VI). Pestic. Monit. J. This issue. (5) Duggiin. R. E.. H. C. Barry, and L. Y. Johnson. 1966. Pesticide residues in total diet samples. Science 151: 101-104. (6) Ditggan, 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. (7) Diiggan. R. £., H. C. Barry, and L. Y. Johnson. 1967. Pesticide residues in total diet samples (II). Pestic. Monit. J. 1(2):2-12. {8) Diiggan, R. £., and J. R. Wcatherwa.x. 1967. Dietary intake of pesticide chemicals. Science 157:1006-1010. (9) Duggan. R. E. 1968. Pesticide residue levels in foods in the United States from July 1. 1963 to June 30. 1967. Pestic. Monit. J. 2(I):2-46. (Abstracted from: U.S. Department of Agriculture and U.S. Department of Healtlt. Education, and Welfare. 1967. The regula- tion of pesticides in the United States.) 10) Duggan. R. £.. and G. Q. Lipscomb. 1969. Dietary intake of pesticide chemicals in the United States (II), June 1966-April 1968. Pestic. Monit. J. 2(4):153-162. /OL. 5, No. 4, March 1972 112) (14) 115) (16) (17) (18) Duggan. R. E.. G. Q. Lipsconjh. E. L. Co.x, R. E. Heatwole. and R. C. Kling. 1971. Pesticide residue levels in foods in the United States from July 1, 1963 to June 30. 1969. Pestic. Monit. J. 5(2):73-212. Food and Agriculture Organization ami World Health Organization. 1967. Evaluation of some pesticide resi- dues in food. Report of a joint meeting of the FAO Working Parly and the WHO Expert Committee on Pesticide Residues, 1966. PL:CP 15: WHO/Food Add./67.32. Hey wood, B. J. 1966. Pesticide residues in total diet samples: bromine content. Science 152:1408. Lehman, A. J. 1965. Summaries of pesticide toxicities. The Association of Food and Drug Officials of the United States. Topeka. Kans. 128 p. Martin. R. J., and R. E. Duggan. 1968. Pesticide resi- dues in total diet samples (III). Pestic. Monit. J. 1(4): 11-20. McGill. A. E. J., and J. Robinson. 1968. Organochlo- rine insecticide residues in complete prepared meals: a 12-month survey in S.E. England. Food Cosmet, Toxicol. 6(l):45-47. McGill. A. E. J.. J. Robinson, and M. Stein. 1970. Methods of estimating dietary exposure of the general population to organochlorine insecticide residues: diet analyses (1965-1967). Submitted for publication. Murthy, G. K.. U. Rhea, and J. T. Peeler. 1971. Levels of antimony, cadmium, chromium, cobalt, manganese, and zinc in institutional total diets. Environ. Sci. Technol. 5(5):436. 341 Pesticide Residues in Sweetpotatoes and Soil — J969 p. F. Sand ', G. B. Wiersma ■, and J. L. Landry' ABSTRACT Paired soil and sweclpolalo samples were gatlwrcd from 92 sites ill 9 major sweetpotato-producing Stales. The average residue levels in sweetpolato soils for DDTR (DDT + TDE + DDE), chlordane, and dieldrin were 1.19, 0.28. and 0.17 ppiu, respectively. In sweetpotatoes, average pesticide residue levels were generally below 0.01 ppin: DDTR was present in 28.3% and dieldrin in 18.5% of the sweetpolato samples. liUrodHction Previous studies have shown that root crops may acquire significant levels of chlorinated hydrocarbon pesticide residues (1,4,5). The study reported here was under- taken to determine the levels of pesticide residues in sweetpotatoes and the soils in which they were grown. Sampling Procedure.'; Samples were collected in 1969 in nine States that are the major producers of sweetpotatoes — Alabama, Cali- fornia, Georgia, Louisiana, Mississippi, North Carolina, New Jersey, Texas, and Virginia. Sampling sites were apportioned among States and among counties within States on the basis of acres of sweetpotatoes grown. Originally, 100 sampling sites were planned, but be- cause of various complicating factors, only 92 were analyzed. • Plant Protection Division, Agricultural Research Service. U. S. De- partment of Agriculture, Hyattsvillc, Md. 20782. = Pesticides Regulation Division, Office of Pesticides Programs, Envi- ronmental Protection Agency, Washington, D.C. 20460. formerly Plant Protection Division. Agricultural Research Service, U. S. De- partment of Agriculture, Hyatisville, Md. ' Pesticides Regulation Division, Office of Pesticides Programs. Envi- ronmental Protection Agency. Gulfport, Miss. 39501, formerly Plant Protection Division, Agricultural Research .Service, U. S. Department of Agriculture, Gulfport, Miss. Sampling sites were randomly located within counties A 50- by 50-foot plot was established in each sweet potato field chosen for sampling, and nine soil cores 2- by 3-inches deep, were taken on a 3- by 3-unit grii system. The soil cores were then composited and siftet i three times through a 'i-inch mesh screen. Materia! that would not pass through the screen was discarded. \ Nine sweetpotatoes were taken at each site, one fo ' every soil core, from as close to the corresponding so f core as possible. Aerial portions of the plant were nc ! sampled. Each sweetpotato was wrapped in aluminur j foil and placed in a plastic bag before shipping to th | laboratory. A nalytical Procedures Sweetpotato and soil samples were prepared and ans lyzed by methods outlined by Wiersma et al. (6). Th lower limit of sensitivity was 0.01 ppm for chlorinate hydrocarbons and 0.05 ppm for organophosphate conn pounds. Tests to determine recovery values were made by forti fication of sweetpotatoes and soil with composite pesti cide standards. The average percent recovery was i for sweetpotatoes and 100"^ for soil. Data for sweet potatoes were corrected for recovery. Confirmation methods, used when necessary, were parti tion coefficients (3), thin layer chromatography and, some cases, preparation of certain pesticide derivative with subsequent GLC analysis of the derivatives. Results and Discussion Average pesticide residues in sweetpotato soils and per cent of sites with residues are given in Table 1. Excep for DDTR (DDT + TDE + DDE) the residue level 342 Pesticides Monitoring Journai TABLE 1. — Organochlorine pesticide residues in sweelpotatoes and soils for nine States, 1969 Residues in Soil Residues in Sweetpotatoes ' Average Range of Pfrceni of Average Range of Percent of Compounds Residue Detected Sites Residue Detected Sites Levels Residues With Levels Residues With IN PPM - IN PPM Residues IN PPM - IN PPM Residues P--DDT 0.13 0.01-1.60 63.0 0.001 0.01-0.04 7.6 r.'-DDT 0.73 0.02-8.26 79.3 0.004 0.01-0.06 19.6 o-TDE <0.01 0.02-0.25 6.5 ND ND D'-TDE O.IO 0.01-1.28 65.2 D.OOl 0.01-0.03 3.3 n'-DDE o.o: 0.01-0.14 29.3 ND ND o'-DDE 0.22 0.01-2.02 82.6 0.003 0.01-0.05 20.7 DTR 1.19 0.01-10.36 82.6 0.009 0.01-0.14 28.3 drill 0.01 0.02-0.11 3.3 ND ND cldrin 0.17 0.01-2.18 60.9 0.004 0.01-0.06 18.5 ilordane 0.28 0.09-5.07 18.5 0.001 0.02-0.08 3.3 •plachlor 0.01 0.01-0.10 13.0 ND ND .piachlor .poxidc 0.01 0.01-0.29 21.7 0.0004 0.01-0.02 3.3 Calculated by dividing the total amount of pesticide used by the number of farms that reported using that pesticide. previous years. Ethyl parathion was used on 34.4% of the sites but was detected in 51.5% of the soil samples. Methyl parathion, which reportedly was not used at all, was found in 11.8% of the soil samples. Diazinon, reportedly used on 22.7 of the sites, was detected in 19.7% of the soil samples, and ethion, used on 7.6% of the fields, was detected in 36.8% of the soil samples. Generally, the average amount of residue detected was considerably less than the amount applied when con- verted to pounds per acre. However. DDT was applied at an average rate of 2.60 lb/ acre, and DDTR was detected at an average residue level of 15.10 ppm or 15.10 lb/ acre for a 3-inch deep acre of soil. Because use records prior to the year of sampling are unknown, it is difficult to pinpoint the source of the DDT. An- other exception was ethion which was applied at an average rate of 1.23 lb/ acre and detected at 1.23 ppm or 1.23 lb/acre for a 3-inch deep acre of soil. Despite the high residue levels and wide distribution of chlorinated hydrocarbon and organophosphate pesti- cides in soil, no residues were detected in the onion samples. See Appendix for paper. chemical names of compounds discussed LITERATURE CITED (/) Bowman, M. C, and M. Beroza. 1965. Extraction p values of pesticides and related compounds in six binary solvent systems. J. Assoc. Off. Agric. Chem. 48(5):943- 952. Vol. 5, No. 4, March 1972 347 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES A Survey of the Lead Content of Fish From 49 New York State Waters Irene S. Pakkala,' Merrie N. White,' George E. Burdick," Earl J. Harris,' and Donald J. Lisk ' ABSTRACT An analytical survey was made of the total lead content of 419 fish of various species sampled In I'J69 from 49 New York State waters and a group of lake trout sampled in 19711 from Cayuga Lake only. Most often, lead concentrations ranged from 0.3 to 1.5 ppm. but a few samples contained levels up to 3 ppm. Fish jrom certain waters including Lakes Canadice, Canadaigiia, Erie. Hemlock, Pleasant, and Raquette and the Hudson River showed higher lead levels more consistently than fish from other waters. No correlation was noted between lead concentration and the size, species. or sex of fish, and lead did not appear to be cutnidative in the lake trout of known age up to 12 rears from Caytiga Lake. Introduction Much has been published about pollution of the en- vironment by lead. Sources of lead contamination are many and varied and include industrial and mining effluents, agricultural pesticides, gasoline, paint, lead shot, atomic explosions, meteoric debris, volcanic dust, natural levels in minerals and soil, and others; lead is present in rocks mainly as the oxide and sulfide. The presence of appreciable levels of lead in city air has been reported (1 .4.5.13.2 1), and a list of the con- centrations of trace metals such as lead in major United States waters has been compiled (14). Lead in seawater has been recorded in the range of 0.03 ppb (22), but levels up to 36 ppb have been reported near Los An- geles (16). Other studies relating lead in water to auto- mobile exhaust (5), outboard motor exhaust (7), and radioactive decay (15) have been published. Residues Pesticide Residue Laboratory, Department of Entomology. N. Y. State College of Agriculture, Cornell University, Ithaca. N. Y. 14850. N. Y. State Department of Environmental Conservation. Division of Fish and Game. Albany. N. Y, 122:6. N. Y. State Department of Environmental Conservation, Rome Pol- lution Laboratory, 8314 Fish Hatchery Rd., Rome, N. Y. 13440. of total lead in freshwater fish in the range of 0.1 to 0.2 ppm (9.12) and high concentrations in specific organs of fish such as the liver or gills have been reported (23). Seafood has been shown to contain up to 2.5 ppm lead (20), and eastern oysters showed concentrations up to 1.000 times over the water concentration (19). The toxicity of various lead salts to fish has been re- ported (21). There are several theories concerning the mechanism of toxicity of lead to organisms. Lead is believed to be an enzyme poison owing to its affinity for amino, imino, and sulfhydryl groups which may comprise reactive sites on enzymes. In this regard, comparative heavy metal toxicities to aquatic organisms agree quite well with their orders of electronegativity, insolubility of their sulfides, and stability of their che- lates. Other hypothesized modes of toxicity of lead are as a precipitant of essential metabolites or as affecting the permeability of cell membranes. All of these pro- posed mechanisms are described in reference 22. A still widely accepted theory of the mode of toxicity of heavy metals in fish is the "coagulation film anoxia theory" credited to Carpenter (2.3) who proposed that heavy metals, such as lead, exert their toxic effect on fish by precipitating or coagulating the normal mucus secreted by the gills and skin. The resultant surface plugging may then interfere with respiration, secretion of waste products, and salt balance, thus causing death. Carpenter (2) detected no lead in the bodies of fish killed in solu- tions of lead nitrate and then externally washed with acetic acid to remove mucus. The acetic acid washings contained most of the lead to which the fish were ini- tially exposed. Other factors which influence the toxicity of heavy metals to fish are pH. dissolved oxygen, tem- perature, water hardness, ion antagonism or synergism, the associated anion, acclimatization, and the nature and condition of the species. Several of these factors have been discussed (6). 348 Pesticides Monitoring Journai The need to survey fish and other species and segments of the environment for heavy metals has been expounded by the Federal Government (/S). The present study re- ports the results of a survey of 419 fish in 49 New York State waters for total lead conducted in cooperation with the N. Y. State Department of Environmental Conserva- tion who made the fish available as part of their 1969 annual statewide fish sampling program. In addition, age and total lead data are presented on a series of lake trout sampled in 1970 in an effort to determine if lead was cumulative in these fish. lead levels in certain fish from Lake Erie and the Hud- son River. The nearness of various waters to large cities might normally explain higher lead concentrations in fish, but many of the samples which were equally high came from waters in largely rural areas. An attempt was made to relate the concentrations of lead with proximity of the sampling site to known deposits of lead in New York State (17). but no correlations were apparent. Similarly, there appeared to be no obvious relationships between fish size, species, or sex and lead concentrations. TABLE 1. — Percent recovery of lead from fish Experimental Methods All fish were netted, and records were kept of species. sex. length, and weight. The fish were decapitated and eviscerated. The remainder was chopped in a food chopper, thoroughly mixed, and frozen in polyethylene bags prior to analysis. Lead was determined by dry ashing 10 g of fish at 485° C using the procedure of Evans and Bandemer (S) except that no magnesium nitrate was added. Lead was separated from interfering metals using ion exchange and then determined colori- metrically as the dithizonate by the method of Johnson and Polhill (10). The percent recoveries of lead added to fish as lead nitrate prior to ashing are given in Table 1. The method was sensitive to about 0.3 ppm of lead in fish. Results and Discussion Table 2 lists the fish collected by their common and scientific names, and Fig. 1 designates numerically the waters where the fish were collected. The results of analysis of the fish for lead, given in ppm on a fresh- weight basis and not corrected for percent recovery, are presented in Table 3. The fish species, sex, length, and weight, and the location of netting are included to the extent that recording was complete. Most of the lead concentrations in fish were between 0.3 and L5 ppm with a few ranging up to 3 ppm. There was little apparent correlation between lead concentrations and sampling location except that fish from Lakes Canadice, Canadaigua, Erie. Hemlock. Pleasant, and Raquette and the Hudson River had higher lead residues more con- sistently. Those from certain other waters may also be high, but the number of samples was insufficient to judge. The only known values for lead in specific waters in the State which could he found were for Lake Erie at Buffalo, the Hudson River below Poughkeepsie. and the St. Lawrence River at Messena which ranged, respectively, from 16 to 90, 5 to 23. and 4 to 48 ppb (14). These levels are admittedly high based on the con- centrations found in ocean water near Los Angeles of 36 ppb (16) and may at least in part explain the higher Vol. 5, No. 4, March 1972 Fish Lead Added (PPM) Percent Recovery Coho salmon 1 70, 70. 1 10 Lake Irciut 1 95. 115. 115, 75 Lake whitefish 1 70. 110 2 95 Northern pike 1 110. 70 3 85. 75 97 4 90 Sniallniouih bass I 125 Yellow perch 1 100 NOTE: Sensitivity level = 0.3 ppm. TABLE 2. — Common and scientific names of fish analyzed in this study Common Name Scientific Name Black crappie Pomoxis mgromaculatus Bowfin Amia caha Brook trout (Speckled trout) Sahelinus fonlinalis Brown catfish (bullhead) and Channel catfish Ictalurus sp. Brown trout Salmo truita Burbot Lola }ola Carp Cyprimts carpio Chain pickerel Esox uiger Cisco Coregonus artedii Coho salmon Oncorhynchus kisutch Freshwater drum Aplodinotus grunniens Gizzard shad Doro.soma cepedianum Goldfish Carassius auratus Lake trout Sahelinus najnaycush Lake whitefish Coregonus clupeaformis Larcemouih bass Microptenis .mlmoides Muskellunge E.SOX rnasquinongy Northern pike Esox lucius Rainbow trout Salmo i^airdneri Rock bass Amhloplites rupeslris Smallmouth bass Xficroplerus dolomieui Splake (Brook and Lake trout cross) Striped bass Morone saxatilis Sturgeon, Atlantic sturgeon, and Shortnose sturgeon Acipcnscr sp. Walleye pike Sdzonsiedion vitreum vitreum White bass (Silver bass) Roccus chrysops White sucker (Sucker) Cato.stomus commersoni Yellow perch Perca sp. 349 FIGURE 1. — New York Slate map xhowing approximate locations of waters where fish were collected Table 4 lists analyses of total lead in a series of lake trout, ranging in age from 1 to 12 years, sampled in 1970 from Cayuga Lake in an effort to determine if lead was cumulative in these fish. The age was accurately known since the fish are annually stocked as fingerlings and marked with the date of stocking. From these limited data, lead did not appear to be cumulative in lake trout. It has been estimated that at present lead inhalation levels, the safe threshold amount in the diet is about 600 fjig per day (II). Considering the relatively insig- nificant portion of our diet that would normally com- prise game fish, the residues of lead reported here would not appear to constitute a hazard. Acknowledginenl The authors thank W. D. Youngs of the Conservation Department, Cornell University, for collecting the Cayuga Lake trout of various ages. LITERATURE CITED (1) Bove. J. L., and S. Siebenberg. 1970. Airborne lead and carbon monoxide at 45th Street, New York City. Science 167:986-987. (2) Carpenter, K. E. 1927. The lethal action of soluble metallic salts on fishes. Br. J. Exp. Biol. 4:378-390. (3) Carpenter. K. E. 1930. Further researches on the action of metallic salts on fishes. I. Exp. Zool. 56:407- 422. (4) Chow. T. J., and J. L. Earl. 1970. Lead aerosols in the atmosphere: increasing concentrations. Science 169: 577-580. (5) Chow, T. J., and M. S. Johnstone. 1965. Lead isotopes in gasoline and aerosols of Los Angeles Basin, Califor- nia. Science 147:502-503. (6) Doudorofj. P.. and M. Katz. 1953. Critical review of literature on the toxicity of industrial wastes and their compounds to fish. II. The metals as salts. Sewage Ind. Wastes 25:802-839. (7) English. J. N.. G. N. McDcrmolt. and C. Henderson. 1963. Pollution eff'ects of outboard motor exhaust — laboratory studies. I. Water Pollut. Control Fed. 35: 923-931. 350 Pesticides Monitoring Journ.\i (S) Evans. R. J., ami S. L. Bandcmcr. 1954. Determina- tion of arsenic in biological materials. Anai. Chem. (16) 26:595-598. (9) Harlcy, J. H. 1970. Discussion on sources of lead in (17) perennial ryegrass and radishes. Environ. Sci. Technol. 4:225. (10) Johnson. E. I., and R. D. A. PoUiill. 1957. The use of an anion exchange resin in the rie'ermination of traces fl^) of lead in food. Analyst 82:238:241. (//) Kchoe. R. A. 1966. Under what circumstances is injes- (l'^> tion of lead dangerous? In Symposium on Environ- mental Lead Contamination. Public Health Service, Dep. Health. Educ, Welfare. Publ. No. 1440:51-58. (12) Kchoe. R. A., F. Thamann. and J. Cholak. I9S7. On '-"^ the normal absorption and excretion of lead. J. Ind. Hyg. 15:257-300. (21) (13) Konopinski. V. ].. and J. B. Upham. 1967. Commuter exposure to atmospheric lead. Arch. Environ. Health 14:589-593. I22) fl4\ Koop. J. F.. and R. C. Kroner. 1970. Trace metals in waters of the United States. Fed. Water Polhit. Control Admin., Dep. of the Interior. Cincinnati. Ohio. ^~^> (15) Langford. J. C. 1971. Particulate Pb. -"'Pb and "'"Po in the environment. Health Phys. 20:331-336. Anonxmoiis. 1971. Lead in the sea. Mar. Pollut. Bull. 2:8. Luedke. E. M.. C. T. fVrucke. and J. A. Graham. 1959. Mineral occurrence of New York State with selected references to each locality. Geol. Survey. Bull. 1072-F., GPO. Washington, D.C. Anonymous. 1970. Pollution: Hazards from metals. Chem. Eng. News. 7 Sept. p. 12-13. Pringle. B. H.. D. E. Hi.ssong. E. L. Kal:. and S. T. Mulawka. 1968. Trace metal accumulation by estu- arine mollusks. J. Sanit. Eng. Div.; Proc. Am. Soc. Civ. Eng. 94:455-475. Scliroeder. H. A., and J. J. Balassa. 1961. Abnormal trace metals in man: lead. J. Chronic Dis. 14:408-425. Tahor. E. C. and W. V. Warren. 1958. Distribution of certain metals in the atmosphere of some American cities. Arch. Ind. Health 17:145-151. U.S. Department of the Interior. Fed. Water Polliit. Control Admin. I96S. Water Quality Criteria, Wash- ington. D.C. 20242. Wetterberg. L. 1966. Acute porphyria and lead poison- ing. Lancet 1:498. TABLE 3. — Residues of total lead in fish from New York Stale waters in 1969 Species ' Tag No. X J. -1 ~i >" Hi D ^ BLUE MOUNTAIN LAKE— NO. Bullhead catfish 6R6527 F 28.4 .379 .6 6R6528 M 28.9 .377 1.2 6R6529 F 27.9 .378 .8 Rainbow trout 6R6522 F 33.0 .393 .5 6R6521 M 33. S .173 .8 Smallmouth bass 6R6526 M 30.5 .337 .5 6R6524 M 28.2 .275 .7 BUTTERFIELD LAKE- NO. 2- Bowfin 22BL-* M 55.9 1 .702 .7 Bullhead catfish 24BL^ F 32.2 .669 .6 23BL^ F 33.0 .685 .7 25BL-4 F 32.11 .680 .7 Largcnunith bass 19BL-4 F 34.8 .657 1.0 21BL-4 M 34.5 .626 .4 20BL^ F 33.0 .573 .7 Northern pike 9BL-4 _ _ _ .6 8BL-4 _ — — .5 lOBL^ — _ _ .8 7BL-t — — — .7 Rock bass 14BL-4 M 22.9 .263 .8 15BL-4 M 22.2 .277 .4 Smallmouth bass llBL-4 _ .7 12BL-4 — — — .6 Sucker 28BL-4 M 38.6 .916 .6 Walleye pike 26BL-4 M 55.9 1.753 .7 29BL-4 M 47.3 1.071 .3 27BL-4 M 48.7 1.268 .4 J. ~i Species ' Tag No. £ Z ^ X ^ n^- -J ■" ^^ S 3 ^ ^ d CANADICE LAKE— NO 3 = Bullhead catfish J6220 - 35.0 .574 1.1 Lake trout J6293 M 47.8 1.246 .5 Chain pickerel J6228 F 46.0 .699 .8 J6222 F 40.7 .471 1.1 Rainbow trout J6225 _ 29.2 .284 1.2 J6226 — 27.4 .243 1.0 Rock bass J62I2 M 21.8 .248 1.0 Smallmouth bass J6210 M 36.1 .751 1.0 J6211 M 28.4 .386 .8 J6291 M 29.2 .409 1.9 J6290 F 33.6 ,603 .9 J6292 F 29.2 .378 1.1 CANANDAIGUA LAKE— NO. 4- Brown trout J6288 M 56.7 2.595 1.3 Lake trout J6287 M 55.2 1.821 .9 J6286 M 52.6 1.545 .8 J6231 ' M Imm. 44.4 .722 t.5 Largemouth bass J6167 M 28.7 .370 .8 Smallmouth bass J6162 F 28.7 .359 I.I CONESUS LAKE— NO. 5 ■ Black crappie J6102 1 — 1 - .6 CAROGA LAKE- -N0.6 = SmallmouUi bass 6R6192 1 F 40.9 1.295 1.0 Vol. 5, No. 4, March 1972 351 TABLE 3. — Residues of total lead in fish from New York Slate waters in 1969 — Continued c ^ATTARAUGU 5 CREEK— NO. 7 - Coho salmon 2F1201 M 41.6 .683 .6 2F1202 M 40.2 .588 .7 2FI203 M 37.9 .588 .6 2F1204 F 54.5 1.77 .6 2F1205 F 56.8 2.09 .6 2F1206 F 61.0 2.19 .7 2F1207 F 60.2 2.23 .5 2F1208 F 63.0 3.04 .5 2F1209 F 64.0 3.00 1.2 CAYUGA LAKE— NO. 8 ■ Largemouth bass Chain pickerel CAY-1 CAY-2 CAY-3 CHENANGO RIVER— NO. 9 = CHITTENANGO CREEK— NO. 10 = 3-CH-l 3-CH-3 43.2 23.4 1.072 .151 COHOCTON RIVER— NO. 11 2CohRl 2CohR2 2CohR3 27.6 26.7 25.4 .256 .251 .194 EIGHTH LAKE— NO. 12 Rainbow trout LAKE ERIE— NO. 13 - Smallmouth bass 3-CHR-l F 22.2 .168 .7 3-CHR-3 F 27.9 .343 .7 3-CHR-2 ^' — Imm. 24.8 .198 .5 3-CHR-4 M 28.6 .295 1.0 Burbot 2-LAER-6 - 58.4 1.980 1.4 Coho salmon 2-LE-Hg-7 F 41.3 .665 .8 2-LE-Hg-6 F 44.5 .764 2.0 LECS 1-9-4-69 M 56.2 2.110 .4 2-LE-Hg-8 M 48.3 1.147 .7 (Sunset Bay) LE-CS-9 F 57.5 2.671 1.0 Do. LE-CS-8 F 55.0 2.392 1.0 Freshwater drum LE-FWD-I M 45.0 1.005 .7 2-LE-Hg-3 F 40.0 .733 .8 2-LE-Hg-42 F 36.8 .670 .5 2-LE-Hg-37 M 36.2 .650 .5 2-LE-Hg^7 F 48.3 1.385 .5 2-LE-Hg-38 M 37.5 .715 .9 2-LE-Hg-45 M 34.3 .570 .7 2-LE-Hg-43 M 35.6 .610 .8 2-LE-Hg-41 F 37.5 .750 .6 2-LE-Hg-46 M 36.2 .565 .9 2-LE-Hg^n F 32.4 .415 .5 2-LE-Hg-44 M 36.8 .610 .9 2-LE-Hg-39 — — — 1.1 2-LE-Hp^S M 48.9 1.395 1.0 2-LE-l — 43.2 .695 .7 2-LE-3 F 30.7 .270 .8 2-LE-Hg-2 F 36.2 .612 .9 2-LE-2 F 50.8 1.750 .6 2-LE-Hg-l M 38.1 .615 .8 LE-FWD-2 M 29.2 .364 .7 Gizzard shad 2-LE-4 Comp osile of . 1 fish 1.5 Lake trout 2-LEL-2 - - - .4 Rock bass 2-LE-Hg-31 M 27.3 .358 1.0 Species ' Tag No. X .1 u J ^ 1" S S " LAKE ERIE— NO. 13 -—Continued Silver bass 2-LE-Hg-5 1 F 37.5 .680 .5 2-LE-Hg-68 F 36.2 .487 1.3 2-LE-Hg-71 F 35.6 .487 .3 2-LE-Hg-53 F 36.2 .615 .7 2-LE-Hg-70 M 34.9 .503 1.3 2-LE-Hg-52 F 36.2 .625 .5 2-LE-Hg-72 F 40.0 .840 1.7 2-LE-Hg-69 M 34.9 .425 .6 Smallmouth bass LE-SMB-1 M 43.5 .932 .5 2-LE-Hg-54 F 40.7 .860 .5 2-LE-Hg — — — .7 2-LE-Hg-50 F 34.9 .645 .5 2-LE-Hg-60 F 39.4 .649 .5 2-LE-Hg-62 F 45.7 1.300 .4 2-LE-Hg-58 M 33.0 .360 .6 2-LE-Hg-56 F 35.6 .682 .7 2-LE-Hg-59 F 37.5 .741 .9 2-LE-Hg-57 M 40.0 .695 .7 Sucker 2-LAER-5 50.8 1.474 1.4 2-LE-Hg- 13 F 51.5 1.530 1.0 2-LAER-4 M 30.5 .334 1.0 2-LE-Hg-l 2 F 48.9 1.296 .8 2-LE-Hg-65 F 44.5 1.150 .8 2-LE-Hg-63 M 46.4 1.190 1.4 2-LAER-3 M 48.3 1.097 .9 2-LE-Hg-l 1 M 45.7 1.040 .9 2-LE-Hg-64 F 46.4 1.260 1.0 2-LE-Hg-67 F 43.2 1.120 1.3 2-LE-Hg-66 F 49.5 1.150 1.1 Walleye pike 2-LE-Hg-23 F 69.3 4.210 .8 2-LE-Hg-25 F 64.7 2.920 .5 2-LE-HP-32 F 63.5 3.375 2.6 2-LE-Hg-4 F 63.5 2.310 1.2 2-LE-Hg-33 M 73.7 5.070 .6 2-LE-Hg-35 F 67.4 3.800 .6 2-LE-Hg-36 F 62.3 3.380 .5 2-LE-Hg-21 F 68.5 4.219 .5 Yellow perch 2-LE-Hg-I6 F 31.7 .515 .7 2-LE-Hg-29 F 33.0 .609 .8 2-LE-Hg-30 F 27.9 .485 .6 2-LE-Hg- 17 F 31.1 .516 1.1 2-LE-Hg-28 F 34.3 .697 .5 2-LE-Hg-26 F 32.4 .612 1.1 2-LE-Hg-20 F 33.3 .605 .8 2-LE-Hg-19 F 36.2 .735 .6 2-LE-Hg-I8 F 34.9 .694 1.1 2-LE-Hg-27 F 30.5 .450 1.1 FERN LAKE— NO. 14 > FORKED LAKE— NO. 15 - Brook trout 6R6641 43.7 .945 1.2 Lake trout 6R6642 M 53.3 .854 .6 Smallmouth bass 6R6648 F 37.1 .950 1.1 Speckled trout 6R6640 F 35.6 .645 .8 FOURTH LAKE— NO. 16 = Lake trout 4-4L-12 F 55.9 1.872 .6 4^L-10 M 37.8 .497 .8 4-4L-11 — — — .7 Sucker 4-4L-23 M 29.2 .301 .7 4^L-22 F 30.2 .336 .5 GENESSEE RIVER— NO. 17 = Smallmouth bass J-6267 352 Pesticides Monitoring Journal TABLE 3. — Residues of total lead in fish from New York State waters in 1969 — Continued HEMLOCK LAKE— NO. 18 = J6204 J6203 J6202 J6I98 J6199 J6197 Jft299 J6298 J6300 28.4 .279 36.1 .739 28.2 .341 31.7 .229 45.7 .754 50.8 1.245 67.5 3.987 77.8 4.270 75.5 4.580 26.2 .344 28.4 .468 HUDSON RIVER— NO. 19 - J2067 J2065 J2064 J2066 6R6667 6R6666 6R6665 J 2070 J 2071 J2072 J 2069 8HUDR2 8HUDR3 46.0 62.0 98.0 64.0 INDIAN LAKE— NO. 20^ .410 1.285 5.076 1.075 57.6 2.256 53.4 2.042 41.1 .780 54.4 2.072 40.6 .800 43.7 .985 LAKE CHAMPLAIN— NO. Northern pike 6R6554 M 73.0 2.735 .4 6R6142 M 64.3 1.433 .7 Walleye pike 6R6553 M 70.6 2.562 .7 6R6144 M 29.7 .380 .6 Whilefish 6R6139 H 38.6 .595 .7 6R6140 M 43.2 .789 .5 6R6I41 M 45.3 .641 .7 6R6143 M 46.0 .873 .7 Channel catfish 5LCCC-1 M 53.4 1.630 .7 5-LCCC-2 F 76.1 6.200 1.0 5-LCCC-3 — 61.0 2.630 .5 6R6592 F 52.0 1.700 .7 (South Bay) 6R6591 M 47.8 1.130 1.0 Do. 6R6593 M 60.5 2.760 2.6 Freshwater drum (South Bay) 6R6588 F 31.7 .306 .9 Do. 6R6590 F 48.8 1.165 .9 Do. 6R6589 M 36.8 .423 .6 Walleye pike (South Bay) 6R6587 M 64.8 3.070 .5 Do. 6R6585 F 40.2 .566 .8 Do. 6R6586 M 54.9 1.455 .3 LAKE ONTARIO— NO. 23 - LAKE GEORGE— NO 22 = Black crappie 6R6676 F 20.3 .109 1.0 6R6675 F 31.2 .584 .5 6R6452 F 28.7 .352 .4 Brown bullhead 6R6680 F 32.8 .686 .7 6R6442 M 33.3 .418 .5 6R6454 F 32.8 .508 .6 Bullhead catfish 6R6679 F 30.0 .469 .9 Chain pickerel 6R6450 M 35.6 .258 .6 Lake trout 6R6672 F 71.0 3.570 1.0 6R573 .7 6R6674 M 68.8 3.125 .5 6R6673 F 70.1 3.241 .7 Laryeniouth bass 6R6441 M 41.1 .973 .6 6R6453 F 36.3 .743 .8 6R6440 M 40.4 .789 .8 Northern pike 6R6677 F 64.0 1.820 .6 6R6671 F 59.5 1.780 .5 6R6404 F 75.0 3.180 .8 6R6407 F 64.7 2.950 .6 6R6406 M 60.5 3.000 1.0 Rainbow trout 6R6678 F 50.0 2.415 .7 6R6681 M 55.3 2.440 .4 6R6682 M 50.8 1.690 .5 6R639 F 41.9 .692 .5 6R6425. F 58.6 2.410 .4 Siiiallniouth bass 6R6449 F 42.4 1.235 .7 White sucker 6R6433 F 53.0 1.139 .5 6R6434 M 46.3 .872 .4 6R6432 M 47.3 .906 1.1 Black crappie 2-LO^ - - .3 Carp J6067 - 27.4 .419 1.0 Coho salmon 69-LO-CSl F 57.7 2.555 .5 20-LO-4 M 58.5 2.640 .7 21-LO-4 F 48.3 .965 .5 2:-LO-t M 50.0 1.400 .4 73-30-69 F 51.3 2.060 .3 (False Duck Is.) 73-29-69 F 55.8 2.040 .6 (Outlet Beach) 73-49-69 F 63.0 3.110 .5 (Amherst Bar) 73-18-69 M 60.1 3.190 .5 (Pt. Petre) 73-27-69 F 56.1 2.090 .7 (Perch Cove) 73-23-69 M 60.4 2.090 .4 (Shelter Val- ley Mouth) 73-47-69 F 64.0 2.890 .5 (Pennicon ReeO 73-16-69 F 56.8 2.460 .4 Do. 73-13-69 M 50.3 1.740 .5 Do. 73-17-69 M 64.8 3.780 1.6 (Wellington Beach) 73-51-69 M 60.5 2.120 .6 Do. 73^4-69 M 64.8 3.010 .5 Do. 73-53-69 M 59.9 2.100 .5 Do. 73-52-69 F 66.0 3.290 .5 Do. 73-48-69 F 64.8 3.010 .4 Do. 73-50-69 M 54.0 1.620 .4 Rock bass J6038 F 22.8 .268 .7 J6097 F 24.1 .288 .9 J6098 M 25.5 .436 .5 J6085 F 22.8 .301 .7 Vol. 5, No. 4, March 1972 353 TABLE 3. — Residues of total lead in fish [mm New York Stale waters in 1969 — Continued Species ' Tag No. X X ■J ^~ LAKE ONTARIO— NO. 23 =— Continued Smallmouth bass 4CI-2 M 27.4 .258 .5 (Carleton Is.) 4CI-1 M 28.9 .320 .5 Do. 4RA2637 F 37.4 .855 .5 (Pt. Penin- 4RA:635 F 33.0 .558 .4 sula) 4RA:f.32 — _ .3 Do. 4RA2638 F 33.6 .644 .4 Do. 4RA2646 F 30..'5 .533 .4 Do. 4RA2644 M 38.1 .892 .3 Do. 4RA2650 M 27.9 .320 .8 Do. 9-LO-4 F 37.6 .826 .4 Do. I6-LO-4 M 40.7 1.014 1.3 Splake 17-LO-4 ' — Imni. 34.8 .523 .5 Sucker 15-LO-4 M 39.1 .657 .9 14-LO^ F 39.1 .703 .5 While bass J 603 8 _ .7 J6027 F 25.5 .272 .7 LAKE PLACID— NO. 24 = Brook trout LP-NE-2 F 30.5 .360 .7 Lake trout 5-NELP-2 41.5 .726 .7 (North End) 5-NELP-l M 31.7 .299 .7 Northern pike 3LP-5 M 76.6 3.870 .7 lLP-5 M 57.4 1.408 .8 2LP-5 M 64.(1 1.642 .7 Rainbow trout 5-LKP-l F 25.4 .225 .8 5-LKP-3 F 40.9 .715 .8 5-LKP-2 F 42.1 .779 .8 Smallmouth bass 5-LKP-4 M 29.2 .336 .8 5-LKP-5 F 46.3 1.420 .7 White sucker 5-LP-W.S-l 43.7 1.440 .7 5-LP-WS-3 — 30.5 .417 .8 Yellow perch 5-LP-5 F . 31.7 .435 .9 LAKE PLEASANT— NO. 25 = Brown bullhead 6R6118 M 34.3 .681 .8 6R6119 F 34.8 .673 1.0 Bullhead catfish 6R6120 M 25.5 .309 .7 Chain pickerel 6R6126 F 35.0 .255 .7 6R6127 F 38.4 .392 .8 6R6128 F 39.2 .405 1.4 Largeinouth bass 6R6131 F 35.0 .622 .6 Rainbow trout 6R6I29 F 42.7 1.068 .9 Rock bass 6R6124 F 26.4 .461 .8 6R6123 K 25.4 .325 1.5 Smallmouth bass 6R6125 _ _ _ 1.1 6R6132 F 32.7 .484 1.1 6R6130 F 49.3 1.775 1.5 Whitefish 6R6117 M 53.8 2.153 .7 6R6116 — 61.0 2.035 .8 Yellow perch 6R6I35 M 30.0 .438 .8 6R6133 M 27.4 .335 .7 LITTLE GREEN POND— NO. 26 = Rainbow trout 5-lgp-8 F 34.1 .392 .9 5-lgp-7 M 32.0 .370 .6 5-lgp-9 F 38.6 .608 .6 Whitefish 5-lgp-l F 53.4 1.805 .8 5-lgp-2 F 57.1 2.041 .7 5-lgp-3 M 50.8 2.050 I.O LITTLE YORK LAKE— NO. 27 = Brown trout Largemouth bass LY-3-1 LY-3-2 34.3 33.2 .456 .720 ONEIDA LAKE— NO. 30- 3-OneL-l 3-OneL-2 59.6 48.3 2.060 1.030 ONONDAGA CREEK— NO. 31 - OS-P154-4-1 OS-PI 54^-2 32.2 29.5 PEPACTON RESERVOIR— NO. 33 = PISECO LAKE— NO. 34 = LONG LAKE— NO. 28 = Largemouth bass 6R6546 F 43.2 1.128 .8 Northern pike 6R6541 F 53.8 1.167 .9 6R6540 M 71.4 2.305 .8 6R6542 M 61.0 1.335 .6 Smallmouth bass 6R6545 F 40.9 .767 .6 6R6544 F 35.6 .672 1.1 LOON LAKE— NO. 29 Smallmouth bass Walleye pike 6R6414 6R6409 6R64I0 6R6408 F F F - ♦.201 ».190 M87 1.232 .9 ■ .7 .4 1.5 OTSEGO LAKE— NO. 32 = Cisco 7-OTSL-l _ 25.9 .161 1.1 7-OTSL-2 M 34.3 .365 .9 7-OTSL-3 F 36.1 .488 .9 Lake trout 7-OTSL-6 _ .6 7-OTSL-5 — — — 1.0 7-OTSL-4 — — — .7 Whitefish 7-OTSL-9 _ .9 7-OTSL-7 — — — .8 7-OTSL-8 — — — .8 Brown trout lPR-7 F 64.8 3.115 .6 2PR-7 F 41.2 .953 .7 3PR-7 F 51.5 1.880 .8 Brown bullhead 6R6105 M 31.7 .425 .9 Whitefish 6R6103 F 38.1 .431 .6 6R6102 F 31.7 .295 .7 RAQUETTE LAKE— NO . 35 = Lake trout 6R6523 - - - .6 Smallmouth bass 6R6207 F 28.9 .287 .8 6R6206 F 27.6 .287 .9 6R6208 F 27.4 .251 .9 Whitefish 6R6245 ■ — 1mm. 33.0 .337 2.9 6R6244 F 34.8 .453 .9 6R66:5 F 31.7 .349 1.3 6R6243 F 35.6 .497 1.5 6R66:7 M 34.0 .388 .8 6R6626 M 35.3 .439 1.1 RUSHFORD LAKE— NO. 36 = Lake trout 2RL-1 1 F 1 75.2 1 4.1951 .5 SARANAC LAKE— NO. 37 = Smallmouth bass 5SL-5 1 F 1 33.2 1 .684 1 .5 354 Pesticides Monitoring Journal TABLE 3. — Residues of total lead in fish from New York State waters in 1969 — Continued , _J Species ■ Tag No. I z t $-~ SALMON RIVER— NO. 38 -' Coho salmon 69-SR-CS-6 M 61.5 1.910 .5 69-SR-CS^ F 56.8 1.983 .4 (Pulaski, N.Y.) 69-SR-CS-2 F 63.0 2.072 .6 69-SR-Sr-lO M 61.8 1.920 .6 69-SR-CS-7 M 60.5 2.046 .7 69-SR-CS-8 M 57.3 1.984 .5 SR-CS-I F 48.8 1.036 .4 69-SR-CS-5 F 53.9 1.661 .5 69-SR-CS-Il F 61.8 1.840 .4 CSJ-SR-2 M 35.6 .620 .6 CSJ-SR-1 M 40.7 .663 "» -> CSJ-SR-3 M 38.1 .544 .4 69-SR-CS-9 F 61.8 1.735 .5 SRCSJ-7(>-l ■ — Imm. 33.0 .444 1.2 SRCSJ-70-2 do. 30.5 .280 .7 SRCSJ-70-3 do. 34.9 .520 .5 SRCSJ-70^ do. 32.4 .400 .5 SRC.SJ-70-5 do. 30.9 .326 .3 SRCSJ-70-6 do. 30.9 .327 .5 SARATOGA LAKE— NO. 39- Walleye pike 1 6R6403 If I — .357 1.5 SCHROON LAKE— NO. 40 - Lake trout 1 1 1 - 1 - .6 SKANEATELES LAKE— NO. 41 - Rainbow trout 3-SKL-l 3-SKL-3 SPRING BROOK— NO. 42 = 5M381 4RA299I 4RA3601 54.4 56.8 61.5 1.710 2.160 2.580 ST. LAWRENCE RIVER— NO. 43 = Brown bullhead 9SL-5 - - .5 Muskellunge lOlSL-4 M 77.5 3.832 .8 Smallmouth bass ISTL^ M 29.5 .398 .7 6STL-4 M 26.8 .263 .6 2STL-4 M 26.9 .280 .5 6SL-5 — — — .5 4STL^ F 30.0 .339 .4 5STL-4 M 29.5 .344 .9 Sturgeon G429 _ 102.5 6.830 .5 G435 — 89.6 4.540 .8 G430 — — 3.630 .9 G432 — 97.3 5.690 .8 ST. LAWRENCE RIVER- NO. 43 =— Continued SUSQUEHANNA RIVER— NO. 44 = Walleye pike Yellow perch 3-Susq.R.-5 3-Susq.R.-4 TROUT LAKE— NO. 45 = UPPER SARANAC LAKE— NO. 46 = Largemouth bass 5-US-2 5-US-l 34.8 31.2 .904 .432 WANETA LAKE— NO. 6R569 6R568 Sturgeon G434 100.8 6.590 .8 (Cont'd) G431 — 103.5 8.200 .8 G433 — 96.3 5.910 .9 l-SL-54 — — — 1.2 3-SL-56 — — — 2.5 (Massena) 2-SL-56 — — — 3.0 Do. 4-SLS-6 M 95.5 7.210 .8 Walleye pike l-STL-Hg-4 _ _ _ .6 (Massena) 4-MAS-l — — — .5 Do. 4-MAS-2 F 45.3 1 .060 .7 Do. 4-MAS-3 F 65.5 3.527 1.0 Chain pickerel (West Shore) 6R6456 F 62.0 1.570 .7 Do. 6R6457 M 46.3 .785 .7 Do. 6R6458 F 49.5 .918 .7 Smallmouth bass 6R6459 F 43.7 1.197 .7 UTOWANA LAKE— NO. 47 = Smallmouth bass 6R6504 F 42.9 .949 .6 6R6505 M 42.5 1.030 .8 Rainbow trout 6R6506 M 43.0 .844 .6 6R6508 F 41.5 .775 .5 WEST CANADA LAKE - NO. 49 = 1 Specific location within waters, if known, given in parentheses. = Numbers refer to location of water in Fig. i. ■ Imm. = immature. ' One fillet. NOTE: — indicates data unknown. TABLE 4. — A verane total lead in Caytiga Lake trout by age of trout, 1970 Age (years) Lead (ppm) 1 0.3 2 0.8 3 1.1 4 1.1 5 0.6 6 0.8 7 1.7 8 0.6 9 0.9 11 0.5 12 0.9 NOTE: Sensitivity level = .3 ppm. Vol. 5, No. 4, March 1972 355 PESTICIDES IN WATER Residues in Ponds Treated With Two Formulations of Dichlobenil ^ A. G. Ogg, Jr.^ ABSTRACT Residue levels of dichlobenil in pond water and hydrosoil were compared after field applications of weltable powder and granular formulations to separate ponds at 10.0 Ib/siirface acre (0.6 ppmw, parts per million by weight, in the water). Water and hydrosoil samples were taken from each pond I day after treatment and periodically thereafter. Maximum residual concentrations in the water, reached 4 and 5 days after treatment with wettahle powder and gran- ules, respectively, were 1.00 and 0.68 ppmw. After 15 days. the residual concentrations were approximately the same and both decreased steadily to the detection limit of 0.001 ppmw after 126 days (last sampling date). The maximum concen- tration of dichlobenil in the hydrosoil was 1.472 ppmv, parts per million by volume, 6 days after treatment with wettable powder and 3.700 ppmv I day after treatment with the granules. Residues in the hydrosoil of the two ponds did not reach similar levels until 34 days after treatment. The residual concentrations from the wettable powder and gran- ular treatments had decreased to 0.039 and 0.025 ppmv, re- spectively, 126 days after treatment. The persistence of dichlobenil in pond water and hydrosoil was similar whether applied as a granular or a wettahle powder formidation. Introdiictiott Dichlobenil is registered for aquatic weed control in ponds, reservoirs, and lakes. However, the treated water cannot be used for irrigation or for consumption by humans or livestock. Fish cannot be used for food or feed for a period of 90 days after treatment. Because placement of restrictions on the use of the water is not always feasible, methods need to be developed to reduce the persistence of dichlobenil without impeding its weed control potential. Contribution of the Plant Science Research Division. Ayriculturiil Research Service. U. S. Department of Agriculture in cooperation with the Washington State University College of Agriculture. Wash- ington State University Scientific Paper No. 3653. Plant Science Research Division. Agricultural Research Service. U. S. Department of Agriculture, Irrigated Agriculture Research and Ex- tension Center, Prosser. Wash. 99350. Several investigators (1.3) have reported that dichlobenil persists in the water and hydrosoil of treated ponds for 120 to 188 days following an application of the 49f granular formulation at recommended rates. However, when Van Valin (3) applied dichlobenil as a wettable powder formulation at 20 ppmw (parts per million by weight), approximately 33 times the recommended rate, no residue could be detected after 85 days. Walsh and HeitmuUer (4) also reported on dichlobenil residues in a pond treated with the wettable powder formulation at 1 .0 ppmw. They found that the concen- tration of dichlobenil in the water and hydrosoil de- creased steadily after treatment until negligible amounts were present after 64 days. The objective of the study reported here was to compare the persistence of dichlobenil applied at the recom- mended rate (10. 0 lb/surface area, 0.6 ppmw in the water) as the wettable powder with persistance of gran- ular formulations. If the same relationship found in the previous studies could be repeated using the recom- mended rate of dichlobenil, it was felt that the wettable powder might prove to be more useful than the gran- ular formulation in situations where prolonged restric- tion of water use is not possible. Materials and Methods A small man-made pond having a surface area of 0.45 acres and an average depth of 5 feet was selected as the test site. The pond was located adjacent to Soap Creek in the MacDonald Forest area 10 miles north of Cor- vallis, Oreg, Water from springs was diverted into the pond to maintain the water level; there was no overflow from the pond. One-eighth of the area was partitioned from the main portion of the pond by a heavy plastic film to form two separate bodies of water. The plastic e.xtended from 12 inches above the water surface into the hydrosoil; mud was used to seal the plastic barrier 356 Pesticides Monitoring Journal along the sides and at the bottom of the pond. Diffusion of minute amounts of dichlobenil through the plastic was considered to be insignificant to the results of this experiment. The smaller area was treated on June 15. 1967. with the wettable powder formulation (50% ac- tive ingredient) at the rate of 10 lb of dichlobenil per surface acre (0.6 ppmw in the water). The larger area was treated on the same date with the granular for- mulation at the same rate. The granules, formulated as coarse clay particles that contained 49f dichlobenil, were applied with a hand- powered granular herbicide spreader. The wettable pow- der was mixed with water and sprayed uniformly over the water surface. Water temperatures, dissolved oxygen concentrations. pH values, and total alkalinity levels were periodically measured and recorded during the study period. Water and hydrosoil samples were taken from each area 1 day after treatment and periodically thereafter. Each sample consisted of a 400-ml composite of five subsamples taken at random in each of the treated areas. Water samples were collected 12 inches above the hy- drosoil. Hydrosoil samples were collected with a special sampling device that collected only the upper '4 inch of the semifluid hydrosoil layer. The last samples were taken 126 days after treatment. Heavy rains caused flooding in the plot area after that date, and further sampling was not possible. All samples were stored in a refrigerator at approximately 0° C until they were analyzed. The method of Meulemans and Upton (2) was modified and used for the extraction and analysis of dichlobenil. The water was extracted by vigorously shaking the sam- ple in a I -liter separatory funnel with 100 ml of re- distilled benzene for 3 minutes. After discarding the aqueous phase, sufficient anhydrous sodium sulfate was added to dry the benzene. After decanting the dried benzene into a graduated cylinder, 5 to 10 ml of ben- zene were used to wash the sodium sulfate. These wash- ings were added to the original benzene portion and the total volume recorded. Recovery of dichlobenil from samples that contained known amounts of herbicide averaged 97%. All residue data were corrected to show the quantity of herbicides present for 100% recovery. It was assumed that the water used in this work had a specific gravity of 1 .0, and therefore results are expressed as parts per million by weight (ppmw). The hydrosoil samples were a variable mixture of min- eral soil, organic matter, and water. Usually, the solid portion comprised about 50% of the samples. When the samples were shaken with benzene, a viscous emulsion formed, and separation into two layers in a separatory funnel did not occur. To overcome this problem, each hydrosoil sample was divided approximately into thirds by transferring the sample into three 250-ml centrifuge bottles. After adding 50 ml of redistilled benzene, each centrifuge bottle was tightly sealed and shaken vigor- ously for 3 minutes. The tubes were then centrifuged for 10 minutes at 5.000 x g to separate the two phases. The benzene layer was carefully removed by aspiration until only a thin film remained. Five to 10 ml of ben- zene were carefully added to the surface of the aqueous layer. After gentle swirling, the remaining benzene was removed by aspiration and combined with the original extract. With some samples, it was necessary to repeat the extraction procedure to remove all of the organic material. The benzene was freed of water by the addi- tion of anhydrous sodium sulfate. The sodium sulfate was then washed with benzene, the solvent portions combined, and the final volume recorded. Recovery of dichlobenil from samples that contained known amounts of herbicide averaged 83%. Due to the inherent var- iability of the hydrosoil samples, results are expressed on the basis of parts per million by volume (ppmv). A Wilkens Model 500-D gas chromatograph equipped with an electron capture detector and a 1-mv recorder was used for the analysis. A flow of nitrogen gas at 42 cc/minute carried the sample through a 5-foot by '/s- inch stainless steel column packed with 10% S. E. 30 on Gas Chromosorb Q (60/80 mesh). Injector, column, and detector temperatures were 150°. 150°. and 175° C, respectively. Duplicate injections of 2 to 4 jul of each sample were made to determine the concentration of dichlobenil. Quantification was based on comparisons of recorded peak height with those of suitable stand- ards. Retention time for dichlobenil was IVi minutes, and the detection limit was 0.001 ppm. Results and Discussion Water temperature near the surface of the ponds was 21° C on the day of treatment and increased to a maxi- mum of 24° C in August. On the last sampling date, October 19, 1967, the water temperature was recorded at 13° C. Both ponds experienced a slight thermal strati- fication during the summer months, having a surface to bottom temperature difference between 2° and 4° C. Dissolved oxygen concentrations varied from 6.9 to 13.4 ppm but usually fell in the range of 8 to 10 ppm. The dissolved oxygen concentration varied considerably and could not be related to the different treatments. The pH value in the ponds usually ranged from 7.5 to 8.5 and total alkalinity (expressed as CaCO.) ranged from 12 to 16 mg/ liter. Maximum concentrations of dichlobenil in the water, reached 4 and 5 days after treatment with wettable pow- der and granules, respectively, were 1.00 and 0.68 Vol. 5, No. 4, March 1972 357 ppmw (Fig. 1). After 15 days, the concentrations in the water were similar, and both decreased rapidly to ap- proximately 0.1 ppmw after 34 days. Thereafter, there was a much slower, but steady decrease in the concen- tration. On the last sampling date, 126 days after treat- ment, the concentrations of herbicide in the water of both ponds were below the detection limit (<0.001 ppmw). FIGURE 1. — Comparison of residues in water samples col- lected from ponds treated with two different formulations of dichlobcnil "- l\ h 1 \ 1 \ wrrrxm f powder "- <,R\M [ ES t 1 > s •- \ \ \ V__ The maximum concentration measured in the water after treatment with the wettable powder formulation was 67% greater than the initial treatment concentra- tion. Inasmuch as the water samples were taken 12 inches from the hydrosoil surface, stratification of di- chlobenil near the bottom of the pond would explain this result. Wilson and Bond (5), who investigated the effects of dichlobenil on pond invertebrates, observed that dichlobenil formed a concentrated layer near the bottom of their test vessels. Their results were based on observations of the immobilizing effect of dichlobenil on invertebrates. The results of Frank and Comes (/) also strengthen the stratification hypothesis. In a pond treated with gran- ular dichlobenil, they found higher concentrations at the 10-foot depth than at the 3-foot depth. The differences in concentrations were most noticeable during the period when maximum concentrations occurred. Van Valin (i) also found higher concentrations of dichlobenil in the water than were initially applied. He discounted stratification of dichlobenil as a probable cause since his samples were made up of subsamples taken from different depths; however, he theorized that some of the powder from the formulation could have been floating at the surface where it could easily become part of the sample. After treatment with the wettable powder and granular formulations the maximum concentrations of dichlo- benil in the hydrosoil were 1.472 and 3.700 ppmv, respectively (Fig. 2). These concentrations occurred 6 and 1 days after treatment, respectively. Residue levels in the hydrosoil of both ponds were approximately 0.4 ppmv 34 days after treatment. After 126 days, the con- centrations had decreased to 0.039 ppmv and 0.025 ppmv in the ponds treated with the wettable powder and granular formulations, respectively. FIGURE 2. — Comparison of residues in hydro-soil samples collected from ponds treated wil/i two different formulations of dichlobenil Residues in the hydrosoil of the pond treated with the wettable powder increased from 0.560 ppmv after 1 day to 1 .470 ppmv after 6 days. These data also suggest that stratification of the dichlobenil near the bottom occurred following an application of the wettable pow- der formulation. The persistence of dichlobenil in pond water and hydrosoil was similar whether applied as a granular or a wettable powder formulation. Ackitowledgment Analytical samples and commercial formulations of dichlobenil were supplied through the courtesy of Thompson-Hayward Chemical Company, Kansas City, Mo. 358 See Appendix for chemic:il name of dichlobenil. Pesticides Monitoring Journal LITERATURE CITED in the Environment. Adv. in Chem. Series 60:271-279. (4) Walsh. G. £., and P. T. HcilmuUcr. 1969. Effects of Frank, P. A., and R. D. Comes. 1967. Herbicide residues dichlobenil upon physical, chemical, and biological fac- in pond water and hydrosoil. Weeds 15:210-213. tors in a fresh water pond. (Abstract) Abstr. of the Weed Mculemans, K. J., and E. T. Upton. 1966. Determina- Sci. Soc. of Amer. Meeting. Las Vegas. Nev. Abstract tion of dichlobenil and its metabolite, 2,6-dichloroben- No. 92. zoic acid, in agricultural crops, fish, soil and water. J. (5) Wilson, D. C. and C. E. Bond. 1969. The effects of the Assoc. Off. Anal. Chem. 49:976-981. herbicides diquat and dichlobenil (Casoron) on pond in- Van Valin, C. C. 1966. Persistence of 2,6-dichloroben- vertebrates. Part I. Acute Toxicity. Trans, of the Amer. zonitrile in aquatic environments. In Organic Pesticides Fish. Soc. 98(3):438-443. /OL. 5, No. 4, March 1972 359 APPENDIX Chemical IWaincs of Compounds Discussed in This Issue ALDRIN AMITROLE ARSENIC BHC BROMIDE CADMIUM CARBARYL CARBOPHENOTHION (TRITHIONT. ) CHLORBENSIDE (MITOXSi) CHLORDANE CIPC 2,4-D DCPA (DACTHALfj?) DDE DDT (including: ils isomers and dehydrochlorinalion products) DIAZINON DICHLOBENIL DICHLOFENTHION (NEMACIDE'B) DICOFOL (KELTHANE") DICHLORVOS DIELDRIN DH'HhNYI, DISULFOTON (DI-SVST()Nm E N DOS U LEAN (THIODAN®) ENDRIN ETHION HEPTACHLOR HEPTACHLOR EPOXIDE LEAD LINDANE MALATHION MCPA METHOXYCHLOR Not less than 957c of 1.2.3,4. 10, 10-hexachIoro-l.4.4a.5,8,8a-hexah.vdro-1.4-c It hio) ethyl | phosphorodilliioalc ft.7,8.9,in,in-hcxachloro-l,5,5a,(i.'),ya-hexahydro-f..'J-methMno-:,4.3-bcnzodioxathicpin 3-oxide l,:.3,4,IIJ,ll)-hcxaehloro-h.7-epoxy-l.4,4a.5,6,7.,x,8a-octah>dro-l.4-c"rfo-iv;i/«-5.8-dimethanonaphthalene «,0.0'.rt'-tetraethyl ,V,.S'-methylenebisphorodilhioatc 1, 4.5,6, 7.S.8-hc ptachloro-3a,4.7, 7a-tetrahydro-4. 7-melhanoindenc l,4.5.6.7.8.8-heptachloro-2.3-epoxy-3a.4.7.7a-letrah>dro-4.7-methanoindan Pb l.2,3,4.5,6-hexachlorocyc!ohexane, ')9'/c or more gamma isomer diethyl mercaptosuccinale. 5-e5ter with 0.0-dimelhyI phosphorodithioate l(4-chloro-o-tolyl)oxy] acetic acid I.l ,]-trichloro-2.2-bis(p-methoxy phenyl let bane 360 Pesticides Monitoring Journai CJiemical Names of Compounds Discussed in Tliis Issue METHYL PARATHION ORTHOPHENYLPHENOL OVEX PARATHION PCP PERTHANE® POLYCHLORINATED BIPHENYLS (PCBs) RONNEL TCNB TDE (DDD) (Including its isomers and dehydrochlorina- tion products) TOXAPHENE ZINEB O.O-dimeihyl 0-p-nitrophenyl phosphorothioale 2-hydroxydipheny[ p-chlorophenyl p-chloro-benzenesulfonate 0,0-diethyl O-p-nitrophenyl phosphorothioate pentachlorophenol l,l-dichloro-2,2-bis(p-ethylphenyl) ethane Mixtures of chlorinated biphenyl compounds having various percentages of chlorination 0,0-dimethyl 0-2.4, 5-trichIorophcnyl phosphorothioate l,2,4,5-tetrachloro-3-nitrobenzene l,l-dichloro-2,-2-bis(p-chlorophcn>l)ethane; technical TDE contains some o.p-isomer also chlorinated camphene containing 67% to 69'^;. chlorine zinc ethylene-l ,2-bisdithiocarbamate A cknowledgment 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 5, Nos. 1-4. of the Pesticides Monilorini,' Journal: Joseph H. Caro E. P. Floyd William F. Gray Thair G. Lament Ralph G. Nash Mildred L. Porter A. W. Taylor Gerald E. Walsh Sidney Williams Alfred J. Wilson, Jr. Susan J. Young Agricultural Research Service Environmental Protection Agency Food and Drug Administration Eish and Wildlife Service Agricultural Research Service Food and Drug Administration Agricultural Research Service Environmental Protection Agency Food and Drug Administration Environmental Protection Agency Food and Drug Administration Vol. 5, No. 4, March 1972 361 SUBJECT AND AUTHOR INDEXES Volumes 1-5, June 1967-March 1972 The following subject and author indexes are cumulative for Volumes 1-5, June 1967-March 1972. of the Pesti- cides Monitoring Jounuil. Subsequent volumes of the Journal will be indexed annually, with the index appear- ing in the last issue. No. 4, of each volume. Primary headings in the subject index consist of pesticide compounds, the media in which residues are monitored, 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 Air Degradation Experimental Design Factors Influencing Residues Food and Feed Humans Plants (other than those used for food and feed) Removal Sediment Soil Water Wildlife Compound headings are also used as secondary headings under the primary media and concept headings and vice versa. When a particular paper discusses five or more organochlorines or three or more organophosphates. herbicides, or heavy metals, the compounds are grouped by class under the media or concept headings; in the primary headings, however, all compounds are listed 362 individually. The specific compounds or elements whicl have been grouped in various combinations by class fo certain papers are as follows: Orga nochlorines Kepone® Organophosphatei aldrin carbophenothion BHC/lindane methoxychlor diazinon chlordane mirex dichlofenthion DDE Perthane® disulfoton DDT TDE ethion dicofol toxaphene fenthion dieldrin malathion endosulfan methyl parathion endrin naled heptachlor/hepta- parathion chlor epoxide ronnel HerhiL ides Heavy Metals amitrole merphos cadmium CI PC PCP copper 2,4-D silvex iron 2,4-DB 2,4,5-T lead DCPA 2,3,6-TBA nickel MCP zinc In the author index, the names of both senior and junioi authors appear alphabetically. Full citation is given however, only under the senior author, with a reference to the senior author appearing under junior authors. Pesticides Monitoring Journai SUBJECT INDEX L'ndrin 3(3):172-176 DDT 4(4):204-208 TDE 4(4):204-208 Aldrin Degradation 2(2): 72-79 Experimental Design 4(2):67-70 4(4)::69-176 Food and Feed 1(2):2-12 I(2):13-14 l(3):2-8 1(4): 1 1-20 2(l):2-46 2(l):58-67 2(2):72-79 2(3):104-108 2(3):133-136 2(4): 140-152 2(4):153-162 3(3):182-185 4(2):42-46 4(3):89-105 5(l):17-27 5(2):73-212 5(4):313-330 5(4):331-341 5(4):342-344 5(4):345-347 Plants (other than those used for food and feed) 5(3):28I-288 Removal 5(2);218-222 Aldrin (cont'd) Wildlife 1(3):9-12 1(3):13-15 2(2):9n-92 3(l):l-7 3(3);145-17l 3(4);227-2J2 3(41:241-252 4(1):8-10 4(3):117-135 4(3):141-144 5(11:1-11 5(1):12-16 5(21:228-232 5(31:242-247 5(31:281-288 Amitrole Food and Feed 4(31:89-105 Water 2(3):123-128 Aramite® Soil 4(3): 145-166 Aroclor 1254". see PCB's Arsenic Food and Feed 1(21:2-12 l(4):ll-20 2(4):140-152 2(41:153-162 3(31:139-141 4(3):S9-I115 5(41:313-33(1 5(41:331-341 Sedii 2(2):93-96 3(l);l-7 5(3):28l-288 1(2):13-14 2(l):58-67 2(2):93-96 2(3):I33-I36 3(3):I82-185 3(41:241-252 4(21:42-46 4(2):67-70 4(3):145-166 5(l):17-27 5(11:28-31 5(21:218-222 5(2):223-227 5(3):259-267 5(3):268-275 5(4):342-344 5(4):345-347 l(2):38-46 3(1): 1-7 3(21:124-135 3(31:190-193 4(2):71-86 5(11:17-27 5(3):28I-288 BHC/Lindane Expermiental De \y.n 4(21:67-70 4(4): 169-176 and Feed 1(2):2-12 l(3):2-8 l(4):2-7 1(41:11-20 2(11:2^6 2(11:58-67 2(21:72-79 2(31:104-108 2(4):140-152 2(41:153-162 4(21:31-41 4(2):42-46 4(3):89-105 5(2):73-212 5(4):313-330 5(4):331-341 4(2):47-50 BHC/Lindane (cont'd) Plants (other thun those food and feed I 5(31:281-288 Removal 2(21:72-79 4(21:31-41 4(31:89-105 Sediment 2(21:93-96 3(11:1-7 5(31:281-288 Soil l(4):30-33 2(0:58-67 2(21:93-96 4(2):42-46 4(21:67-71) 5(11:28-31 5(31:259-267 5(31:268-275 Water 1(21:38-46 1(3): 13-15 3(21:124-135 4(11:I4-2(1 4(21:71-86 5(31:281-288 Wildlife 1(21:21-28 l(3):9-12 l(3):13-15 2(2):90-92 3(11:1-7 3(2): 102-1 14 3(31:145-171 3(4):227-232 4(11:8-10 4(2):5l-56 4(3):l 17-135 4(31:141-144 5(11:1-11 5(21:228-232 5(31:242-247 5(31:281-288 Bidrin"' Plants (other than (hose food and feed) 1(21:49-53 Bromides and Feed 1(21:2-12 1(41:11-20 2(11:2-46 2(41:140-152 2(41:153-162 4(31:89-105 5(31:73-212 5(41:313-330 5(41:331-341 Cadmium Food and Feed 2(4): 140-152 2(4):153-I62 4(31:89-105 5(4):313-330 5(4):33l-34l Vol. 5. No. 4, March 1972 363 Cadmium (cont'd) Wildlife 4(3): 136-140 Captan Soil 4(3):145-166 Carbaryl Food and Feed 1(2):2-12 !(4):n-20 2(1); 2-46 2(3):104-108 2(4):153-I62 2(4):163-166 4(3):89-105 5(2):73-212 5(4):331-34l Removal 2(4)1163-166 Carbophenotbion Food and Feed 2(l):2-46 2(3):104-108 5(2):73-212 5(4):345-347 Water 4(2):71-86 Wildlife 1(3):9-12 Chlorbenside Food and Feed 2(l):2-46 2(4):140-15: 2(4):I53-162 4(3):89-in5 -1(2):73-212 5(4):331-34I Chlordane Food and Feed 1(2):2-12 1(4): 2-7 1(4): 11-20 2(l):2-46 2(l):58-67 2(3):133-136 2(4):153-162 4(2):42-46 4(3):89-105 5(2):73-212 5(4):313-330 5(4):331-341 .'i(4):342-344 5(4):345-347 Removal 5(2):218-222 Sediment 3(l):l-7 Soil l(4):30-33 2(l):58-67 2(3): 133-136 3(4):241-252 4(2):42-46 4(3):145-I66 5(0:28-31 5(2):218-222 5(2):223-227 5(3):248-250 5(3):259-267 5(3):268-275 5(4):342-344 5(4):345-347 1(3):13-15 4(2):71-86 fe 1(3):9-12 l(4):21-26 3(3):145-171 3(4):241-252 5(1):1-11 5(1):12-16 5(2):228-232 5(3):248-25n CIPC Food and Feed 1(2):2-12 1(4): 1 1-20 2(4):153-162 5(4):31 3-330 5(4):331-34l Copper/Copper Sulfate Sediment 3(3):186-189 Water 3(3):186-189 4(1):11-13 Wildlife 4(31:136-140 D 2,4-D Experimental De^i^n 4(4): 184-203 Food and Feed U2):2-12 1(4): 11-20 2(1):2^6 2(3):104-108 2(4): 140-152 2(4):153-162 4(3):89-105 4(3):111-113 5(2):73-212 5(4):313-330 5(4):331-341 Plants (other than those used fci food and feed) 1(3):I6-21 4(41:184-203 Removal 4(4): 184-203 Sediment 1(3):16-21 Soil 4(3):145-166 Water l(2):38-46 1(3):16-21 3(2):I24-135 4(4): 184-203 5(2):2I3-2I7 Wildlife 1(3):16-21 4(4): 184-203 5(2):213-217 Oacthal®, seee DCPA 2,4-DB Food and Feed 1(2):2-12 5(4):313-330 5(4):331-341 DCBP (4,4'-dicfalorobenzophenone) Wildlife 3(31:142-144 DCPA Food and Feed 1(2):2-12 2(l):2-46 4(3):89-I05 5(2):73-212 5(4):313-33fl 5(4):331-34l HDD. see TDE DDE. see also DDT Experimental Design 4(4): 169-176 Factors Influencint* Residues l(2):15-20 1(2):35-37 2(2):80-85 2(3):109-122 3(4):204-211 3(4):212-218 4(2):47-50 5(3):235-241 364 DDE (cont'd) Food and Feed 1(2):2-12 I(3):2-8 l(4):2-7 l(4):ll-20 2(l):2-46 2(l):47-50 2(I):51-54 2(3):104-108 2(3):129-133 2(4):140-152 2(4): 153-162 3(2):70-101 3(3):182-185 4(2):27-30 4(2):3M1 4(2):42-46 4(3):89-105 5(2):73-212 5(3):276-280 5(4):313-330 5(4):33I-34I 5(4):342-344 5(4): 345-347 Humans l(2):15-20 2(2): 80-85 4(2):47-50 Plants (other than those used for food and feed) 3(2):70-I01 4(l):2-7 5(3):28l-288 Removal 2(l):47-50 4(2):31-41 4(2):51-56 4(3):89-105 Sediment 2(2):93-96 3(l):l-7 3(4):219-226 5(1): 17-27 5(3):281-288 5(3):289-294 Soil l(4):30-33 2(1):51-S4 2(2):93-96 2(3):129-133 3(2):70-10l 3(3):182-185 3(4):241-252 4(l):2-7 4(2):42-46 5(1):28-31 5(2):223-227 5(3):248-250 5(3):251-258 5(3):259-267 5(3):268-275 5(3):276-280 5(4):342-344 5(4):345-347 Water l(2):38-46 1(3):13-15 3(2): 124-135 3(3): 190-193 3(4):212-218 3(4):219-226 4(l):14-20 4(2):71-86 4(4):216-219 5(3):235-24I 5(3):281-288 5(3):289-294 Wildlife l(2):21-28 1(2): 29-34 1(2): 35-37 I(3):13-15 l(4):21-26 1(4): 27-29 2(2):90-92 2(3): 109-122 Pksticides Monitoring Journal DDE (cont'd) Wildlife (cont'd) 3(I):l-7 3(2): 102-114 3(2):115-123 3(3): 142-144 3(3):145-171 3(4): 198-200 3(4):204-:il 3(4):212-218 3(41:219-226 3(4):227-232 3(4):233-240 3(4): 24 1-252 4(l):2-7 4(l):8-ll) 4(2):51-56 4(2):57-61 4(2):62-66 4(3):114-116 4(3):117-135 4(3): 136-140 4(3):141-144 5(1):1-11 5(2):228-232 5(3):235-241 5(3):242-247 5(3):248-250 5(3):251-257 5(3):281-288 5(3):289-294 DDT, see also DDE, TDE Air 4(4): 204-208 Degradation l(2):54-57 Experimental Design 2(2):97-100 4(2):67-70 4(4): 169-176 Factors Influencing Residues l(2):15-20 l(2):35-37 2(2):80-85 2(3): 109-122 3(4):212-218 4(2):47-50 4(4): 204-208 5(3):235-241 Food and Feed 1(2):2-12 l(3):2-8 l(3):22-25 1(4): 2-7 I(4):ll-20 2(l):2-46 2(l):47-50 2(l):51-54 2(l):58-67 2(3):I04-108 2(3):129-133 2(4): 140-152 2(4):153-162 3(2):70-101 3(3):182-185 4(l):21-24 4(2):27-30 4(2):31^1 4(2):42^6 4(3):89-105 4(3):106-110 5(2):73-212 5(3):276-280 5(4):313-330 5(4):331-341 5(4):342-344 5(4):345-347 Humans 1(2): 15-20 2(2):80-85 4(2):47-50 Plants (other than those used for food and feed) 3(2):70-101 4(l):2-7 5(3):281-288 Vol. 5, No. 4, March 1972 DDT (cont'd) Removal 2(l):47-50 4(2):3M1 4(2):51-56 4(3):89-105 Sediment 2(2):93-96 3(l):l-7 3(4):219-226 5(3):281-288 5(3):289-294 5(3):301-308 Soil l(3):22-25 1(4): 30-33 2(l):51-54 2(l):55-57 2(l):58-67 2(2):93-96 2(3): 129-133 2(4): 172-175 3(2):70-101 3(3):182-185 4(l):2-7 4(l):21-24 4(2):42Jt6 4(2):67-70 4(3): 145-166 5(1):28-31 5(2):223-227 5(3):248-250 5(3):251-258 5(3):259-267 5(3):268-275 5(3):276-280 5(4):342-344 5(4): 345-347 Water 1(2): 38^6 l{3):13-15 3(2):124-135 3(3): 190-193 3(4):212-218 3(41:219-226 4(1): 14-20 4(2):71-86 4(4):216-219 5(31:235-241 5(31:281-288 5(3):289-294 5(3):301-308 Wildlife !(2):2I-28 l(2):29-34 l(2):35-37 1(3):9-12 1(31:13-15 1(41:21-26 1(4): 27-29 2(2):90-92 2(3): 109-122 3(l):l-7 3(2):102-114 3(2):1 15-123 3(31:142-144 3(31:145-171 3(4): 198-200 3(41:212-218 3(4):219-226 3(4):227-232 3(41:233-240 4(l):2-7 4(1):8-10 4(2):51-56 4(2):57-61 4(2):62-66 4(3):106-110 4(31:114-116 4(31:117-135 4(3):136-140 4(3):141-144 5(1):1-11 5(11:12-16 5(2):228-232 5(31:235-241 5(31:242-247 DDT (cont'd) Wildlife (cont'd) 5(3):248-250 5(3):251-258 5(3):281-288 5(31:289-294 Degradation General DDT 1(21:54-57 Food and Feed aldrin 2(21:72-79 Diazinon Food and Feed 1{2):2-12 l(4):n-20 2(l):2-46 2(l):58-67 2(3):104-108 2(41:140-152 2(41:153-162 4(31:89-105 5(l):17-27 5(2):73-212 5(41:313-330 5(4):331-341 5(41:345-347 .Soil 2(11:58-67 5(11:17-27 5(31:259-267 5(41:345-347 Dichlobenil Scdniicnl 5141:356-359 Water 5l41:.156-359 Dichlofenthion Food and Feed 5(4):345-347 Soil 5(31:259-267 5(4):345-347 Dicblorvos Food and Feed 5(4):331-341 Dicofol Food and Feed 1(21:2-12 1(41:11-20 2(11:2-46 2(3):104-108 2(41:140-152 2(41:153-162 4(31:89-105 5(21:73-212 5(41:313-330 5(4): 33 1-341 5(41:345-347 Removal 4(31:89-105 Soil 5(31:259-267 5(31:268-275 5(4): 345-347 Wildlife 4(3):141-144 Dieldrin Experimental Design 4(21:67-70 4(4):169-176 Factors Influencing Residues 1(21:35-37 2(2):86-89 4(21:47-50 4(41:177-183 Food and Feed 1(21:2-12 1(21:13-14 1(3): 2-8 l(3):22-25 l(4):2-7 365 Dieldrin (cont'd) Food and Feed (cont'd) 1(4): 11-20 2(l):2-46 2(l):51-54 2(l):58-67 2(2):72-79 2(3):104-108 2(3):133-136 2(4):140-152 2(4):153-162 3(2):70-101 3(3):182-I85 4(2):31-41 4(3):89-105 5(l):17-27 5(2):73-212 5(4):313-330 5(4):33I-341 5(4):342-344 Humans 2(2):86-89 4(2):47-50 Planis (other than those used for food and feed) 3(2):70-ini 5(3):281-28a Removal 2(2):72-79 4(2):31-41 4(3):89-105 5(2):2I8-222 Sediment l(4):27-29 l(4):30-33 2(2):93-96 3(l):l-7 4(4): 177-183 5(3):28I-288 5(3):289-294 Soil 1(2):13-14 l(3):22-25 l(4):30-33 2(I):51-54 2(l):58-67 2(2):93-96 2(3):133-136 2(4): 172-175 3(2):70-101 3(3):182-185 3(4):241-252 4(2):67-70 4(3):145-166 5(l):17-27 5(1):28-31 5(2):218-222 5(2):223-227 5(3):248-250 5(3):251-258 5(3):259-267 5(3):268-275 5(4):342-344 Water l(4):30-33 3(l):l-7 3(2):124-135 3(3): 190-193 4(l):14-20 4(2):71-86 4(4):177-183 4(4):216-219 5(0:17-27 5(3):281-288 5(3):289-294 Wildlife 1(2):35-37 1(3):9-12 I(3):13-I5 1(4): 27-29 2(2):90-92 3(l):l-7 3(2): 102-1 14 3(2):115-123 3(3): 142-144 3(3):145-171 3(4): 198-200 3 (4): 227-232 366 Dieldrin (cont'd) Wildlife (cont'd) 3(4):233-240 3(4):24I-252 4(0:8-10 4(2):5l-56 4(2):57-61 4(2);62-66 4(3):114-n6 4(3:117-135 4(3): 136-140 4(3):I4I-I44 4(4):177-183 5(0:1-11 5(0:12-16 5(2):228-232 5(3): 242-247 5(3):248-250 5(3):251-258 5(3):281-288 5(3):289-294 5(3):295-300 Diphenyl Food and Feed 5(4):33l-341 Disulfoton Food and Feed 4(3):89-105 5(4):33I-34I Di-Syston®, see Disulfoton Dithiocarbamates (includes Zineb) Food and Feed I(4):ll-20 2(4):140-152 2(4):153-162 4(3):89-105 5(4):313-330 5(4):331-341 Endosulfan Food and Feed 1(2):2-12 l(4):Il-20 2(0:2-46 2(4): 140-152 2(4):I53-I62 4(3):89-105 5(2):73-2l2 5(4):313-330 5(4):33l-34l 5(4): 345-347 Removal 4(3):89-105 Sediment 5(3):289-294 Soil 1(3): 22-25 4(3): 145-166 5(3):259-267 5(3):268-275 5(4):345-347 Water 5(3):289-294 Wildlife 5(3):289-294 Endrin Air 3(3): 172-176 Experimental Design 3(3):172-176 4(2):67-70 4(4): 169-176 Factors Influencing Residu 3(4):212-218 Food and Feed 1(2):2-12 l(4):2-7 l(4):ll-20 2(0:2-46 2(0:58-67 2(2):72-79 2(3): 104-108 Endrin (cont'd) Food and Feed (cont'd) 2(3):133-136 2(4): 140-152 2(4):153-162 3(2):70-101 3(3):182-185 4(3):89-105 5(0:17-27 5(2):73-2l2 5(4):313-330 5(4):331-341 5(4):345-347 Plants (other than those used for food and feed) 5(3):28l-288 Removal 2(2): 72-79 2(4):167-171 4(3):89-105 Sediment l(4):27-29 2(2):93-96 3(0:1-7 4(4): 177-183 5(3):281-288 5(3):289-294 Soil l(3):22-25 2(0:58-67 2(2):93-96 2(3):133-136 3(21:70-101 3(3):182-185 3(4):241-252 4(2):67-70 4(3):145-166 5(0:28-31 5(3):259-267 5(3):268-275 5(4):345-347 Water l(2):38-46 2(4):167-171 3(0:1-7 3(2):124-135 3(4):212-218 4(2):71-86 4(4):177-I83 5(0:17-27 5(3):281-288 5(3): 289-294 Wildlife l(2):21-28 l(3):9-12 l(3):!3-15 I(4):2I-26 l(4):27-29 2(2):90-92 3(0:1-7 3(3):142-144 3(3):145-171 3(4):201-203 3(4):212-218 3(4):227-232 3(4):241-252 4(0:8-10 4(2):5l-56 4(3):117-135 4(3):I41-144 4(4):177-183 5(0:1-11 5(2):228-232 5(3):242-247 5(3):281-288 5(3):289-294 Ethion Food and Feed 1(2):2-12 1(4): 11-20 2(0:2-46 2(3): 104-108 2(4):I40-152 2(4):153-I62 4(3):89-105 5(2):73-212 5(4):313-330 Pesticides Monitoring Journal Ethion (cont d) Food and Feed (cont'd) 5(4):331-341 5(4):345-347 Removal 4(3):89-105 Soil 4(3): 145-166 5(4):345-347 4(2):71-86 Experimental Design General l(l):Introduction (editorial) 2(2):71 (editorial) 3(4): 197 (editorial) 5(l):37-43 (editorial) DDT 2(2):97-100 Air Monitoring endrin 3(3):172-176 5(1);67 Chemicals Monitoring Guide 1(1):20-21 5(1):68-71 Food and Feed Monitoring l(l):l-5 5(l):44-46 Human Monitoring l(l);6-7 5(l):44-46 Methodology 1(4): 1 (editorial) 2(1):1 (editorial 4(4); 169-176 2,4-D 4(4): 184-203 Reporting Data 1(2):1 (editorial) 1(3):1 (editorial) 2(3): 101 (editorial) 2(4):139 (editorial) Soil Monitoring 1(1):16-19 5(l):63-66 parinol 4(4):209-215 Water Monitoring 1(1):13-16 5(0:54-62 Wildlife Monitoring 1(0:7-13 5(0:47-49 5(0:50-52 L 5(0:53 Factors Influencing Residues Age DDE l(2):15-20 2(2):80-85 4(2):47-50 DDT l(2):15-20 2(2):80-85 , 4(2): 14-20 < dieldrin 2(2): 86-89 lead 5(4):348-355 Climatological Conditions DDT 4(4):204-208 dieldrin 4(4):177-183 TDE 4(4):204-208 Geographical Location DDE 3(4):204-211 5(3):251-258 'Vol. 5, No. 4, March 1972 Factors Influencing Residues (cont'd) Geographical Location (cont'd) DDT 5(3):251-258 dieldrin 5(3):251-258 organ ochlorines 5(3):242-247 TDE 5(3):251-258 Lipid Levels DDE 5(3):235-241 DDT 5(3):235-241 TDE 5(31:235-241 pH malathion 4(0:14-20 Resistance and/or Tolerance organochlorines 3(4):212-218 Sex DDE l(2):15-20 2(2):80-85 4(2):47-50 DDT l(2):15-20 2(2):80-85 4(2):47-50 dieldrin 2(2):86-89 4(2):47-5n Species. Strain, or Race DDE T(2):35-37 2(2):80-85 2(3): 109-122 DDT l(2):35-37 2(2):80-85 2(3):109-122 dieldrin l(2):35-37 2(2):86-89 heptachlor/heptachlor epoxide l(2):35-37 TDE 2(3): 102-122 Storage of Samples DDT l(2):54-57 parinol 4(4):209-215 Fenthion Water 4(2):7l-86 Food and Feed Alfalfa, see also Grain and Forage aldrin 1(2):13-14 DDE 2(0:51-54 2(3):129-133 5(3):276-280 DDT 2(0:51-54 2(31:129-133 4(0:21-24 5(31:276-280 dieldrin 1(2):13-14 2(0:51-54 heptachlor/heptachlor epoxide 1(2):13-14 methoxychlor 2(0:51-54 TDE 5(31:276-280 Dairy Products, see also Total Diet arsenic 3(3):139-141 Food and Feed (cont'd) Dairy Products (cont'd) DDE 2(0:47-50 DDT 2(0:47-50 dieldrin 2(0:51-54 organochlorines l(3):2-8 2(0:2-46 2(2):72-79 4(2):31-41 TDE 2(0:47-50 Dietary Intake, see also Total Diet arsenic 2(4): 153-162 5(4):331-341 bromides 2(0:2-46 2(4): 153-162 5(2):73-212 5(4):331-341 cadmium 2(4): 153-162 5(4):331-341 carbaryl 2(0:2-46 2(4):153-162 5(41:331-341 chlorbenside 2(41:153-162 dichlorvos 5(4):331-341 diphenyl 5(41:331-341 dithiocarbamates 2(4): 1 53-162 5(41:331-341 herbicides 2(11:2-46 2(41:153-162 5(21:73-212 5(4): 33 1-341 organochlorines 2(11:2-46 2(41:153-162 5(21:73-212 5(41:331-341 organophosphales 2(0:2^6 2(4):153-162 5(2):73-212 5(41:331-341 PCB's 5(41:331-341 PCNB 2(41:153-162 TCNB 2(41:153-162 tetradifon 2(41:153-162 Eggplant carbaryl 2(41:163-166 Eggs, see also Total Diet organochlorines 2(0:2-46 5(21:73-212 Fruits, see also Total Diet carbaryl 2(0:2^6 5(2):73-212 lead 1(4): 8- 10 organochlorines 2(0:2^6 5(2):73-212 organophosphales 2(1):2^6 5(2):73-2l2 tetradifon 2(0:2-46 5(2):73-212 367 Food and Feed (cont'd) Grains and Cereal (for human use), see also Tolal Diet aldiin 5(l):17-27 arsenic 3(3):139-141 carbaryl 2(l):2^6 5(2):73-212 diazinon 5(1): 17-27 dieldrin 5(l):17-27 endrin S(l):17-27 heptachlor/heptachlor epoxide 5(1): 17-27 methyl paraihion 5(l):17-27 organochlorines 2(l):2-46 5(2):73-212 organophosphates 2(l):2-46 5(2):73-212 parathion 5(1): 17-27 PCP 2(l):2-46 5(2):73-2I2 Grain and Forage (for use as animal feed), see also Alfalfa aldrin 5(l):17-27 2,4-D 4(3):111-113 DDE 2(l):5I-54 4(2): 27-30 DDT 2(l):5I-54 4(2):27-30 4(3):106-I10 diazinon 5(l):17-27 dieldrin 2(l):51-54 5(l):17-27 endrin 5(0:17-27 heptachlor/heptachlor epoxide 5(l):17-27 malathion 2(l):2-46 5(2):73-212 methoxychlor 2(I):5I-54 methyl parathion 5(l):I7-27 organochlorines 2(0:2-46 3(3): 182-185 5(2):73-212 parathion 5(0:17-27 TDE 4(2): 27-30 toxaphene 4(2):27-30 Infant and Junior Foods carbaryl 2(3):in4-108 2,4-D 2(3):104-108 organochlorines 2(3): 104-108 5(2):73-212 organophosphates 2(3): 104-108 2,3,6-TBA 2(3): 104-108 tetradifon 2(3): 104-108 368 Food and Feed (cont'd) Leafy and Vine Vegetables, see also Total Diet arsenic 3(3):139-141 carbaryl 2(4): 163-166 chlorbenside 2(0:2-46 5(2):73-212 DCPA 2(0:2-46 5(2):73-212 lead 1(4):8-10 organochlorines 2(0:2-46 5(2):73-212 organophosphates 2(0:2-46 5(2):73-212 PCNB 2(0:2-46 5(2):73-212 Meat, Fish, and Poultry (includes beef, beef fat, pork, fish, shellfish, and fowl), see also Total Diet DDE 2(0:47-50 5(3):276-280 DDT 2(0:47-50 4(0:21-24 4(3):106-110 5(3):276-280 dieldrin 4(2):31-41 MCP 5(2):73-212 organochlorines 5(2):73-212 TDE 2(0:47-50 5(3): 276-280 Nuts (Tree) organochlorines 2(0:2-46 5(2):73-212 Processed Foods carbaryl 2(0:2^6 organochlorines 1(4): 2-7 2(0:2-46 organophosphates 2(0:2-46 Root Crops (includes potatoes, carrots, sugar beets), see also Total Diet aldrin 2(3):133-136 arsenic 3(3): 139-141 chlordane 2(3):I33-136 DDT l(3):22-25 dieldrin l(3):22-25 2(3):I33-136 endrin 2(3):133-136 heptachlor/heptachlor epoxide l(3):22-25 lead 1(4):«-10 organochlorines 2(0:2-46 3(3): 182-185 5(2):73-212 5(4):342-344 5(4):345-347 Food and Feed (cont'd) Root Crops (cont'd) organophosphates 2(0:2^6 5(2);73-212 5(4):342-344 5(4):345-347 Tobacco, see Plants (other than those used for food and feedi Total Diet, see also Dietary Intake arsenic I(2):2-12 l(4):ll-2n 2(4):140-152 4(31:89-105 5(4):313-330 bromides 1(2):2-12 1(4): 11-20 2(41:140-152 4(31:89-105 5(4):313-330 cadmium 2(4):140-152 4(3):89-105 5(4):313-330 carbaryl 1(2):2-I2 1(4): 11-20 4(31:89-105 chlorbenside 2(41:140-152 4(3):89-105 dithiocarbamates 1(4): 11-20 2(4): 140-152 4(3):89-105 5(4):3I3-330 HCB 5(4):313-330 herbicides I(2):2-12 I(4):ll-20 2(4): 140-152 4(3):89-I05 5(4):313-330 mercury 2(4): 140-152 organochlorines 1(2):2-12 1(4): 1 1-20 2(0:2-46 2(4):140-152 4(3):89-105 5(41:313-330 organophosphates 1(21:2-12 l(4):ll-20 2(4):I40-152 4(3):89-105 5(4):313-330 orthophenylphenol 5(4):313-330 ovex 4(3):89-105 PCB's 5(4):3I3-330 PCNB 1(2):2-12 2(4): 140-152 TCNB 1(2):2-12 l(4):lI-20 2(4): 140-152 4(3):89-105 5(41:313-330 tetradifon 1(2):2-12 2(4):140-152 Turnips, Turnip Peels, Turnip Greens, see also Root Crop, Leafy and Vine Vegetables DDE 3(21:70-101 DDT 3(2):70-101 Pesticides Monitoring Journal <'ood and Feed (cont'd) Turnips (cont'd) dieldrin 3(2)170-101 endrin 3(2):70-101 Vegetable Oil Seeds and Products, see also Total Diet arsenic 3(3):139-141 DDE 3(2):70-101 DDT 3(2):70-101 dieldrin 3(2):70-101 endrin 3(2):70-101 merphos 2(l):58-67 organochlorines l(3):22-25 l(4):2-7 2(l):58-57 4(2):42-46 5(2):73-212 organophosphates 2(l):58-67 trifluralin 2(l):58-57 Jenife 923® Soil 4(3):145-166 H ICB Experimental Design 4(4):169-176 Food and Feed 5(4):3I3-330 5(4):331-341 Wildlife 4(3):U7-I35 leptachlor/Heptachlor Epoxide Experimental Design 4(2):67-70 4(41:169-176 Factors Influencing Residues l(2):35-37 Food and Feed 1(2):2-12 1(2):13-14 l(3):2-8 1(3):22-25 l(4):ll-20 2(1):2^6 2(3):104-108 2(4):140-152 2(4):I53-162 4(2):31-41 4(2):42-46 4(3):89-105 5(l):17-27 5(2):73-212 5(4):313-330 5(4):331-341 5(4):342-344 5(4):345-347 Humans 4(2):47-50 Plants (other than those used for food and feed) 5(3):281-288 Removal 5(2):218-222 Sediment 2(2):93-96 3(l):l-7 5(3):281-288 'OL. 5, No. 4, March 1972 Heptachlor/Heptachlor Epoxide (cont'd) Soil 1(2):13-14 I(4):30-33 2(2):93-96 3(4):241-252 4(2):42-46 4(2):67-70 4(3):145-166 5(l):17-27 5(1):28-31 5(2):218-22 5(2):223-227 5(3):248-250 5(3):259-267 5(3):268-275 5(4):342-344 5(4):345-347 Water 1(2):38^6 1(3):13-15 3(2):124-135 4(l):14-20 4(2):71-86 4(4):216-219 5(l):17-27 5(3):281-288 Wildlife l(2):35-37 I(3):9-12 I(3):13-15 2(2):90-92 3(I):l-7 3(2): 102-1 14 3(2):I15-123 3(3): 142-144 3(31:145-171 3(41:227-232 3(4):241-252 4(1):8-10 4(31:117-135 4(31:136-140 4(3):I41-144 5(1):1-11 5(11:12-16 5(2):228-232 5(3):242-247 5(3):248-25n 5(31:281-288 Hexachlorobenzene, see HCB Humans Blood DDE 2(2);80-85 DDT 2(2):80-85 Fat DDE 1(21:15-20 2(21:80-85 DDT I(2):15-20 2(21:80-85 dieldrin 2(2):86-89 Serum organochlorines 4(2):47-50 Iron Wildlife 4(3):136- Isodrin Sediment 3(11:1-7 Water 3(11:1-7 Kelthane®, see Dicofol Kepone® Soil 4(31:145-166 L Lead Food and Feed 1(41:8-10 Wildlife 4(31:136-140 5(41:348-355 Lindane, see BHC/Lindane M Malathion Factors Influencing Residues 4(11:14-20 Food and Feed 1(21:2-12 I(4):ll-20 2(l):2-46 2(I):58-67 2(3): 104-108 2(4):140-152 2(4):153-162 4(3):89-105 5(2):73-212 5(41:313-330 5(41:331-341 Soil 2(11:58-67 4(31:145-166 Water 4(11:14-20 4(21:71-86 Wildlife 1(21:21-28 Matacil® Plants (other than those used for food and feed) 1(21:49-53 MCP Food and Feed 1(21:2-12 2(4):I40-I52 2(41:153-162 4(31:89-105 5(21:73-212 5(4):33I-34I Mercury Food and Feed 2(41:140-152 Soil 5(l):32-33 Merphos Food and Feed 2(11:58-67 Soil 2(0:58-67 Metacide®, see Methyl Parathion Methoxychlor Experimental Design 4(21:67-70 Food and Feed 1(21:2-12 1(3):2-8 1(41:11-20 2(1):2^6 2(l):51-54 2(2):72-79 2(4):140-152 2(4):153-162 4(3):89-105 5(21:73-212 5(41:313-330 5(41:331-341 369 Methoxychlor (cont'd) Removal 2(2);72-79 Sediment 2(2):93-96 Soil 2(l):5l-54 2(2):9,1-96 4(2):67-70 5(3):259-267 Water 1(3):13-I5 Wildlife U3):9-12 3(l):I-7 4(1):8-10 4(3):14I-I44 5(2):228-232 Methyl Parathion, see also Parathion Food and Feed 1(4): 11-20 2(0:2-46 2(l):58-6'' 2(4): 140-152 2(4V53-162 4{ .89-105 5(l):17-27 5(2):73-2I2 5(4):313-330 5(4):331-341 5(4):345-347 Plants (other than those used for food and feed) 4(l):2-7 Parathion (cont'd) Food and Feed (cont'd) 2(1) !-46 Soil Water 2(l):58-67 4(l):2-7 4(31:145-166 5(4):345-347 3(4):212-218 4(2):71-86 Wildlife l(2):21-28 3(4):212-218 4(l):2-7 Mirex Wildlife 4(3):I41-144 Mitox®, see Chlorbenside N Naled Soil 4(3):145-166 Nemacide®, see Dichlofentbion Nickel Wildlife 4(3): 136-140 o Orthophenylphenol Food and Feed 5(4):313-330 5(4):331-34l Ovcx Food and Feed 4(3):89-105 5(4):331-341 Soil 4(3): 145-166 Parathion, see also Methyl Parathion Food and Feed l(2):2-12 l(4):ll-20 2(I):58-67 2(3): 104-108 2(4):140-152 2(4):153-162 4(3):S9-105 5(l):I7-27 5(2):73-212 5(4):313-330 5(4): 33 1-34 1 5(4):345-347 Plants (other than those u food and feed) 4(l):2-7 Soil 2(l):58-67 4(l):2-7 4(3): 145-166 5(l):17-27 5(3):259-267 5(41:345-347 Wafer l(2):47-48 4(2):71-86 Wildlife l(2):2l-28 4(I):2-7 Parinol Experimental Design 4(4):209-2l5 Factors Influencing Residu 4(4):209-215 Soil 4(4):209-215 PCB's Experimental Design 4(4):169-176 Food and Feed 5(4):3l3-330 5(4):331-341 Sediment 5(3):289-294 Water 5(3):289-294 Wildlife 3(l):l-7 3(4): 198-200 4(1):8-I0 4(2):51-56 4(3):I14-II6 4(3):II7-I35 4(3):141-144 4(3):169-176 5(0:1-11 5(21:228-232 5(31:289-294 PCNB Food and Feed 1(2):2-I2 2(0:2-46 2(4): 140-152 2(4):153-162 5(21:73-212 PCP Food and Feed 1(2):2-12 1(4): 1 1-20 2(0:2-46 2(41:140-152 2(4):153-162 4(3);89-105 5(21:73-212 5(4):331-341 Perthane® Food and Feed 1(2):2-12 2(0:2-46 2(41:140-152 2(4): 153-162 4(31:89-105 5(21:73-212 5(4):33l-34l 370 Perthane® (cont'd) Soil 5(31:268-275 Phorate Food and Feed 1(4): 11-20 2(41:140-152 2(4): 153-162 Picloram Soil 3(31:177-181 Plants (other than those used for food and feed) Algae 2.4-D 4(41:184-203 organochlorincs 1(41:21-26 5(31:281-288 Aquatic Plants 2,4-D 1(31:16-21 4(4): 184-203 organochlorincs 1(41:21-26 5(31:281-288 Comfers Bidrin l(2):49-53 Matacil 1(21:49-53 Zectran 1(21:49-53 Leatherstem DDE 4(0:2-7 DDT 4(0:2-7 methyl parathion 4(0:2-7 parathion 4(0:2-7 TDE 4(0:2-7 Tobacco DDE 3(2):70-101 DDT 3(2):70-10l dieldrin 3(21:70-101 Polychlorinated Biphenyls, see PCBs R Removal Food and Feed carbaryl 2(41:163-166 DDE 2(0:47-50 DDT 2(0:47-50 ethion 4(31:89-105 organochlorincs 2(21:72-79 4(2):31-4I 4(31:89-105 TDE 2(11:47-50 Plants (other than those used fo food and feed) cndrin 2(4):167-17l Soil aldrin 5(21:218-222 chlordane 5(21:218-222 dieldrin 5(21:218-222 heptachlor heptachlor epoxidi 5(21:218-222 Pesticides Monitoring Journai Removal (cont'd) Water 2.4-D 4(4): 184-203 Wildlife DDE 4(2):51-56 DDT 4(2):51-56 TDE 4(2):51-56 Ronnel Food and Feed 1(2):2-12 2(4):140-!52 2(4): 153-162 4(3):89-105 5(4):331-341 Sediment copper copper sulfate 3(31:186-189 2,4-D 1(3):16-21 DDE 3(4):219-226 5(l):17-27 DDT 3(4):219-226 5(3):301-308 dichlobenil 5(4):356-359 dieldrin 1(4): 27-29 l(4):30-33 4(4):I77-183 endrin l(4):27-29 4(4):I77-183 organochlorines 2(2):93-96 3(I):l-7 5(3):281-288 5(3):289-294 PCB's 5(3): 289-294 TDE 3(4):219-226 Sevin?. see Carbaryl Silvex Food and Feed l(2):2-12 Water 1(21:38-46 3(21:124-135 Soil, see also Sediment General aldrin 5(2): aramite 4(3): arsenic 4(3): 5(2): atrazine 5(2): caplan 4(3): chlordai 5(2): 2.4-D 4(3): DDE 4(1) 5(3): DDT 4(1): 4(1): 5(3): dieldrin 5(2): 5(3): 218-222 145-166 145-166 223-227 223-227 145-166 :218-222 145-166 :2-7 : 25 1-258 21-24 251-258 Soil (cont'd) General (cont'd) Genile 923 4(31:145-166 heptachlor, heptachlor epoxide 5(21:218-222 mercury 5(l):32-33 merphos 2(0:58-67 methyl parathion 4(l):2-7 organochlorines l(4):30-33 2(2):93-96 3(4):241-252 4(2):67-70 4(3): 145-166 5(I):28-31 5(21:223-227 5(3):248-250 organophosphatcs 4(3):145-166 ovex 4(3):145-166 parathion 4(l):2-7 parinol 4(4): 209-2 15 picloram 3(3):177-18l TDE 4(l);2-7 5(31:251-257 Irifluralin 4(31:145-166 Alfalfa Fields aldrin 1(21:13-14 DDE 2(31:129-133 5(3):276-280 DDT 2(3):129-133 4(l):21-24 5(3):276-280 dieldrin 1(2):13-14 heptachlor/heptachlor epoxide 1(2):13-14 TDE 5 (3): 276-280 Cranberry Bog DDT 2(4):172-175 dieldrin 2(4): 172-175 Field Crop Soils (includes vegetable, tobacco, peanut, and soybean fields) DDE 3(2):70-101 DDT 3(2):70-I01 dieldrin 3(2):70-10I endrin 3(2)170-101 organochlorines 2(11:58-67 4(21:42-46 5(3):259-267 5(31:268-275 organophosphates 2(11:58-67 5(3):259-267 tetradifon 5(31:268-275 trifluralin 2(1): 58-67 Grain and Forage Fields (includes com fields) aldrin 5(l):17-27 diazinon 5(l):17-27 Soil (cont'd) Grain and Forage Fields (cont'd) dieldrm 5(11:17-27 endrin 5(11:17-27 heptachlor heptachlor epoxide 5(11:17-27 methyl parathion 5(l):17-27 organochlorines 3(31:182-185 5(31:268-275 parathion 5(11:17-27 tetradifon 5(3):268-275 Movement (includes translocation) aldrin 2(3):133-136 5(21:218-222 chlordane 2(3):133-I36 5(21:218-222 DDE 3(21:70-101 DDT 2(I);55-57 3(2);70-10l dieldrin 2(31:133-136 3(21:70-101 5(21:218-222 endrin 2(31:133-136 3(21:70-101 heptachlor heptachlor epoxide 5(2):218-222 organochlorines 4(21:42-46 picloram 3(31:177-181 Orchards DDE 2(l):5l-54 DDT 2(l):5l-54 dieldrin 2(0:51-54 meihoxychlor 2(0:51-54 organochlorines 5(31:259-267 5(3):268-275 organophosphates 5(3):259-267 tetradifon 5(3):268-275 Root Crop Fields DDE 3(2):70-10l DDT 3(2):70-101 dieldrin 3(2):70-IOI endrin 3(2):70-10I organochlorines l(3):22-25 3(3): 182-185 5(41:342-344 5(41:345-347 organophosphates 5(41:342-344 5(4):345-347 2,4,5-T Food and Feed 1(4): 11-20 2(4):140-152 2(4): 153-162 1(2): 38-46 3(2):I24-135 Vol, 5, No, 4, March 1972 371 2,3,6-TBA Food and Feed 2(3):104-108 2(4): 140-152 2(4):I53-162 TCNB Food and Feed U2):2-12 l(4):ll-20 2(4): 140-152 2(4):153-I62 4(3):89-105 5(4):313-330 5{4):331-341 TDE (DDD) Air 4(4):204-208 Experimenlal Design 4(4): 169-176 Factors Influencing Residues 3(4):212-21g 4(4): 204-208 5(3):235-241 Food and Feed 1(2):2-12 l(3):2-8 1(4): 2-7 U4):ll-20 2(l):2-46 2(l):47-50 2(31:104-108 2(4): 140-152 2(4):153-162 3(3):182-I85 4(2):27-30 4(2):31-41 4(3):89-105 5(2):73-212 5(3):276-280 5(4):313-330 5(4):331-341 5(4):342-344 5(4):345-347 Humans 4(2):47-50 Plants (other than those used for food and feed) 4(l):2-7 5(3):281-288 Removal 2(l):47-50 4(2):31^1 4(2):51-56 4(3):89-105 Sediment 2(2):93-96 3(l):l-7 3(4):219-226 5(3):281-288 5(31:289-294 Soil 2(2):93-96 3(3): 182-185 4(l):2-7 4(3):145-166 5(1):28-31 5(2):223-227 5(3):248-250 5(3):251-258 5(3):268-275 5(31:276-280 5(4):342-344 5(4):345-347 Water l(2):38-46 3(2):124-135 3(41:212-218 3(4):219-226 4(l):14-20 4(2):71-86 5(31:235-241 5(3):281-288 5(3):289-294 Wildlife l(2):21-28 l(2):29-34 .^72 TDE (DDD) (cont'd) Wildlife (cont'd) 1(3):9-12 l(4):2-7 1(41:21-26 l(4):27-29 2(2): 90-92 2(3): 109-122 3(l):l-7 3(2):102-114 3(2):U5-123 3(3):142-144 3{3):145-171 3(4): 198-200 3(4):212-218 3(4):219-226 3(4):227-232 3(4):233-240 4(l):2-7 4(1):8-10 4(2):5l-56 4(2):57-61 4(2):62-66 4(3):I14-116 4(31:117-135 4(31:136-140 4(3):I41-144 5(1):1-1I 5(2):228-232 5(3);235-241 5(3):242-247 5(31:248-250 5(31:251-258 5(31:281-288 5(3):289-294 Tedion*, see Tetradifon Tetradifon Food and Feed l(2):2-I2 2(11:2-46 2(3): 104-108 2(4):140-152 2(41:153-162 5(2);73-212 Soil 5(3): 268-275 Thimet®, see Phorate Thiodan®, see Endosulfan Toxaphene/Strobane® Factors Influencing Residues 3(4):2I2-218 Food and Feed 1(21:2-12 l(4):2-7 2(11:2-46 2(11:58-67 2(4): 140-152 2(4): 1 53-162 4(21:27-30 4(31:89-105 5(21:73-212 5(4):313-330 5(4):331-341 5(41:345-347 Removal 4(31:89-105 Scdii 3(l):I-7 2(11:58-67 4(31:145-166 5(21:223-227 5(3):268-275 5(4):345-347 3(4):212-218 fe 1(3):9-12 3(l):l-7 3(31:145-171 3(4):212-218 4(11:8-10 4(2):57-6I 5(l):l-ll 2,4,5-TP, see Silvex Trifluralin Food and Feed 2(0:58-67 Soil 2(I):58-67 4(31:145-166 Trithion®, see Carbopbenotbioi w Water, see also Sediment General malathion 4(1): 14-20 organochlorines 1(41:21-26 4(1): 14-20 Estuarinc Waters DDE 5(31:235-241 DDT 5(31:235-241 dieldrin 4(4): 177-183 endrin 4(41:177-183 organochlorines 1(31:13-15 3(11:1-7 5(31:281-288 TDE 5(31:235-241 Ground Water (includes wells) aldrin 5(11:17-27 dieldrin 5(11:17-27 endrin 5(11:17-27 heptachlor/heptachlor epoxid 5(i):17-27 Irrigation Waters copper sulfate 3(31:186-189 4(11:11-13 parathion 1(21:47-48 Ponds aldrin 5(11:17-27 2,4-D 1(3):I6-2I 4(41:184-203 dichlobenil 5(41:356-359 dieldrin 5(1): 17-27 endrin 5(I):I7-27 heptachlor/heptachlor cpoxidi 5(11:17-27 Rivers and Streams aldrin 5(11:17-27 2.4-D 5(21:213-217 DDE 3(41:219-226 4(4):216-219 DDT 3(41:219-226 4(4):2I6-2I9 5(3):30I-308 dieldrin 4(41:216-219 5(11:17-27 endrin 5(1): 17-27 heptachlor heptachlor epoxide 4(41:216-219 5(11:17-27 herbicides 1(21:38^6 3(21:124-135 Pesticides Monitoring Journal iVatcr (cont'd) Rivers and Streams (cont'd) organochlorines l(2);38-46 3(0:8-66 ' 3(2):124-135 4(2):7l-86 5(3):289-294 organophosphates 4(2):71-86 PCB's 5(3):289-294 TDE 3(4)::i9-:26 Runoff amitrole 2(3):123-128 dieldrin l(4):30-33 5(1): 17-27 endrin 2(4):167-171 heptachlor heplachlor epoxide 5(11:17-27 methyl parathion 3(4):212-218 organochlorines 3(4):212-2I8 Surface Slicks aldrin 3(3):I90-193 DDE 3(3):I9n-193 DDT 3(3):190-I93 dieldrin 3(31:190-193 Wildlife Birds DDE 1(21:29-34 4(l):2-7 5(3);251-258 DDT 1(2): 29-34 4(11:2-7 5(3):25l-258 dieldrin 5(3):251-258 HCB 4(3):117-135 methyl parathion 4(l):2-7 organochlorines 2(2):90-92 3(21:102-114 3(21:115-123 3(3): 142-144 3(41:227-232 4(3):117-135 4(3):141-144 5(31:248-250 parathion 4(11:2-7 PCB's 4(31:117-135 4(31:141-144 TDE 1(21:29-34 4(11:2-7 5(31:251-258 Bird's Eggs heavy meals 4(31:136-140 , organochlorines y 3(41:227-232 ■ 4(31:136-140 n PCB's 4(4): 169-176 Deer and Elk DDE 5(31:251-258 DDT 4(3):10o-110 ,, 5(31:251-258 1^ dieldrin ■ 5(31:251-258 Vol. 5, No. 4, March 1972 Wildlife (cont'd) Deer and Elk (cont'd) TDE 5(3):251-258 Fish 2,4-D 1(3):16-21 4(4): 184-203 5(2):213-217 DDE l(2):35-37 2(3): 109-122 3(4) :21 9-226 3(41:233-240 4(21:62-66 5(31:235-241 5(31:251-258 DDT 1(21:35-37 2(31:109-122 3(41:219-226 3(4):233-240 4(2): 62-66 5(3):235-241 5(3);251-258 dieldrin l(2):35-37 3(4):233-240 4(21:62-66 5(31:251-258 endrin 3(41:201-203 factors influencing residues 5(31:235-241 HCB 4(31:117-135 heptachlor heptachlor epoxide 1(21:35-37 lead 5(41:348-355 methyl parathion 3(41:212-218 organochlorines 1(41:21-26 1(41:27-29 3(11:1-7 3(3):145-171 3(4):212-218 4(2):51-56 4(21:57-61 4(31:117-135 5(11:1-11 5(11:12-16 5(21:228-232 5(31:281-288 5(31:289-294 PCB's 3(11:1-7 4(21:51-56 4(3): 117-135 4(4): 169-176 5(1):1-11 5(2):228-232 5(3):289-294 TDE 2(31:109-132 3(41:219-226 3(41:233-240 4(21:62-66 5(3):235-241 5(3):251-258 Invertebrates (other than shellfish) DDE 3(4):2l9-226 5(31:251-258 DDT 3(41:219-226 5(31:251-258 dieldrin 5(31:251-258 5(31:295-300 organochlorines 1(41:27-29 3(41:241-252 5(31:248-250 5(31:281-288 Wildlife (cont'd) Invertebrates (cont'd) TDE 3(41:219-226 5(31:251-258 Rabbits DDE 5(31:251-258 DDT 5(31:251-258 dieldrin 5(31:251-258 TDE 5(31:251-258 Reptiles and Amphibians DDE 3(41:204-211 4(11:2-7 5(31:251-258 DDT 4(11:2-7 5(31:251-258 dieldrin 5(31:251-258 methyl parathion 4(11:2-7 organochlorines 1(21:21-28 organophosphates 1(21:21-28 parathion 4(l):2-7 TDE 4(l):2-7 5(3):251-258 Rodents DDE 4(11:2-7 5(31:251-258 DDT 4(11:2-7 5(31:251-258 dieldrin 5(3):251-258 methvl parathion 4(l):2-7 parathion 4(l):2-7 TDE 4(l):2-7 5(31:251-258 Seals DDE 3(41:198-200 4(31:114-116 DDT 3(41:198-200 4(31:114-116 dieldrin 3(41:198-200 4(31:114-116 PBC's 3(41:198-200 4(31:114-116 TDE 3(41:198-200 4(31:114-116 Shellfish carbophenothion 1(31:9-12 2,4-D 1(31:16-21 4(41:184-203 DDE 3(41:219-226 5(31:235-241 DDT 3(41:219-226 5(31:235-241 dieldrin 4(41:177-183 endrin 4(41:177-183 factors influencing residu 5(31:235-241 373 Wildlife (cont'd) Shellfish (cont'd) organochlorines I(3):9-12 I(3):13-15 l(4):21-26 3(l):l-7 4(3):1 17-135 5(3):242-247 5(3):281-288 PCB's 4(3);1I7-135 Wildlife (cont'd) Shellfish (cont'd) TDE 3(4):219-226 5(3):235-241 Whales organochlorines 4(1):8-10 PCB's 4(I):8-10 Zooplankton 2,4-D 4(4): 184-203 Zectran® Plants (other than those used io food and feed) l(2):49-53 Zinc Wildlife 4(3): 136-141) Zineb, see Dithiocarbamates AUTHOR INDEX Anas. R. E., and Wilson, A. J., Jr. Organochlorine pesticides in fur seals. 3{4):198-200 Anas. R. E.. and Wilson. A. J., Jr. Organochlorine pesticides in nurs- ing fur seal pups. 4(3) :1 14-116 Anderson. R. J. Editorial: Federal Committee on Pest Control in FY 1969. 3(4):197 Anonymous. Criteria for defining pesticide levels to be considered an alert to potential problems. 5{I):36 Applegate. H. G. Insecticides in the Big Bend National Park. 4(l):2-7 Applegate, H. G.. see Culley. D. D. Archer. T. E. Toxaphene and DDT residues in ladino clover seed screenings. 4(2):27-30 B Bagley, G. E., see Krantz, W. C. Bagley. G. E.. see Mulhern, B, M. Baldwin. M. K.. see Richardson, A. Barrentine, B. F.. and Cain. J. D. Cooperative study . . . Section B: Mississippi — Residues of endrin and DDT in soybeans grown on soil treated with these compounds. 3(2) : 77-79 Barry. D., see Cole, H. C Ford. J. H.. Bolton. G, C. . E. H.. and Parsons. D. A. Pesti- the lower iippi River bv the blu Barry. H. C. see Duggan. R. E. Barthel. W. F., Hawthorne, J. McDowell. L. L., Grissinger cide residues in sediments of tributaries. 3(1) :8-66 Baumgarner, p., see Cole, H. Bedford. J. W.. see Zabik. M. J. Belisle. a., see Mulhern, B. M. Bennett. H. J., and Day, J. W.. Jr. Absorption of endr gill sunfish Lcpornis macrochirus. 3(4):20I-203 Benson. W. W., see Watson. M. Benville. p. E.. Jr., see Earnest, R. D. Bolton. G. C, see Barthel. W. F. Bomberg. J., see Sand, P. F. BoswELL, T. O., see Lehner. P. N. BovEV, R. W., Dowler, C. C, and Merkle, M. G. The persistence and movement of picloram in Texas and Puerto Rican soils. 3(3):177- 181 Bradford, A., see Cole, H. Bradicich. R., Foster, N. E., Hons, F. E.. Jeffus, M. T.. and Kenner. C. T. Arsenic in cottonseed products and various commodities. 3(3):139-141 Brady. U. E.. see Wallace, J. B. Braun, H. E., see Frank. R. Breidenbach, a. W. Editorial. 2(2) ;71 Brown, E.. and Nishioka, Y. A. Pesticides in selected western streams — a contribution to the national program. l(2):38-46 Brown. I. F., Jr., see Polzin. W. J. Bruns, V. F., see Nelson, J. L. Bugg, J. C, Jr., Higgins, J. E., and Robertson, E. A., Jr. Chlorinated pesticide levels in the eastern oyster {Cra^sostrea virfiinica) from selected areas of the south Atlantic and Gulf of Mexico. 1(3):9-I2 Burdick, O. E., see Pakkala, I. S. Butcher, J. W., see Fahey, J. E, 374 Cahill. W. p.. see Ware. G. W. Cain. J. D.. see Barrentine. B. F. Campbell. W. V., sec Sheets. T. J. Canter, L. W.. see Rowe, D. R. Carlile, B. L.. see Nelson, J. L, Carver, T. C. Estuarine monitoring program. 5(1):53 Carver. T. C, see Johnson. R. E. Casper. V. L. Galveston Bay pesticide study — water and oyster samples analyzed for pesticide residues following mosquito control pro- gram. 1(3): 13-15 Cassady. J. C. sec Davies, J. E. Cavin, G. E.. see Seal, W. L. Chesters, G.. see Frazier. B. E. Chesters. G., see Trautmann, W. L. Chopra, S. L,, see Mann, G. S. Cole, H., Bradford, A., Barry. D., Baumgarner, P.. and Frear, E. H. Pesticides in hatchery trout — differences between species anc residue levels occurring in commercial fish food. I(2):35-37 Collier, C. W.. see Stevens. L. J. Cook. H. R.. see Duggan, R. E. Copeland. F., see Lehner, P. N. Corcoran, E. F., see Sera. D. B. Corneliussen, P. E. Pesticide residues 2(4):140-152 Corneliussen, P. E. Pesticide residues 4(31:89-105 Corneliussen, P. E. Pesticide residues 5(4):313-330 Corneliussen. P. E.. see Duggan. R. E. Cory, L.. Fjeld, P.. and Serat, W. Distribution patterns of DDT residues in the Sierra Nevada Mountains. 3(4):204-211 Coutant, C. C, see Nelson, J. L. Cox, E. L., see Duggan, R. E. Crabtree. a. N.. see Richardson, A. Cromartie. E., see Mulhern. B. M. Cromartie. E.. see Reichel. W. L. Crouch. G. L.. and Perkins. R. F. Plar control of the Douglas-fir tussock Culley. D. D.. and Applegate. H. C total •t samples (IV) et samples (V). in total diet samples (VI). total ing a surveillance program for oth in Oregon. 2(2) :97-l(X) Insecticide concentrations in ■ildlifc at Pn Texas. l(2):21-28 D Dahlgren, R. B., see Linder, R. L. Davies, J. E.. Edmundson, W. F.. Schneider, N. J., and Cassady, J. C. Problems of prevalence of pesticide residues in humans. 2(2):80-85 Davies, J. E., see Edmundson, W. F. Dawsey. L. H.. see Seal. W. L. Day, J. W.. Jr.. see Bennett, H. J. Demoranville. I. E.. see Deubert, K. H. Deubert, K. H.. and Demoranville. I. E. Copper sulfate in flooded cranberry bogs. 4(1):11-13 Deubert. K. H., and Zuckerman. B. M. Distribution of dieldrin and DDT in cranberry bog soil. 2(4): 172-175 DeWitt, J. B. Editorial: The validity of pesticide "values." 2(3):I03 Dorough, H. W.. and Randolph. N. M. Cooperative study . . . Section E: Texas— Residues of DDT and endrin in peanuts and soybeans grown in soil containing these pesticides. 3{2):90-93 Dowler, C. C, see Bovey. R. W. Pesticides Monitoring Journal )RESSMAN, R. C, see Lichthnberg, J. J. UFFY, J. R., see Fredeen, F. J. H. lUGGAN, R. E. Editorial. 1(2) :1 lUGGAN, R. E. Chlorinated pesticide residues in fluid milk and other dairy rroducis in the United States. 1(3):2-8 UGGAN, R. E. Pesticide residues in vegetable oil seeds, oils, and by- products. l{4):2-7 UGGAN, R. E. Pesticide residue levels in foods in the United States from July 1. 1963 to June 30, 1967. 2(l):2-46 UGGAN, R. E. National Pesticide Monitoring Program (Revised). In- troduction. 5(1 ):35 UGGAN, R. E., and Cook, H. R. National food and feed monitoring program. 5(l):37-43 lUGGAN, R. E., and Corneliussen, P. E. Dietary intake of pesticide chemicals in the United Slates (III), June 1968-April 1970. 5(4): 331-341 )UGGAN, R. E., and Lipscomb, G. Q. Dietary intake of pesticide chem- icals in the United States (II), June 1966-ApriI 1968. 2(4):153- 162; Erratum 3(2):137 )UGGAN, R. E., and McFarland, F. J. Assessments include raw food and feed commodities, market basket items prepared for consump- tion, meat samples taken at slaughter: l(l):l-5 )UGCAN, R. E., Barry. H. C, and Johnson, L. Y. Pesticide residues in total diet samples (II). 1(2):2-12 >UGGAN, R. E., Lipscomb, G. Q.. Cox. E. L.. Heatwoi^e, R. E., and Kling, R. C. Pesticide residue levels in foods in the United States from July 1, 1963 to June 30, 1969. 5(2):73-2I2; Erratum 5(3):3I0 UGGAN. R. E.. see Martin. R. J. 'UKE, T. W., and Wilson, A. J., Jr. Chlorinated hydrocarbons in vers of fishes from the northeastern Pacific Ocean. 5(2):228-232 USTMAN, E. H., Martin. W. E . Heath. R. G., and Reichel, W. L. Monitoring pesticides in wildlife. 5(l):50-52 USTMAN. E. H.. see Johnson, R. E. lUTT, G. R., see Laubscher, J. A. ■ARNEST. R. D.. and Benvilie. P. E.. Jr. Correlation of DDT and lipid levels for certain San Francisco Bay fish. 5(3):235-241 iDGERTON, p. J., see Strickler, G. S. ;Dmundson, W. F., Davies, J. E., and Hull, W. Dieldrin storage levels in necropsy adipose tissue from a south Florida population. 2(2):86-89 ■DMUNDSON. W. F., see Davies, J. E. •llCHELBERGER. J. W., SCC LiCHTENBERG. J. J. ■STESEN, B. J., see Ware. G. W. ■AHEY. J. E.. Butcher, J. W., and Turner, M. E. Monitoring the effects of the 1963-64 Japanese beetle control program on soil, water, and silt in the Battle Creek area of Michigan. l(4):30-33 Feltz, H. R., Savers, W. T., and Nicholson, H. P. National monitor- ing program for the assessment of pesticide residues in water. 5(l):54-62 ■'ERGUson. D. E., see Finley. M. T. •ETZER. L. E., Jr., see Guerrant, G. O. -INLEY, M. T., Ferguson, D. E.. and Ludke, J. L. Possible selective mechanisms in the development of insecticide-resistant fish. 3(4): 212-218 "JELD. P., see Cory, L. ■LETCHALI, O. H., see Ketchersid. M. L. "oehrenrach, J., Mahmood. G., and Sullivsn. D. Chlorinated hydro- carbon residues in shellfish (Pelecvpoda) from estuaries of Long Island, New York. 5(3):242-247 'ORD. J. H . see Barthel, W. F. 'oster. N. E,, see Bradicich. R. ■rank, R., Braun, H. E., and McWade, J. W. Chlorinated hydro- carbon residues in the milk supply of Ontario, Canada. 4(2):31-41 -razier, B. E., Chesters, G.. and Lee, G. B. "Apparent" organo- chlorine insecticide contents of soils sampled in 1910. 4(2):67-70 -redeen, F. J. H., and Duffy. J. R. Insecticide residues in some components of the St. Law-rence River ecosystem following ap- plications of DDD. 3(4)::i9-226 'REAR, D. E. H., sec Cole. H. •UHREMANN, T. W.. see Lichtenstein, E. p. GoN, M., see Wassermann, M. Green, R. S., and Love, S. K. Network to monitor hydrologic en- vironment covers major drainage rivers. 1(1):13-16 Greichus. A., see Greichus. Y. A. Greichus. Y. A.. Greichus, A., and Rieder. E. G. Insecticide residues in grouse and pheasant of South Dakota. 2(2):90-92 Grissinger, E. H., see Barthel, W. F. Glerrant, G. O., Fetzer, L. E., Jr.. and Miles. J. W. Pesticide residues in Hale County. Texas, before and after ultra-low volume application of malathion. 4(l):14-20 H Hall. T. F.. see Wojtalik. T. A. Halliday. H. E.. see Molbry. R. J. Hansen. D. J., and Wilson, A. J.. Jr. Significance of DDT residues in fishes from the estuary near Pensacola, Fla. 4(2):51-56 Harris. C. R.. and Sans. W. W. Absorption of organochlorine insecti- cide residues from agricultural soils by crops used for animal feed. 3(3): 182-1 85 Harris. C. R.. and Sans. W. W. Insecticide residues in soil on 16 farms in southwestern Ontario— 1964, 1966, and 1969. 5(3):259-267 Harris. C. R.. see Miles. J. R. W. Harris. E. J., see Pakkila. I. S. Harvey. T. L.. see Knutson, H. Hawthorne. J. C see Barthel, W. F. Heath, R. G. Nationwide residues of organochlorine r>esticides in wings of mallards and black ducks. 3(2):1I5-123 Heath, R. G., see Dustman, E. H. Heatwole. R. E.. see Dugcan, R. E. Helm. J. M.. see Moubry. R. J. Henderson. C, Tnglis. A., and Johnson. W. L. Organochlorine in- secticide residues in fish— fall, 1969 (National Pesticide Monitor- ing Program). 5(1):1-11: Erratum 5(3):310 Henderson. C. Johnson. W. L., and Inglis, A. Organochlorine in- secticide residues in fish (National Pesticide Monitoring Program). 3(3):I45-I71 Henderson, C. see Inglis, A. Higer, a. L.. see Kolipinski, M. C. Higgins, J. E.. see Bugg, J. C, Jr. Hill. L. O.. see Wojtalik. T. A. HoLDEN, A. V. International cooperative study of organochlorine pesticide residues in terrestrial and aquatic wildlife, 1967 1968. 4(3):117-135 HoNS. F. E., see Bradicich, R. Hopkins, T. L.. see Knutson. H. Hull, W., see Edmundson, W. F. Hutton, G. L. Editorial: Change in sponsorship for the Pesticides Monitoring Journal. 4(1 ):1 I iNGiis. A., Henderson, C, and Johnson, W, L. Expanded program for pesticide monitoring of fish: 5(l):47-49 Incus. A., see Henderson, C. IsoM, B G., see Smith, G. E. Jackson. M. D.. see Sheets. T. J. Jahn, C. D., see Ware, G. W. Jeffus. M. T., see Bradicich, R. Jensen, H. P., see Moubry. R. J. Johnsen. R. E.. see Mullins. D. E. Johnson, D. W., and Lew. S. Chlorinated hydrocarbon pesticides in representative fishes of southern Arizona. 4(2):57-6I Johnson, L. G., and Morris, R. L. Chlorinated hydrocarbon pesticides in Iowa rivers. 4(4):216-219 Johnson. L. G., see Morris, R. L. Johnson, L. Y.. see Duggan. R. E. Johnson, R. E., Carver, T. C. and Dustman, E. H. Indicator species near top of food chain chosen for assessment of pesticide base levels in fish and wildlife — clams, oysters, and sediment in es- tuarine environment. 1(I):7-13 Johnson. W. C. see Godsil, P. J. Johnson, W. L., see Henderson, C. Johnson, W. L., see Inglis, A. jABicA. J.. see Watson. M. jEary, j. M. Editorial: Introduction — pesticides and the total en vironment. 1 ( 1 ) :unnumbered pages 3ENTRY, J. W.. see Sand, P. F. jISH, C. D. Organochlorine insecticide residues in soils and soil in vertebrates from agricultural lands. 3(4):241-252 [jOdsil, p. j., and Johnson, W. C. Pesticide monitoring of the aquatic biota at the Tule Lake National Wildlife Refuge. l(4);21-26 v^ol. 5. No. 4, March 1972 Kadoum, a. M., see Knutson, H, Kenner, C. T., see Bradicich, R. Ketchersid, M. L., Fletchall, O. H., Santelmann, P. W.. and Merkle, M. G. Residues in sorghum treated with the isooctyl ester of 2,4-D. 4(3) :1 11-1 13 Kleinman, a. Investigation of lead residues on growing fruits and vegetables. 1(4): 8-10 375 Kling. R. C, see Duccan, R. E. Knutson. H.. Kadoum. A. M.. Hopkins, T. L., Swoyer. G. F., and Harvey, T. L. Inseclicide usage and residues in a newly developed great plains irrigation district. 5(l):17-27 KoLipiNSKi, M. C, HiGER, A. L., and Yates, M. L. Organochlorine in- secticide residues in Everglades National Park and Loxahatchec National Wildlife Refuge, Florida. 5(3):28l-288 Krantz, W. C, Mulhern, B. M.. Bagley. G. E.. Sprunt, A.. IV. LiGAS, F. J., and Robertson, W. B., Jr. Organochlorine and heavy metal residues in bald eagle eggs. 4(3): 136-140 Lamont. T. G., .see Mulhern, B. M. Lamont, T. G., see Reichel. W. L. Landry, J. L., see Sand, P. F. Larson, J. E., Pieper, G. R., and Ratsch, H. C. Systemic activity of Zectran, Matacil, and Bidrin injected into conifer trunks. 1(2): 49-53 Laubscher. J. A.. Dinr, G. R., and Roan, C. C. Chlorinated insecti- cide residues in wildlife and soil as a function of distance from application. 5(3):251-258 Lee, G. B., see Frazier, B. E. Lehner. p. N., Boswell. T. O., and Copeland, F. An evaluation of the effects of the Aecles ae^ypti Eradication Program on wildlife in south Florida. I(2):29-34 Lew. S., see Johnson, D. W. Lichtenberg, J. J., Eichelberger, J. W., Dressman. R. C, and Long- bottom, J. E, Pesticides in surface waters of the United States — a 5-year summary. 1964-68. 4(2):7I-86 Lichtenstein, E. p.. Schultz. K. R., and Fuhremann, T. W. Effects of a cover crop versus soil cultivation i. i the fate and vertical distribution of insecticide residues in soil 7 to 11 years after soil treatment. 5(2):218-222 LiGAS. F. J., see Krantz, W. C. LiNDER. R. L., and Dahlgren, R. B. Occurrence of organochlorine in- secticides in pheasants of South Dakota. 3(4) :227-232 Lipscomb, G. Q. Pesticide residues in prep .ei. baby foods in the United Stales. 2(3): 104-108 Lipscomb, G. Q., see Duggan, R. E. LisK, D. J., see Pakkala. L S. Locke. L. N., see Mulhern. B. M. Longbottom, J. E., see Lichtenberg, J. J. Love, S. K. Editorial: Units for reporting pesticid's. 1(3) :l Love. S. K., see Green. R. S. LuDKE. J. L., see Finley. M. T. Lyle. W. E.. sec Moubrv. R. J. Lyman. L. D., Tompkins. W. A., and McCann. J, A. Massachusetts pesticide monitoring study. 2(3): 109-122 Miller. C. W.. Tomlinson. W. E., and Norgren. R. L. Persistcn and movement of parathion in irrigation waters. l(2):47-48 Mitchell. W. G.. see Wiersma. G. B. Mistric, W. J., see Sheets. T. J. MoDiN. J. C. Chlorinated hydrocarbon pesticides in California h, and estuaries. 3(1) :l-7 Morris. R. L.. and Johnson. L. G. Dieldrin levels in fish from lo- streams. 5(1):12-16 Morris. R. L.. see Johnson. L. G. MouBRY. R. J.. Helm. J. M.. and Myrdal. G. R. Chlorinated pestici residues in an aquatic environment located adjacent to a l' mercial orchard. l(4):27-29 MouBRY. R. J.. Myrdal. G. R.. and Halliday. H. E. Dieldrin resid in an orchard-dairy area of Wisconsin. 2(l):51-54 MouBRY. R. J.. Myrdal. G. R.. and Jensen. H. P. Chlorinated hydi carbon pesticide residues in or on alfalfa grown in soil with previous history of aldrin and heptachlor application. 1(2):]3- MouBRY. R. J., Myrdal. G. R.. and Lyle, W. E. Investigation determine the respective residue amounts of DDT and its analopi in the milk and back fat of selected dairy animals. 2(0:47-50 MouBRY, R. J., Myrdal, G. R.. and Sturges, A. Rate of decline chlorinated hydrocarbon pesticides in dairy milk. 2(2):72-79 Move. H. A., see Wheeler. W. B. Mulhern. B. M., Reichel. W. L.. Locke. L. N.. Lamont. T. ( Belisle. a.. Cromartie. E.. Bagley. G. E.. and Prouty, R Organochlorine residues and autopsy data from bald eagles, I*^' 68. 4(3):I41-I44 Mulhern, B. M., see Krantz. W. C. Mulhern. B. M., see Reichel. W. L. MuLLiNS. D. E.. Johnsen. R. E.. and Starr. R. I. Persistence organochlorine insecticide residues in agricultural soils of Co^ rado. 5(3):268-275 Myrdal. G. R.. see Moubry. R. J. N Nelson. J. L., Bruns, V. F.. Coutant, C. C, and Carlile, B. L. havior and reactions of copper sulfate in an irrigation cant' 3(3):186-189 Newsom. J. D., see McLane. M. A. R. Nicholson, H. P., see Feltz, H. R. Nishioka, Y. a., see Brown. E. Norgren. R. L.. see Miller. C. W. Ogg. a. G.. Jr. Pesticides in ponds treated dichlohcnil. 5(4):356-359 'ith two formulations M Mahmooo. G.. see Foehrenbach. J. Manicold. D. B.. and Schulze, J. A. Pesticides in selected western streams— a progress report. 3(2 ): 124-135; Erratum 3(3):195 Mann, G. S.. and Chopra. S. L. Residues of carbarvl on crops. 2(4): 163-166 Manthey. J. A., see Polzin. W. J. Marston. R. B.. Schults, D. W., Shirovama, T., and Snyder, L. V. Amitrole concentrations in creek waters downstream from an aerially sprayed watershed sub-hasin. 2(3):123-128 Marston. R. B., Tyo. R. M.. and Middendorff, S. C. Endrin in water from treated Douglas fir seed. 2(4): 167-171 Martin, R. J., and Ducgan, R. E. Pesticide residues in total diet samples (III). l(4):lI-20 Martin, W. E. Organochlorine insecticide residues in starlings. 3(2): 102-114 Martin, W. E., see Dustman, E. H. Mason, J. W.. see Rowe. D. R. McCann, J. A., see Lyman. L. D. McCaskill, W. R., Phillips. B. H.. Jr., and Thomas, C. A. Residues of chlorinated hydrocarbons in soybean seed and surface soils from selected counties of South Carolina. 4(2):42-46 McDowell, L. L.. sec Barthel. W. F. McFarland, F. J., see Duggan. R. E. McLane. M. A. R.. Stickel. L. F.. and Newsom. J. D. Organo- chlorine pesticide residues in woodcock, soils, and earthworms in Louisiana. 1965. 5(3):248-250 McWade. J. W.. see Frank. R. Meehan. W. R.. see Sears, H. S Merkle, M. G.. see Bovev. R. W Merkle. M. G.. see Ketchersid. M. L. Middendorff. S. C, see Marston, R. B. Miles, J. R. W., and Harris, C. R. Insecticide residues in a stream and a controlled drainage system in agricultural areas of south- western Ontario, 1970. 5(3):289-294 Miles, J. W., see Guerrant. G. O. 376 Pakkala. I. S., White, M. N.. Burdick, G. E.. Harris, E. J., and Li." D. J. A survey of the lead content of fish from 49 New Yo State waters. 5(4):348-355 Pare. B. E.. see Zabik. M. J. Papendick. R. I., see Willis. G. H. Parr. J. F.. see Willis. G. H. Parsons. D. A., see Barthel, W. F. Perkins, R. F.. see Crouch. G. L. Phillips, B. H.. Jr.. see McCaskill. W. R. Pieper. G. R.. see Larson. J. E. PioNKE. H. B., see Trautmann, W. L. Polzin, W. J., Brown, I. F., Jr., Manthey, J. A., and Probst. G. \ Soil persistence of fungicides — experimental design, sampling, chei ical analysis, and statistical evaluation. 4(4):209-215 Priester. L. E.. see Reed. J. K. Probst. G. W.. see Polzin. W. J. Prouty. R. M.. see Mulhern. B. M. Prouty, R. M., see Reichel, W. L. R Randolph, N. M., see Dorough, H. W. Ratsch, H. C, see Larson, J. E. Reed, J. K., and Priester. L. E. Cooperative study . . . Section I South Carolina — DDT residues in tobacco and soybeans grov in soil treated with DDT. 3(2):87-89 Reed. J. P., see Winnett. G. Reichel. W. L.. Cromartie. E.. Lamont, T. G.. Mulhern. B. M., ai Prouty. R. M. Pesticide residues in eagles. 3(3): 142-144 Reichel. W. L.. see Dustman, E. H. Reichel, W. L., see Mulhern, B. M. Reinert. R. E. Pesticide concentrations in Great Lakes fish. 3(4! 233-240 Richardson, A.. Robinson, J.. Crabtree. A. N.. and Baldwin. M. I Residues of polychlorobiphenyls in biological samples. 4(4):169-r Pesticides Monitoring Journa; ;der. E. G., see Greichus. Y. A. AN, C. C see Laubscher, J. A. BERTSON, E. A.. Jr.. see Buoc. J. C. Jr. BERTSON. \V. B.. Jr.. see Kkantz. W. C. BINSON. J., see Richardson. A. WE, D. R., Canter. L. W.. Snyder. P. J., and Mason. J. W. Diel- drin and endrin concentrations in a Louisiana estuary. 4(4) : 177- 183 ha, J. G., and Sumner. A. K. Organochlorine insecticide residues in soil from vegetable farms in Saskatchewan. 5(1):28-31 MD. P. F. Editorial. 3(2) :69 ID, P. F., WiERSMA. G. B., and Landry, J. L. Pesticide residues in sweetpotatoes and soil. 5(4):34:-344 ND. P. F., Gentry, J. W., Bomberg, J., and Schechter, M. S. National Soil Monitoring Program studies high-, low-, and non-use areas. 1(1):16-19. ND. P. F.. Wiersma, G. B., Tai. H.. and Stevens, L. J. Preliminary study of mercury residues in soils where mercury seed treatments have been used. 5(l):3:-33 ND, P. F., sec Wiersma. G. B. NS. \V. W.. see Harris. C. R. STELMANN. P. W.. seC KeTCHERSID. M. L. VERS. W. T.. see Feltz. H. R. HECHTER. M. S. Chemicals Monitoring Guide for the National Pesti- cide Monitoring Program. 1(1):20-21 HECHTER. M. S. Editorial: The need for confirmation. 2{1):I HECHTER. M. S. Revised chemicals monitoring guide for the National Pesticide Monitoring Program. 5(11:68-71 HECHTER. M. S.. see Sand. P. F. HNEIDER. N. J., see Davies. J. E. HULis. D. W., see Marston. R. B. HULTZ. K. R., see Lichtenstein. E. P. kulze, J. A., see Manigold. D. B. hutzmann. R. L., see Wiersma. G. B. \L, W. L.. Dawsey. L. H.. and Cavin. G. E. Monitoring for chlori- nated hydrocarbon pesticides in soil and root crops in the Eastern States in 1965. l(3):22-25 ARS. H. S.. and Meehan. W. R. Short-term effects of 2.4-D on aquatic organisms in the Nakwasina River Watershed, southeastern Alask.T. 5(21:213-217 3A. D. B.. and Corcoran, E. F. Surface slicks as concentrators of pesticides in the marine environment. 3(31:190-193