, BOSTON PUBUC LIBRARY I G0V6RNMENT OOCUMtNTS UtPARTMtMT D RRCFJVED FEB 1 6 2000 I The Pesticides Monitoring Journal is published quarterly under the auspices of the Federal Working Group on Pest Management (responsible to the Council on Environ- mental Quality) and its Monitoring Panel as a source of information on pesticide levels relative to humans and their environment. The Working Group is comprised of representatives of the U.S. Departments of Agri- culture; Commerce; Defense; the Interior; Health. Education, and Welfare; Slate; Transportation; and Labor; and the Environmental Protection Agency. The Monitoring Panel consists of representatives of the Agricultural Research Service. Animal and Plant Health Inspection 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. The Pesticides Monitoring Journal is published by the Technical Services Division, Office of Pesticide Programs. U.S. Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies represented on the Monitoring Panel which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and articles. However, pertinent data in summarized form, together with 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. Publication of scientific data, general information, trade names, and commercial sources in the Pesticides Monitoring Journal does not represent endorsement by any Federal agency. 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. For further information on Journal scope and manuscript prepara- tion, see Information for Contributors at the back of this issue. Editorial Advisory Board members are: John R. Wessel, Food and Diiig Administration, Chairtnan Robert L. Williamson. Animal and Plant Health btspection Service Anne R. Yobs, Center for Disease Control William F. Durham. Environmental Protection Agency Gerald E. Walsh, Environmental Protection Agency G. Bruce Wiersma, Environmental Protection Agency William H. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Herman R. Feltz, Geological Survey Address correspondence to; Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington. D.C. 20460 Editors Martha Finan Joanne Sanders CONTENTS Volume 10 June 1976 Number 1 Page EDITORIAL ^^ 1 BRIEF Residues of DDT and DDE in livers of waterfowl, northeastern Louisiana — 1970-71 2 Donald H. White RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Uptake of the mosquito larvicide temefos by the salt marsh snail. New Jersey — 1973-74 George Fitzpatrick and Donald J. Sutherland Mercury in eggs of aquatic birds. Lake St. Clair — 1973 Rey C. Stendell, Harry M. Ohlendorf, Erwin E. Klaas, and James B. Elder Nationwide residues of organochlorines in starlings, 1974 10 Donald H. White RESIDUES IN FOOD AND FEED Pesticide residues in total diet samples, Spain — 1971-72 18 J. M. Carrasco, P. Cunat, M. Martinez, and E. Primo GENERAL Organochlorine pesticides in the Hawaii Kai Marina, 1970-74 24 Russell Tanita, Jerry M. Johnson, Michael Chun, and John Maciolek APPENDIX Chemical names of compounds discussed in this issue 30 ERRATA 31 Information for contributors : revised 32 EDITORIAL Journal Enters Tenth Year; Expands Information for Contributors Scanning the first nine volumes of the Pesticides Moni- toring Journal, the researcher is struck by two tradi- tions: that the publication has honored its primary goal of disseminating findings of the National Pesticides Monitoring Program, and that those findings have been presented intelligibly. It is appropriate that this, the tenth volume of the Journal, should introduce a revised Information for Contributors (see back page of this issue). A periodical in its tenth year of publication should be able to draw on its own history in refining subject matter and editorial policy. In 1967 the scope of the Journal was described as "qualified data and interpretive information which con- tribute to the understanding and evaluation of pesticides and their residues in relation to man and his environ- ment." Since that first issue authors, reviewers, advisors, and editors have proved this to be a workable definition for a specialized technical journal with worldwide dis- tribution. As each contributor projected his/her inter- pretation of the scope in the varied studies published here, certain refinements emerged. These refinements are reflected in the definition of monitoring which appears in this issue: "repeated sampling and analysis of environ- mental components to obtain reliable estimates of levels of pesticide residues and related compounds in these components and the changes in these levels with time. I It can include the recording of residues at a given time { and place, or the comparison of residues in different i geographic areas." No less significant than the scope of a publication is the manner of its presentation. The most dramatic findings in the scientific world are valuable only so far as they are understood by the reader. Thus the revised Information for Contributors contains expanded instruc- tions for authors in the preparation of manuscripts. The Journal staff consulted numerous style manuals, tech- nical publications, and Federal and private-industry editors to achieve a consensus on controversial points. Style policies are listed in sometimes scrupulous detail, as befits a publication striving to present technical find- ings consistently and lucidly to an international audi- ence. Appropriate idiosyncrasies appear: recycled paper, for example, is acceptable in original manuscripts if it does not degrade the quality of reproduction. The manner of citing literature references has been simpli- fied to meet author demand: sources are numbered in alphabetical order rather than in order of their appear- ance in the text. Criteria established by the Journal staff and the Editorial Advisory Board and approved by the Monitoring Panel are the fruits of a decade of author/editor communica- tion. We are fortunate. Almost unanimously our authors have been cooperative. They are ripe for ideas which render their papers readable and credible, and eager to offer their own suggestions on scope and delivery of monitoring studies. Such cooperation among profes- sionals has served us well. Throughout the world the Pesticides Monitoring Journal is considered an authori- tative source of information on the monitoring of pesticide residues. Vol. 10, No. I.June 1976 BRIEF Residues of DDT and DDE in Livers of Waterfowl, Northeastern Louisiana — 1970-71 ' Donald H. White 2 ABSTRACT A study was conducted to determine the levels of DDT and DDE in the livers of 10 species of waterfowl collected in Louisiana from 1970 to 1971. Livers of 48 of 50 specimens contained detectable levels of DDT and/or DDE. DDT residues ranged from 0.01 to 10.90 ppm; DDE levels ranged from 0.02 to 38.69 ppm. Introduction Residues of DDT and its metabolites are commonly found in tissues and eggs of waterfowl species (9). DDE is by far the most persistent metabolite and occurs most frequently in nature: residues may range from barely detectable levels to hundreds of ppm in certain tissues (7). DDE has impaired reproductive success of mallards {Anas platyrhynchos) and black ducks {Anas rubripes) in experimental studies, resulting in thin shells, cracked eggs, and poor hatchability {3.5). Because organochlorines are highly fat-soluble, residues concentrate in adipose tissues. The extent of this con- centration depends upon the exposure and the physio- logical condition of the organism determined by bio- logical demands such as migration, feeding activity, and reproduction (9). When analyzed for organochlorines, adipose tissues or whole bodies of organisms give some indication of their past history of pesticide exposure. Studies of Japanese quail (Coturni.x coturni.x japonica) showed that DDE reached peak levels in the liver about 3 weeks after initial exposure and then rapidly de- clined (6). In another study, a known concentration of radiolabeled DDT was applied to a fenced 4-acre marsh (2). Wild mallards and lesser scaup {Aythya affinis) were released intermittently into the area. Ducks were collected and their tissues were analyzed for DDT and,/ ' Dcparlmcnl of Biolopy, Northeast Loui«ii.^n.^ University. Monroe, I. a. = Present Address: Fisli and Wildlife Service. U.S. ncpartmcnt of Interior. Patuxent Wildlife Kescarch Center. Laurel. Md. 20811. Re- prints available from litis address. or its metabolites. Residues in duck livers generally peaked about 2 weeks after application and then de- clined. Thus the avian liver does not appear to be a major accumulator of organochlorine residues. How- ever, high residues in the liver may reflect recent in- gestion of contaminated food items when the animal is not exposed to a continuous level of toxicant. Collection and Analytical Procedures Waterfowl were shot at several locations within Ouachi- ta Parish in northeastern Louisiana during the fall and winter of 1970-71. The ducks were frozen soon after collection and maintained in a freezer until analysis. Five livers from each of 10 species of duck were analyzed for residues of DDT and DDE. DDT and DDE were extracted from the livers follow- ing essentially the methods of Boyle et al. (/). Each duck was thawed and the liver was dissected from the body and weighed. The liver was homogenized in a Waring blendor with 5 g NaoSO, and 175 ml hexane. The supernatant was decanted, the process was repeated, and the combined supernatanis were filtered to remove large particles of liver tissue. The hexane solution was evaported to near dryness on a steam bath, diluted to 25 ml with hexane, and transferred to a 125-mI separa- tory funnel. Four 25-ml volumes of acetonitrile were added to the separatory funnel and each volume was drained off as it layered on the bottom of the hexane solution. The acetonitrile fractions were combined, evaporated to dryness on a steam bath, and diluted to 10 nil with hexane. The sample was placed on a column of previously standardized florisil and eluted with 500 ml of a 9:1 hexane : petroleum ether solution. After florisil cleanup the cliiate was evaporated to dryness on a steam bath and diluted to 2 ml with hexane. This final extract was analyzed for DDT and DDE residues. Pesticides Monitoring Journal Determinations were made by injecting 1 fA of the sample solutions into a Hewlett-Packard model 402 gas chromatograph with an electron-capture detector. The column was glass, 4 ft by 4 mm, packed with 4 percent SE-30 80/100 mesh chromosorb W-AWDMCS. Temperatures for column, injector, and detector were 180°, 225°, and 255°C, respectively. Carrier gas was 5 percent methane in argon at 80 ml/min. DDT and DDE in the samples were tentatively identi- fied by comparing retention times with those of stand- dard solutions. All residues then were confirmed by thin-layer chromatography (TLC) according to the method of Morley and Chiba (4). Some PCB inter- ference may be reflected in the DDT results, although TLC did not indicate any. All residues are expressed as ppm wet weight. Limits of sensitivity were 0.01 ppm for both DDT and DDE. Recovery percentages from spiked samples averaged 94 percent for DDT and 90 percent for DDE. Analytical results were not corrected for recovery. Results and Discussion Table 1 shows the means, standard errors, and ranges of DDE and DDT residues in livers of ducks collected in Louisiana during the fall and winter months of 1970- 71. Forty-eight of the 50 livers analyzed had detectable levels of DDE. DDT, or both. There was wide variation in concentrations of the two compounds among species and individuals. Detectable residues of DDE in livers ranged from 0.02 to 38.69 ppm: DDT levels ranged from 0.01 to 10.90 ppm. Four samples contained trace residues of dieldrin. Livers from northern shovelers (Anas clypeata). blue- winged teal (Anas discors) , and green-winged teal (Anas crecca caroUnensis) contained the highest mean residues of DDE and/or DDT. These species commonly feed in very shallow water and are often found to- gether (8). Although the ducks were collected in north- eastern Louisiana, findings should not be interpreted on a local basis since waterfowl are highly mobile species and may cover a wide range of habitats. The data do suggest however, that some of the ducks may have eaten highly contaminated food items. LITERATURE CITED (/) Boyle, H. W.. R. H. Burtschell, and A. A. Rosen. 1966. Infrared identification of chlorinated insecticides of poisoned fish. Org. Pestic. Environ. 60:207-218. (2) Dindal, D. L. 1970. Accumulation and excretion of Ci^s DDT in mallard and lesser scaup ducks. J. Wildl. Manage. 34(2):74-92. (i) Heath. R. G.. J. W. Spann. and J. F. Kreilzer. 1969. Marked DDE impairment of mallard reproduction in controlled studies. Nature 224(5214) :47-48. (4) Morley, H. V., and M. Chiba. 1964. Thin-layer chro- matography for chlorinated pesticide residue analysis without cleanup. J. Ass. Offic. Anal. Chem. 47(2): 307-309. (5) Longcore, J. R., F. B. Samson, and T. W. Whittendale. 1971. DDE thins eggshells and lowers reproductive success of captive black ducks. Bull. Environ. Contam. Toxicol. 6(6):485-490. (6) Liidke. J. L. 1974. Interaction of dieldrin and DDE residues in Japanese quail (Coturnix coturnix japonicaj. Bull. Environ. Contam. Toxicol. 1 1 (4) :297-302. (7) Siickel, L. F. 1968. Organochlorine Pesticides in the Environment. Spec. Sci. Rep. — Wildl. No. 119. Wash- ington, D.C. 32 pp. (S) While. D. H. 1975. Environments of Fresh Water Feeding Sites of Waterfowl in Autumn on the Welder Wildlife Refuge in Southern Texas. Ph.D. thesis, Univ. Ark.. Fayetteville, Ark. 62 pp. (9) White. D. H., and L. F. Slickel. 1975. Impacts of chemicals on waterfowl reproduction and survival. Trans. First Int. Waterfowl Symp., St. Louis. Pp. 132-142. TABLE 1. Residues of DDE and DDT in livers of waterfowl, northeastern Louisiana — 1970-71 Residues, ppm Wet Weight ' DDE DDT SPEcms X ± S.E. Mallard (Anas plaiyrhynchos) 0.76 ± 0.20 Pintail (Anas aciila) 0.47 ± 0.14 Gadwall (Anas slrepera) 0.56 ± 0.09 American Wigeon (Anas americana) 0.36 ± 0.21 Northern Shoveler (Anas clypeata) 8.63 ± 4.14 Blue-Winged Teal (Anas discors) 12.47 ± 6.50 American Green-Winged Teal (Anas crecca caroUnensis) 1.32 ± 0.30 Wood Duck (Aix sponsa) 0.16 ± 0.03 Ring-Necked Duck (Aythya collaris) 1.26 ± 0.82 Lesser Scaup (Aythya affinis) 0.17 ± 0.03 Range 0.33 - 1.37 0.13 - 1.06 ND- 0.56 ND- 1.21 0.35- 26.67 1.68- 38.69 0.55- 2.55 0.02- 0.22 0.06- 4.94 0.09- 0.31 X±SE. 0.59 ±0.52 1.28+0.46 0.32 ±0.29 0.39 ±0.35 0.03 ± 0.03 0.16 ±0.11 4.54 ± 2.03 2.26 ± 0.86 0.92 ± 0.65 0.03 ± 0.02 Range TR- 2.95 TR- 2.40 ND- 1.64 ND- 1.95 TR- 0.19 TR- 0.65 TR - 10.90 TR- 4.41 TR- 3.80 ND- O.IO NOTE: ND = not detected. TR = trace residues detected below limit of quantification, 0.01 ppm. S.E. = standard error. * Results represent residues in livers of five birds of each species. Vol. 10, No. 1, June 1976 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Uptake of the Mosquito Larvicide Temefos by the Salt Marsh Snail, New Jersey— 1973-74 '•' George Fitzpatrick ' and Donald J. Sutherland * ABSTRACT Uptake of the mosquito larvicide temefos (Abate) by the salt march snail (Melampus bidentatus Say) in New Jersey was measured by gas-chromaloi^raphic analysis. Measurable quantities of temefos were found in the snails within I day after the first treatment with a 2 percent granular formula- tion but 3 weeks elapsed before uptake occurred following treatment with a temefos emulsion. Residues in the snails exposed to the granular formulation were generally more than 10 times higher than those in snails exposed to the emulsion although application rates of the granular formu- lation were only about three times higher than those of the emulsion. Residues in snails exposed to the emulsion fell below de- tectable levels less than 3 weeks after cessation of treatments although measurable amounts were found in snails exposed to the granular formulation for more than 5 weeks after the last treatment. The persistence of temefos in M. bidentatus suggests the potential for its movement through food webs exposed to the granular formulation. Introduction Since the decline in use of persistent insecticides, the role of relatively nonpersistent organophosphorous com- pounds in mosquito control programs has been increas- ing {10). At present, the organophosphorous insecticide temefos, also known as Abate, is the larvicide most frequently used in New Jersey for salt marsh mosquito control {12). The salt marsh snail {Melampus hidentatus [Basomma- tophora: MelampidacI), which is generally less than 10 mm long, occurs in large numbers in the high littoral zone, areas of salt marshes flooded infrequently by high tides {1,9). Coincidcntally, the high littoral zone is the ' Paper of the Journal Series, New Jersey Agricultural Experiment Station, Rutgers. The State University of New Jersey, New Brunswick, N.J. ' Presented in part to the Entomoloftical Society of America, Eastern Branch, Philadelphia. Pa., October 13. 1975 ' Department of Entomology. Drawer F,M, Mississippi State University, Mississippi Slate. Miss, 397f>2, Reprints availahic from this address. * Department of Entomolog)' and F.conomic Zoology. Rutgers, The State University of New Jersey, New Brunswick, N.J. habitat most suitable for salt marsh mosquito breeding {8). Therefore, insecticides for control of salt marsh' mosquito larvae are frequently applied to marshes har- boring large populations of AY. bidentatus, an important food source for a number of animals {3,7). Measurable residues of DDT have been detected in M. bidentatus from treated marshes (3,5). The objectives of the present study were to determine the magnitude and rate of temefos uptake by M. bidentatus in salt marshes subjected to multiple treat- ments, and the persistence of temefos residues in snails after cessation of treatments. Materials and Methods Treatments with a 2 percent granular formulation at 0.112 kg actual insecticide/ha. (O.IO lb/acre) included four applications to a Spartina alternifiora salt marsh plot at approximately 2-weck intervals in 1973 and 10 applications to an 5. patens salt marsh plot at approxi- mately 2-week intervals in 1973. In 1974 an S. patens salt marsh plot was treated approximately every other week for 8 weeks, then once again in approximately 6 weeks. All granular formulations were applied to a salt marsh plot near Tuckerton, N.J. Treatments with a temefos emulsion at 0.037 kg actual insecticide/ha. (0.032 lb/acre) consisted of four applications at ap- proximately 2-week intervals to an S. patens salt marsh plot near Manahawkin, N.J., in 1974. All applications were made by a Bell 47G4 helicopter, flying at 96.5 km/h (60 mph) at an altitude of 3.0-6.1 m (10-20 ft). The working swath width was 10.7 m (35 ft) for the granular formulations and 15.2 m (50 ft) for the emul- sion. The treated areas have been described previously {4). Samples of M. bidentatus were collected from the treat- ed plots, placed on ice, and frozen within 2,5 hours after collection. Each sample was a composite of at least 15 snails; differences in weights of various samples ^ reflect differences in snail sizes and availability of snails. Pesticides Monitoring Journal Before extraction, the snails were washed to remove grass, mud, or granular particles, then blotted dry on paper towels. Temefos was extracted three times in methylene chloride from whole-snail homogenate which included the shell. Extracts were washed twice in distilled water and cleaned with hexane and acetonitrile. Final preparations were dissolved in acetone for injection into the gas chromatograph. Further details of the extraction and cleanup have been published elsewhere (4). Recovery was 97 percent. The gas chromatograph used was a Micro-Tek model 220 with a flame photometric detector utilizing the phosphorous mode. The glass column was 6 mm (0.25 in.) OD, 4 mm ID, and 40.6 cm (16.0 in.) long. It was packed with 2 percent OV-101 on 80-100 mesh Gas-Chrom Q. Off-column injections were made utiliz- ing a glass insert containing silanized glass wool ap- proximately 1.3 cm (0.5 in.) from the pwint of release of the sample from the injection needle. Inlet tempera- ture was 270°C, column temperature was 230°C, and detector temperature was 220 °C. The carrier gas was prepurified nitrogen and the flow rate was 100 ml/min. Residues in the snails including shells are expressed in ppm wet weight. Average water content was 29 percent of the total wet weight including shells. Results and Discussion M. bidentatus samples from untreated salt marsh plots and snail samples taken in the test plots before the first treatment were free of temefos. The limits of detecta- bility varied with the weight of the sample and day-to- day fluctuations in the sensitivity of the gas chromato- graph; for samples weighing between 1 and 2 g, the sensitivity was about 0.01 ppm. Measurable uptake of temefos was observed in samples of M. bidentatus from the plots treated with either the emulsion or granular formulations. In 1974 snails from the S. patens plot treated with the granular formulations contained 0.09 ppm temefos residue 1 day after the first treatment (Table 1). In 1973 samples were taken 9 days after the first treatment; the residue was 0.44 ppm in the 5. patens plot (Table 2), and 1.10 ppm in TABLE 1. Temefos residues in Melampus bidentatus sampled from a Spartina patens sail marsh plot treated five times with a 2 percent granular formulation, Tuckerton, N.J.—1974 TABLE 2. Temefos residues in Melampus bidentatus sampled from a Spartina patens salt marsh plot treated JO times with a 2 percent granular formulation, Tuckerton, N.J.—1973 Treatment Sampling Sample Weight, Temefos residue, Date Date 0 PPM WET WEIGHT July 9 July 10 2.8 0.09 July 23 July 26 2.7 0.82 Aug. 6 Aug. 8 2.7 0.50 Aug, 20 Aug. 21 2.8 0.46 Oct. 3 3.1 0.19 Oct. 7 Oct. 29 2.5 0.16 Nov. 19 1.3 0.38 Treatment Sampling Sample Weight, Temefos residue, Date Date G PPM wet weight Apr. 23 1.4 <0.06 Apr. 25 May 2 2.3 0.44 May 7 0.8 0.54 May 10 May 11 1.3 0.63 May 21 1.5 0.83 May 23 May 27 0.9 6.67 June 4 1.2 0.78 June 6 June 7 1.9 0.06 June 18 July 3 1.3 0.80 July 5 July 6 1.5 2.14 July 17 2.1 0.77 July 18 July 19 1.1 0.69 Aug. 3 2.1 1.05 Aug. 4 Aug. 15 0.7 0.64 Aug. 17 Aug. 20 0.5 8.75 Aug. 30 2.3 1.04 Sept. 4 Sept. 5 1.6 1.35 TABLE 3. Temefos residues in Melampus bidentatus samples from a Spartina alterniflora salt marsh plot treated five times with a 2 percent granular formulation, Tuckerton, N.J. —1973 Treatment Sampling Sa MPLE Weight, Temefos residue, Date Date G PPM wet weight Apr. 25 May 2 0.7 1.101 May 7 0.2 1.336 May 10 May 11 0.4 0.386 May 23 June 6 June 15 1.1 0.443 TABLE 4. Temefos residues in Melampus bidentatus sampled from a Spartina patens salt marsh plot treated four times with an emulsion, Manahawkin, N.J. — 1974 Treatment Sampling Sample Weight. Temefos residue, Date Date G PPM wet weight July 2 July 3 4.6 <0.01 July 11 4.7 <0.01 July 16 July 17 1.9 <0.02 July 22 2.5 0.038 July 31 Aug. 1 4.1 0.013 Aug. 14 Aug. 15 2.7 0.031 Aug. 27 2.6 0.059 Sept. 5 6.5 <0.01 Sept. 13 2.7 <0.03 the S. alterniflora plot (Table 3). In contrast, uptake of temefos did not occur in M. bidentatus from the S. patens plot treated with the emulsion in 1974 until 6 days after the second treatment and 20 days after the first. At that time a residue of 0.038 ppm was detected (Table 4). In the first 17 days of this 20-day period, the three samples taken contained no measurable resi- dues of temefos. In general, levels of temefos were much lower in snails exposed to the emulsion than in those exposed to the granular formulation. The highest residue in snails from the emulsion-treated plot was 0.059 ppm after four treat- ments; the highest residue found in snails exposed to the granular formulation was 8.75 ppm after nine treat- ments. Moreover, there were eight samples from granu- VoL. 10, No. 1, June 1976 lar-treatcd plots that had residues greater than I.O ppm, illustrating the general trend of higher residues in snails treated with this formulation. The differences in uptake can he attributed to a number of factors. Chemical monitoring of the emulsion-treated plot revealed that the first treatment was applied at a very low actual rate: 26 percent of that expected (W. F. Carey, 1975. Analytical Chemist, Department of Entomology and Economic Zoology, Rutgers, The State University of New Jersey. New Brunswick. N.J.: per- sonal communication). This could have been at least partly responsible for the absence of measurable uptake until after the second treatment. The actual amount of active ingredient applied per unit area with emulsion was approximately one third (37 g/ha. ) the amount applied with the 2 percent granular formulation (112 g/ha.1. Another factor to consider is the chance of a snail's ingesting a granule. If this occurred in only one snail in a sample, the influence on the total residue could be considerable. Highest residues occurred in snails col- lected during the 1973 tests when there were 10 granu- lar treatments. Because there were fewer treatments in the 1974 tests, there was less tcmefos available for absorption by the snails. There was generally a great deal of variability in resi- due levels in all time periods, especially in the 1973 tests which involved more samples. This may be attri- buted to an uneven deposition of the insecticide on the marsh. Granular formulations applied aerially often do not cover the target area uniformly (//). If the temefos applications did generate sporadic aggregations of granules, randomly selected samples of snails could have varied considerably in temefos residue levels. Table 4 shows that temefos residues in snails exposed to four emulsifiable concentrate formulation treatments rose gradually as the number of treatments increased and then decreased to levels below the limits of detec- tion after the last treatment. During this same treatment schedule the population density of M. hidentatus in the treated plot declined steadily as the number of treat- ments increased. After the last treatment snail density increased to pretreatment levels (4). There were no significant changes in population density in the untreated plots or in the plots treated with other insecticides. This material is to be presented elsewhere (6). Data indi- cate that the temefos residues in snails may be related to a significant but reversible decline in population density. Laboratory toxicity data suggest that these levels of temefos are not acutely toxic to M. hidentatus (4). It can be surmised, therefore, that treatments of temefos emulsion resulting in residues in M. hidentatus to levels approaching 0.0.59 ppm are likely to affect popul.itions through an interaction involving some other component of the salt marsh community. I he mechanism of the overall population decline is unknown. Residues of temefos in M. hidentatus exposed to the granular formulation persisted for more than *> weeks after the last of a series of treatments. This raises some serious questions concerning the longevity of this formu- lation in the environment. Recovery of temefos residues from Spartina roots and salt marsh mud more than 4 months after the last of a series of granular treatments has been reported (2). If toxicant release were to be protracted over a long period, the effects could be similar in some ways to those of a persistent insecticide, with potential for passage through food webs. However, temefos residues in samples taken from the plot treated with the emulsion were undetectable less than 3 weeks after the last treatment (Table 4). pLirthcr research is necessary to determine the extent of temefos movement through food webs which might be exposed to multiple treatments of the granular formu- lation. A cknowled^ments This work was carried out in the laboratory of Professor William F. Carey. Rosa ladevaia provided valuable technical assistance. LITERATURE CITED (/) Aplcy, M. L. 1970. Field studies on life history, gona- dal cycle, and reproductive periodicity in Melampus bidciuuliis (Pulmonata: Ellobiidae). Malacologia 10 (2):381-397. (21 Carey, W. F. 1974. Initial studies of Abate® in a salt-marsh ecosystem — chemical studies. Proc. 61st ■Ann. Meet. N. J. Mosq. Exterm. Assoc. 61:129-137. (.?) Fenii;no. F., L. G. MacNamara, and D. M. Jobbins. 1969. Ecological approach for improved management of coastal meadowlands. Proc. 56th Ann. Meet. N. J. Mosq. Exterm. Assoc. 56:188-203. (4) Filzpalrick, G. 197.5. Impact of Temefos and Other Mosquito I.arvicides on the Salt Marsh Snail Melampus hidentatus Say ( Ba^ommatophora: Ellobiidae). Ph. D. thesis. Rutgers, The State University of New Jersey. 120 pp. (5) Foeluenbadi. J. 1972. Chlorinated pesticides in estu- arine organisms. J. Water Poll. Cont. Fed. 44(4): 619-624. (6) Fitzpatrick, G., ami D. ]. Sutherland. Impact of the mosquito larvicides temefos and chlorpyrifos on popu- lations of the salt marsh snail Melampus hidentatus Say. In preparation. (7) Hausinann. S. A. /9.?2. A contribution to the ecology of the salt marsh snail (Melampus hidentatus). Am. Nat. 66(707): 54 1-545. ( 4 0,430 0 44 0,40-0.45 Common tern - 1 ^ 1,090 1.09 0.87-1.31 2 2 0,730 0,73 0.69-0.77 ' Samples collected from Stony Island, ' Samples collected from St, Clair flats live positions in the food chain (2,5.16.17) . indicating that mercury is being concentrated at higher trophic levels and that birds feeding at the higher trophic levels ingest greater amounts of mercury. Mallards' diet con- sists of about 90 percent plant material (10). black- crowned night herons feed extensively on fish and aquatic arthropods U3), and common terns feed al- most exclusively on small fish (/). The concentration of contaminents in the eggs of these four species is below 6 ppm, a level shown to impair reproduction in captive mallards (S). However, ring- necked pheasants (Phasiamis colchicus) with low dietary levels of mercury laid eggs containing 0..'5-1.5 ppm mercury and had significantly lower hatchability than had control specimens (4). Eggs from night herons and terns collected from the Lake .St. Clair area in 1973 contained mercury levels within this range. The coefficients of variation show that differences in residue levels occur between clutches rather than within clutches (Table 2). Mercury levels in eggs from the TABLE 2. Summary of mercury residues in f,?,e.T of four species of birds, Lake St. Clair, Michigan — 1973 Species Black-crowned Great Common Mallard NIGHT heron egret TERN No. eggs analyzed 41 27 7 7 No, clutches represented 6 7 2 5 Arithmetic mean mercury residue. ppm wet weight 0,05 0.45 035 1,15 Range, ppm wet weight <0,05-0,14 0,20-0, 76 0.21-0.45 069-2,16 Coefficient of variation: Among clutches 32.4 28.3 33.8 40,4 Within clutches 15.5 19.3 8.9 19.4 NOTE: Analyses based on complete clutches same clutch were quite similar. Differences between clutches are significant and prob.ihly reflect differences in the extent of exposure to mercury by individual females. Mercury contamination varied only slightly within cltitchcs of field-collected eggs of herring gulls (Lanis ari:enialiis) and California gulls (Lams cali- lornicu\) (16); the same was true of eggs of black ducks (Amis ruhripcs) when the adults had been fed low levels of methylmercury (6). Mercury levels apparently declined in eggs of two of the three species between 1970 (3) and 1973 (Table 3). The decline was most dramatic in the mallard (P <0.01) whose level of contamination in 1973 was only about 10 percent of that in 1970. A significant TABLE 3. Comparison of 1970 and 1973 mercury contamination of aquatic bird egcs from the Lake St. Clair area Mercury Residues, ppm wet weight 1970 1973 Species No. clutches Arithmetic .MEXN Median No. Range clutches Arithmetic MEAN Median Range Mallard > Nighi heron ' Common lern ' 7 5 5 0.99 0.77 2.73 0.74 0.74 1.5 0.23-2.7 14 0.46-1.1 7 0.63-6.25 5 0.07 0.44 1.30 0.06 0.40 I.3I <0.05-0.14 0.190.67 0.77-2.16 NOTE: Sec Literature Cited, reference 1, for 1970 study. Annly^cs bnscd on one cjip r.mdomly selected from cnch clutch. For 197.1 mallards. 7 whole clutches and lionyl clutches were collected. ' Samples collected from St. Clair flats, ■■'Samples collected from Stony Island, cpRs from each of 7 addl Pesticides Monitoring Joitrnal decline also occurred in eggs of the black-crowned night heron IP <0.()5) although mercury levels in common terns showed only a slight reduction (P >0.05). It is noteworthy that the greatest decline in mercury con- tamination occurred in eggs of the mallard, the species that feeds most extensively on lower trophic level or- ganisms. Available mercury may be retained longer in the higher levels of the food chain. Mercury poisoning of Swedish wildlife, particularly seed-eating birds and certain avian predators, was at- tributed to the use of mercurial seed dressings. The use of these dressings was restricted in 1966 and within 2-.'' years significant declines occurred in mercury contami- nation of certain .Swedish birds (11.12). In 1970, discharges from chlor-alkali plants were recog- nized as one of the major industrial sources of mercury pollution in the United States (IS). Resulting legal actions forced many manufacturers to reduce their mercury discharge. Mercury introduced into water systems by industrial effluents is primarily incorported into bottom sediments, and mercury may be exchanged between these sedi- ments and the overlying water for a period of 10-100 years (9). However, mercury-contaminated sediments may be naturally separated from the overlying water when they are covered with clean silt deposits following curtailment of the discharge. At Lake St. Clair this may have contributed to the rapid decline of mercury resi- dues in eggs of aquatic birds. The St. Clair River flows rapidly and is laden with sediments at its confluence with Lake St. Clair. A cknnwled^ment Authors wish to acknowledge William F. Shake, William Fuchs, and Michael F. StoU for their assistance in collecting the eggs. Robert G. Heath provided statistical advice. LITERATURE CITED (/) Bcni. A. C. 1921. Life Histories of North American Gulls and Terns. U.S. Natl. Mils. Bull. No. 113. 345 pp. (2) Berp, W., A. Johncls. B. Sjoslrand. and T. Weslermark. 1966. Mercury content in feathers of Swedish birds from the past 100 years. Oikos 17(l):71-83. (3) Dii.<:tnwri, E. H., L. F. Slickel. and J. B. Elder. 1972. Mercury in wild animals, Lake St. Clair, 1970. Pp. 46-52 in Hartiing and Dinman, eds. Environmental Mercury Contamination. Ann Arbor Science Publish- ers, Ann Arbor, Mich. (4\ Fimreite, N. 1971. Effects of dietary methylmercury on ring-necked pheasants. Can. Wildl. Serv. Occasional Paper No. 9. 37 pp. (5) Fimreile, N. 1974. Mercury contamination of aquatic birds in northwestern Ontario. J. Wildl. Manage. 38 ( 1):120-I31. (6) Finlcy, M. T.. and R. C. SlcndcU. 1975. Unpublished results. Fish and Wildlife Service, U.S. Department of Interior, Patu\ent Wildlife Research Center, Laurel, Md. (7) Halch. W. R., and W. L. Ott. 1968. Determination of sub-microgram quantities of mercury by atomic ab- ■^orption spectrophotometry. Anal. Chem. 40(14): 2085-2087. (H) Heinz. G. 1974. Effects of low dietary levels of methyl mercury on mallard reproduction. Bull. Environ. Con- tam. Toxicol. 1 1(4 ) :386-392. (9) Jcrnclov. A. 1969. Conversion of mercury compounds. In Miller and Berg, eds. Chemical Fallout. Charles C. Thomas, Springfield, 111. 531 pp, (10) Kortrighi, F. H. 19.^3. The Ducks, Geese and Swans of North America. Wildlife Management Institute, Washington, D.C. 476 pp. (//) l.jnnfffiien, L. 1971. Mercury in the liver of the wood pigeons Coliimha p. pahimhiis in 1964 and 1967. Ornis Scand. 2(1 ): 13-15. (12) Mahnhcrg, T. 1973. Pesticides and the rook Corvus fruf;ilef;ns in Scania, Sweden between 1955 and 1970. Oikos 24(3) :377-387. (13) Palmer. R. S. 1962. Handbook of North American Birds, Vol. 1. Yale University Press, New Haven. Conn. 557 pp. ( 14) Parker, C. E. 1970. Mercury — major new environmen- tal problem. The Conservationist 25(T):6-9. (15) Tiirney, W. G. 1972. The mercury pollution problem in Michigan. Pp. 29-31 in Hartung and Dinman. eds. Environmental Mercury Contamination. Ann Arbor Science Publishers, Ann Arbor, Mich. {16) Vermeer, K. 1971. Survey of mercury residues in aquatic bird eggs in the Canadian prairie provinces. Trans. N. Am.' Wildl. Nat. Resour. Conf. 36:138-152. {17) Vermeer. A'., F. A. J. Arm.-^trona. and D. R. M. Halch. 1973. Mercury in aquatic birds at Clay Lake, Western Ontario. J. Wildl. Manage. 37(1):58-61. (18) Wallace, R. A.. W. Fulkerson. W. D. Sliiillx. and W . S. Lvon. 1971. Mercury in the environment, the human element. ORNL-NSF-EP-1. Nat. Tech. Inf. Serv., Springfield. Va. (79) Wilcoxen, F., and R. A. Wilco.w 1964. Some Rapid Approximate Statistical Procedures. Lederle Labora- tories, New York. 60 pp. Vol. 10, No. 1, June 1976 Nationwide Residues of Organochlorines in Starlings, 1974 ' Donald H. White ABSTRACT Organoclilorine residues in slarlini;s (Sturnus vulgaris) from 126 collection sites were monitored during the jail of 1974. DDE. DDT. polychlorinaled hiphcnyls (PCB'.s). and ben- zene hexachloride were present in all samples. Dicldrin. heptachlor expoxidc, hexachlorohenzcne, and oxychlordane were present in approximately 97 percent of the samples. DDE, dicldrin. and PCB residues in starlings were signifi- cantly lower than they had been in 1972. Introduction The Fish and Wildlife Service, U.S. Department of Interior, began nationwide monitoring of organochlorine residues in starlings (Sturnus vulgaris) in 1967-68 as part of the National Pesticides Monitoring Program. Residue data from these original collections were to serve as baseline readings from which future trends in residue levels might be detected. Monitoring was sched- uled for 2-year intervals thereafter. Starlings were se- lected because their range is the continental United States, they are considered expendable, and their omni- vorous feeding habits should reflect residues from a wide range of food sources (3). This paper presents the results of the analyses of the 1974 starling collection including residue levels from each collection site: a com- parison of nationwide averages of DDl:, dicldrin, and polychlorinatcd biphcnyls (PCB's) in the four collection periods since 1967-68; and the distribution of 1974 residues by frequency of occurrence at collection sites. Collection Method.s Harlier papers (3-5) discuss collection proccdiues in detail. The sample area lies within the contiguous 48 States and consists of 40 blocks of 5° latitude and longitude. During the initial study, 1.^9 collection sites were randomly selected uilhin these blocks; these sites were to be used for each biannual collection. In 1974, samples were obtained from 126 of these sites. Table 1 TABLE 1. Starling collection sites listed by State and countw 1974 State Alab.Tma Arizona Arkansas California Connecticut Florida Georgia la.ilio Illinois Indiana lo«a Kansas County ' Fish and Wildlife Service, U.S. Department of Interior, Patiixent Wildlife Research Center, Laurel, Md. 20811. Marion Talladega Navajo Yavapai Maricopa Graham Yell/ Pope Lonoke/ Pulaski Colusa Shasta Modoc Ventura Stanislaus Monterey Inyo Kern Imperial Weld Montrose Crowley New London Bay Madison Polk Hardee Pike Wayne Nez Perce Owyhee Franklin Minidoka Stephenson Adams Kane Hendricks Fremont Jasper Marshall Phillips Kearny Nemaiia Marion 3-H-l 4-H-3 3-C-3 3-C-4 4C-1 4-C-2 3-G-2 3-G-3 2-A-l 2-A-2 2-A-3 3-A-l 3-A-2 3-A-3 3-B-l 3-B-4 4-B-l 2-D-4 3-D-l 3 D2 2-K-2 4-H-l 4 1-3 5 11 5-1-2 4-H-4 4 1-2 1-B-l 2-B-l 2C-3 2-C-4 2-G-l 2-G-3 2H-2 2-H-3 2-F-3 2-G-2 2-G-4 2-E-2 3-E-l 2-F-4 3-F-2 (Continued next page) Pesticides Monitoring Journal TABLE 1 (contd.). Starling collection sites listed by State and county, 1974 State County Sitt; State County Site Kentucky Ohio 3-H-2 Ohio Pickaway 2-M Hopkins 3-H-4 Wood Noble 2-1-2 2-1-3 Louisiana Jefferson 4-G-3 Rapides 4-G-4 Oklahoma Greer Canadian 3-E-4 3-F-l Maine Penobscot l-K-2 Nowata 3-F-3 Michigan Chippewa 1-H-l Okmulgee 3-F-4 Grand Traverse l-H-2 Oregon Yamhill l-A-3 Kent 2-H-l Lane l-A-4 Ingham 2-H-4 Klamath Baker 2-A-4 :-B-4 Minnesota Swift l-F-2 Harney 2-B-2 Mississippi Leake 4-G-l Pennsylvania Somerset 2-J-2 Harrison 4-G-2 Luzerne 2-J-3 Jackson 4-H-2 South Carolina Aiken 4-1-1 Missouri Butler 3-G-l BoMinger 3-G-4 South Dakota Potter Butte 1-E-l l-E-2 Montana Meagher 1-C-l Hughes l-E-4 Missoula l-C-4 Brown I-F-3 Richland 1-D-l Yellowstone l-D-4 Tennessee Davidson 3-H3 Nebraska Keith 2-E-3 Texas Kinney 4-E-3 Brown 2-E-4 Cochran 4-E-4 Lancaster 2-F-l Comal 4-F-l Clay 2-F-2 Clay San Patricio 4-F-3 5-F-l Nevada While Pine 2B-3 Humboldt 2-B-4 Utah Weber 2-C-I Nye 3-B-2 Duchesne 2-C-2 Clark 3-B-3 Sevier/Millard 3-C-l New Mexico Bernalillo Torrance 3-D-3 3-D-4 Vermont Addison 1-K-l Luna 4-D-l Virginia Amherst 3-1-4 Otero 4-D-2 Prince George 3-J-2 Chaves 4-D-3 Caroline 3-J-3 Quay 3-E-2 Washington Pierce 1-A-l New York Jefferson 2-J-4 Yakima l-A-2 Rensselaer 2-K-l Spokane Whitman l-B-2 l-B-3 North Carolina Wilkes 3-M Union 3-1-2 Wisconsin Trempealeau l-G-3 Macon 3-1-3 Clark l-G-2 Pender 3-J-l Wyoming Big Horn l-D-2 North Dakota McLean I-E-3 Crook l-D-3 Grand Forks 1-F-l Goshen 2-D-l Ransom l-F-4 Wn-h-ikie 7 n-2 lists the collection sites for 1974 by State and county; Figure 1 shows their actual locations within sampling blocks. Normally a starling sample consists of a pool of 10 birds taken by trapping or shooting, although a few samples may be smaller. Each pool is wrapped in aluminum foil, placed in a polyethylene bag, frozen as soon as possible, and shipped to WARF Institute, Madison, Wis., for analysis. Analytical Procedures Prior to analysis the feet, beaks, wing tips, and skins were removed from birds in each composite sample and the sample was weighed and ground in a food grinder. A 20-g portion of the homogenate was ground with 100 g NaoSO, and dried at room temperature for 72 hours. The dried sample was placed in a 43-by-123-mm Whatman extraction thimble and extracted for 8 hours on a Soxhiet extractor using 150 ml ethyl ether and 150 ml petroleum ether. The solvent extract was evaporated to 10-15 ml on a steam bath and diluted to 50 ml with petroleum ether. A 15-ml aliquot of the sample was placed on previously standardized florisil and eluted with 150 ml of 3 percent ethyl ether in petroleum ether, followed by 240 ml of 15 percent ethyl ether in petroleum ether. After florisil cleanup the resulting solutions were evaporated on a steam bath to 10-15 ml and diluted to 25 ml with petroleum ether. The Armour-Burke method (/) was used for PCB separation on those samples with high concentrations of PDT and/or its metabolites. This method is to be used on all samples in future starling monitoring efforts be- cause of speculation that PCB interference may have influenced past results. Determinations were made by injecting 10 ii\ or less of the sample solutions into a Barber-Coleman Pesticide Vol. 10, No. 1, June 1976 11 FIGURE 1. Starling collection sites, 1974 Analyzer model 5360. Instrument conditions for DDE. TDE, DDT. dieldrin. and PCBs were: Coliiriin: 1219-mm-ln-4-nim i;l.''-'> packed with 5 percent IX:-:00 on KO/ lOO Gas-Chrom Q Tcmpcraliircs: Colnmn MO C Injector 217 C Detector 238°C Carrier gas: Nitrogen at SO ml/min Insiriitnient conditions for HC B, BHC. hcptachlor epox- ide, and oxychlordanc were: C'oliinin 12l9-mni-hy-4-inm glass packed uilli 11 percent niixedptiase OVI" QF-l on SO/ tIKl Cia^C'luom Q Temperatures Column :00°C Inieclor 225 C IJcleclor 200 C Carrier (tas Njirojien at SO ml/min Residues in 10 percent of the samples were confirmed by mass spectrometry. All residues are expressed as ppni uet weight. They may be converted to dry or lipid weight by dividing a gi\cn wct-wcight value by 0.29 or 0.05. the mean pro- portions, respectively, of dry and lipid material in the samples. Limits of sensitivity were 0.005 ppm for or- ganochlorine pesticides and 0.01 ppm for PCB's. Re- coveries ranged from 54 to 120 percent. Analytical results were not corrected. Resiilfs and Discussion Table 2 lists residues of DDE. TD!', DDT. dieldrin. PCB's. hcptachlor epoxide. BHC. HCB. and oxychlor- danc by .State and collection site of 1974 samples. .Since some starlings are migratory, findings should not be interpreted on a statewide basis. Residues do not necessarily reflect year-round levels because collections were made only in the fall. DDE. DDK. PCB's. and BHC were present in all 126 pooled samples at levels equal to or exceeding limits of analytical sensitivity. Dieldrin. hcptachlor epoxide. HCB. and oxychlordanc were present in approximately 97 percent of the sam- ples, b'ndrin was detected in nine samples (0 006-0.065 ppm) and niirex was detected in 14 samples (0.054- 4.47 ppm ). 12 PpsTtctDES Monitoring Johrnai. TABLE 2. Organochlorine residues in starlings, continental United States — 1974 Sm No. Residues, ppm Wet Weight State DDE TDE DDT DlELDRlN PCBs Heptachlor Epoxide BHC HCB OXYCHLOR- DANE Alabama 3-H-l 4-H-3 1.20 0.027 TR 0.013 0.025 0.13 0,005 0.008 0.042 1.88 0.006 ND 0.009 0.016 TR TR TR ND Arizona 3-C-3 3-C-4 4-C-l 4-C-2 0.13 0.52 9.11 1.48 ND ND 0.023 ND 0.011 0.013 0.038 0,008 TR 0.079 0.035 TR 0.083 0.042 0.017 0.063 TR 0.007 0.028 TR 0.021 0,010 0.017 0.012 ND TR 0.052 TR TR 0,008 0.027 TR Arkansas 3-G-2 3-G-3 0.26 9.11 0.006 ND 0,035 0,040 0.005 ND 0.25 0.042 0.010 0.005 0.056 0.008 ND ND 0.007 TR California 2-A-l 2-A-2 2-A-3 3-A-l 3-A-2 3-A-3 3-B-l 3-B-4 4-B-I 0.39 0.52 0.43 3.65 1.82 1.04 1.30 1.04 2.71 TR TR TR 0.013 TR 0.008 TR TR 0005 0,005 0.008 0.008 0.033 O.OIS 0021 0.023 0021 0.019 0.021 0.20 0,013 0,042 0,13 0,042 0017 0019 0,042 0,025 0,058 0,021 0,13 0.042 0.10 0,071 0,042 0,042 TR 0.008 TR 0008 0.005 0,021 0.014 0.005 0.008 0.005 0.005 0007 0.012 0012 0 006 0.005 0.005 0,008 0040 0,230 TR TR 0,038 0.042 0.006 0,007 0.017 0.008 TR TR 0.012 0.006 0.013 0,007 0,013 0.015 Colorado 2-D-4 3-D-l 3-D-2 0.81 0.16 0.12 0.006 TR 0.041 0.021 0.005 0006 0,025 0.038 0.063 0,063 0.038 0.029 0 012 TR TR 0.014 0006 TR TR 0.006 0.006 0.012 TR TR Connecticut 2-D-2 0.04 TR 0,017 0.008 0.083 ND TR TR ND Florida 4-H-l 413 5-1-3 5-1-2 0.73 0.42 0.007 0.18 0.014 TR TR TR 0.029 0023 0,023 0,015 0.26 0,005 0,13 0.017 0.15 0.10 0.13 0.083 0069 TR 0,007 TR 0.019 TR 0.009 TR TR TR ND ND 0.071 0.023 0.021 0.008 Georgia 4-H^ 4-1-2 0.29 0.10 TR 0.008 0,015 0,017 TR TR 0.033 0.20 TR TR TR 0.000 ND ND TR 0.005 Idaho 1-B-l 2-B-l 2-C-3 2-C-4 0.33 0,23 0.60 0.34 TR ND TR 0.012 0,007 TR 0 042 0,025 0.18 0,02 0,021 0,048 0,013 0013 0,27 0,013 TR 0012 0.013 0.038 0 039 0.014 0.012 0.052 9.11 TR TR TR TR TR 0.007 0.017 Illinois 2G1 2-G-3 2-H-2 0.22 0,096 0.40 TR TR TR 0 021 0,025 0 025 0.22 0.17 0.10 0,15 023 0,19 0.071 0083 0.061 0.026 TR TR TR 0 17 0.006 0,027 0,046 0,031 Indiana 2-H-3 0.075 O.OIO 0,029 0.083 0.25 0.013 TR 0.14 0,007 Iowa 2-F-3 2-G-2 2G-4 0.085 0.096 0.20 ND TR TR 0.013 0.010 0.009 0,22 0,23 0.60 0.021 0.021 0.025 0.075 0.079 0.18 0.019 TR TR TR TR TR 0.079 0.046 0.10 Kansas 2-E-2 3-E-l 2-F-4 3-F-2 0.063 0.096 0.077 0.10 TR ND ND TR 0.038 0.005 0.006 0.008 0,042 0017 0,10 0,042 0.029 0.008 0.033 0.050 0,012 0.31 0.031 TR TR TR 0.021 TR TR 0,009 TR TR 0.017 0,083 0,025 0.011 Kentucky 3-H-2 3-H-4 0.10 0.62 TR TR 0.021 0.006 0,023 0,033 0,15 0,042 0.005 TR TR TR TR ND 0.007 TR Louisiana 4-G-3 4-G-4 0.27 1.67 0.005 0.013 0.065 0044 0,007 0,015 0,47 0,033 0,027 0.013 TR 0.021 TR TR 0,012 TR Maine l-K-2 0.21 TR 0.015 0,010 0.10 0.007 TR TR 0,005 Michigan 1-H-l 1-H.2 2-H-l 2-H-4 0.060 0,27 0.29 0.36 0.017 0,011 0,010 TR 0.048 0.029 0,022 0,018 0,096 TR TR TR 0.46 033 0.17 0,15 TR 0005 0,010 0,014 TR TR 0.023 TR 0,006 TR TR TR TR 0,010 0.011 0.007 Minnesota l-F-2 0.042 TR 0.006 0.017 0,063 TR TR ND 0.006 Mississippi 4-G-l 4-G-2 4-H-2 2.24 0.52 0.57 ND 0,017 0,015 0.021 0.017 0.025 0.017 0.73 1.01 0,042 0,10 0,063 TR 0.092 0.29 0.035 0,012 0.023 ND ND TR TR 0.15 0.18 Missouri 3-G-l 3G-4 0.73 0.10 ND ND 0.031 0.023 0050 0 083 0,12 0,063 0.054 0.054 0.014 0.012 0.038 TR 0016 0.021 Montana 1-C-l l-C-4 1-D-l 1-D^ 0.096 0.070 0.007 0.035 0.019 0.013 TR ND 0.033 0.067 0.008 TR 0.013 0,021 TR TR 0,31 0,74 0050 0,025 0.016 0,010 ND 0.008 0,030 0,007 0,007 0.009 0.006 TR 0,007 TR 0.008 TR ND TR Nebraska 2-E-3 2-E-4 2-F-l 2-F-2 0.11 0.097 0.077 0.077 0.008 ND 0.006 TR 0.019 0,011 0,027 TR 0,013 0,057 0 120 0.027 0,054 0.067 0.140 0.013 0.012 0.17 0.023 0.011 0.029 0,057 0,025 0,014 TR 0,26 0,007 TR ND 0.13 0.013 0 006 (Continued next page) Vol. 10, No. I, June 1976 13 TABLE 2 (cont'd.). Organochlorine residues in starlings, continenlal United States — 1974 - Residues, ppm Wet Weight Heptachlor OXVCHLOR- State Site No. DDE TDE DDT DiELDRIN PCBs Epoxide BHC HCB DANE Nevada 2-B-3 0.89 TR 0.006 0.020 0.033 0.005 0.010 TR 0.006 2-B-4 0.26 0.011 0,028 0.029 0,013 0.009 0.015 0.005 0.012 3-B-2 0.067 TR 0.005 0.045 0,042 0.012 0,007 TR 0.007 3-B-3 0.30 TR 0008 0.040 0.042 0.013 0,009 TR 0.009 New Mexico 3-D-3 0.17 TR 0.005 0.015 0.042 0,012 0.024 TR 0,008 3-D.4 0.52 ND 0010 0,008 0.10 0.005 0007 TR TR 4-D-l 0.89 TR 0006 TR 0 10 ND TR TR TR 4-D-2 0.94 ND 0,006 0,010 0.13 0.023 0.012 TR 0.005 4-D-3 3.70 0.006 0,015 0.008 0.042 TR 0,007 ND TR 3-E-2 0.12 ND 0.006 TR 0.13 0.006 0.018 TR 0.005 New York 2-J-4 0.62 TR 0.010 ND 0.006 0.005 TR TR TR 2-K-l 0,56 0.006 0.013 0.010 0.13 TR 0.010 TR TR North Carolina 3 1-1 0.23 TR 0,011 TR 0.096 0007 0.008 TR 0009 3-1-2 0.40 0.006 0,025 0.11 0,22 0.01 1 0.009 TR 0.015 3-1-3 0.33 TR 0,010 0.015 0.063 TR 0010 TR 0.005 3-J-l 0.65 ND 0.021 ND 0.13 0.023 0.010 TR 0.019 Norlh Dakota I-E-3 0.017 TR TR TR 0.021 TR 0.033 TR TR l-F-1 0.097 ND TR 0.010 0.017 0,038 0.094 TR 0.012 l-F-4 0.038 TR 0.012 0.005 0.083 0,007 0,017 TR 0.007 Ohio 2-1-1 0.098 0.010 0.035 0.058 0.19 O.OIO 0.010 0.029 0.009 2-1-2 0.025 TR 0.021 0.092 0.13 0.009 TR 0.013 0.008 2-1-3 0.072 0,006 0.006 0,006 0.075 TR TR TR TR Oklahoma 3-E-4 0.18 ND 0.007 0.014 0.042 TR TR 0.006 TR 3-F-l 0.18 TR 0.013 0.063 0.058 0,006 0,009 TR 0.010 3-F-3 O.IO TR 0.006 0.017 0.063 0,005 TR 0,005 TR 3-F-4 0.085 ND 0,007 0.013 0.063 0,007 TR TR TR Oregon l-A-3 0.52 0.012 0 031 0.038 0,083 TR 0.014 0.13 TR l-A-4 0.15 TR 0013 0.052 0.042 0,013 0,020 0.038 TR 2-A-4 0.45 TR 0,00b TR 0.063 0,008 0,007 TR 0.007 l-B-4 0.094 TR 0,006 0,017 0,042 0,006 0.007 0.007 TR 2-B-2 0.28 0,021 0,021 0.040 0.042 0,007 0.007 0.031 0.010 Pennsylvania 2-J-2 0.11 TR 0,023 0.081 0 16 0023 0.022 TR 0.021 2-J-3 0.11 TR 0.010 0.029 0.063 0,017 0.021 TR 0.030 South Carolina 4-1-1 1.88 TR 0.021 0.008 0.063 0.010 0.018 ND 0.012 South Dakota 1-E-l 0.07 ND 0,008 TR 0.063 0,006 0.023 TR 0,008 l-E-2 0.035 ND 0,005 TR 0.083 0.007 0.025 TR ND l-E-4 0.090 TR 0.015 TR 0.10 TR 0.008 TR TR l-F-3 0.046 ND 0,006 TR 0.054 0.005 0.015 TR TR Tennessee 3-H-3 0.11 TR 0,023 0.010 0.15 TR 0.005 TR 0.013 Texas 4-E-3 0.49 ND 0,007 0,006 0,063 TR 0 005 TR TR 4-E-4 5.47 0.008 0,013 0.013 0.063 0,13 0,015 0.038 0.021 4-F-l 0.20 ND 0,006 TR 0.063 0.015 0.014 0.010 0.011 4-F-3 0.47 ND 0,010 0.005 0.17 0.017 0.013 0.015 0.007 5-F-l 1.04 ND 0,015 0.005 0.021 0,006 0,009 0.012 0.006 Utah 2-Cl 0.13 TR 0.017 0.019 0.10 0006 0,017 0.009 0.007 2-C-2 0.11 TR 0.008 0.015 0,033 0,007 0,005 TR TR 3-C-l 0.69 TR 0.021 0.094 0.042 0.033 0,017 0,017 0.013 Vermont 1-K-l 0.56 0,015 0.021 0.035 0.42 0,050 0,11 TR 0.090 Virginia 3-1-4 0.15 TR 0.010 TR 0.063 0.013 0,013 TR 0.008 3-J-2 0,10 0.010 0,035 0.007 0.27 0.013 0,007 024 0,017 3-J-3 0 19 0.005 0,025 0.005 0,13 0,006 TR TR TR Washington l-Al 0.054 TR 0,010 0.006 0,10 0.006 0,019 0.005 0.009 l-A-2 2.29 TR 0.010 0.019 0.021 TR 0,005 0.19 ND l-B-2 0.098 Tl< 0010 0,007 0,083 0.008 0,009 0.55 ND l-B-3 0.21 IR 0.006 0.067 0.042 TR 0.03 1 0.36 TR Wisconsin l-G-3 0.055 TR 0.006 0.008 0,092 TR 0.010 TR TR I-G-2 0.062 0.006 0,021 ND 0.13 TR 0,0 1 11 TR 0.007 Wyoming l-D-2 0.026 ND TR 0.008 0.013 TR TR IR TR l-D-3 0.046 TR 0 013 0.008 0096 TR 0.007 TR TR 2-D-l 0.46 TR 0.010 0.17 0,042 TR 0,009 IR 0.009 2-D-2 0.11 0.009 0.019 0.006 0.17 0.017 0.013 TR 0.021 NOTE: Limits of sensitivity were 0 005 ppm for organochlorine pesticide and 0 01 ppm fo TR = trace residues detected at levels below limits of quantification. ND = not delected. PCB'- 14 Pesticides Monitoring Journal I 1 .007.46 .91 1.37 1.83 2.28 2.74 3.19 3.65 4.10 5.01 5.47 Residues, ppm wet weight 8.66 911 FIGURE 2. Distribution of DDE residues in starlings, continental United States — 1974 Table 3 lists the arithmetic means, ranges, and geo- metric means of DDE, dieldrin. and PCB residues in starlings from each collection period from 1967-68 through 1974. The geometric mean is an approximation of the median. Therefore, about 50 percent of the values for a given compound fall above the geometric mean and about 50 percent fall below it. Statistical comparisons were made between DDE. dieldrin, and PCB residues from 1972 and 1974 to detect trends. Because of skewness, data were log transformed and then subjected to analysis of variance. Mean residues of DDE. dieldrin. and PCB's were significantly lower (P < 0.001) in 1974 than in 1972. DDE residues de- creased 22 percent, dieldrin decreased 42 percent, and PCB's decreased 74 percent nationwide. It is conceiv- able that the decline in usage of DDT and dieldrin are reflected in a decline of residues in animal populations. Longcore and Mulhern (2) found that levels of DDE in eggs of the black duck (Anas nibripes) had decreased between 1964 and 1971, and White and Heath (7) 1967-68 1970 1972 1974 ' TABLE 3. Arithmetic means, ranges, and geometric means of DDE. dieldrin, and PCB's in starlings, continental United States — 1967-74 No. Pools Residues, ppm Wet Weight DDE Dieldrin PCB's 2 Year X±S.E. Range Geom.X X ± S.E. Range Geom.X X±S.E. Range Geom.X 360 1.637 ±0.270 0.037-48.20 125 0.839 ±0.148 0.047—14.80 130 0.788 ±0.124 0.023-11.70 126 0,617 ±0.1 18 0.007-9.11 0.579 0.139 ±0,016 TR - 1.18 0.355 0.117 ±0.038 0.005-3.59 0.387 0.098 ±0.018 TR-I.56 0,229 0.057 ±0.011 NO -1,01 0.084 — - - 0.036 0 663 ±0.196 0.09 —24.30 0.358 0,035 0,425 ±0.153 0.037—19.90 0,215 0,019 0 112 ±0,016 0,006-1,88 0,068 >lVlean residues of DDE, dieldrin, and PCB's significantly lower in 1974 than in 1972. P < 0.001. - PCB's were not analyzed in 1967-68. Vol. 10, No. 1, June 1976 15 reported declines of DDE, dieldrin. and PCB's in black ducks and mallards {Anas phiiyrltyncho':) between 1969 and 1972. Table 4 shows the distribution of DDE. dieldrin. and PCB residues by frequency of occurrence at collection TABLE 4. Distribution of residues in slarlinijs by frequency of occurrence at collection sites, continental United States — ]974 DDE DlElDRlN PCB's No. SiTBS Nn . Sites No. Sites Range, ppm WITH Residues WITH Residues WITH Residues ND-0.01 2 50 2 >0.01 -0.1 39 61 89 >0.1 - I.O 67 14 34 >1.0- 10.0 18 1 1 NOTE: ND = not dcteclcd sites for 1974. Residues are generally low. between 0 and 1.0 ppm for most compounds. For all three com- pounds the data are skewed to the left. Figure 2 further illustrates this skcwness in 1974 DDE residues. Statis- tical comparisons using a parametric test should not be made with these raw data (6). Figure 3 shows the distribution of the same data after log transformation. Data are normally distributed and may be tested for differences by parametric methods. Conclusions Residues of DDE, dieldrin. and PCB's in starlings have declined nationwide since 1972. This decrease corres- ponds to a decline in environmental levels of organo- chlorines. indicating that starlings can provide infor- mation on residue trends over a period of time. A cknowledgments Special thanks are extended to the following for their help with starling collections: Donald Donahoo, James Elder. Robert Hillen. Harry Kennedy, David Lenhart, and l.arry Thomas. Earlcne Swann compiled the tables and Pamela Kramer constructed the map. .007 .0)0 .014 .021 .029 .042 .060.086 .123 .176 253 362 .518 741 106 1.52 2.17 311 4.45 6.37 9.11 Residues, ppm wet weight FIGURE 3. Distribution of DDE residues in \tarlini;s after lov translormation. continental United States— 1974 "^ Prsru iDFs Monitoring Jolirnai LITERATURE CITED (/) Armour, ]. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Ass. OfRe. Anal. Chem. 53(4) :76l -768. (2) Longcore, J. R., and B. M. At ul hern. 1973. Organo- chlorine pesticides and polychlorinated biphenyls in black duck eggs from the United States and Canada — 1971. Pestic. Monit. J. 7(1 ) ;62-66. (i) Martin, W . E. 1969. Organochlorine insecticide resi- dues in starlings. Pestic. Monit. J. 3(2) : 102-1 14. [4) Martin, W. E., and P. R. Mckcr.son. 1972. Organo- chlorine residues in starlings — 1970. Pestic. Monit. J. 6(l):33-40. (5) Nickcrson, P. R., and K. R. Barbchenn. 1975. Organo- chlorine residues in starlings, 1972. Pestic. Monit. J. 8(4):247-254. (6) Snedecor, G. W., and W. G. Cochran. 1967. Statistical Methods. Iowa State University Press, Ames, Iowa. 593 pp. (7) White. D. H.. and R. G. Heath. 1976. Nationwide residues of organochlorines in wings of adult mallards and black ducks, 1972-73. Pestic. Monit. J. 9(4): 176-185. Vol. 10, Nc. I.June 1976 17 RESIDUES IN FOOD AND FEED Pesticide Residues in Toted Diet Samples, Spain — 1971-72 '■' J. M. Carrasco,^ P. Cunat,'' M. Martinez,'' and E. Primo --^ ABSTRACT Avcidtic pesticide residue levels were determined for the 17 main food groups in the average Spanish diet. Using these levels and the estimated average intake of these foods. authors computed an individual's average daily consumption of pesticides from each of these food groups and her/his total diet. Foods were acquired over a 1-year period from the market of Valencia, a city that gets supplies from an agricultural area where pesticide consumption is appreciably higher than that of the rest of the country. Thus average residue levels found must he higher tluin the national average. Except for fruits and vcgelahles, the different items com- posing each food group were sampled in proportion to the amount consumed in the average Spanish diet. Foods form- ing each group were homogenized into composite samples. All foods were analyzed raw. The most frequently detected pesticides were DDT and BHC. Malathion was detected at levels less than 0.10 ppm in .some samples of vegetable oils, pears, and apples. DDT and BHC levels varied from uiuletcctable to amounts less than 1 .0 ppm. Highest levels were fotind in lard. An individual's average daily intake of pesticides was cal- culated to be 78 tig DDT, a sum which includes residues of o.p'-DDT, p.p'-DDT, and p.p'-DDF. and 13.8 fig y-BHC. These levels are much lower than the nuiximum acceptable daily limits established by the United Nations Food Agri- cultural Organization and World Health Organization. Introduction Part of a series of studies on pesticide contamination in agricultural products (3,4,5,11), the present paper represents authors' attempts to determine the extent of pesticide contamination of the various food groups com- posing the average Spanish diet (9) and compute an * Previously published in Revlsta de ARroqtiiniica y Tecnolo^ia tie Alimrnlox, Vol. 12. No. i. 'Technical School of Agricultural Enpinccring. Pasco al Mar, 21, Valencia, Spain. " Institulc of Agricultural Chemistry and Food Technology, Valencia, Spain. individual's average daily intake of pesticides from these foods and her/his diet. Pesticide residue levels are also being determined for the average diet in the U.S., Canada, and England (l .6,7,12). Results of these studies and the present study are evaluated by comparing them with the maximum daily levels of pesticide intake from foods established by the United Nations Food Agricul- tural Organization (FAO) and World Health Organi- zation (WHO) (13). Scimpling Constituent foods of the average Spanish diet were classified into 17 groups. 1 able I lists the foods which TABLE 1. Average per capita yearly food consumption, Spain— 1969 ' Food CONSUMED, Food CROUP Products Kg/ person/ year T. n.Tiry products 11. Meats 111 l-UBs IV. lish Fresh milk 78.94 Powdered milk 0.25 C'otulcnscd nulk 2.51 Butter 0.35 Cheese 1.53 Total 83.58 Beef 7.24 Mutton and g lal meat 5.35 Pork 2.02 Hoisc meat 1.31 Poultry S.08 Liver 0.44 Sausages and giblets 6.37 Canned meat 0.27 Meat soups 0.16 Total 28.44 F.ggs 14.22 Fresh sardines 4.10 Fresh whitebait 1.40 Iresh jurel 1.90 1-resh codling 4.70 l-rcsh hake 1.10 Fresh codlish 1.80 Salted codlish 1.00 Canned lish 1.60 Shclllish 0.80 (ithcr fresh fish 6.30 Frozen fish 0.50 Total 25.20 (Continued next page) 18 Pi-STiciDES Monitoring Journal TABLE 1 (cont'd.). Average per capita yearly food consumption, Spain — 1969' Food consumed. Food consumed. Food group Products Kg/ PERSON/ YEAR Food group Products Kg/ PERSON/YEAR V. Fats Lard 4.71 Peaches 1.50 Margarine Total 0.14 Apricots Cherries and berries 0.20 4.8! 0.60 Plums 0.70 VI. Vegetable oils Olive oil 24.10 Melons 7.40 Other vegetable oils 0.66 Grapes 5.00 Total 24.76 Other fresh fruits Chestnuts 3.60 0.20 VII. Bakery goods Bread 134.50 Nuts 0.10 Flour Italian pastry 5.80 4.50 Other dried fruits Total 0.27 57.47 Biscuits 2.30 Rolls 4.10 XIII. Canned foods Vegetables Legumes 1.31 Total 151.20 0.03 Olives 0.96 VIII. Grains Rice 9.70 Marmalade 0.13 Other (except wheat) 0.20 Quince Juices Other fruits 0.37 0.40 0.38 Tomatoes Total 9.90 18.50 Total IX. Vegetables 3.58 Lettuce 3.30 Green beans 3.60 XIV. Sweets and condiments Sugar 14.10 Cabbages and sprouts 4.40 Chocolate 2.14 Peppers 3,30 Cacao 0.43 Artichokes 1.90 Honey 0.05 Beets 2,20 Turron (Spanish Peas 0.70 confectionery) 0.21 Spinach 0,80 Other sweets 0.30 Onions, leeks, tende r onions 5.60 Salt 3.92 Cauliflower 1.10 Vinegar 1.20 Other vegetables 8.90 Garlic 0.52 Total 54.30 Other dressings Total 0.22 23.09 X. Tubers Potatoes 109,50 Carrots Total 0.30 XV. Water Tap water Mineral water 200.00 109.80 2.90 Soda and seltzer 15.30 XI. Legumes Beans Chick peas 5.90 6.90 Total 218.20 Lentils Other legumes 2.10 0.10 XVI. Alcoholic drinks Wine Beer 47.90 2.00 Total 15.00 Other Total 3.20 53.10 XII. Fruits Oranges 20.60 Lemons Other sour fruits 0.60 0.30 XVII, Beverages Coffee Malts 1.46 0.81 Bananas Apples 7.30 5.90 Other 11,00 Pears 3.20 Total 13.27 ' See Literature Cited, reference 9. compose each group and the average amount of each food an individual consumes each year (9). Samples were acquired at random between March 1971 and March 1972 in different markets in Valencia. They were mixed into composite samples according to their proportion in the average diet. Because they are seasonal, some foods, especially those in the fruit and vegetable groups, were studied indi- vidually. Because residue levels in foods from these groups are similar (J), authors studied only the foods which are eaten in greatest volume and considered their residue levels representative of all foods in the group. Analytical Procedures All foods were analyzed raw. Unless specified otherwise, samples were composed of 100-g mixtures of foods from the designated group and pesticide residues were ex- tracted and purified as delineated in the Pesticide Ana- lytical Manual of the Food and Drug Administration, U.S. Department of Health, Education, and Welfare [14). Samples of dairy products were homogenized in a blendor and shaken at high speed for 2 minutes. Fifty g of this mixture was weighed in a 400-ml glass and analyzed according to the method expounded by Faubert et al. (8). Samples of meat and fish products were diced into 0.5- to 1-g pieces and ground in a glass mortar with 100 g washed sand and 200 g anhydrous sodium sulfate. Ac- cording to Faubert 's method (S). pesticide residues were extracted from 40 g of this homogenized mixture, which is equivalent to 10 g of the sample. The whites and yolks of three eggs were homogenized by shaking for 3 minutes. This mixture was added to sufficient anhydrous sodium sulfate (45-50 g) to make it dusty and dry. Then it was extracted by Soxhiet for 6 hours with 250 ml 2:1 n-hexane:acetone. The extract was dried by shaking for 10 minutes with 25 g an- VoL. 10, No. 1, June 1976 19 hydrous sodium sulfate, filtered, concentrated in a Kuderna-Danish evaporator to 25 ml. and purified by partition with acetonitrilc according to the method out- lined by Onley and Mills (10). Purified extracts were then chromatographed in an alumina column (<*?) and eluted with 100 ml hexane and 100 ml hexane mixed with 6 percent ethyl ether. White rice samples were ground until they could pass through a 1-mm sieve. Fifty g cereal was added to 350 ml 65:35 acetonitrile: water for 30 minutes, ground at a high speed for 3 minutes, and ccntrifuged for 10 minutes at 2,000 rpm. Floating liquid was poured into a I -liter separatory funnel and 100 ml bidistilled petro- leum ether was added. Fifty-g samples of dry legumes were moistened for 30 minutes with 350 ml of a 65:35 mixture of acetonitrile: water, ground for 5 minutes at a high speed, and filtered. The resulting mixture was centrifuged for 10 minutes at 2,000 rpm. .Samples of sweets and condiments weighing 50 g were placed in a 400-ml glass with 100 ml bidistilled water, shaken for 15 minutes, poured into a mixer with 200 ml acetonitrile, and ground for 5 minutes. Potable water samples were acidified with 2 ml of IN HCI and extracted with three portions of 100 ml n- hexane. Samples were added to 10 g anhydrous sodium sulfate, shaken for 5 minutes, poured through filter paper, and concentrated in a rotory evaporator to 10 ml in a vacuum and to 2 ml in an airstream. Alcoholic drinks were extracted as the potable water except that 10 ml ethanol was added at the aqueous phase to break up the emulsions formed during the extraction with n-hexane. Extracts were concentrated to 10 ml in a rotary evaporator in vacuum and chroma- tographed in an alumina column according to the method used for meat products. A I -liter sample of beverages was placed in a separatory 2-liter funnel. Pesticide residues were extracted accord- ing to the procedures described for water. Fat and vegetable oil samples weighed 3 g and tuber samples consisted of peeled and washed potatoes. Bakery samples were ground in a blendor for 3 minutes with a 65:35 mixture of acetonitrile: water and poured through filter paper before extraction. Analyses were performed on a Perkin-Elmer model F-11 gas chromatograph according to the methods recom- mended by FDA (/-/) or those used by the authors in earlier work (2). Electron-capture and sodium ther- mionic detectors were used. Columns were glass packed with either 10 percent DC-200 or 10 percent DC-200 and 15 percent QF-1 on Gas-Chrom Q. All results are reported on a whole-product basis. One of every four samples was checked for recovery, which varied from 80 to 110 percent for DDT, lindane, a-BHC, aldrin, dieldrin. and endrin. Results have not been corrected. To confirm the identity of pesticide residues, thin-layer chromatography was used implementing either the FDA method (14) or the authors' earlier procedures (5). DDT residues were also confirmed by alkaline degra- dation to DDE (2). Results and Discussion Table 2 shows the average organochlorine pesticide residue level in each food group. Average contamination by BHC varies from undetectable levels in tubers and fruits to 0.4 ppm in lard. DDT levels vary from un- detectable to 0.8 ppm in meats and fats. These results agree with the well-known fact that all chlorinated in- secticides accumulate in the fat tissues of animals be- cause they are liposolublc. Residues of other chlorinated insecticides were not found. Malathion was the only organophosphorous in- TABLE 2. Average pesticide residue in 17 food groups, Spain — 1971-72 Residues, ppm Food croup a-BHC 7-BHC p,p'-DDE o.p'-DDT p,p'-DDT I. Dairy Products 0.005 0.004 0.006 ND 0.004 II. Meats 0.033 0.070 0.167 0.023 0.186 III. Eggs 0.019 0.019 0.151 ND 0.198 IV. Fish 0.01 1 0.009 0.078 ND 0 106 V. Fats 0 150 0.268 0.218 0.061 0.160 VI. Vegetable oils 0.016 0.009 0.012 ND 0.012 VII. Bakery Goods 0.005 0.003 0.003 0.002 0.016 VIII. Grains 0.004 0.003 0.002 ND 0.013 IX. Vegetables 0.002 0.001 0.001 0.002 0.004 X. Tubers ND ND 0.001 ND 0.001 XI. Legumes 0.005 0.003 ND ND 0.004 XII. Fruits ND ND ND 0.001 0.002 XIII. Canned vegetables 0.008 0.005 ND 0.001 0.004 XIV. Sweets and condiments 0.005 0.004 0.003 0.008 0.009 XV Water ND ND ND ND ND XVI. Alcoholic drinks 0001 ND ND ND ND XVII. Beverages N!) ND ND ND ND NOTE: ND = residue levels < 0.001 ppm. 20 Pesticides Monitorino Journal iecticide detected. It was found in several samples of vegetable oils, pears, and apples at levels less than 0.1 ppm. <.elthane (dicofol) and Tedion (tetradifon) residues ■vera detected in some samples of fruits and greens. rhe highest level found was 0.2 ppm. Table 3 presents a sample distribution according to the contamination levels of every pesticide detected. It also shows the maximum content of every compound found for each food group. The percentage of samples in each food group without any detectable residues is shown in Table 4. Table 5 shows the average contamination of fruits and vegetables. TABLE 3. Distribution of food samples according to contamination by different pesticides Distribution ACCORDING TO CONTAMINATION DUE TO DIFFERENT pesticides, % Highest Not Trace: 0.011-O.OSO Greater than 1 1 i\J riL«.j 1 LEVEL, Food croups ' Pesticides ' DETECTABLE 0 001-0.010 PPM PPM 0 050 PPM PPM a-BHC 20 75 5 0 0.015 7-BHC 35 55 10 0 0.018 I. Dairy products p.p'-DDE 50 20 30 0 0.026 o,p'-DDT 95 5 0 0 0.004 p,p -DDT 50 40 10 0 0.018 a-BHC 15 30 50 10 0.200 7-BHC 0 0 60 40 0.160 11. Meats p,p'-DDE 25 15 20 40 0.635 o.p'-DDT 65 20 10 5 0.230 p.p'-DDT 15 10 25 50 0.845 a-BHC 40 15 40 5 0.105 7-BHC 25 35 35 5 0.100 m. Eggs p.p'-DDE 10 10 35 45 0.469 o.p'-DDT 100 0 0 0 NO P.p'-DDT 20 10 25 35 0566 a-BHC 55 15 30 0 0.050 7-BHC 70 15 15 0 0.050 IV. Fish p.p'-DDE 15 25 15 45 0.250 o.p'-DDT 90 0 5 5 0.120 p.p'-DDT 15 0 25 60 0.231 o-BHC 0 0 10 90 0.260 7-BHC 0 0 0 100 0.390 V. Fats p.p'-DDE 0 0 10 90 0.510 p.p'-DDT 30 0 10 60 0.410 a-BHC 75 5 10 10 0.125 7-BHC 90 0 5 5 0.090 VI. Vegetable oils p.p'-DDE 90 0 0 10 0.160 p.p-DDT 90 0 0 10 0.160 Malathion 80 0 20 0 0.040 a-BHC 25 65 10 0 0.023 7-BHC 45 55 0 0 0.010 VII. Bakery goods p.p'-DDE 50 35 15 0 0.015 o.p'-DDT 55 35 10 0 0.016 p.p'-DDT 25 30 45 0 0.050 a-BHC 35 60 S 0 0.015 7-BHC 40 55 5 0 0.012 VIII. Grains p.p'-DDE 75 20 5 0 0.012 p,p'-DDT 40 20 40 0 0.044 a-BHC 68 30 2 0 0.017 7-BHC 71 29 0 0 0.007 p.p'-DDE 80 19 0 0 0.016 IX. Vegetables o.p'-DDT 73 25 2 0 0.024 p.p'-DDT 71 20 9 0 0043 Kelthane 82 S 9 4 0 130 Tedion 87 10 1 2 0.110 X. Tubers p.p'-DDE 75 25 0 0 0.004 p.p'-DDT 75 25 0 0 0.004 a-BHC 35 55 10 0 0.016 XI. Leguines 7-BHC 40 50 10 0 0.012 p.p'-DDT 55 35 10 0 0.025 a-BHC 71 28 1 0 0.018 7-BHC 78 19 3 0 0.013 p.p'-DDE 72 28 4 0 0.005 XII. Fruits o.p'-DDT 72 14 14 0 0.024 p.p'-DDT 57 19 23 1 0.103 Kelthane 87 3 5 5 0.200 Tedion 92 1 4 3 0.200 a-BHC 45 50 0 5 0.100 7-BHC p.p'-DDE p.p-DDT 85 10 0 5 O.IOO XIII. Canned vegetables 85 60 15 30 0 10 0 0 0.010 0.021 (Continued next page) Vol. 10, No. 1, June 1976 21 TABLE 3. (cont'd. ). Distrilnilion of food samples according to contamination by different pesticides Distribution ACCORDING TO CONTAMINATION DUE TO different pesticides. % Not Trace: 0.0 1-0.050 Grfater than level. FOOU GROUPS ' Pesticides = DETECTABLE 0.001-0.010 PPM PPM 0.050 PPM PPM a-BHC 45 45 10 0 0.015 t-BHC 50 40 10 0 0014 XIV. Sweets and condiments P.P-DDE 80 IS 5 0 0029 o.p-DDT 50 35 15 0 0.045 p,P-DDT 50 15 30 5 0.066 a-BHC 50 50 0 0 0.006 XV. Alcoholic drinks 7-BHC 70 30 0 0 0.008 p.p-DDT 10 90 0 0 0.005 'There were no detectable residues in groups XV and XVI, water and beverages, respectively. - Pesticides not listed were not detected in the specified food group. TABLE 4. Food samples not contaminated bv pesticides, Spain— 1971-72 Samples with Food group NO DETECTABLE RESIDUES, % I. Dairy Products 20 II. Meats 0 III. Eggs 10 IV. Fish 10 V. Fats 0 VI. Vegetable Oils 50 VII. Bakery Goods 10 VIIl. Grains 25 IX. Vegetables 38 X. Tubers 60 XI. Legumes 20 XII. Fruits 39 XIII. Canned vegetables 30 XIV. Sweets and condiments 15 XV. Water 100 XVI. Alcoholic drinks 90 XVII. Beverages 100 Based on the pesticide residue levels in each food group and an individual's average yearly intake of these foods (Table 1), authors have estimated the average amount of pesticides an individual in .Spain consumes daily from each food group and her/his diet: 78.4 /xg DDT, in- cluding p.p'-DDJ. o.p'-DDT, and p,p'-DDE, and 13.8 fig y-BHC (Table 6). These levels are much lower than the daily maximum acceptable concentrations established by FAO and WHO: 250 fig DDT and 625 fig y-BHC for persons who weigh 50 kg (110 lb). DDT and BHC levels cal- culated in this study are similar to, but a bit higher than, comparable levels found in the U.S. (55 fig DDT and 3 fig y-BHC per day) and England (44 fig DDT and 6.6 fig y-BHC per day) according to Smith (12) and Abbott et al. (/). Highly toxic pesticides such as diel- drin, which are common in the other countries men- tioned, were not detected in Spain. Acknowledgment Authors are grateful to Jose Alberola Matoses for his collaboration in the analysis of pesticide residues by gas-liquid chromatography. TABLE 5. Average pesticide residue levels in fruits and vegetables. Spain — 1971-72 Residues, ppm Product a-BHC 7-BHC p.pDDE o,p'-DDT P,p'-DDT Oranges 0.001 Bananas ND Apples ND Pears 0.001 Peaches 0.001 Melons 0.002 Grapes ND Tomatoes 0.001 Lettuce 0.003 Green beans 0()O2 Onions ND NOTE: ND = < 0.001 ppm. 22 ND ND ND 0.004 0.001 ND ND ND 0.002 0.001 ND ND 0.001 ND ND ND ND 0.006 0.001 0.002 0,001 ND ND 0.001 O.OOI ND 0.001 ND 0.015 0002 0.002 0.001 ND ND 0.002 0.001 0.009 0.007 ND 0.045 0.001 0.007 0.004 ND Pfsth ides Monitoring Journal LITERATURE CITED (/) Abbott. D. C. D. C. Holmes, and J. O'G. Tatton. 1969. Pesticide residues in the total diet in England and Wales. 1966-1967. II. Organochlorine pesticide residues in the total diet. J. Sci. Food Agr. 29(4) :245-249. (2) Cariasco, J. M.. P. Ciiiial, M. Martinez, and E. Prima. 1972. Pesticide contamination of average Spanish diet food cnstituents. Rev. Agroquim. Tecnol. Aliment. 12(3):463-476. (i) Carrasco. J. M.. ]. Cunat. M. Martinez. E. Primo. and J. Alberola. 1971. Contamination of agricultural prod- ucts with pesticides. IV. Contamination levels of fruits and vegetables. Rev. Agroquim. Tecnol. Aliment. ll(2):236-248. {4) Carrasco, J. M.. R. M. Martinez, and P. Cunat. 1969. Contamination of agricultural products with pesticides. III. Fate of hydrocyanic residues in oranges after fumigation. Rev. Agroquim. Tecnol. Aliment. 9(4): 574-577. (5) Cunat. P., J. M. Carrasco, and M. Martinez. I96S. Contamination of agricultural products with pesticides. II. Pesticide residues in tomatoes. Rev. Agroquim. Tecnol. Aliment. 8(4) :472-477. (6) DuKV"". R- E.. and P. E. Corneliiissen. 1972. Dietary intake of pesticide chemicals in the United States (III) June 1968— April 1970. Pcstic. Monit. J. 5(4) :331-341. (7) Diiggan, R. E., and ]. R. Weatlierwax. 1967. Dietary intake of pesticide chemicals. Science 157(3792): 1006-1010. (5) Faubcrt. M. J.. H. Egiin, E. W. Godly, E. W. Ham- mond, ]. Robiirn, and 1. Thomson. 1964. Clean-up of animal fats and dairy products for the analysis of chlorinated pesticide residues. Analyst 89(1056): 168-174. (9) National Institute of Statistics. 1969. Survey of family budgets. II. Food consumption. Madrid. 360 pp. ilO)Onley. J. A., and P. A. Mills. 1962. Detection and estimation of chlorinated pesticides in eggs. J. Ass. Offic. Anal. Chem. 45(4) :983-9X7. (//) Prima, £., J. M. Carrasco, and R. M. Martinez. 1967. Contamination of agricultural products with pesticides. I. Residues of m;ilathion. ziram, lebaycide. kelthane, and Tedion on fruits and its fate before harvest. Rev. Agroquim. Tecnol. Aliment. 7(1):98-I04. (12) Smith, D. C. 1971. Pesticide residues in the total diet in Canada. Pestic. Sci. 2(2):92-95. (U) United Nations. Food Asriculliiral Organization/ World Health Organization. 1969. Residues of Pesti- cides in Foods. WHO Technical Report No. 525. 50 pp. (14) U.S. Department of Health. Education, and Welfare. Food and Drug Adminislrali-ChIordanc Sample size — — — — 1,360 22 — — — — 8,260 6 303 60 601 67 2,290 28 334 20 ND 2 3 1.518 80 871 100 2,165 100 2,155 1,472 4,456 1.332 100 5,950 100 8,589 100 3,134 100 2,862 100 2,966 97 2,601 100 2,053 100 2,302 92 5 6 36 NOTE: — = no data. 1 WRRC monitoring data from station 1, Hawaii Kai Marina. Food and Agriculture Organization/World Health Or- ganization (F.AO'VVHO) as safe in food consumed by humans (Table 5). Conchisinns Results have shown that dieldrin. chlordane. and p.p'- DDT were distributed throughout the study site. Be- cause the mountains serve as a windbreak (Fig. 1), drift from outside areas can be considered a negligible influence. .So. too. are industrial and agricultural ac- tivities since few. if any, operate in the Hahaione Valley. An Epidemiologic .Studies Program survey (7) of households in the valley indicated that household use of dieldrin and chlordane was negligible. Other dieldrin sources were confined to treated mill-work and fumi- gation of homes for dry wood termites. Thus it is doubtful that these uses could account for the levels noted in the present study. The pest control treatment for subterranean termites was the only activity discovered by the Epidemiologic Studies Program survey that could account for the pesticide levels observed in the marina. Aldrin and chlordane were used in these operations. All home sites within the survey area were treated for subterranean termites prior to construction. Aldrin, which has a half- life of 3'/2 months (3) (Table S), is readily converted to dieldrin and was the likeliest source of the dieldrin in this study. TABLE 8. Persistence of some organocltlorine insecticides ill soil ' Average ANNUAL half- life Time FOR 95% DOSE disappearance, years Chemical LB/ acre KG/HA. iears Range Average Aldrin 1-3 1.1-3.4 0.3 1-6 3 Chlordane 1-2 1.1-2.2 1.0 3-5 4 DDT 1-2.5 = 1.1-2.8 2.8 4-30 10 Dieldrin 1-3 1.1-3.4 2.5 5-25 8 Endrin ^ 1-3 1.1-3.4 2.2 3-20 7 Heptachlor 1-3 1.1-3.4 0.8 3-5 3.5 Lindane 1-2.5 1.1-2.8 1.2 3-10 6.5 Isobenzan 0.25-1 0.3-1.1 0.4 2-7 4 ' See Literature Cited, reference 3. Vol. 10, No. 1, June 1976 Pest control activities were the only apparent source of dieldrin and aldrin within the Hahaione watershed. Water column pesticide levels were in the low pptr range. Oyster pesticide levels were in the low ppb range, well within the range of residues accepted as safe by FAO/WHO in foods consumed by humans. LITERATURE CITED (/) Bcvcnue. A.. ]. W. Nylin. Y. Kawano, and T. W. Kelley. 1972. Organochlorine pesticide residues in water, sediment, algae, and fish, Hawaii — 1970-1971. Pestic. Monit. J. 6(1): 56-64. (2) Butler, P. A. 1969. Monitoring pesticide pollution. Bioscience 19f 10) :S89-S91. (-?) Edwards, C. A. 1970. Persistent Pesticides in the En- vironment. CRC Uniscience Series. Butterworths, Lon- don. 7iS pp. (4) Eisler, R. 1970. Acute Toxicities of Organochlorine and Organophosphorous Insecticides to Estuarine Fishes. Bureau of Sport Fisheries and Wildlife, U.S. Department of Interior. Technical Paper 46. 12 pp. (5) Eisler. R. 1970. Factors Affecting Pesticide Induced Toxicity in an Estuarine Fish. Bureau of Sport Fish- eries and Wildlife, U.S. Department of Interior. Tech- nical Paper 45. 20 pp. (6) Federal Wiilcr PoUiilion Control Adiniuistralion. 1968. Report of the Conmiittee on Water Quality Criteria. LIS. Department of Interior. 234 pp. (7) Hawaii Epidemioloi;ical Studies Program. 1975. An- nual Report No. S — January through December, 1974. Pacific Biomedical Research Center, University of Hawaii. 176 pp. (cS'l Panel on Pesticide Monitoring, Working Group on Pesticides. 1971. Criteria for defining pesticide levels to be considered an alert to potential problems. Pestic. Monit. J. 5(1 ):36. (9) SUidlz. C. D. 1971. An Examination of Some Chlori- nated Pesticide Residues in the Water, Sediment, and Selected Biota in the Ala Wai Canal, Oahu, Hawaii. Unpublished Master's Thesis. University of Hawaii. 49 pp. (10) Slate of Hawaii. 1969. Evaluation of Pesticide Prob- lems in Hawaii, Department of Agriculture. Honolulu, Hav\'aii. (//) Tindle. R. C. 1972. Handbook of Procedures for Pes- ticide Residue Analysis. Bureau of Sport Fisheries and Wildlife, U.S. Department of Interior. Sections I-O — VI-O. (12) U.S. Army Engineer District. 1975. Draft: Environ- mental Statement for the Department of the Army Permit Actions in the Hawaii Kai Marina, Oahu, Hawaii. 26 pp. 29 APPENDIX Chemical Names of Compounds Discussed in This Issue ABATE ALDRIN See temefos. Not less than 95% of l,2,3,4,IO,10-Hcxachloro-l,4,4a,5,8,8a-hexahydro-l,4cnrfo-fj:o-5.8 dimethanonarhthalene BIIC (BENZENE HEXACHLORIDE) CHLORDANE HDD DDE DDT DICOFOL DIELDRIN ENDRIN HCB HEPTACHLOR EPOXIDE ISOBENZAN KELTHANE LINDANE MALATHION MIREX OXYCHLORDANE PCB'S (POLYCHLORINATED BIPHENYLS) TDE TEDION TEMEFOS TETRADIFON 1,2,3.4.5.6-Hcxachlorocyclohexane (mixture of isomers). Commercial product contains several isomers of which aumma is most active as an insecticide. 1,2,3,5.6,7. 8,8-Oclachloro-2, 3, 3a,4,7,7a-hexahydro-4,7-methanoindcne. The technical product is a mixture of several compounds including heptachlor, chlordene, and two isomeric forms of chlordane. See TDE. Dichlorodiphenyl dichloro-cthylene (degradation product of DDT) p.fj'-DDE: l,l-Dichloro-2,2-bis(p-chlororhenyn ethylene o.p'-DDE: l,l-Dichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)elhvlene Main component (p,p-DDT): a-Bis(p-chlorophenyl) 3,p,3-trichloroethane Other isomers are possible and some are present in the commercial product. o.p-nOT: ll,l.l-Trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl) ethanel 4,4'-Dichloro-a-trichloro-melhylbcn2hydrol Not less lh.an 85% of 1.2.3,4.10,10-Hexachloro-6,7-ero.xy-l,4,4a,5.6.7,8,8a-octahydro-l,4cHrfo-f.vo-5,8-dimethano- naphthalene l,2,3,4,10.10-Hexachloro-6,7-epoxy-I,4,4a,5,6,7.8.8a-octahydro-1.4-fndo-pn<;t)-5.8-dimcih3nonarhthalene Hexachlorobenzene 1,4,5,5,7,8,8-Heptachloro 2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-mcthanoindane l,3,4,5,6,7,8,8-Octachloro-l,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran See dicofol. Gamma isomer of benzene hexachloride, 1,2,3.4,5.6-hexachlorocyclohexane, of 99 + % purity S-[l,2-bis(ethoxy-carbonyl) ethyl) 0,0- dimethyl phosphorodithiate Dodecachlorooctahydro-1.3,4-metheno-2H-cyclobuta|cdlpcntalene 2,3,4,5,6,6a,7,7-Octachloro-la,lb,5,5a.6,6a-hcxahydro-2.5-methano-2H-indeno(l,2-fl)oxirene Mixtuics of chlorinated biphenyl compounds having various percentages of chlorine 2,2-Bis(p-chlorophenyl)-l.l-dichloroethane See telradifon. 0,0,0',0'-Tetramethyl O.O'-thiodi-p-phenylene phosphorothioate p-Chlorophenyl 2,4,5-trichlorophenyl sulfone 30 Pesticides Monitoring Journal ERRATA Pesticides Monitoring Journal, Volume 9, Number 3, pp. 124-133. In the paper "Mirex Nontarget Organ- isms after Application of Experimental Baits for Fire Ant Control, .Southwest Georgia — 1971-72," the Table 1 column caption should read "Components of Bait, % by weight." Table 2 should read: TABLE 2. Application patterns of mircx bait in three Georgia counties, 1971-72 Formulation: Area Bulk Date County Mirex, 7o Treated Rate '.= 1.40 kg/ha. (4.20 g/ha.) 1.40 kg/ ha. (2.10 g/ha.) 1.12 kg/ha, (Correct as published) (1.68 g/ha.) 1.12 kg/ha. (1.12g/ha.) 1.12 kg/ha. (1.12g/ha.) 1.40 kg/ ha. (4.2 g/ha.) ' Numbers in parentheses show amount of actual toxicant, i.e., mirex, applied to each hectare. ' 1.40 kg/ha = 1.25 lb/acre; 1.12 kg/ha = 1.0 lb/acre. Vol, 10, No. 1, June 1976 31 Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators associated with pesticide monitoring, research, and other programs concerned with pesticides in the environ- ment. Other subscribers work in agriculture, chemical manufacturing, food processing, medicine, public health, and conservation. Articles are grouped under seven headings. Five follow the basic en\ iionmental components of the National Pesticide Monitoring Program: Pesticide Residues in People; Pesticide Residues in Water: Pesticide Residues in Soil; Pesticide Residues in Food and Feed; and Pesticide Residues in Fish. Wildlife, and Estuaries. The sixth is a general heading: the seventh encompasses briefs. Monitoring is defined here as the repeated sampling and analysis of environmental components to obtain reliable estimates of levels of pesticide residues and related compounds in these components and the changes in these levels with time. It can include the recording of residues at a given time and place, or the comparison of residues in different geographic areas. The Journal will publish results of such investigations and data on levels of pesticide residues in all portions of the environment in sufficient detail to permit interpretations and con- clusions by author and reader alike. 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However, pertinent data in summarized form, together with 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 mtendcd as a primary medium for the publication of basic research. Publication of scientific data, general information, trade names, and commercial sources in the Pesticides Monitoring Journal does not represent endorsement by any Federal agency. 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. For further information on Journal scope and manuscript prepara- tion, see Information for Contributors at the back of this issue. Editorial Advisory Board members are: John R. Wessel, Food and Drug Administration, Chairman Robert L. Williamson. Animal and Plant Health Inspection Service Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Gerald E. Walsh, Environmental Protection Agency G. Bruce Wiersma, Environmental Protection Agency William H. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Herman R. Feltz, Geological Survey Address correspondence to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, D.C. 20460 Editor Martha Finan CONTENTS Volume 10 September 1976 Number 2 Page RESIDUES IN FOOD AND FEED Or'^'anocliloiinc insccliciilc rc\iitiics //; vc'^chihlcs nj ilic Kiliikyiishii Di\tiicl. Japan— 1971-74 35 M. Suzuki. Y. Yaniato. and T. Watanabc Oritdnoclilorinc pcslicitlc rr.sidiic.s in sirjarhccl pulps and nwlasscs from 16 States. 1971 41 H. S. C. Vang. G. B. Wiersma. and \V. G. MilLhell RESIDUES IN FISH. WILDLIFE. .AND E.STUARIES Orf;aiioclt!orinc residues in three hat species from four localities in Maryland and West I'irsinia. 1973 44 Donald R. Clark. Jr.. and Richard M. Proiity RESIDUES IN .SOIL V Pesticide resiiliies in iirhati soils from 14 I'ntted Slates cities. 1970 54 Ann E. Carey. G. Bruce Wiersma. and Han lai RESIDUES IN WATER Distrihution of pesticides and polychlorinated hiplienyls in water, sediments. and sexton of the upper (treat I akis 61 W. A. Glooschenko. W. M. J. Slrachan, and R. C . }. Sampson GENERAL Residues of quintozeiie. its coniamiihuits and melaholiie\ in soil, lettuce. and witloof -chicory. I3eli;ium — 1969-74 68 W. Dcjonckheere. W. Sleurbaut. and R. H. Kips APPENDIX 74 ERRATUM 75 Information for contributors 76 RESIDUES IN FOOD AND FEED Organochlorine Insecticide Residues in Vegetables of the Kitakyushu District, Japan — 1971-74 M. Suzuki,' Y. Yamato,' and T. Watanabe " ABSTRACT The residue levels of organochlorine insecticides BHC, DDT, cndrin, and dicldrin in the Kitakyushu District. Japan, were monitored from 1971 to 1974. Agricultural uses of these insecticides were banned in 1970. BHC i.wmcrs. a- , fi- . y- , and 5-BHC were detected in all vegetable samples taken: li-BHC residue appeared in the highest levels. The propor- tions of eacli BHC isomer in total BHC residues were much different from those in the technical product. Average resi- due levels of a- , ft- , ',- , and d-BHC, dicldrin, endriii. and DDTR (p.p'-DDT-\-p.p'-DDE-]-p.p'-TDE+o.p'-DDT) in 197! were 0.007, 0.042, 0.010. 0.008, 0.021, 0.010, and 0.041 ppm in radishes, and 0.004, 0.007, 0.009, 0.003, 0.087, 0.031. and 0.009 ppm in cucumbers. Levels found in 1974 were 0.002, 0.003, <0.00l, <0.001, 0.005, 0.006, and <0.00! ppm in radishes, and <0.001, 0.001. 0.001. <:0.00I. O.OOS. 0.009, and undetectable in cucumbers. These residues were translocated from the insecticide-contaminated field soils to the vegetables through their roots. Residue levels of dicldrin and cndrin frequently exceeded the pesticide tolerance limits of Japan, but DDTR residues were only slightly above the specified levels. Introduction Organochlorine insecticides such as BHC. DDT. aldrin, dicldrin, and endrin have been applied extensively to agricultural fields, orchards, and forests in Japan for the past two decades to control pest damage. BHC was sprayed on rice paddies, and aldrin, dieldrin, endrin, and DDT were applied mainly to vegetable fields to control soil worms or orchard pests. Japan produced 41.742 tons of BHC in 1967 and 45.695 tons in 1968. and 4.936 tons of DDT in 1968. The nation imported 767 tons of cyclod'ene insecticide in 1968. The contamination of cows' milk by BHC, ' Pesticide Residue Llibor.^tory. The Kitakyushu Municip.-!! Institute of Environmcni.tl Health Sciences. Tobata-ku. Kitakyushu, Japan 804 - Department of Food Science and Technology. Faculty of Agriculture. The University of Kyushu, Higashi-ku, Fukuoka, Japan mainly /3-BHC, was reported in 1969. Agricultural and forest uses of BHC, DDT. aldrin, dieldrin. and endrin were banned in late 1970 because of the public concern with contaminated foods. During 1971. the first year after the ban. only 2.000 tons of BHC were produced. Thereafter the production of BHC and DDT and the im- portation of cyclodiene insecticides were almost ceased. Determination of organochlorine insecticides in food- stufl's using a gas-liquid chromatograph with an electron- capture detector in Japan was initially conducted by Nishimoto et al. (7) in 1966. Many similar studies were conducted subsequently. Because BHC, one of the most heavily used insecticides in Japan, had been applied to the fields without purifying the insecticidally active y- BHC(lindane), other isomers such as a-, /8-, and S-BHC have been generally found in vegetables. The composi- tion of technical BHC includes 53-70 percent a-BHC. 3-14 percent /3-BHC, 11-18 percent y-BHC, and 6-10 percent R-BHC. Residues of dieldrin, endrin, and DDTR {p.p'-DDT+p.p-DDE+p.p'-TDE-ho.p'-DDT) were also detected in vegetables. The main objective of the present study was to monitor organochlorine insecticide residues in vegetables com- monly cultivated and consumed in the Kitakyushu Dis- trict, Japan (Fig. 1 ). Sampling Procedures All the vegetable samples were taken directly from the fields in which they were grown according to the sched- ule in Table 1. Although sampling procedures varied depending on the sample, approximately 1 kg of each vegetable was collected, wrapped in a polyethylene bag, and immediately taken to the laboratory for analysis. Typical samples were a head of cabbage and Chinese cabbage, a root of radish, or three or four roots of turnips and carrots. Vol. 10, No. 2, September 1976 35 1 { 1 t? S Japan Sea r I KiTAKYilSHU f _ «tt-vir P*^^^ Pacific ^^ Osaka Tokyo ^"'^^ FIGURE 1. Map oj Japan showing the Kitakyushu District A nalytical Methods EQUIPMENT AND REAGENTS Chronialographic columns, 22 x 300 mm Three-ball Snyder columns with ground glass fittings 5-ml graduated concentrator with ground glass fittings Shimadzu GC-5AIEE gas chromatograph with dual tritium foil electron-capture detectors n-He\ane redistilled twice in an all-gas distillation system Nanograde diethyl ether Reagent grade anhydrous sodium sulfate heated 2 hours at 625°C to eliminate interferences Florisil washed thoroughly with distilled water, dried at 110°C, heated at 625°C for 2 hours, deactivated slightly by adding 1 percent distilled water by weight. and mixed well for 30 minutes in a glass-stoppered flask prior to usage TABLE I. Schedule for sampling vcgelahlcs for organo- chlorinc insecticide analyses. Kitakyushu District. Japan— 1971-74 Vegetable No. Samples Taken Vegetable No. Samples Taken March 21, 1971 Radish Spinach 7 Cabbage 4 7 July 13, 1971 Cucumber Eggplant 6 Tomato 4 Cabbage 5 2 September 14, 1971 Carrot Radish 1 Cabbage 1 Turnip 1 J November 5, 1971 Radish Chinese Cabbage Cabbage 15 Spinach 8 Turnip 7 Carrot 6 4 5 July 16. 1972 Cucumber Eggplant 8 Radish 1 Cabbage 1 7 November 17, 1972 Radish Chinese Cabbage Cabbage 5 Spinach 4 Turnip 4 4 4 July 9, 1973 Cabbage Cucumber 6 Eggplant 5 Carrot 5 3 December 13, 1973 Radish Chinese Cabbage 8 Cabbage 6 Turnip 5 3 September 4. 1974 Cucumber 4 Novemher 21, 1974 Radish Chinese Cabbage Cabbage Spinach Turnip PREPARATION OF SAMPLES .Samples were chopped, mixed thoroughly, and homo- genized in a mixer. The root vegetables were washed with cold water to remove adhered soil, and wiped dry. The 100-g homogenized samples were placed in lOO-ml beakers, capped with Parafilm. and stored in a refrigera- tor at -20°C until extraction. EXTRACTION All analyses were performed in duplicate and the results represent an average of duplicate analyses. The extrac- tion and partition procedures corresponded to AO.AC Official Methods (/). However, only 200 ml of 6 per- cent diethyl ether in n-hexane was used to elute the organochlorine insecticide residues from a florisil col- umn. The cluate was concentrated to approximately 3 ml under a three-ball Snyder column. After addition of heptachlor epoxide as an internal standard, the concen- trated eluate was filled up to 5 ml, and 5 /j1 of the eluate was injected into a gas chromatograph. Recovery was v\ell above 90 percent; results v\ere not corrected. GAS CHROMATOGRAPHY Analyses were made with a gas chromatograph equipped with a dual tritium foil electron-capture de- tector. A multiple column system employing three col- umns with various polarities was utilized in accordance with the previous report (12) to identify and determine residues. The presence of each insecticide was con- firmed by comparing the gas-chromatographic retention times of the three columns employed. Operating condi- tions were: Column: U-shaped glass. 3 mm ID, 200 cm long (i) 2 percent OV-17 (ii) 2 percent diethylene glycol succinate — 0.5 percent phosphoric acid (iii) ."i percent Apiczon L grease. 36 Pesticides Monitoring Journal These were coated on 80/100 mesh Gas-Chrom Q. Carrier gas: prepurified nitrogen at a flow rate of: (i) 45 ml/min (ii) 100 ml/min (iii) 100 ml/min Temperatures: Detector: (i) 190°C; (ii) 190°C: (iii) 210°C Injector: (i) 210°C: (ii) 210°C: (iii) 220°C Column: (i) 190°C; (ii) 190°C; (iii) 210°C Retention times of p.p'-DDT were approximately 15 minutes on the 0V-I7 column. 12 minutes on the di- cthylene glycol succinate-phosphoric acid column, and 12 minutes on the Apiezon L grease column. Twenty- five percent of full-scale deflection was obtained with 0.4 X 10 " g dieldrin on the Apiezon L- grease column. Therefore 0 004 ppm dieldrin in a vegetable sample showed that deflection. Minimum detectable levels of dieldrin. y-BHC. and p.p'-DDT in vegetable samples were 0.0002. 0.0005, and 0.0016 ppm. respectively. through the extraction and gas-chromatographic pro- cedures. Results and Discussion The residues detected in vegetable samples are shown in Tables 2-5. BHC isomers were detected in all sam- ples. Insecticide residues in the vegetables might have been transferred from the soil by the roots or taken up from the atmosphere. These insecticides have been pro- hibited on arable land in Japan since 1970. BHC isomers were detected in all samples taken because of the high level of contamination of field soils by BHC. one of the most widely used insecticides in the agricultural fields of Japan (//). BHC isomers were relatively well absorbed by the vegetables (13): ,8-BHC was dominant among BHC isomers because it was the most persistent in soil (15) and the hydrosphere (10). The percentage of /3-BHC in total BHC was gradually increased; that of a-BHC has decreased. The percent- ages of BHC isomers in total BHC in 1973 cabbage samples were 7.8 percent a-BHC. 76.5 percent /3-BHC, 5.9 percent y-BHC. and 9.8 percent S-BHC. The quan- tities in 1972 radish samples were 2.8 percent a-BHC, 80.0 percent /3-BHC, 11:5 percent y-BHC. and 5.7 per- TABLE 2. Organochlorinc insecticide residues in vcgelahlcs. Kilakyiisliii District. Japan — 1971 Vegetable No. SAMPLES a-BHC e-BHC 7-BHC 5-BHC Dieldrin Endrin DDTR Radish 22 Average, ppm wet weigtit 0.007 0.042 0.0 to 0.008 0.021 0.010 O.Wl Range, ppm wet weight T-0.076 0.001-0.401 T-0.049 T-0.031 T-0.136 0.001-0.023 0.002-0.083 Positi\e samples, % 100.0 100.0 100.0 100.0 68.2 40.9 18.2 Chinese Cabbage 8 Average, ppm wet weight 0.016 0.041 0.025 0,008 0.027 0,003 0.006 Range, ppm wet weight 0.002-0.070 0.002-0.187 0.001-0.142 T-0,031 0.002-0.077 NA NA Positive samples, % 100.0 lOO.O 100.0 100.0 37.5 12.5 12.5 CUCUMBEH 6 Average, ppm wet weight 0.004 0.007 0.009 0.003 0.087 0,031 0.009 Range, ppm wet weight 0. 001-0.006 0,003-0.019 0.002-0.018 0.001-0.011 0,002-0.200 0.012-0,067 NA Positive samples, 7c lOO.-O 100.0 1 00.0 100.0 50.0 50.0 16.7 Tomato 6 Average, ppm wet weight 0.003 0.008 0.003 0.001 ND ND ND Range, ppm wet weight 0.002-0.006 0.002-0.030 0.001-0.011 T-0,006 NA NA NA Positive samples, % 100.0 100.0 100.0 100.0 0 0 0 Eggplant 6 Average, ppm wet weight 0.008 0.010 0.006 0002 0.006 ND ND Range, ppm wet weight 0.003-0.026 0.003-0.036 0.002-0.017 0.001-0.006 0.002-0.009 NA NA Positive samples, % 100.0 100.0 100.0 100.0 33.3 0 0 Cabbage 19 Average, ppm wet weight 0.008 0.014 0,012 0.005 0.005 0.029 0.222 Range, ppm wet weight 0.001-0.037 0.006-0.046 0.002-0.094 T-0.028 0.001-0.009 T-0.076 0.003-0.652 Positive samples, % 100.0 100.0 100.0 100.0 47.4 26.3 15.8 Spinach 10 Average, ppm wet weight 0.005 0.040 0.007 0.008 0.008 0.063 0.023 Range, ppm wet weight 0.001-0.055 0.001-0.072 0.001-0.016 0,001-0.021 0.001-0.027 0.006-0.121 0.005-0.036 Positive samples, % 100.0 100.0 100.0 100.0 80.0 20.0 30.0 Turnip 5 Average, ppm wet weight 0.001 0.016 0.002 0.001 0.004 0.002 0.020 Ranee, ppm wet weight T-0.003 0.002-0.050 T-0.004 T-0.002 0.003-0.005 NA 0.009-0.031 Positive samples. Tc 100.0 100.0 100.0 100.0 60.0 20.0 40.0 Carrot Avcrnyc, ppm wet weight Range, ppm wet weight Positive samples, % 0.041 0.134 0.021 0.026 0.035 0.017 0.003 0.002-0.192 0,012-0,350 0.001-0.083 0.001-0.068 T-0.110 NA NA 100.0 100,0 100.0 100.0 83.3 16.7 16.7 NOTE: T = trace f<0.001 ppm wet weight). ND = not detected. NA = not applicable. Vol. 10, No. 2, September 1976 37 TABLE 3. OrganocMorinc insecticide residues in vei;eliil 2 Ohio 6 2 Oregon 2 -> Utah 6 6 Washington 4 4 Wyoming 6 4 TOTAL 57 114 65 1 15 NOTE: — = no sample collected. ' Concentrated Steffens' filtrate. bean oil, and tallow was similar to methods reported previously (/). The molasses and filtrate were extracted by weighing a 20-g sample into a 100-mI beaker and then thinning with 20 ml distilled water so that less than 5 percent of the sample adhered to the beaker. This mixture was poured into a 500-ml separatory funnel and 150 ml redistilled hexane was added and mixed a few seconds by shaking. Fifty ml isopropanol was added, and the mixture was shaken again and allowed to settle. The mixture was then washed three times with 150 ml dis- tilled water and the aqueous layers were discarded. The hexane layer was then filtered through a sodium sulfate filter tube into a 500-ml conical jointed flask. The excess solvent was evaporated through a .Snyder column to about 5 ml and transferred to a graduated centrifuge tube or other container. The extract was diluted to 10 ml with hexane and stored at low tem- perature for gas chromatography. No cleanup was necessary. Analyses were performed on gas chromatographs equipped with tritium foil electron affinity detectors for organochlorine compounds and flame phytometric de- tectors for organophosphorus compounds. Pesticides and related chemicals detectable by these methods are listed in Table 2. A multiple-column system employing polar and nonpolar stationary phases was used to iden- tify the pesticides. Dual-column gas chromatography was employed for each sample: the main column and one of the two alternative supplementary columns. Instrument parameters were: Columns glass, 6 mm OD by 4 mm ID, IS.'? cm long packed with one of the following: 1.5 percent OV- 17/ 1.95 percent QF-l on 100/ 120 mesh diatoport (alternative and supple- mentary column) Organochlorine Compounds Organophosphorus Compounds Aldrin Benzene hexachloride isomers Dicldrin o.;i -DDE p,P -DDE o.p-TDE p.p -TDE o.p-DDT p.p -DDT Endrin Heptachlor Heptachlor epoxide Polychlorinaled biphenyls Technical chlordane Toxaphene Trifluralin DEF Diazinon Ethion Ethyl parathion Malatliion Methyl parathion Phorate Trithion 3 percent DC-200 on 100/120 mesh gas-chrom 0 (main column) 9 percent QF-l on 100/120 mesh diatoport (alternative and supplementary column) Carrier Gases 5 percent methane-argon at a flow rate of 80 ml/min Prepurified nitrogen at a flow rate of 80 ml/min Temperatures Detector Injection port Column QF-l Column DC-200 Mixed column 200°C 250°C 166°C 170°-175°C 185°-190°C Generally, the limit of minimum detection was 0.01 ppm. Mixed pesticides such as polychlorinated bi- phenyls, toxaphene, and chlordane are exceptions, and the limits for these pesticides range from 0.03 to 0.05 ppm. RECOVERY Recovery rates from sugarbeet pulp ranged from 89 to 105 percent except heptachlor epoxide which w.ts 82 percent. Recovery rates from molasses and filtrate ranged from 83 to 88 percent with an average of 87 percent. Results presented here were corrected for re- covery. Results and Discussion All residue results were reported on the sample as it had been received. Nearly 15 percent of the 114 pulp samples contained pesticide residues as shown in Table 3. Residues of /)./>-DDE, o.p'-DDT, p.p -DDT. dicldrin, toxaphene, and o.p'-DDE were found but the arithmetic mean concentrations of all these residues were less than 0.01 ppm. The mean dicldrin residue value for pulp was below 0.01 ppni and maximum value detected was 0.01 ppm. W.ilker et al. (6) reported the dicldrin residue of dried sugarbeet pulp for three dilTcrent pesticide treatments 42 Pesticides Monitoring Journal TABLE 3. Arithmetic mean and range of pesticide residues in sugarbeet pulp and related materials from processing plants No Positive Heptachlor Anal- yses Samples, o.p Mean -DDE Range P.P Mean -DDE Range o.p Mean -DDT Range P.P Mean -DDT Range DiELDRIN TOXAPHENE Epoxide Materul Mean Range Mean Range Mean Range Pulp 114 14.7 <0.01 ND-0.01 <0.01 ND-0.16 <0.01 ND-0.01 <0.01 ND-0.05 <0.01 ND-0.01 <0.03 ND-0.34 ND ND Molasses 65 0 ND ND ND ND ND ND ND ND ND ND ND ND ND ND Soybean Oi 4 50.0 ND ND ND ND ND ND ND ND 0.02 ND-0.05 ND ND <001 ND-0.01 Tallow 1 100.0 ND ND ND ND ND ND ND ND 0.01 NA ND ND ND ND C.S.F.i 15 0 ND ND ND ND ND ND ND ND ND ND ND ND ND ND NOTE: ND = not detecled. NA = not applicable. Limit of minimum detection is generally 0.01 ppm except for toxaphene, which ranges from 0.03 to 0.05 ppm. All residues were reported on the sample as it had been received ' Concentrated Steffens' filtrate. of soil in their pilot laboratory study: the mean of their three dieldrin residue values was 1.096 ppm and the range was 0.089-1.712 pprr. The difference between findings of these two studies may reflect ditTercnces in handling and processing practices between industrial processing plants and the pilot laboratory. No pesticide residues were found in samples of molas- ses or concentrated Steffens' filtrate, a fact which may result from the manufacturing process. Pulp is e.x- tracted with water at 79.4'C. Since chlorinated hydro- carbons are quite insoluble in water, much of the pesticide residue may remain in the pulp. Even if resi- dues were found in the juice, it is highly probable that the severe treatments with milk of lime, sulfur dioxide, and activated carbon would remove or destroy residues. Because the concentrated Steffens" filtrate and molasses are both derivatives of juice, it is not surprising that no pesticide residues could be detected. The detection of dieldrin and heptachlor epoxide in soybean oil is consistent with the result of a previous study (!) which showed that soybeans contained mean levels of 0.12 ppm dieldrin and less than 0.01 ppm heptachlor epoxide. All pesticide residues detected in the study of sugar- beet pulp, that is, DDT, dieldrin, and toxaphene. had been commonly applied to soil or mixed with dry seed prior to planting for control of various sugarbeet pests such as wireworms, root maggots, and cutworms. Therefore, the detected residues are indication of cause and effect of pesticide application. Conclusion Use of sugarbeet pulp as cattle feed presents a poten- tial problem of pesticide entry into cattle and eventually into the human food chain. However, the small amount of residues present in the pulp may never build up enough in the human food chain to endanger health. Molasses from sugarbeet processing does not present such a problem. LITERATURE CITED (/) Carey. A. E.. G. B. Wiersma. H. Tai, and W. G. Mitchell. 1973. Organochlorine pesticide residues in soils and crops of the corn belt region. United States — 1970. Pestic. Monit. J. 6(4) :369-376. (2) Johnson, J. R., and S. E. Bischcl. 1962. Insecticide resi- dues in sugarbeet byproducts. J. Amer. Soc. Sugar Beet Technol. 12(3) :255-258. (3) Miins. R. P.. M. W. Stone, and F. Foley. 1960. Resi- dues in vegetable crops following soil applications of insecticides. I. Econ. Entomol. 53(5) :832-835. (4) Shieves. R. N. 1967. Chemical Process Industries. Mc- Graw-Hill Book Co., pp. 631-633. (5) U.S. Department of Agriculture — Plant Protection Di- vision. 1970. Sugar Beet Pulp Sampling at Sugar Beet Processing Plants in the Conterminous United States. 4 pp. (6) Walker. K. C, J. C. Maitlen. J. A. Onsager. D. M. Powell, and L. I. Butler. 1965. The Fate of Aldrin, Dieldrin, and Endrin Residues during the Processing of Raw Sugarbeets. U.S. Department of Agriculture, pp. 1-10. Vol. 10, No. 2, September 1976 43 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES OrganochJorine Residues in Three Bat Species from Four Localities in Maryland and West Virginia, 1973 ' Donald R. Clark, Jr., and Richard M. Prouty ABSTRACT In 1973. 119 hats of ihrcc species were collected from four localities in Maryland and West Virginia. The collection in- cluded 43 big brown bals (Eptesiciis fuscus), 43 little brown brown bats (Myotis lucifugus), and 33 eastern pipistrellcs (Pipistrellus subflaviis). The bats were collected from Round Top Mountain, Washington Co., Md.; Trout Cave, Pendle- ton Co., W. Va.: Monlpelier Barn. Prince Georges Co.. Md.; and Xorth East Methodist Church in Cecil Co., Md. Resi- dues of ZDDT were highest in carcasses of bals from Rouiul Top Mountain, which is surrounded by apple orchards. Bats from Trout Cave had the lowest residues, a circu/nstance which probably reflects the absence of agriculture and in- dustry in the area. A polychlorinated biphenyl (PCS) and oxychlordane were highest at Monlpelier Barn. Sources of the PCB are unknown, but chlordane is used against termites and in gardening at nearby Iwusim; developments. Residues in bats from Xorth East Methodist Church were low except for dieldrin. Among species, little brown bats usually had the highest residue concentrations in their carcasses, whereas big brown bats had the lowest. When DDE in carcass fal of all species irn? above 60-90 ppm. it became measurable in brain tissue. Above 60-90 ppm. DDE levels in brains rose with increasing levels in carcass lipids. Residues of the PCB tended to respond simi- larly. Residue levels in brains were greatest in little brown hats: the maximum level of the PCB. 7.9 ppm, was more than twice thai of DDE. Uurodiiction Several authors have postulated that organochlorine in- secticides may have caused declines in bat populations {2,7,11.12,15,16,19). Free-living bats have been sam- pled for organochlorine residues in Britain {/.?), Ari- zona and Mexico f/7), Australia {1.10). and Texas (6). Data also indicate that \roclor 1260. a polychlori- nated biphenyl (PCB), cause/ stillbirths in a Maryland colony of big brown bats {Epicsicus fu.scus) {4). The > Fish .md Wildlife Service, U.S. Der.nrtment of Inlerior, Paliixcnl Wildlife Research Cenicr, Laurel, IVld. 20811 extent of contamination of bat populations is only partly described by these few studies. Furthermore, proper interpretation of such residue data will not be possible until tissue levels of residues are experimentally correlated with toxicological effects. At four ecologically diverse localities, authors sampled residues in three bat species (big brown bat: little brown bat. Myotis lucifugus: and eastern pipislrelle. Pipistrel- lus suhfiavus) , which are common and wide-ranging in North America. Materials and Methods All three species were present at the two collection localities in the Allegheny Mountains. One locality. Round Top Mountain, has several abandoned mine tunnels adjacent to the Potomac River. 5.4 km south- west of Hancock. Washington Co., Md. Extensive apple orchards arc located near this site. The second locality. Trout Cave, is adjacent to Highway 220, 5.6 km south- west of Franklin, Pendleton Co.. W. Va. The surround- ing area is mostly undisturbed forest. Additional infor- mation about these two sites is available elsewhere (i'^.9). Big brown and little brown bats were collected at a third locality. Montpelier Barn, at Montpelier Slate Historical Site, Laurel. Prince Georges Co., Md. This locality is in the urbanized corridor between Washing- ton. D.C.. and Baltimore. Md. It is surrounded by hous- ing developments, shopping centers, and highways. Only little brown bats occur at the fourth site, the attic of the Methodist Church in North East. This is a town of 1,600 residents in Cecil Co.. Md., at the northern end of the Chesapeake Bay. Authors collected bats at or near the extremes of the animals' fat cycles in spring and f.ill 197.''. Collection dates were: Round Top Mountain, .April .^ and October .11; Trout Cave. April 12 and November 1: Montpelier Barn. April 26 and October 2; and North East Metho- dist Chtirch. May 2 and October ?>. Numbers of b.ils caught on these dates are given in Table 1. To obt.iin 44 Pesticides Monitoring Journal TABLE 1. Summary of principal organocMorine residues in carcasses of 110 bats, Maryhiiid and West Viriiinia — 1973 RtSIDUE LEVELS, PPM WEF weight PCB DDE DDT TDE DiELDRIN OX^'CHLORDANE Geom Geom. Geom. Geom Geom. Geom. Sample n Mean Range Mean Range Mean Range Mean Range Mean Range Mean Range Round Top Mountain Spring BBB -' 6 1.27 0,50-2.4 11,16 4.6-67 0.86 0.41-2.1 0,22 0,11-0.50 0.55 0.34-1,1 0,20 0.15-0.31 9 3 1.48 1.2-1.8 7.29 2,2-32 0.41 0.20-0,95 0.04 ND-0-14 0,56 0.28-0.81 0.10 ND-0.19 LBB e 2 7.75 6.0-10 10.78 8,3-14 1,08 0,83-1,4 0,62 055-0.71 0,73 0.3S-1.4 0.43 0.38-0,48 EPB cC 7 8.18 3.4-20 6.39 0,93-21 0.59 0.44-1.1 0,22 0,100.48 0,29 0.14-0.74 0,36 0.23-0.60 9 3 6.01 2.3-11 3.32 2.6-4.4 0.52 0.34-0.68 0,18 0.15-0.22 0,30 0.22-0.56 0.36 0.28-0.46 Fall BBB cf 3 0.77 0.55-0.91 635 2.9-17 0.41 0.22-1.3 ND ND-ND 035 0.11-082 0.04 ND-0.13 LBB d 3 4.60 3.7-6.4 38.54 14-87 2.45 1.4-5.0 0,49 0,21-2,0 0,64 0.37-1.1 0.65 0.52-1.0 9 I 2.3 23 2.0 0.77 1.3 0,38 EPB .f 5 3.76 0.60-9.1 9.72 4.0-34 0.74 0.33-1.4 0.27 ND-1.9 0.52 0.22-1,2 0.40 0.15-0.58 Trout Cave Spring BBB cT 10 0.75 0.45-0.99 0.67 0,36-1.9 0.14 ND-0.25 ND ND-ND 0,20 ND-0,28 0,02 ND-0.11 LBB ff 7 4.21 1.2-26 2.83 0 69-18 0.55 0.17-3.2 0.55 ND-1.9 0,64 ND-22 0,45 0 07-1.9 EPB c' 10 1.74 0.56-8.1 2.21 0.14-6.9 0.67 0-12-1.9 0,32 ND-0,96 0 14 ND-0,49 0,27 ND-0.63 9 3 1.19 ND-2.6 2.56 1.0-12 0.83 0.12-3.2 0,49 ND-1.0 041 0,20-0,63 0,24 0.11-0.40 FaU BBB d- 1 0.27 0.29 ND ND ND ND 9 2 0.50 0.50-0.50 0,23 0.17-0.32 0.21 ND-0.47 ND ND-ND ND ND-ND ND ND-ND LBB cf 1 10 2.9 0.96 0.14 0,18 0,29 9 4 4.69 1,3-12 1.90 0.85-4.9 1.60 ND.20 0,44 ND-2,2 0.22 0.13-0.31 035 0.18-0.61 EPB ^ 2 0.60 0,59-0,61 0.38 0.26-0.55 ND ND-ND ND ND-ND ND ND-ND 0.19 0.10-0.28 9 3 0.71 ND-2.9 1.38 0.35-4.2 0.15 ND-0.31 0,17 ND-0,36 0.09 ND-0.31 0,13 ND-0.21 Montpel ER Barn Spring BBB -f 4 4.99 4.1-5.7 5.32 4.5-5.9 0.70 0.63-0.86 0.23 0,18-0,35 0.50 0.43-0.62 0.81 0,66-0,93 9 3 2.87 2.3-3.2 3,48 3.0-3.8 0,32 0.27-0.40 0.04 ND-0.11 0,51 0.44-0.58 0.40 0,31-0,58 LBB 9 5 11.61 3.9-21 3.00 1.9-7.6 0,54 0,28-1.1 0.25 ND-0,52 1,04 0.71-1.5 1.52 1.1-2.7 Fall BBB ^ 2 2.50 2.4-2.6 2.05 2.0-2.1 0.42 0.39-0.45 ND ND-ND 0.59 0.48-0.73 0,31 0.24-0.41 V 3 0.48 0.14-1.5 0.59 0.19-2.0 0.05 ND-0.15 ND ND-ND 0.26 0.12-0.47 0.11 ND-0.17 North East Church Spring LBB 9 11 3.22 1.6-5.9 1.80 0,71-3,7 0,38 0,13-1,3 0.29 ND-0.87 1.01 0.45-3.2 0.52 ND-3.0 Fall LBB 9 6 2.34 1.4-4.0 1.47 0.70-3.1 0.30 0.18-0,64 0.09 ND-0.18 0.70 0.24-3.2 0.63 0.31-1.2 NOTE: BBB = big brown bat. LBB = little brown bat. EPB = eastern pipistrelle bat. n = number of bats sampled. additional samples of stomach contents for chemical analysis, authors collected nine more bats in July 1973 after their evening feeding flights: on July 11 four big brown bats (3 males. 1 female) and one little brown bat (male) were collected at Montpelier Barn, and on July 25 two big brown bats (males) and two little brown bats (1 male, 1 female) were caught at Trout Cave. In sum, 1 19 bats were collected and analyzed. Bats were frozen at capture and later thawed and weighed before dissection. Brains, carcasses, pooled samples of masticated insects from stomachs, and guano samples were analyzed. Wings, feet, and skin were re- moved and discarded, the head was severed at the base of the skull, and the brain was removed after clipping away the top of the cranium with iris scissors. Major masses of head masculature were placed with the car- cass for analysis and the skull was dried and stored. The gastro-intestinal tract was removed from the re- maining body portion, which was then analyzed as car- cass. The occlusal tip width of the upper left canine (canine tip width, CTW) was measured using a 30X dissecting microscope and ocular micrometer. This mea- surement was used as an indicator of relative age [3). Samples were placed individually into cleaned and weighed glass jars, weighed, and rcfrozen until grinding. All samples were analyzed at the Patuxent Wildlife Re- search Center. Personnel immunized against rabies pre- pared the tissue under a bacteriological hood in an iso- lated area of the laboratory because bat tissues can carry rabies. After extraction, no special precautions were required. The material was thawed and ground with anhydrous sodium sulfate to remove moisture. The resultant mixture was transferred to a paper extraction thimble and extracted with hexane on a Soxhlet appara- tus for approximately 7 hours. The extract was cleaned Vol. 10, No. 2, September 1976 45 On a florisil column with 200 ml of 6 percent ethyl ether in hexane. Pesticides and polychlorinated biphcnyls (PCB's) were separated into three fractions on a Silicar column and analyzed with a Hewlett-Packard 5753 gas-liquid chrom.itograph equipped with a Ni" detector, auto- matic sampler, digital integrator, and a 4 percent SE- 30/6 percent QF-1 column at 190°C. The flow rate of 5 percent methane in argon was 60 ml/min for columns and 40 ml'min for purge. DDE was quantitated by peak height to avoid errors from PCB interference: other pesticides were measured by digital integration of area, and the PCB was quantified by comparing total peak area with that of Aroclor 1260, the compound whose pattern matched it most closely. Samples were analyzed for p.p'-DDE. p.p'-TDE. p.p'- DDT, dicldrin, heptachlor epoxide, mirex, oxychlor- dane, c/i-chlordane and/or trans-nonach\or, cis-non- achlor. hexachlorobenzene (HCB), toxaphene, and PCB's. Average percent recoveries from spiked tissues of mallard duck (Anas platyrhynchos) were DDE. 96; TRE, 103: DDT. 112: dieldrin, 101: heptachlor epox- ide, 104: oxychlordane. 98: c/5-chlordane, 100; cis- nonachlor. 98; HCB, 69; and the PCB, 101 percent. Residue data were not adjusted for recovery. The lower limit of sensitivity was 0.1 ppm for pesticides and 0.5 ppm for PCB in carcass and guano samples. The small size of brain and stomach samples limited sensitivity to 0.5 ppm. Residues in 12 percent of the samples were confirmed with a gas chromatograph ' mass spectrometer equipped with a temperature-programmed 1 percent SE-30 col- umn. Program rate was 2°C/min; initial temperature. 135°C, rose to a maximum of 220°C. Operating con- ditions were: flow rate. 35 ml/min helium: oven tem- perature. 200°C: flash heater, 220T; separator, 240''C; and ion source, 290°C. The ionization potential was 70 eV, and the accelerating voltage was 3,5 kV. Results are given as ppm wet weight unless lipid weight is designated. Guano was weighed dry as it came from the roost and masticated insects were weighed as they came from stomachs. Because the residue data were positively skewed, they were log transformed for all statistical testing. Geome- tric means are given for residue data. DilTorenccs be- tween means were tested for significance using Student's /-test adjusted for sample size US). Significance levels were: "=0.05>P>0m; **=0.01>P>0.001 : and ***=P<0.00]. Residue levels reported as not delected (ND) entered computations as zeros. Results and Discussion RESIDUFS ACCORDINC, TO AGt: When the 119 bats sampled were subdivided by species. locality, and sex, four groups remained which included ten or more bats each: female little brown bats at North East Methodist Church (n^l7); male big brown bats at Trout Cave (n=\i): male pipistrelles at Trout Cave («^12); and male pipistrelles at Round Top («=12). For each of these four groups, the regression between CTW and ^ug of residue in the carcass was calculated for the PCB, DDE, DDT, TDE, dieldrin, and oxychlordane. DDE declined significantly with in- creased CTW among male pipistrelles from Trout Cave (r=0.63*. slope=-1.42). Similarly, the PCB declined among female little brown bats at North East Methodist Church, but the correlation coefficient was not signifi- cant (/--0.46, 0.1>P>0.05, slope =-0.81 ). These negative relationships resemble those found for the PCB in female big brown bats and their newborn young from both Montpclier Barn (4) and a house attic in Gaithersburg, Md. (5). They differ, however, from the relationship of DDE in female free-tailed bats {Tadiiiida hrasiliensis) , which dropped abruptly after the first year of life and then increased with age (6). For the data at hand, the overall effect of age on residue load is minor and was ignored in subsequent analysis, RESIDUES ACCORDING TO SEX After subdividing samples by species, locality, and season, authors were able to conduct eight tests between means for males and females for the PCB, DDE, DDT, dieldrin, and oxychlordane. and seven tests for TDE. Six of 47 tests based on total /xg in carcasses showed significant differences: males had higher residues than females in all six samples. Five of the six tests were for the spring sample of big brown bats from Mont- pclier Barn and included the PCB (r=3.60*), DDE (/=2.63*), DDT (/=5.04**), TDE (f=3.67*), and oxychlordane (r=3.14*). The sixth was the spring sample of big brown bats from Round Top and the chemical was TDE (/--3.17*). When residues were treated as ppm, six of six signifi- cant tests also showed males with greater residues than females. Five of the six significant tests were again from the spring sample of big brown bats from Montpelier Barn: the PCB, ?=4.47**; DDE, t=4.73**; DDT, /=6.01**: TDE, r=3.84*: and oxychlordane, r=3.83*. The sixth was the fall sample of big brown bats from Montpelier Barn: the chemical was DDT (r=4.9I*). Because high residues of PCB's and DDE have been found in bat milk (5,6). authors believe that lactation played a role in producing these differences in residues between males and females. None of the eight male/ female tests for dieldrin showed a signific;int difference, but means for females, ex- pressed as both /jg and ppm, were greater than those for males in seven cases. The probability of this hap- pening if the sexes were equ;illy likely to show a greater ~ 'i any single comparison is P=0.03*. Thus the 46 Pesticides Monitoring Journal kinetics of dieldrin in males and females may be unique among these toxicants. Even though significant differences involved only big brown bats, it seems clear that comparisons of samples with markedly different proportions of males and fe- males must be made cautiously regardless of species, RESIDUES ACCORDING TO SEASON After subdividing samples by species, locality, and sex. authors were able to conduct 10 tests between means for spring and fall for the PCB, DDE, DDT, dieldrin, and oxychlordane, and 8 tests for TDE. When residues were expressed as total ixg in carcasses, 10 of 58 tests showed significant differences, but 6 of these showed greater residues in the spring and 4 showed greater resi- dues in the fall. All 10 tests involved males. .Samples with significantly more residues in the spring were big brown bats at Montpelier Barn (DDE, /=3.22*; TDE. /=10.15***), big brown hats at Round Top (TDE. f=5.12**; oxychlordane, t—2.19*). big brown bats at Trout Cave (dieldrin, /=2.36*). pipistrelles at Trout Cave (DDE, r = 3.24**). Samples with more residue in the fall were big brown bats at Montpelier (dieldrin, r=3.46*), little brown bats at Round Top (oxychlor- dane, /=3.40*), and pipistrelles at Round Top (DDT. r=2.35*; dieldrin, /=2.34*). Both significant tests with TDE showed higher residue in the spring. The spring mean for TDE was greater than that for fall in seven of eight cases (P=0.03*). Corresponding decreases in DDT did not occur during hibernation; thus increased TDE through breakdown of DDT is not indicated. In sum, no spring/fall pattern in ix% residues appeared in the bats except, perhaps, for TDE. Considering that /ig residues did not change consistently with season, and that the bats store abundant fat be- fore winter, it is predictable that residues expressed as ppm would be greater in spring. Twelve of 58 tests showed significant dilfcrcnces: spring amounts were greater in all 12 cases. Male samples were big brown bats at Montpelier Barn (the PCB, r=6.42**): DDE, r= 10.08***; DDT, r=4.37*; TDE. t=4.68**; o.xy- chlordane. f=4.69**), big brown bats at Trout Cave (the PCB, f = 3.52**; TDE, /=3.18*), big brown bats at Round Top (oxychlordane, f=3.69**), and pipis- trelles at Trout Cave (DDT, ;=:2.72*). Female samples were big brown bats at Montpelier Barn (DDT. t= 4.20*; oxychlordane. f=3.10*) and little brown bats at North East Methodist Church (TDE, r=2.31*). Au- thors conclude that utilization of stored fat during win- ter caused residues to be more concentrated in bats in the spring. RESIDUES ACCORDING TO LOCAIITY Data comparing quantities of residues in bats accord- ing to locality (Table 2) were restricted as much as possible and include only spring males for the big brown bat and pipistrelle. For the little brown bat, the Round Top and Trout Cave samples were also spring males, but spring females had to be used for Montpelier and North East Methodist Church. Comparisons among means for the little brown bat must be made with this difference in mind. Authors drew several conclusions from Table 2. First, bats from Round Top consistently had the highest resi- dues of SDDT. whereas bats from Trout Cave usually had the smallest amounts of all residues. Presumably the Round Top data reflect previous use of DDT in the apple orchards, and the Trout Cave data reflect the TABLE 2. Comparisons of quantities of residues in hats by locality. Maryland and West Viri;inia — 1973 PCB Mean residue in carcass, hG DDE DDT TDE Dieldrin Oxychlordane Big Brown Bat ' Round Top Montpelier Trout Cave 10.52" 40.48 » 5.82 = 87.75^ 43.23 > 5.19" 6.80" 5.75" I.Ol" 1.72" 1.89 = 0.00 >> 4.33 » 4.09" 1.46" 1.58" 6.63" O.Il'^ Little Brown Bat • Round Top Montpelier Trout Cave North East 25.83"" 45.88" 13.44"" 14.02" 35.67" 11.85"" 9.02"" 7.90" 3.53" 2.18" 1.79" 1.63" 2.04" 0.87" 1.55" 1.17" 1.41" 4.10"'- 1.77 "<• 4.46" 1.40" 6.04" 1.40" 1.79" Round Top Trout Cave 23.87" 4.92" Eastern Pipistrelle Bat ' 18.67' 6.18" 1.72 = 1.90" 0.65" 0.85" 0.84" 0.37" 1.03" 0.73" NOTE: Superscripts indicate statistical significance among means. Shared superscripts indicate means that are not significantly different at a minimum of 95 percent confidence, ' Samples include only spring males. Sample sizes are given in Table I, -Samples are spring males from Round Top Mountain and Trout Cave; spring females are from Montpelier and North East. Sample sizes are given in Table 1. Vol. 10, No. 2, September 1976 47 absence of agriculture and industry from that area. Second, residues of PCB and ovyehlordtine were high- est at Montpelier Barn for the two species that occur there. .Sources of PCB's in such urhan situations are diffuse and ditlicuh to idenlif\- (/-7l. (Isychlordane may come from household usage of chlordanc on orna- mental \egetation or it may come from efforts to con- trol termites. Third, whereas most residues seem lov\ at North East Methodist Church when considering only the little brovsn bat. residiies of dieldrin were high, compar.ible to those at Montpelier Barn. Sources of the dieldrin are not known. Because results among the species are similar, authors believe that sex differences among samples of little brown bats had little effect on the means. .Authors repeated the comparisons of Table 2 but utilized data for all bats from each locality by disre- garding dilferences in season and sex. Even though means were changed somewhat by this procedure, the conclusions were not. Residues in guano correspond with those in the bat carcasses, but they occurred only infrequently in stom- ach contents (Table 3). This result could be anticipated because guano samples were large (16-20 g), relatively dry. and originated from perhaps 50-500 different bats TABLE 3. Residues in masticated insect samples from hat stomachs, and in i^iinno. Maryland and West Virginia — 1973 Residues, ppm wet weic.ht PCB DDE DDT TDE Dieldrin Oxychlordane Big Brown Bat: Stomach Contents Montpelier ' Trout Cave ■ ND ND ND ND ND ND ND ND ND ND ND ND Little Brown Bat: Stomach Contents Trout Cave " North East ' 1.40 ND ND ND ND ND ND ND ND 0.06 ND ND Little Brown Bat: Guano Montpelier ' North East ' 0.96 0.51 0.32 ND ND 0.28 0.10 ND 0.18 0.75 0.10 ND NOTE: ND = not detected ^ Two pooled samples; one was from four hats and ttie other was from five. - One pooled sample from two bats. ^ Two pooled samples; one was from 1 1 bats and the other was from 6. * Single sample of 16-20 g. TABLE 4. Comparisons of residue concentrations antont; hat species from Maryland and West ^'irc;inia — 1973 Mean residues in carcass, ppm wet weight PCB DDE DDT TDE Dieldrin Round Top Mountain ' Oxychlordane LBB EPB BBB 7.75« 8.18" 1.27" 10.78 ■' 6.39" 11.16» I.08» 0.59 » 0.86" 0.62 » 0.22" 0.22"'' 0.73 » 0.29" 0.55 » 0.43" 0.36" 0.20'' Trout Cave ' LBB FPB BBB LBB BBB 4.21" 1.74" 0.75" 11.61" 2.87" 2.83" 2.21" 0.67" 0.55" 0.67" 0.14" 0.55" 0.32" 0.00" Montpelier Barn ' 3.00" 3.48" 0.54" 0.32' NOTE: BBB -. big brown bat LBB ;: little brown bat. EPB = eastern pipisircllc bat. Superscripts indicate statistical significance among means. ' Samples include only sprmg males. Sample si/cs arc given in Table I. 'Samples include only spring females. Sample sizes arc given in Table 1. 0.25" 0.04" 0.64" 0.14" 0.20" 1.04" 0.51" 0.45' 0.27" 0.02" 1.52" 0.40" 48 Pestk ides Monitoring Journal feeding at various times of the year. Samples of stom- ach contents were smaller (0.398, 4.401, and 8.595 g for big brown bats; 1.033. 1.261, and 1.610 g for little brown bats), contained more moisture, and represented fewer bats feeding at fewer times of the year. Analyses of guano may be useful for surveying bat colonies for harmful levels of organochlorine residues. RESIDUES ACCORDING TO SPECIES Residues (Table 4) must be expressed as concentra- tions rather than as total weight because individuals of the three species sampled differ in average weight. Within samples from each locality, data are restricted to a single se,\ and season. Several conclusions emerge. First, where all three species occur, little brown bats and pipistrelles frequently have significantly more resi- dues than have big brown bats. Where little brown bats and pipistrelles differ significantly, little brown bats have more residues. Second, at Montpelier Barn none of the DDT-group compounds showed significant differences between species. When all data were compiled and com- parisons among species were repeated, conclusions were similar except that means for little brown bats at Mont- pelier Barn were higher for all six residues and the differences were significant for all compounds except DDE. The relatively low residue accumulation by big brown bats, whether the result of smaller dietary intake, more efficient excretion, or both, may be at least partly re- sponsible for the occurrence of this species in highly urbanized localities. The same data in Table 4 show relatively high residue accumulation by little brown bats. Knowledge of this propensity, if it is characteristic of other species in the genus, could be important in management of the en- dangered gray bat {Myotis ^lisescens) and Indiana bat {My Otis social is). RESIDUES IN BRAINS Residues of DDE in brains may be expected to vary in relation to the ratio of DDE to lipid in the entire ani- mal. Indeed, when DDE in carcass fat was above cer- tain concentrations, it became measurable in brains and increased with increasing levels in carcass lipids (Fig. 1. 2). It appears that DDE residues enter the brain sooner and increase more rapidly in the little brown bat than in the big brown bat (Fig. 1). Such comparisons of present data, however, may be misleading. Even maximum brain levels of DDE are low (Fig. 1,2). Brain levels of DDE ranging up to 8.2 ppm were found in Maryland big brown bats (5). The bat with the maximum level was young, feeding entirely on milk, and contained only 140 ppm DDE in its carcass lipids. Residue data for the young bat lead authors to suspect that a greater percentage of total DDE residue is found in the brain during the first weeks of life. For comparison, previously reported residues in free- tailed bats (6) are included in Figure 2. Maximal brain levels for adult free-tails are similar to those in big and little brown bats. Higher levels were found in nurs- ing young, especially those that had been deprived of food and had fallen to the cave floor. The dependency of brain levels of the PCB on concen- trations in carcass fat is not so clear as it is for DDE (Fig. 3). Authors do not know why the PCB should be less dependent. Brain levels of the PCB reached 7.9 ppm among adult little brown bats; this is more than twice the maximum found among adults for DDE. Experimental data are needed before the significance of this concentration of the PCB can be judged. The highest brain level of Aro- clor 1260 found previously (4.8 ppm) was in a nursing neonate big brown bat that contained only 90 ppm in its carcass fat (5). Again, the percentage of residue in the brain may be greater during the first weeks of life. The PCB was recovered from the brain of only one pipistrelle (0.66 ppm). In sum, adult little brown bats accumulated the greatest brain residues of both DDE and the PCB; thus this species may be more susceptible to poisoning than are the other two. OTHER RESIDUES In addition to the six residues discussed thus far, there were six others found in carcasses infrequently and/or in small quantities. At Round Top, four big brown bats contained up to 0.25 ppm heptachlor epoxide, and three contained traces (<0.1 ppm) of /ram-nonachlor. Three pipistrelles contained traces of ?/o«5-nonachlor, and one contained a trace of f»-chlordane. At Trout Cave, one big brown bat contained a trace of heptachlor epoxide. Three little brown bats contained as much as 0.44 ppm /ran^-nonachlor, three had up to_ 0.61 ppm c(>-chlordane, and one contained 4.5 ppm heptachlor epoxide. One pipistrelle had 0.12 ppm heptachlor epoxide and another contained 1.1 ppm ruirex. At Montpelier Barn, 13 big brown bats contained up to 0.52 ppm heptachlor epoxide, nine contained up to 0.88 ppm HCB, eight had up to 0.45 ppm trans-non- achlor. five had up to 0.27 ppm cw-chlordane, and five contained traces of c/^-nonachlor. Six little brown bats had as much as 4.2 ppm c/i-chlordane. five had up to 0.54 ppm heptachlor epoxide, four had up to 0.17 ppm HCB, three contained up to 0.42 ppm c/j-nonachlor, and two had up to 0.85 ppm (/■n«j--nonachlor. At North East Methodist Church. 13 little brown bats contained up to 4.4 ppm ci.s-chlordane (12 contained less than 0.5 ppm), six had up to 1.2 ppm c/5-nonachlor, five had up to 0.17 ppm trans-nonach\or, and one had 0.18 ppm heptachlor epoxide. Vol. 10, No. 2, September 1976 49 r ND E a. a < m LU o G ND ND Little brown bat O 007 ' ■ ■ ■ ■ • iJ_LJJ> ■ « ■ ■ ■ I I Eastern pipistrelle T V W . */ ■ ' ■ Big brown bat n7 Tvn □▼ • <^ I I I I I 1 1 1 I I DDE IN CARCASS, ppm lipid weight o Round Top O Montpelier Q Trout Cave O North East Church • Round Top O Montpelier O Trout Cave O D ■ A A o ^ FIGURE I. Rcldiiouship of DDE rcsiiliics in hiain lo ihosc in carcass lipuls of liiilc lirown hat. eastern pipistrelle, and bit; brown bat Among these lesser residues, the unique occurrence of HC'B at Montpelier Barn is surprising. The source of the fungicide in this urban location is not known. Only three bat brains that contained detectable oreano- chlorinc residues had materials other than a PCB and DDF; all three were collected in the spring. A male pipistrelle from Trout Cave had 0.46 ppm oxychlor- dane. and two female liille brown bats from Montpelier Barn contained 0..'>() ppm and 0.56 ppm oxychlordane. The laller bal also had 0.42 ppm dicldrin m its brain. CDMI'AKISONS WITH OTllhR IOC AI ITIhS AND SCFCIFS Jcirencs reported residues of I3i:)E. DDT. and dicldrin in four pipistrelles (Pipisirclliis pipistieUiis) collected in Britain (/.?). Average carcass residues uerc .''..''.'' ppm 50 i'LsiKiDF.s Monitoring Journal DDE. 1.99 ppm DDT, and 0.20 ppm dieldrin (authors' calculations). Carcass residues v\ere given for three other bats belonging to three other species, but the highest concentrations were among the four pipistrelles. Numerous means for DDE and dieldrin from the pres- ent study (Table 1 ) are larger than those for the pipi- strelles of JcfFeries (13). However, for DDT, only the mean for fall-captured little brown bats at Round Top is larger than the corresponding value reported by Jef- feries. The pipistrclle population sampled by Jcfferies apparently experienced more direct exposure to DDT than did most populations sampled in Maryland and West Virginia. Jefferies also reported that PCB's were not found in the bats he analyzed (/,?): this differs from findings of the present study. DDE residues in carcasses among cave populations of free-tailed bats in Arizona (17) and Texas (6) were generally lower than those in carcasses at Round Top, higher than those at both Trout Cave and North East Methodist Church, and similar to those at Montpelier Barn. PCB's were rare in free-tails, occurring in one from Arizona (1-2 ppm) and in four from Texas (0.48- 1.2 ppm). Five free-tailed bats found dead on the Uni- versity of Arizona campus in Tucson had apparently been exposed directly to DDT; amounts in carcasses averaged 61.4 ppm (range: 2.4-550 ppm) (/7). Car- casses of five female big brown bats collected from a house in Tucson contained an average 117.0 ppm DDE (range: 65-160 ppm) (17). These values are the high- est reported thus far for free-living bats. Pooled samples from each of three bat species (Eptesi- ciis puinilis. Tapliozoiis geoigianus, and Pteropus alccto) from the Northern Territory of Australia con- tained mostly trace residues (/). Levels reached as high as 1.82 ppm DDE. 0.25 ppm DDT. and 4.03 ppm dieldrin in the pooled whole animal samples of E. puinilis. PCB's were not accounted for in the analytical procedures of the Australian study (/). Dunsmore et al. (10) reported DDT and metabolites in carcasses of the Australian bat Minioplerus schreibersii: judging from the total /zg quantities detected, average concen- trations in seven samples must have ranged up to 1.4 ppm. PCB's were not reported. 6 - V 'S 5 - 5 5 E Q. O. 4 3 Free-tailedbat Y See Literature Cited (6) ▼ z < cc CO z UJ Q 2 1 - T O o ND - ouu u m (tfjt^0p U7 1 10 100 DDE IN CARCASS, ppm lipid weight Q Adult 9 ^ Adult O Q Young O from cave ceiling m Young O from cave ceiling ^ Young O from cave floor a Young O from cave floor FIGURE 2. Rclalioiwliip of DDE icsiduvs in liniin In llii>.\e in carcass lipids of frcc-ltiilcd hal Vol. 10. No. 2. September 1976 51 Acknowlcdi'iiicnt'! Authors arc gr.ilcfiil to the tollouing persons for their contribiilion to this sliitly: B. H;ir\ey and C, H.mJIey, who provided information about bat colonics; R. Pine, J. Ailes. I.. Carpenter. K. Nelson, and T. I.ufriu. who helped to collect spcciniens: G. Pcrrygo. P. Pcrrygo, H. Robey, and C. Poukish, who graciously provided access to property under their care; and R. McArlhur, who made important suggestions concerning treatment of d.it.i. Finally, we thank F. Dustman and I.. .Stickcl for their comments on the manuscript. I-ITERATURE CITED (/) nrsi. S. M. 197.^. Some orpanochlorine pesticide resi- dues in wildlife of the Northern Tcrrilorv, Australia. 1470-71. Ausl. J. Hiol. Sei. 261 .'>): 1 161-11 70. (2) IlniakMiui. S.. andJ . II . /'. 7". van ,lcr Iliift. 1972. Bats pesticide conflicts. TNO-Nieuws 27( 10):579-583. (.') Chrisiiiw. ]. J. 1956. The natural history of a summer apizregation of the big broun bat. Eptcsictis juscii.': Itisciis. Am. Midi. Nal. 55( 1 ) :66-').S. (4) Clark. /). R.. Jr.. and T. G. I.anionl. 1976. Organo- chlorinc residues and reproduction in the big brown bat. J. Wildl. M.inage. 4( 2) :249-:.'i4. (5) Clark, D. R.. Jr.. and T. G. Lamonl. 1976. Organo- chlorine residues in females and nursing young of the big brown bat {Epivsicii\ jiiscus). Bull. Environ. Con- lam. Toxicol. 15(1 ):l-8. (rt) Clark. D. R.. Jr., C. O. Martin, and D. M. Swincford. 1975. Orpanochlorine insecticide residues in the free- tailed bat {Tadaritia /'r(jA(7(c//.t/.?) at Bracken Cave, Texas. J. M.mimal. .S6( 2) :429-44.1. (7) Cnrknim. E. L. 1970. Insecticides and guano bats. Ecology 51 (.'>): 76 1-762. (.S) Davics. W. E. 1950. The caves of Maryland. State of Md. Dept. Geol., Mines Water Resour. Bull. No. 7. 76 pp. (9) navu's. W. E. 1958. Caverns of West Virginia. State of W. Va. Geol. Econ. Surv. XIX(A). 330 pp. ( Un Diinsmorc. J. D.. I . S. Hall, and K. H. Kollek. 1974. DDI" in the benl-winged bat in .Australia. Search 5(3): 110-111. { 1 1) Findlcy. J. .S. 1973. The status of southwestern bat populations. I'ages 12-17 in Symposium on Rare and Endangered Wildlife of the Southwestern United Slates. N. Me\. Dept. Game Fish. Santa Fe. N. Mex. 1/2) Gould. E. 1970. Bal conservation. Page 313 in .About Bats. Edited b\ B. Slaughter and D. Walton. Southern Methodist Univ. Press. Dallas. Tex. 8 - □ 7 - Little brown ba t i 6 5 - D 1 E a a. Z < cc CO 4 3 2 1 ND - ^ o • f z 1 I 1 1 1 fc^brf CD ^ 1 - Big brown bat T T ■ ■ ND n n T nmjv m m armmmimmaf o torn c^ m m ND 1 10 100 PCB IN CARCASS, ppm lipid weight Q Round Top O ^ Round Top O □ t\^ontpelier O g Montpelier O ^ Trout Cave O ■ ^ Trout Gave Cf O North East Church O FIGURE 3. Rclalionship of PCIi (.-Xroclor 1260) rt\idnis in brain lo iho.-^c in caruis.'i lipids for two bal .spccic.i, Maryland and Uc.\l \'iri;inia — 197 J 52 PESTtciDES Monitoring Journal (13) Jcfferics, D. J. 1972. Organochlorine insecticide resi- (17) Rcidingcr, R. J., Jr. 1972. Factors influencing Arizona dues in British bats and their significance. J. Zool. bat population levels. Unpublished Ph.D. dissertation, 166:245-263. Univ. Ariz., Tucson, Ariz. 172 pp. (14) Martell. J. ^l. D. A. Rkkcr, and F. R. Sicf^cl. 1975. ^,g^ simp.^o,,. G. C. A. Roc. ami R C. l.rnonrin. I960. PCB s m suburban watershed, Reston, Va. Environ. Sci. Quantitative Zoology. Harcourt, Brace and Co., New Technol. 9(9):872-875. York. 440 pp. (15) Mobr, C. E. 1972. The status of threatened species of cave-dwelling bats. Bull. Nat. Speleological Soc. 34(2): ( 19) Sichhiiii;.^, R. E. 1970. Bats in danger. Oryx 10(5): 33-47. 311-312. (16) Punt, A. 1970. Round table discussion on bat conser- vation: summary. Proc. 2nd Int. Bat Conf. Bijdragen tot de Dierkunde 40( 1 ) :3-4. Vol. 10, No. 2, September 1976 53 RESIDUES IN SOIL Pesticide Residues in Urban Soils from 14 United States Cities, 1970 Ann E. Carey,' G. Bruce Wiersma,' and Han Tai ' ABSTRACT Soil in 14 cities was sampled and analyzed for arsenic and chlorinated hydrocarbon pesticide residues. Heavy loads of chlorinated hydrocarbon residues were detected in the soil. In addition to DDT and its metabolites, chlordane. dieldrin, endrin, heptachlor, heptachlor epoxide, and toxaphene were detected. Distinct variation appeared in some residue levels amonti cities. Pesticide residue levels in urban soils were generally higher than the re.<:idue levels detected in cropland soils of the same States. Introduction The deterioration of urban environmental quality has been the object of an increasing number of scientific investigations. Most of these have been concerned with air and water pollution. Very few investigations have focused on contamination of urban soil and fewer still on contamination with pesticides, a problem associated primarily with agricultural soils. It has been estimated that only about half the 470 mil- lion kg active ingredients (a.i.) in pesticides and for- mulated products produced in the United States in 1970 were used in domestic agriculture. Most of the remaining portion is assumed to have been used by in- dustries, public agencies, and householders (3). Al- though total pesticide use in urban and suburban areas hardly equals agricultural use. these compounds arc applied to a much smaller land area. In a study of pes- ticide use conducted for the U..S. Environmental Pro- tection Agency (EPA), the average amount of pesti- cides applied to lawns and gardens in the three cities surveyed was estimated to be between 5.9 and 1 1.9 kg/ ha. a.i. (3). ' Project Officer. Nalion;il Soils MonitorinR Program, Tcchnic.il Serv- ices Division, U.S. Environmcm.Tl Protcclion Agency, Wasliinglon. DC, 20460 = Chief. Pollui.nnt Palhw-iys Branch. Environmental Monitoring and Support Laboratory. U.S. Environmental Protection Agency, Las Vegas. Nev. ' Supervisory Chemist. Pesticide Monitoring Laboratory. Technical Services Division, U.S. Environmental Protection Agency, Bay St. Louis. Miss. Little information has been published on pesticide resi- due levels in urban soil. Fahey, Butcher, and Murphy (/) found that 86.5 percent of the soil samples col- lected from Battle Creek, Mich., contained chlorinated hydrocarbon pesticide residues. In another study, Purves (i) found the levels of certain trace elements to be higher in urban garden plots than in rural plots. In 1969, Wiersma, Tai, and Sand (4) sampled eight U. S. cities and found that the occurrence of DDT and its metabolites (DDTR) among urban sampling sites ranged from 40 percent in Houston, Tex., to 100 per- cent in Miami, Fla. Average DDTR residues in lawns and gardens were significantly higher than those in un- kept areas within the cities. Reported here are the re- sults for the second year of urban soil monitoring. Sampling Procedures Fourteen U. S. cities were selected for sampling during the summer and fall of 1970. The cities were stratified by population: there was one city with a population greater than 1,000.000: si.x cities between 100,000 and 1.000.000; and five cities between 25,000 and 100,000: and two cities of less than 25,000. Randomly allocated sample sites were selected within the political bound- aries of each city. Sites were 231 m-, usually 15.2-by- I5.2-m plots. Sixteen soil cores, each 5.1 cm in diameter by 7.6 cm deep, ucre taken on an evenly spaced 4-by-4 grid. The cores were then composited, sieved through a 6. .■'-mm mesh, and sent for analyses to the EPA Pesti- cide Monitoring Laboratory in Gulfport, Miss, (now located at the NASA Mississippi Test Facility. Bay St. Louis). A iiolytical Procedures PREPARATION OF SAMPLES A .300-g soil sample was moistened with 80 ml water and extracted with 600 ml .3:1 hex.ine:isopropanol by concentric rotation for 4 hours. The liquid was de- canted, the .ilcohol was removed by three water washes. 54 Pesticides Monitoring Journal and the hexane extract was dried through anhydrous sodium sulfate. The sample extract was then stored at low temperature for subsequent gas-chromatographic (GC) analysis. GAS CHROMATOGRAPHY Analyses were performed on gas chromatographs equipped with tritium foil electron affinity detectors for organochlorine compounds and thermionic or flame photometric detectors for organophosphorus com- pounds. A multiple-column system employing polar and nonpolar columns was used to identify and confirm pesticides. Instrument parameters were: Columns Glass, 6 mm OD by 4 mm ID, 183 cm long, packed with one of the following: 9 percent QF-1 on 100/120 mesh Gas-Chrom Q; 3 per- cent DC-200 on 100/120 mesh Gas-Chrom Q; or 1.5 percent OV-17/1.95 percent QF-1 on 100/120 mesh Sepulcoport. Carrier Gases 5 percent methane-argon at a flow rate of SO ml/min; prepurified nitrogen at a flow rate of 80 ml/min. Temperatures Detector Injection port Column QF-1 Column DC-200 Mixed column 200°C 250°C 166°C 170°-175°C 185°-190°C Sensitivity (minimum detectable levels) of organochlo- rine compounds ranged from 0.002 to 0.03 ppm except for mixtures of polychlorinated biphenyls (PCB's), chlordane, toxaphene, etc., whose minimum detectable levels were 0.05 to 0.1 ppm. Minimum detectable levels for organophosphorus compounds were approximately 0.01 to 0.03 ppm. When necessary, residues were con- firmed by thin-layer chromatography or /7-values. The compounds detectable by this method are listed in Table 1. Atomic absorption spectrophotometry was used to de- termine arsenic content. The soil sample was first ex- TABLE 1. Organochlorine compounds dileclablc by chemical methodology of ihc present study Alachlor Aldrin Chlordane DDTR (o.p-DDT; p.p-DDT; o.p'-DDE; P.P-DDE; o,p-TDE; p.p-TDE) Dieldrin Endrin Heptaclilor Heptachlor epoxide Lindane (t-BHC) Methoxychlor PCB's PCN's Toxaphene Trifluralin tracted with 9.6N hydrochloric acid (HCl) and re- duced to trivalent arsenic with stannous chloride. The trivalent arsenic was partitioned from HCI solution to benzene, then further partitioned into water for the absorption measurement. A Perkin-Elmer Model 303 instrument was used and absorbance was measured with an arsenic lamp at 1972 A with argon as an aspirant to an air-hydrogen flame. The minimum detection limit was 0.1 ppm. RECOVERY STUDIES For organochlorine pesticides, the average recovery rate in soil was 90 to 110 percent. Recovery values for ar- senic ranged from 70 to 80 percent. All residue levels are expressed on a dry-weight basis and are corrected for percent recovery. Results Results of the chemical analyses are presented in Table 2. For each city, the total number of sites is given as well as the arithmetic and geometric mean values for each residue, the range of residue values detected, and the number and percentage of sites with detectable residues. The geometric mean estimate was used as an alternative to the arithmetic mean as a measure of central tend- ency for the data evaluation. Pesticide residue data fre- quently contain a large number of zero values, resulting either from the absence of pesticides or their presence at levels below analytical sensitivity. The data are sel- dom distributed normally, as shown by tests for skew- ness and kurtosis, but can be described by a log-normal distribution. After repeated tests for significant kurtosis and/or skewness, the In (X -|- 0.01 ) transformation was used in determining the logarithmic means. The antilogs of these figures minus 0.01 were taken to get estimates of the geometric means and 95 percent con- fidence intervals in the untransformed dimension (Table 2). The geometric mean estimate was calculated only for those compounds with more than one positive de- tection. Of the 356 urban sites sampled, 204 or 57 percent of the sites had detectable levels of pesticide residues ex- cluding arsenic. Residues of DDTR (the sum of all DDT isomers and metabolites) and chlordane were de- tected in all 14 cities. However, the frequency of occur- rence within each city varied considerably. DDTR was detected in 51 percent of all samples analyzed but the frequency of detection ranged from 7 percent in Au- gusta, Maine, to 89 percent in Greenville, Miss. Simi- larly, chlordane was found in 19 percent of all samples but individual city frequencies ranged from 5 percent in Cheyenne, Wyo., to 44 percent in Grand Rapids, Mich. Residues of heptachlor and heptachlor epoxide were de- tected in three and ten of the fourteen cities, respec- VoL. 10, No. 2, September 1976 55 TABLE 2. Pesticide residues in soil from 14 United Stales cities, 1970 PisnciDE No. Positive Sites Percent Positive Sites Range of Residues, ppm Arith. Mean Geom. Mean 95% CI Upper 95 % CI Lower Augusta, Maine: 27 Sites Arsenic Chlordane Dietdrin Endrin Hepiachlor Hepiachlor Epoxide Toxaphene o,p -DDE r,p-DDE o.P -DDT P.p -DDT o.P -TDE P.P -TDE DDTR 27 3 ND ND ND ND ND ND 2 1 2 ND 2 2 100.00 II. 1 7.4 3.7 7.4 7.4 7.4 0.40-15.30 0.21- 0.27 0.14- 0.42 0.20 0.25- 0.61 0.14- 0.46 0.53- 1.69 5.39 0.03 0.02 0.01 0.03 0.02 0.08 4.0312 0.0043 0.0027 0.003 1 0.0027 0.0040 5.6517 0.0115 0.0080 0.0095 0.0081 0.0128 2.8746 0.0000 0.0000 0.0000 00000 0.0000 Charleston, S.C: 27 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE P.P DDE o.P -DDT P.P -DDT o.p-TDE P.P-TDE DDTR 27 7 ND ND ND I ND 1 19 8 17 1 15 20 100.00 25.9 3.7 3.7 70.4 29.6 70.0 3.7 55j6 74.1 0.40-10.10 1.01- 1.35 0.07 0.03 0.01- 2.21 0.07- 8.47 0.06-33.80 0.05 0.03-. 0.29 0.0644.48 3.35 0.12 <0.01 <0.01 0.16 0.36 1.54 <0.0I 0.06 2.12 2.1325 0 0094 0.0417 00163 0.0858- 0.0250 0,1589 3.1817 0.0245 0.0810 00417 0.2143 0.0474 ,0.3863 1.4282 0.0009 0.0194 0.0034 0.0309 0 0113 0.0620 Cheyenne, ^yo. : 19 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE p.p -DDE o,p -DDT P,p-DDT o.p-TDE P.P-TDE DDTR 17 1 ND ND ND 1 ND ND 3 ND ND ND ND 3 89.' 5.j 5.3 15.8 15.8 0.20- 5.50 8.99 0.32 0.03. 0.09 0.03- 0,09 1.23 0.47 0.02 0.01 0,01 0.5658 0 0031 0,0031 1.2893 0.0079 0.2451 0.0000 0.0000 Grand Rapids, Mich.: 23 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE P.P-DDE o.p-DOT P.P'-DDT o.p-TDE P.P-TDE DDTR 22 10 ND ND 1 5 ND ND 19 5 19 1 3 95.6 43.5 4.3 21.7 82.6 21.7 82.6 4.3 13.0 1.70-112.0 0.15- 6.58 0.13 0.03- 0,23 0.02- 2.67 0.04- 0.71 0.05- 2.67 0.01 0.12- 0.60 0.d2- 6.66 9.11 0.71 001 0.02 0.20 0,09 0.33 <00l 0.04 0.66 3.7194 0.0556 0,0066 0,0564 0,0108 0.1154 • 0.0051 0.1833 7.2176 0.1713 0.0159 0,1103 0,0295 0,2342 0.0144 0.3897 1.9144 0.0137 0.0006 00266 00009 0,0544 0,0000 0.0834 Greenville, Miss.: 28 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE p.p -DDE o.P -DDT P,P -DDT o.p-TDE P.P-TDE DDTR 27 2 1 ND ND ND 3 1 24 8 25 1 10 25 96.4 7.1 3.6 10.7 3.6 85.7 28.6 89.3 3.6 35.7 89.3 2.6048.90 0.37- 1.40 0.48 7.73-33.40 0.15 0.01- 1.79 0.05- 0,88 0,02- 3.03 0,12 0,02- 0.74 0.05- 5.87 8.10 0.06 0.02 1.94 0.01 0.18 0.10 0.44 <0,0l ons 0.80 5.4608 0.0036 0.0119 * 0 0641 0,0141 0,1666 « 0.0148 0.2471 9.1897 0.0111 0.0437 0.1134 0,0335 0,2997 0 0330 0.4724 3.2434 0.0000 0,0000 0.0345 0 0033 0.0907 0 0043 0.1270 (Continued next page) 56 Pesticides Monitoring Journal TABLE 2 (cont.)- Pesticide residues in soil from 14 United States cities, 1970 Pesticide No. PosmvB Sites Percent Positive Sites Range of Residues, ppm Arith. Mean Geom. Mean 95 % CI Upper Honolulu, Hawaii: 21 Sites 95 % CI Lower Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o,p'-DDE p.p'-DDE o,p'-DDT r,p'-DDT o,p'-TDE p,p'-TDE DDTR 21 6 ND ND ND I ND 1 4 1 4 1 4 4 100.00 28.6 4.8 4.8 19.0 4.8 19.0 4.8 19.0 19.0 050-17.40 1.00-13.90 0.06 0.12 0.14- 0.65 0.11 0.26- 0.47 0.33 0.15- 0.52 0.57- 1.83 3.34 1.27 <0.01 0.01 0.07 0.01 0.06 0.02 0.05 0.21 2.1024 0.0406 0.0009 0.0096 0.0087 0.0140 3.1464 0.1609 0.0257 0.0274 0.0242 0.0461 1.4037 0.0050 0.0001 0.0002 0.0002 0.0003 Memphis, Tenn.: 28 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE P,p-DDE o,p'-DDT P,P'-DDT o,p'-TDE P.p-TDE DDTR 28 6 16 1 1 3 ND ND 12 7 12 ND 13 18 100.0 21.4 57.1 3.6 3.6 10.7 42.9 25.0 42.9 46.4 64.3 1.90-20.10 0.11- 8.02 0.02-12.80 0.07 0.23 0.02- 0.70 0,01- 1.62 0.04- 0.24 0.02- 0.91 0.02- 0.22 0.01- 2.92 6.63 0.36 1.07 <0.01 0.01 0.03 0.10 003 0.17 0.04 0.34 5.7837 0.0138 0.0525 0.0034 0,0162 00086 0.0319 0.0159 0.0702 7.1097 0.0379 0.1399 0.0095 0.0353 0.0188 0.0741 0.0308 0.1582 4.7036 00018 0.0161 OOOOO 0.0052 0 0020 0.0109 0.0064 0.0283 Mobile, Ala.: 29 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o,p -DDE p,P-DDE o,p'-DDT p,p'-DDT o,p'-TDE P.P-TDE DDTR 29 7 3 ND 1 6 ND ND 9 5 9 ND 9 11 100.0 24.1 10.3 3.4 20.7 31.0 17.2 31.0 31.0 37.9 0.30- 5.20 0,10- 2.50 0.04- 0.36 0.01 0.01- 0.09 0.02- 0.02- 0.02- 0.02- 0.02- 0.50 0.22 1.06 0.19 1.37 1.12 0.18 0.02 <0.01 0.01 0.05 0.02 0.09 0.03 0.19 0.8168 0.0157 0.0035 0.0036 0.0109 0.0044 0.0140 0.0088 0.0240 1.0731 0.0403 0.0092 0.0074 0,0237 0,0100 0.0321 0.0181 0.0575 0.6212 0.0032 0.0000 0.0006 0.0030 0.0003 0.0037 0.0027 0.0071 Philadelphia, Pa.: 26 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p-DDE P.P'-DDE o.p-DDT p,p'-DDT o.p -TDE P,P'-TDE DDTR 26 11 ND ND ND 2 ND ND 17 10 19 2 10 20 100.0 42.3 7.7 65.4 38.5 73.1 7.7 38.5 76.9 2.20-30.90 0.18- 4.59 0.08- 0.11 0.03- 1.42 0.04- 1.06 0.04- 3.53 0.20- 0 45 0.03- 1.17 0.07- 6.98 10.48 0.76 0.01 0.15 0.17 0.56 0,03 0,09 1.00 8.5081 0.0705 0.0020 0.0431 0.0275 0.1456 0.0030 0.0181 0.2315 11.1912 0.2185 0.0055 0.0876 0.0681 03310 0.0090 0.0408 0.5492 6.4677 0.0191 0.0000 0.0188 0.0080 00610 0.0000 0.0055 0.0943 Portland, Oreo.: 25 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heptachlor Epoxide Toxaphene o.p -DDE p.p -DDE o.p'-DDT P.p -DDT o.p-TDE P.p'-TDE DDTR 25 3 2 ND ND ND ND ND 16 2 11 3 10 17 100.0 12.0 8.0 64.0 8.0 44.0 12.0 40.0 68.0 0.80-26.00 0.40- 0,59 0.08- 1.19 0.03- 1.46 0.09- 0.29 0.07- 2.63 0 07-1.288 0.04- 3.46 0.03- 7.64 6.63 0.06 0.05 4.5113 0.0059 0.0032 0.15 0.0413 0.02 0.0025 0.24 0.0328 0.06 0.0045 0.22 0.0235 0.67 0.0923 6.5622 0.0169 0.0103 0.0852 0.0075 0.0812 0.0131 0.0582 0.2262 3.1004 0.0000 0.0000 0.0176 0,0000 0,0101 0,0000 0.0064 0.0343 (Continued next page) Vol. 10, No. 2, September 1976 57 TABLE 2 (cont.). Pesticide residues in soil f mm 14 United States cities, 1970 Pesticide No. Positive Sites Percent PosmvE Sites Range OF Residues, ppm Arith. Mean Geom. Mean 95% CI Upper 95 % CI Lower Richmond, Va.: 27 Sites Arsenic Chlordane Dieldrin Endrin Ilepiachlor Hcptachlor Epoxide Toxaphene o.p-DDE P,P-DDE o.p -DDT p.P-DDT o.p -TDE P.p-TDE DDTR 26 5 4 ND ND 5 ND 2 17 4 7 2 17 18 96.3 18.5 14.8 18.5 7.4 63.0 14.8 25.9 7.4 63.0 66.7 0.10-14.80 0.18- 6.42 0.07- 2.99 0.01- 0.10 0.09- 0.15 0.01- 4.24 0.18- 3.25 0.22-15.10 0.04- 0.46 0.03- 5.65 0.03-28.33 2.39 0.51 0.14 0.01 0,01 0.35 0.16 0.79 0.02 0.40 1.73 1.2014 0.0154 0.0075 0.0034 0.0021 0.0544 0.0081 0.0234 0.0022 0.0509 0.0034 2.1517 0.0474 0.0210 0.0076 0,0058 0.1257 0,0229 0.0696 0.0067 0.1163 0.0076 0.6689 0.0012 0.0000 0.0002 0.0000 0.0206 0.0000 0.0040 0.0000 0.0194 0.0002 SiKEsTON, Mo.: 27 Sites Arsenic Chlordane Dieldrin Endiin Heplachlor Heptachlor Epoxide Toxaphene o,p-nDE P.P'-DDE o.p -DDT p.p-DDT o.p-TDE P.p-TDE DDTR 26 2 1 ND ND ND 1 ND 7 2 6 ND 5 7 96.3 7.4 3.7 3.7 25.9 7.4 22.2 18.5 25.9 1.00- 7.20 0.30- 1.19 0.33 16.10 0,02- 0.12- 0.10- 0.06- 0.03- 0.23 0.14 0.49 0.21 0.89 3.00 0.06 0.01 0.6O 0.03 0,01 0,06 0.02 0.12 2.2217 0,0036 0,0084 0,0022 0,0101 0.0053 0.0147 3.5780 0.01 II 0.0187 0,0061 0,0245 0,0121 0,0374 1.3781 0.0000 0.0018 0.0000 0.0017 0.0006 0.0029 Sioux City, Iowa: 22 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Heplachlor Epoxide Toxaphene o,p-DDE P,P-DDE o,P -DDT P.P-DDT o.p -TDE P,P-TDE DDTR 21 4 ND ND ND 1 ND ND 5 ND 4 ND 2 5 95.5 18.2 4.5 22.7 18.2 9.1 22.7 4.20-24.70 0,30- 3,00 0.06 0.01- 0.43 0.05- 0.19 0.04- 0.07 0.06- 0.69 10.25 0.24 <0.01 0.03 0.02 0.01 0.06 7.0473 0.0127 0.0062 0.0055 0,0018 0.0094 13.9439 0.0408 0.0156 0.0139 0,0051 0,0245 3,5593 0,0001 0.0002 0.0001 0,0000 0.0009 Wilmington, Del.: 27 Sites Arsenic Chlordane Dieldrin Endrin Heptachlor Hcptachlor Epoxide Toxaphene o.p-DDE P.p' DDE o.p-DDT P,p-DDT o,p'-TDE p.p'-TDE DDTR 24 2 ND ND ND 1 ND 1 11 7 11 1 9 11 88.9 7.4 3.7 3.7 40.7 25.9 40.7 3.7 33.3 40.7 0.60-32,00 0.04- 0.07 0.02 9.10 <0.01 <0.01 3.5252 0.0015 0.09 <0.01 * 0.01- 0.30 0.05 0.0155 0.02- 0.26 0.03 0.0074 0.07- 0.83 0.11 0.0246 0.12 <0.01 » O.OI- 0.60 0.06 0.0139 0.08- 2.20 0.25 0.0362 NOTE: Compounds not listed were not delected in residue analyses. ND -- not detected. Asterisk = geometric mean estimate not calculated wiih only one positive detection. 8,6773 0,0040 0,0322 0,0161 0,0551 0.0312 0.0911 1.4286 O.OOOO 0.0055 0.0015 0.0084 0.0038 0.01 1 1 tively; dieldrin w;is detected in six and endrin in only one. Arsenic is a naturally occurring clement in soil, which accounts for its detection in 97 percent of the samples analyzed. As a result, it is diflicult to determine whether the arsenic residues present reflect human-associated activity in addition to natural hackground levels. In the present study, geometric mean values for arsenic ranged from 0,5658 ppm in Cheyenne to 8.5081 ppm in Philadelphia, Pa. -Sampling sites in all cities except Mohile, Ala., were categorized as either lawn or waste according to the criteria established by Wiersma, et al. (4). 58 Pesticides Monitoring Journal Lawn was defined thus: 1. Mowed grass close to a house, factory, or other structure. 2. Mowed grass in municipal parks or other city- owned or city-maintained land. 3. Garden or cultivated areas. 4. A yard that was in obvious proximity to a home. Waste included: 1. Vacant lots where grass was apparently un- kept. 2. Small wooded lots, brush or overgrown fields. 3. Areas such as power lines and gas lines. 4. E.xposed soil around construction sites, eroded areas, and the like. A r-test based on the transformed variate In (X + 0.01 ) was used to compare residue levels of selected com- pounds in lawn and waste areas (Table 3). Residue TABLE 3. Slatistical sif;iuficance of differences between resi- due levels of specific chemicals in lawn and waste areas of 13 United Stales cities, 1970^ TABLE 4. Comparison of selected compounds in urban and cropland soils of 12 States, 1970^' CrrY2 DDTR Arsenic Cm-ORDANE Augusta, Maine ** • NS Charleston, S.C. NS ** NS Cheyenne, Wyo. NS NS NS Grand Rapids, Mich. * NS NS Greenville, Miss. NS NS NS Honolulu, Hawaii * NS NS Memphis. Tenn. «* NS NS Philadelphia, Pa. • NS * Portland, Oreg. *f NS NS Richmond, Va. 1 NS NS Sikeston, Mo. NS * NS Sioux City, Iowa NS NS NS Wilmington, Del. NS NS NS NOTE: NS = not significant. • = significant (P<0.05). •• = highly significant (P<0.01). ^ Based on r-tests of the transformed variate In fx + O.OI), U.S. En- vironmental Protection Agency. = Mobile, Ala., omitted because lawn and waste sites had not been differentiated. levels of DDTR were significantly higher (p<0.05) in lawn areas than in waste areas in seven of the thirteen cities tested. Differences may reflect multiple sources of pesticide applications (e.g.. householders, municipali- ties) within the cities. No significant difference oc- curred between DDTR levels in lawn and those in waste areas of southern cities: perhaps this is a subtle reflec- tion of the extensive use of DDT in the regional agri- culture before the compound was banned. The r-test based on In (X 4- 0.01) was also used to compare residue levels of chlordane in lawn sites with those in waste sites among all cities except Mobile. Only in Philadelphia were the chlordane levels in lawns significantly higher than in waste areas. In three of the thirteen cities arsenic levels in lawns were significantly greater (/7<0.05) than in waste areas. Perhaps human- associated activitv is responsible for this difference; Wilmington Cropland " Mean Residues, ppm dry WT Arsenic DDTR Chlordane Maine Augusta Cropland -^ 4.0312 * 7.7028 0.0040 NS 0.0220 0.0043 NS 0.0016 South Carolina Charleston Cropland 2.1325 NS 1.3588 0.1589 NS 0.3110 0.0094 NS 0.0031 Wyoming Cheyenne Cropland * 0.5658 NS 0.3003 0.0031 NS ND 0.0043 NS 0.0095 Michigan Grand Rapids Cropland 3.7194 NS 3.4326 0.1833 *« 0.0064 0.0556 • * 0.0018 Mississippi Greenville Cropland 5.4608 NS 5.0177 0.2471 NS 0.6326 0.0036 NS 0.0008 Tennessee Memphis Cropland 5.7837 NS 6.9335 0.0702 • • 0.0102 0.0138 NS 0.0050 Alabama Mobile Cropland 0.8168 NS 0.2747 0.0240 * • 0.2247 0.0157 NS 0.0016 Pennsylvania Philadelphia Cropland 8.5081 NS 7.1960 0.2315 0.0125 0.0705 • * 0.0131 Virginia Richmond Cropland •> 1.2014 NS 1.2054 0.0034 NS 0.0038 0.0154 0.0038 Missouri Sikeston Cropland 2.2217 4.0719 0.0147 * « 0.0021 0.0036 NS 0.0063 Iowa Sioux City Cropland 7.0473 2.4065 0.0094 0,0025 0.0127 NS 0.0092 Delaware 3.5252 0.0362 NS NS 4.2810 0.0091 0.0015 NS 0.0123 NOTE: ND = compound not detected. NS = urban/ cropland difference not significant. * = urban/ cropland difference significant (r<0.05). •• — urban/ cropland difference highly significant (p<0.01). 1 Cropland data from National Soils Monitoring Program. FY-70, un- less otlierwisc indicated. - Comparisons for Honolulu, Hawaii, and Portland, Oreg., omitted be- cause no cropland data are available. 'New England Slates' data: Connecticut. Maine, Massachusetts. New Hampshire. Rhode Island, and Vermont. ' Cropland data from National Soils Monitoring Program. FY-69. "' Virginia/ West Virginia d,ita. ' Mid-Atlantic States' data: Delaware, Maryland, and New Jersey. Vol. 10, No. 2, September 1976 59 however, the question cannot accurately be resolved here. Natural arsenic levels in soil are dependent on parent material and most urban soil profiles are dis- turbed by such actions as construction, removal of top- soil, or use of fill from other areas. Table 4 compares geometric means of three selected residues in urban soils and cropland soils in the same State or agricultural region. Generally, DDTR and chlordane residues detected in urban soils were higher than residues in corresponding cropland soils from those States or groups of States. However, there were statis- tically significant differences (p<0.05) between the geometric means of DDTR for corresponding urban and cropland soils in only six of thirteen locations and sig- nificant differences for chlordane in only three of thir- teen locations. Conclusions The cities sampled in 1970 generally had heavy loads of chlorinated hydrocarbon pesticides in soil. This coin- cides with results of the previous year's urban sampling published by Wiersma et al. (4). In over half the thir- teen cities tested in 1970. DDTR residues in lawn areas were significantly higher than in waste and unkept areas. There appeared to be some distinct variation in pesticide residue levels among cities. Finally, pesticide residue levels were generally higher in urban soils than in cropland soils of the same States. LITERATURE CITED (/) Fahey. J. £., J. W. Butcher, ami R. T. Murphy. 1965. Chlorinated hydrocarbon insecticide residues in soils of urban areas. Battle Creek, Michigan. J. Econ. Entomol. 58(3): 1026-1027. (2) Purve.i, D. 1968. Trace element contamination of soils in urban areas. Int. Soc. Soil Sci.. Trans. 9th Cong. 2:351-355. (3) U.S. Environmental Protection Agency. 1972. Office of Water Programs. The use of pesticides in suburban homes and gardens and their impact on the aquatic en- vironment. 487 pp. (4) Wiersma, G. B.. H. Tai. and P. F. Sand. 1972. Pesticide residues in soil from eight cities — 1969. Pestic. Monit. J. 6(2):126-129. 60 Pesticides Monitoring Journal RESIDUES IN WATER Distribution of Pesticides and Polychlorinated Biphenyls in Water, Sediments, and Seston of the Upper Great Lakes — 1974 W. A. Glooschenko,' W. M. J. Strachan,' and R. C. J. Sampson ° ABSTRACT Samples of water, seston, and sediment from the upper Great Lakes were collected durinc; the summer of 1974 for analyses of polychlorinated biphenyls (PCB's), !5 organo- chlori/ie pesticides, and 17 orpanophosphorits pesticides. Samples were taken from 9 sites in Lake Huron. 2 in the North Channel, 5 in Georgian Bay. and 17 in Lake Superior. In the water samples all compounds analyzed were below quantification limits and trace<: of lindane were found in each sample. In seston samples, PCB's were above quantification limits at nearly every station and some traces of dieldrin and DDE were measured. Sediments contained PCB compounds at all stations. Dieldrin was occasionally observed, and DDT and/or its derivatives DDE and TDE were found in over one-third of all samples. No clear correlation was found between quantities of these compounds in sediments and either the percentage of clay or organic matter in the sam- ples. Nor were any definite geographic trends present in terms of distributions observed, although concentrations were higher in areas of higher sedimentary deposition such as deeper basins. No organophosphorus compounds were detected in any sample. The highest level of DDT residues detected, 20 ppb, was lower than levels found in other studies in the lower Great Lakes and some tributary river sediments of Georgian Bay. In general. DDT residues were higher in Lake Huron and Georgian Bay sediments than in Lake Superior although PCB's were higher in some Lake Superior sediments. Introduction Except for limited literature on tributaries (3,14) no information is available in the literature regarding levels of organochlorine and organophosphorus pesti- cides and polychlorinated biphenyls (PCB's) in water and sediments of Lakes Superior and Huron including Georgian Bay. In order to investigate the occurrence of these compounds, a survey cruise was conducted on the upper Great Lakes in late July and early August 1974, ^ Process Research Division, Canada Centre for Inland Waters, P.O. Box 5050, Burlington, Ontario. Canada L7R 4A6 -Water Quality Branch (Ontario Region), Inland Waters Directorate, P.O. Box 5050, Burlington, Ontario, Canada and samples of water, sediments, and seston (suspended particulate material consisting of plankton and both in- organic and organic detrital materials) were collected. Sampling was confined to open lake waters. This study is part of the Upper Lakes Reference Group research program on Lakes Superior and Huron, a pro- gram under the auspices of the International Joint Com- mission (IJC). Sampling Figure 1 indicates the approximate locations of sam- pling stations which were chosen on the basis of prox- imity to major rivers, industrial plants, or municipal areas. Because a fairly large vessel was employed, no station was nearer to shore than 1 km except channel stations 18 and 30, Hence samples do not reflect im- mediate influence from these source areas. Several back- ground central lake sites were also chosen. The collec- tion and analysis procedures for the three sample types are given below. WATER Samples were collected using a 6-liter Van Dorn bottle triggered at a depth of 1 m. Two liters of this sample were filtered through a 47-mm-diameter Whatman GF/C filter and refrigerated in acid-washed glass bottles. After approximately 30 days in storage at 4°C in the dark, samples were extracted by procedure B described in the Analytical Methods Manual under "Procedure for the Analysis of Organochlorinated Pesti- cides and PCB's in Water" (9). Florisil cleanup was not used because backgrounds were free of interfering substances. Filters were not analyzed. After electron- capture gas-chromatographic (GC) analysis for organo- chlorine pesticides and PCB's, residues of the extracts were further examined for organophosphorus pesti- cides by gas chromatography using flame photometric detection in both phosphorus and sulfur modes, Gas- chromatographic procedures for the organophosphates are outlined in other publications (18,19) but the ■Vol. 10, No. 2, September 1976 61 FIGURE 1. Upper Great Lakes samplini; stations preparation and extraction of organophosphorus samples under the same conditions as the organochlor- ines is an untested procedure. SESTON Sampling occurred whenever the vessel reached the sta- tions and, as a consequence, scston masses and hence the concentrations therein may not be strictly compar- able from station to station. Samples were collected with a plankton net which swept a cross-section of 0.126 m- (40 cm diameter). It was dragged 2 m from the bot- tom or else 100 m deep, whichever was more shallow. Collected material was passed through GF/C filters and stored, frozen and dark, in glass jars. They were sub- sequently homogenized in acctonitrile and the homo- genate plus washings were treated according to methods outlined in the Analytical Methods Manual under "I'ro- ceduic for the Analysis of Organochlormatcd Pesticide and PCB's in Fish and Sediments" (9), The extracts were further examined for organophosphatcs using the GC flame photometric detector system indicated for wa- ter samples. Since very little material was available on the filters and the filters were not preweighed, the seston yield could not be determined directly. Instead, a mean of a second box of filters (72.9 ±1.1 mg) was obtained and subtracted from the weight of the dried seston plus filters. SEi:)IMI£NT.S Shipek surface samples were obtained at each station and stored frozen in polyethylene bags until analyzed. In previous studies at the Canadian Centre for Inland Waters, the bags have not contaminated samples except with phthalates. which do not interfere with the analyses discussed here. The Eh of the sediments was measured at the time of sampling and examination for sediment type performed later at the laboratory. Separate 10-g subsamples were employed for detecting moisture and toxic organics. Moisture content was determined by weighing the subsampic before and after 48 hours dry- 62 Pesticides Monitoring Journal ing at 135°C. Toxic organics were analyzed as recom- mended in the Analytical Methods Manual under "Pro- cedure for the Analysis of Organochlorinated Pesticide and PCB's in Fish and Sediments" (9). The extraction step was carried out by ultrasonic dispersion in a 1:4 water:acetonitrile solution rather than by homogeniza- tion and, as in the water samples, organophosphorus pesticides were examined in the extract residues. Analysis The PCB's and 15 organochlorines have been tested for stability in tap water at 4°C in the dark (A.S.Y. Chau. Water Quality Branch, Inland Waters Directorate. 1971: unpublished results). Except for heptachlor, quantitative recoveries of 80-100 percent were obtained in all cases after 6 weeks in storage. Additional details are available in other publications (9 and citations therein). Stability of deep-frozen seston and sediment has not been determined. Liquid-liquid partitioning and florisil cleanups were used for the seston and sediment samples. These, coupled with quantitative identification on three or more GC columns of varying polarity, were considered adequate confirmation of compound identity. Columns employed were: 3 percent OV-101 on 80/100 mesh Chromosorb W-HP 1.5 percent OV- 17/ 1.95 percent OV-210 on 80/ 100 mesh Gas-Chrom Q 4 percent OV-IOl/6 percent OV-210 on 80/100 mesh Gas-Chrom Q 5 percent OV-210 on 100/120 mesh Gas- Chrom Q 3 percent OV-225 on 80/100 mesh Gas-Chrom Q AH chromatograms were run isothermally at 200°C (in- jector 250°C) with a pulsed, linearized '^Ni detector at 300°C. The carrier gas was 5 percent methane in argon at 60-75 ml/min, purged at 15 ml/min. Compounds were identified and quantified using an Autolab comput- ing integrator with a 2 percent retention window. PCB's were quantitated using a modified version of the method of Webb and McCall (25) in which all GC peaks present in Aroclor 1242, 1254, and 1260 were examined and the amount of PCB was calculated by summing the contribution of each peak. PCB's and p,p'- DDE could be readily resolved on column 3 and p,p'- DDT was further confirmed by dehydrochlorination of the concentrate using a solid matrix derivatization tech- nique (2). Analytical limits of each compound for the sample types examined are given in Tables 1 and 2. These figures are TABLE 1. Qiianlificatinn limits for organoclilorine pesticides ami polychlorinalcd biphcnyls Compound Quantification Limit Water, PPB Seston,' NG Sediment, PPM Lindane Heptachlor Heptachlor epoxide Aldrin Dieldrin Endhn p.p'-DDE p,p-TDE p.P -DDT o.p -DDT a-Chlordane 3-Chlordane a-EndosiiUan /5-EndosuUan p.p'-Methoxychlor PCB's o.oo.s o.nn5 0.005 0.005 0.005 0.01 0.005 0.005 0.005 0.005 O.OI 0.01 0.01 0.01 0.01 0.1 1 1 1 1 1 10 1 1 1 1 5 5 10 10 50 10 0001 0.001 0.001 0.001 0.001 0.001 0 001 0.001 O.OOI 0.001 0.005 0.005 0.01 0.01 0.05 0.012 ' Because seston weights were variable, estimated limits are given as absolute quantities rather than as a concentration. These should be compared with the absolute amounts in Table 3. = The limit of quantilation for PCB's in this survey is 1/10 that of the referenced procedure as a result of evaporating the extraction solvent to 1 ml rather than 10 ml. TABLE 2. Quant ificalion limits for organophosphorus pesticides Compound Quantification Limit Water, 1 Seston, Sediment, ppii PO PPM Phorate 0.003 50 0.01 Diazinon 0.005 100 0.02 Disulfoton 0.003 50 0.01 Ronnel 0.005 100 0.02 Methyl Parathion 0.005 100 0.02 Malathion 0.005 100 0.02 Parathion 0005 100 0.02 Crufomate 0.025 500 0.1 Methyl Trithion 0.01 200 0.04 Elhion 0.005 100 0.02 Carbophenothion 0.01 200 0.04 Imidan 0,05 1000 0.2 Azinphosmethyl 0.05 1000 0.2 Azinphosethyl 0.05 1000 0.2 Phosphamidon 0.03 500 0.1 Dimethoate 0.005 100 0.02 Fenitrothion o.no5 100 0.02 ' Limits are half of those noted in the referenced procedures because 2-liter samples were employed. The absolute quantity that this repre- sents, which is indicated under scslon and under sediments, is calcu- lated for sample size. In all cases, organophosphates have not been processed by the same method used to derive the original limits. the quantification levels, the lowest level to which an analytical laboratory will attach a quantity. In general, the detection limit is a level at which the compound is observable but not quantifiable. For such, the designa- tion TR for trace is employed and it is generally about 10 percent of the quantification limit. Results and Discussion WATER No organochlorine pesticides or PCB's were detected in the filtered water samples at levels above the quantifica- tion limits given in Table 1. There were detectable amounts of lindane in each of the water samples ex- VoL. 10, No. 2, September 1976 63 amined. In addition, station 4 in the middle of Lake Huron indicated trace amounts of both heptachlor and dieldrin. and station 3 off Goderich. Ontario, showed traces of p.p'-DDE. A study conducted in 1964-68 on 1 1 sites in the Great Lakes found dieldrin to be the main pesticide detected in the region, especially in the Detroit River and St. Mary's River at Sault Stc. Marie. The other two pesticides detected were BHC in the Saginaw and Detroit Rivers and lindane which was de- tected at a concentration of 0.003 ppb in St. Mary's River {12). Levels detected in the present study were similar to those reported for the Illinois waters of Lake Michigan (,21) where such pesticides as DDT, hepta- chlor epoxide, and dieldrin were all below 0.001 ppb. The inability to detect PCB's in water contrasted with studies in Lakes Erie and Ontario where PCB's in sur- face waters average 0.027 ppb and 0.030 ppb. respec- tively (Canada Centre for Inland Waters. 1972: unpub- lished data). However, these levels are slightly below the Centre's current quantification limits in water. SESTON Data for the organochlorines and PCB's in the seston are given in Table 3. Quantification of seston in the water column and hence the concentration therein were TABLE 3. Residues of dieldrin, p.p'-DDE, and PCB's in seston, upper Great Lakes — 1974 Station No. Compound Dieldrin p.p'-DDE PCBs ' Absolute Concentration, Quantity. PPM 10 "0 1 TR ND 180 6.0 2 TR TR 230 8.1 3 TR ND 240 4.9 4 TR TR ND 5 TR ND 50 1.0 6 TR TR 180 1.5 7 TR TR 220 1.2 8 TR 150 2.1 10 TR TR 170 6.7 11 TR ND 74 1.3 12 TR ND 140 5.9 13 ND TR 33 0.7 14 TR ND 26 1.0 16 TR TR 85 0.8 17 TR TR 32 0.5 19 TR ND 37 0.9 20 ND ND TR 22 TR ND 30 1.1 23 TR TR 24 1.0 24 TR TR TR 25 TR ND 95 1.3 26 TR ND ND 27 TR ND 47 0.8 28 TR ND 49 1.3 29 TR ND TR 30 — TR 15 0.5 31 ND ND TR 32 TR ND ND 33 ND ND ND 34 TK ND TR NOTE: TR = Iracc. ND = not delected. ' Ci>nccnlr;ilions arc ba^cd upon Ihc didcrcncc between filler phis ses- lon wciiihl and the mean filler ueiilbl of 72'' mg ( :t I . I my.\. The mean seston Meittht so derived and used was 47.0 mg with a minimum value of 23.7 mg. calculated from the dry weight of seston plus filter minus the mean filter weight of 72.9 ± 1.1 mg. Only PCB's were observed at quantifiable levels and these occurred at nearly every station. This agrees with observations of other workers who have examined the Great Lakes for the presence of these ubiquitous com- pounds (10.21). PCB concentrations in seston ranged from nondetectable or trace levels at stations 4, 20. 24, 26, 29, and 31-34 to a maximum of 8.1 ppm in station 2 in the middle of Lake Huron. Two of the highest levels, 6.7 ppm at station 10 and 5.9 ppm at station 12, were found in Georgian Bay, indicating possible local sources of this compound. It is significant that these levels are only slightly higher than PCB concentrations in oceanic zooplankton, which is probably best called seston due to the mode of collection (5,8,20). Although generally Lake Superior samples have lower PCB con- centrations than have those of Georgian Bay and Lake Huron, there are some stations which have levels of the same magnitude: the outlet to St. Mary's River and the mouths of Black and TTiunder Bays near Marathon. Ontario. Dieldrin and p.p'-DDE were also observed but only in trace amounts. The former appeared almost throughout the sampling region; the latter appeared frequently in Lake Huron and Georgian Bay but only seldom in Lake Superior. It is significant that, even in the open lake water and especially in Lake Superior, dieldrin and PCB's are pres- ent, the latter in quantifiable amounts. SEDIMENTS The survey placed major emphasis on sediments, which are the ultimate sink of many organic and inorganic particulate materials in the upper Great Lakes. Results of sediment analyses are given in Table 4. PCB's oc- curred in higher concentrations than any other sub- stance. The two highest values, 1.3 ppm and 90 ppb. were found in Lake Superior off Marathon, Ontario (station 22). and in the middle of the lake (station 21). respectively. Lowest values were found in Lake Huron; residues in Georgian Bay were slightly higher. DDT and its degradation products (SDDT) were gen- erally higher in Lake Huron and Georgian Bay than in Lake Superior. The highest iDDT value was 22 ppb at station 4 which lies in the depositional Goderich Basin of Lake Huron (24). Half of this was analyzed as p.p'-DDT and half was p.p'-DDE. indicating lack of total degradation. Other maximum values, 20 ppb (sta- tion 10), 12 ppb (station 12), and 11 ppb (station 11), occurred in Georgian Bay. This is significant in the wake of other studies which have shown high concen- trations of iDDT in tributaries to Georgian Bay, mainly from past insect control in recreational areas (3,14). At these three stations, DDE and TDE made up most of the iDDT analyzed, indicating active degradation of 64 Pesticides Monitoring Journal TABLE 4. Distribution of organochloriiics in sediment, upper Great Lakes — 1974 Station No. Sediment TlPE Potential, Organic Carbon, '^ Concentrations, mc/g DRY WEIGHT -l-MV PCBs DiELDRIN P,p'-DDE P,P-TDE p,p'-DDT o,p'-DDT DDT 130 o.n TR TR ND ND ND ND ND 480 0.50 0.01 ND' 0.002 ND ND ND 0.002 240 — TR ND ND ND ND ND ND 460 2.70 0,01 ND 001 ND 0.012 ND 0.022 90 0.15 TR ND ND ND ND ND ND 455 0.31 TR ND ND ND ND ND ND 440 0,31 TR TR ND ND ND ND ND 500 2.1 0.01 TR 0,005 ND 0.007 ND 0.012 300 0.94 0.02 TR 0,004 0,009 0.006 0,001 0.020 95 3.6 0,02 ND 0005 0,006 ND ND 0.011 450 0,23 0.02 ND 0,003 ND ND ND 0.003 475 0,25 TR ND ND ND ND ND ND 430 0.16 TR ND ND ND ND ND ND 407 0.09 0.01 ND ND ND ND ND ND 470 0.51 TR ND 0,002 ND ND ND 0,002 375 0.03 TR ND 0,005 ND ND ND 0.005 488 0.20 0.02 ND 0,005 ND ND ND 0.005 198 0.68 TR ND ND ND ND ND ND 450 1.2 TR ND ND ND 0,007 ND 0.007 493 2.4 0.09 ND 0.002 ND 0,003 ND 0.005 165 3.1 1,31 TR ND ND ND ND ND 475 1.3 0,01 ND ND ND ND ND ND no 1,4 0,02 ND 0.006 ND ND ND 0.006 147 0,77 TR ND ND ND ND ND ND 138 0,12 TR ND ND ND ND ND ND 475 0,21 0,01 ND ND ND ND ND ND 490 1.2 TR ND ND ND ND ND ND 470 0.22 0,01 ND ND ND ND ND ND 100 1.7 0,02 ND 0.007 0.005 ND ND 0.012 490 0,17 0,02 ND ND ND ND ND ND 500 0,26 0.02 ND ND ND ND ND ND 465 — 0.01 ND ND ND ND ND ND 505 0.23 0.02 ND ND ND ND ND ND 2 3 4 5 6 7 8 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 Sand Sand Sand Clayey silt Sand Sand Clay Clayey sand Clay Sandy silt Silty clay Sand Sandy clay Sand Sandy clay Sand Sand Sand Clayey sand Clay Sandy silt Clayey sili Silty clay Clavey silt Sand Sand Clay Sandy clay Silty clay Sandy silt Clayey sand Sand Sand NOTE: TR = trace. ND = not detected. — = not determined. ' Aroclor 1260 the original compound. Another high value for SDDT, 12 ppb, was found in Torch lake (.station 30) in the Keweenaw waterway, which is also a recreational area. Highest values of 5;DDT were lower often by an order of magnitude than levels of SDDT analyzed previously in sediments of creeks draining southern Ontario to- bacco-growing areas (3.4.7,13) and mixed agricultural areas just south of the Canadian Shield, the Bay of Quinte watershed in Lake Ontario, and the Muskoka Lake System which drains into Georgian Bay near sta- tion 12 (14). One study (14) showed mainly DDE and TDE in such sediments, but no o.p'-DDT or dieldrin. Results of the present survey confirm this pattern. Areas which revealed p.p'-DDT (stations 4, 8, 10, 20. 21) and o.p'-DDT (station 10) were located in basins of high-sediment deposition (R. L. Thomas. Canada Centre for Inland Waters, 1975: personal communi- cation), which may explain why DDT is accumulating there. The single exception was station 10 in Georgian Bay off Collingwood, Ontario. Sediments of these sites are characterized generally by the presence of either clay, clayey silt, or clayey sand and higher organic carbon content than sediments from other stations. All also have redox potentials of at least +300 mv. indicating oxidizing environments. SDDT. especially TDE. generally appears to be degraded at faster rates in anaerobic environments (11.22). The three lowest redox potentials found were at stations 5 (-f90 mv), 11 (+95 mv), and 30 ( + 100 mv). Station 5 in Saginaw Bay is characterized by sandy sediments in an area of active sediment transport which may explain the levels of DDT and PCB's below detection limit as there are potential inputs of these compounds in the area. However, station 1 1 off Penetanguishene, Ontario, and station 30 in Torch Lake, Keweenaw Peninsula, Michigan, appear to be zones of deposition in terms of sediment type; both are high in TDE and DDE, in- dicating degradation. Of interest are the higher levels of DDE found in the sediments of stations 16 and 17 near the Straits of Mackinac. Station 16 lies in the depositional Mackinac Basin; station 17 is in an area of undilTcrcntialed tills and bedrock (24). These higher levels may represent inputs from Lake Michigan or local insect control in the recreational or urban areas of adjacent Michigan. The former hypothesis may be supported by the fact that of all the Great Lakes, Lake Michigan appears to be highest in pesticide residues evidenced by compara- tive fish analyses. Lake Superior fish had the lowest con- centrations: one-fourth to one-seventh the level of those in Lake Michigan fish (15-17). Lake Huron fish occu- pied the middle range of all the lakes, below Ontario fish but higher than Erie fish. Vol. 10, No. 2, September 1976 65 The PCB data demonstrate no clear correlation between sediment concentration and either sediment texture, or- ganic carbon content, or redox potential. SDDT data, however, indicate that the highest sediment concentra- tions of the parent compound were found in geologic basins where accumulation of sediments also tended to be higher in clay content and organic carbon, and had higher redox potential. Dieldrin was found only in trace amounts at stations 1. 7. 8, 10. and 22: there appear to be no similarities in the nature of sediment environ- ments at these stations and the significance of these trace amounts is uncertain. Other organochlorine compounds were below detection limits at all stations. This may be explained by use patterns. In Ontario, the major use of organochlorines is in Lake Huron watersheds for such field crops as corn, soybeans, and small grains. Previous studies indi- cate that the main soil residues in these areas were aldrin, dieldrin. endrin. and SDDT (/.6). Since the late 1960"s, however, use of many organochlorine com- pounds has diminished. Aldrin and dieldrin were banned for agricultural purposes in Ontario in 1970, and DDT was banned except for two uses in 1970. One would also have expected highest residues of DDT and dieldrin from orchards and vegetable and tobacco soils. Apparently no data have been published on the limited acreages of orchards in the Georgian Bay watershed and no studies are available to determine what inputs might come from these limited areas compared to recre- ational or municipal inputs from the same region. Michigan corn-belt soils analyzed for residues contained only dieldrin and DDT-related compounds: however, the sampling area could influence only the southern portion of Lake Huron (/). The absence of correlation between possible sources of pesticides and sediment concentration could result from causes other than the nature and transport of sediments: atmospheric input, for example. W. M. J. Strachan (Canada Centre for Inland Waters. 1975: unpublished data) found PCB levels in atmospheric precipitation at Burlington, Ontario, to range from 0.02 to 0.0.5 ppb on a limited number of samples; at Parry Sound on Geor- gian Bay levels were less than 0.02 ppb. Also detected were nine organochlorine pesticides at levels between 0.001 and 0.026 ppb: p.p'-Dm and a-cndosulfan oc- curred at the highest levels. Another study of air sam- ples at Buffalo, N.Y., on Lake Erie detected p.p-DDT and o,p'-DDT at levels of 11.0 and 2.9 ng/m\ respec- tively (2.?). Authors presunu that levels of such pesti- cides are lower in the atmosphere over the upper Great Lakes. Unforlunately, no data exist on the magnitude of atmospheric pesticide contributions to the Great Lakes. Conrliisinns This survey indicates low concentrations of PCB's, DDT and/or its degradation products TDE and DDE. 66 and traces of dieldrin in sediments and seston of Lakes Superior and Huron and Georgian Bay. These com- pounds were below detection limits in water samples. No other organochlorine compounds were detected nor were any organophosphorus compounds found in any of the samples analyzed. The source of these compounds is not known. In the Lake Superior watershed, agriculture is very limited: hence pesticides probably are not used in great volume. Unfortunately, use patterns of pesticides in the upper Great Lakes have not been published so inputs cannot be estimated nor are data available on use patterns of pesticides in recreational or urban areas around the up- per Great Lakes. Atmospheric inputs also require fur- ther study. Consequently, it cannot be ascertained whether the low concentrations of pesticides found in the upper lakes are due to use patterns, environmental degradation of such compounds, or both. Continuing surveillance is necessary to determine whether the organochlorine com- pounds detected are degrading in these lakes now that uses of some compounds such as DDT and dieldrin have been banned in the area. Such a program also would indicate whether compounds such as endosulfan ,md chlordane, whose us:igc is increasing, are accumu- lating in the upper Great Lakes environment. A cknowledgmenis The authors would like to express their gratitude to the members of the Technical Operations Section. Canada Centre for Inland Waters, and the crew of the C.S.S. Limnos for their assistance in the sampling program. Authors thank N. Harper and M. Zarull for their ship- board processing of samples. N. Rukaviana for sedi- mentary particle size analyses, and J. D. Patterson and R. Luft for many of the analyses. LITERATURE CITED (/) Carey, A. E., G. B. Wiersitm, H. Tat. and W. G. Milchcll. 1973. Organochlorine pesticide residues in soils and crops' of the Corn Belt region. United States — 1970. Pestic. Monit. J. 6(4) :369-376. (2) Chau. A. S. Y.. and M. Lanoucltc. 1972. Confirmation of pesticide residue identity-II. Derivative formation in solid matrix for the confirmation of DDT, DDD. methoxychlor. perthanc, tis- and trans-chiordane, hep- tachlor and heptachlor epoxide residues by gas chro- matography. J. Ass. Offic. Anal. Chem. ."55(5) : 1058- 1066. (.?) Frank. R.. A. E. Arm.uroni;. R. G. BnUcn-:. H. E. Braiin, and C. W. Douglas. 1974. Organochlorine in- seeticitlc residues in sediment and fish tissues. Ontario. Canada. Pestic. Monit. J. 7(3 '4) : 165-180. (4) Frank, R.. K. Mnnlvomcrv, fl. F. Braiin. A. H. Bcrsl. and K. I.oflii^. 1974. DDT and dieldrin in watersheds draining the tobacco belt of southern Ontario. Pestic. Monit. J. 8(3):184-20l. Pesticides Monitoking Journal (5) Giam, C. S.. ^f. K. Wong. A. R. Hanks, W. M. Sack- elt, and R. L. Richardson. 1973. Chlorinated hydro- carbons in plankton from the Gulf of Mexico and northern Caribbean. Bull. Environ. Contam. Toxicol. 9(6):376-382. (6) 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. 5(3) :259-267. (7) Harris. C. R., W . W. Sans, and J. R. W . Miles. 1966. Exploratory studies on the occurrence of organochlor- ine insecticide residues in agricultural soils in south- western Ontario. J. Agr. Food Chem. 14(4) :398-403. (S) Harvey. G. R.. H. F. Miklas. V. T. Bowen. and W. G. Stcinhauer. 1974. Observations on the distribution of chlorinated hydrocarbons in Atlantic Ocean organisms. J. Mar. Res. 32(2) : 103-1 18. (9) Inland Waters Directorate. 1974. Analytical Methods Manual. Water Quality Branch. Ottawa, Canada. 188 pp. {10) International Joint Commission. 1972. Great Lakes Water Quality Board Third Annual Report, Appendix B. Surveillance Subcommittee Report, Windsor, On- tario. 212 pp. (//) Kearney, P. C. and D. D. Kaufman. 1972. Microbial degradation of some chlorinated pesticides. In Na- tional Academy of Sciences, Degradation of Synthetic Organic Molecules in the Biosphere. Washington, D.C.. pp. 166-189. (12) Lichtenberg, 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- 68. Pestic. Monit. J. 4(2) :71-86. (13) Miles, J. R. W., and C. R. Harris. 1971. Insecticide residues in a stream and controlled drainage system in agricultural areas of southwestern Ontario. Pestic. Monit. J. 5(3):289-294. (14) Miles. J. R. W., and C. R. Harris. 1973. Organochlo- rine insecticide residues in streams draining agricultu- ral, urban-agricultural, and resort areas of Ontario, Canada— 1971. Pestic. Monit. I. 6(4) :363-368. (15) Reinert, R. E. 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4) .-233-240. (16) Reinert, R., and H. C. Bergman. 1974. Residues of DDT in Lake Trout (Salvclinus namuycosh) and Coho Salmon (Oncorhvnchus kisKtch) from the Great Lakes. J. Fish. Res. Board Can. 31 (2) : 191-199. (17) Rcinkc, J., J. F. Utlie, and D. Jamicson. 1972. Organo- chlorine pesticide residues in commercially caught fish in Canada— 1970. Pestic. Monit. J. 6(l):43-49. (75) Ripley. B. D., J. A. Hall, and A. S. Y. Chau. 1974. Determination of fenitrothion, phosphamidan. and dimethoate in natural waters. Environ, Lett. 7(2): 97-118. (19) Ripley. B. D.. J. Wilkinwn. and A. S. Y. Chan. 1974. Multi-residue analysis of fourteen organophosphorous pesticides in natural waters. J. Ass. Offic. Anal. Chem. 57(5):1033-1042. (20) Riseborough. R. W., V. Vreeland, G. R. Harvey. H. P. Mikhis, and G. M. Carmignani. 1972. PCB residues in Atlantic Zooplankton. Bull. Environ. Contam. Toxicol. 8(6):345-355. (21) Schacht, R. A. 1974. Pesticides in Illinois Waters of Lake Michigan. U.S. Environ. Prot. Agency Rep. EPA 660/3-74-002. 55 pp. (22) Scihunathan. N. 1973. Microbial degradation of insec- ticide in flooded soil and in anaerobic cultures. Residue Rev. 47:143-165. (23) Stanley. C. W.. J. E. Barney. M. R. Helton, and A. R. Yobs. 1971 . Measurement of atmospheric level of pes- ticides. Environ. Sci. Technol. 5(5) :430-435. (24) Thomas. R. L.. A. L. W. Kemp, and C. F. M. Lewis. 1973. The surficial sediments of Lake Huron. Can. J. Earth Sci. 10(2) :226-271. (25) Webb. R. G., and A. C. McCall. 1973. Quantitative PCB standards for electron capture gas chromatog- raphy. J. Chromatogr. Sci. 11(71:366-373. Vol, 10, No, 2, September 1976 67 GENERAL Residues of Qiiintozene. Its Contaminants and Metabolites in Soil, Lettuce, and Witloof-Chicory, Belgium — 1969-74 ' W. Dejonckheere," W. Steurbaut," and R. H. Kips - ABSTRACT Authors studied contamination of soils used to raise lettuce in greenhouses and witloof-chicory (French endive) in forc- ing beds. The crops had been treated with the fungicide quintozene; residues detected included qiiintozene. its tech- nical impurities and metabolites hexachlorobenzene. penta- chlorohenzene, pentachloroaniline, and pentachtorothioani- sole. Analyses of 72 soil samples indicated that soils remain contaminated with these chemicals one or more years after application. This is attributed to the high persistence of quin- tozene, its impurities and metabolites, and the almost annual application of the fungicide. Analyses of the crops show that quintozene, hexachlorobenzene, and pentachloroaniline are talien up from contaminated soils, especially by lettuce. Pentachlorothioanisole, although present in the soils, was not delected in the crops. Introduction The fungicide quintozene Ipentachloronitrobenzene (PCNB)] is used on lettuce and witloof-chicory (French endive) to control Rhizoctonia bottom rot and Botrytis gray mold rot. This practice generally produces residues of quintozene and related compounds in the marketable product [3.4). When applied to lettuce in a greenhouse and to witloof-chicory in a forcing bed. the fungicide is taken up by the plants from the soil. Due to the stability of the compound a large fraction of the applied dose remains in the soil after the crop has been harvested (1,4,6). Successive yearly applications of quintozene to lettuce foliage or soil and to witloof-chicory soil may increase quintozene content of the soil. Residues may then be • Sponsored by the Council for Scientific Research in Industry and Agriculture (I.W O.N.I. , Institvuit tot Aanmocdiging van hct Wcicn schaprelijk Ondir/oek in Nijverhcid en Landbouw) and the Belgian Ministry of A^ricullurc. - Department of Crop Protection Chemistry, Faculty of Agricultural Sciences. Si.ite University of Gent. Coupure links, 533-B-9000 Gent, Belgium found in crops grown on soils which have not been treated during the current growing season. This explains why certain experiments have shown no correlation between the residue content in lettuce and witloof- chicory and the dose applied during that particular growing season. In order for authors of the present study to obtain some reliable data on the degree of contamination fol- lowing yearly quintozene treatments, soil samples from lettuce greenhouses and from witloof-chicory forcing beds were analyzed. Apart from quintozene, amounts were also determined for hexachlorobenzene (HCB), pentachlorobenzene (QCB), pentachloroaniline (PCA), and pentachloro- thioanisole (PCTA); these chemicals were present as a result of the quintozene treatments (Fig. \; 8). For a number of soils where no quintozene was applied after sampling, residues were analyzed in the lettuce CI H Cl^v!^^;^CI Clc<>sCI Cl'<;3;^CI CI HCB NOj CI*s^^CI CI QCB CI PCNB SCH3 Clk^;;-^CI CI CI PCA PCTA FIGURE 1. Breakdown of PCNB: HCB and QCB are pres- ent as contaminants of the technical grade quintozene: PCA and PCTA are quintozene metabolites. 68 Pesticides Monitoring Journal and witloof-chicory crops grown in these soils to deter- mine the uptake of the compounds from the soil. Sampling Random soil samples were taken by inspectors of the Belgian Ministry of Agriculture. In total 72 plots were sampled: 24 from lettuce greenhouses and 48 from witloof-chicory forcing beds. Every soil composite con- sisted of five samples, each containing five cores of approximately 2.5 cm taken at random to a depth of 30 cm. After mixing, a subsample was taken for analysis. The soil samples were accompanied by a statement about the quintozene treatments on the sampled area during the five previous years; information provided by the grower was sometimes vague. Samples were not air- dried nor sieved before analysis. In order to obtain an accurate picture of the uptake of quintozene and its technical contaminants and me- tabolites from the soil, lettuce and witloof-chicory were sampled from plots that were not treated with quinto- zene during the growing season. The 21 lettuce samples consisted of five heads taken at random in 21 greenhouses. The yellowing outer leaves were removed prior to analysis. After cutting up the leaves a subsample was taken for analysis. The 21 wit- loof-chicory samples which weighed about 2 kg each were taken randomly from 21 forcing beds. The crop was cleaned as customary before marketing, and cut into small pieces; a subsample was taken for analysis. Materials and Methods Reagents and apparatus used were: Petroleum-ether: freshly distilled Acetone: freshly distilled Sodium sulfate: anhydrous, technical grade Sodium chloride: technical grade Ultra turax mixer: type 645 N Janke-Kunkel KG Gas chromatographs: Varian. models 1400 and 2400, fitted with electron-capture detectors and glass columns filled with 2 percent OV- 225 or 3 percent of a 3:22 OV-17:OV-210 mixture on Gas-Chrom Q. EXTRACTION AND ANALYSIS A 50-g soil subsample or a 100-g sample of finely chopped lettuce or witloof-chicory leaves was blended for 3 minutes with 200 ml of a 1:1 mixture of petro- leum ether:acetone filtered through a Buchncr filter and rinsed with 50 ml of the same solvent mixture. The extract was transferred to a 1 -liter separating fun- nel and shaken twice with 200 ml HO and 25 ml of a saturated NaCl solution. Water layers were discarded and the petroleum-ether phase was dried over anhy- drous Na^SO,. In most cases the resulting solution was concentrated and directly analyzed by gas chromato- graphy using the 2 percent OV-225 column. Confirma- tion was obtained on the OV-17 — OV-210 column (Fig. 2). Recoveries ranged between 85 and 95 percent. Limits of detection for the normal procedure without concentration were: 0.01 ppm, HCB; 0.02 ppm. PCNB; 0.05 ppm. PCA and PCTA. After a tenfold concentra- tion of the petroleum-ether extract, detection limits were one tenth the rates mentioned above (5,6). Di- chloran and endosulfan were sometimes detected in soil samples but in much smaller amounts than quintozene and related compounds. Results and Conclusions Tables 1 and 2 show the results of the soil analyses and the quintozene dosage rates indicated by the growers. Tables 3 and 4 summarize the results for lettuce and witloof-chicory soils, respectively. Tables 5 and 6 show the results of soil and plant analysis for lettuce and w itioof-chicory. The recommended application rates of active ingredient (a.i.) in lettuce vary according to the references: 0.125- 0.2 g/m- (10), 3-4 g/m- (2), and 8-10 g/m= (14). No actual dosage recommendation is available for witloof- chicory but the general tendency is to apply about 5 g a.i./m-. Information obtained from growers indicates that more quintozene is applied each year to witloof-chicory than to lettuce. This is mainly due to the facts that several crops are grown in the same year, each preceded by a quintozene treatment, and that all are grown on the same topsoil. Compounding the higher quintozene resi- dues in witloof-chicory soils are the dark, indoor grow- ing conditions which do not favor decomposition of the fungicide. A certain amount of information about quintozene breakdown and metabolism has been published (8 9, 11-13. 15). The literature indicates that microbiological processes, influenced by temperature, humus, oxygen, and water content of the soil, influence the breakdown. Physical processes such as evaporation and leaching may affect the rate of disappearance of pesticides from the soil. Wang and Broadbent (15) showed that for quintozene, evaporation plays an important part in warm and wet soils. Mainly because of the low solu- bility of quintozene, leaching is negligible (13). De- jonckheere et al. (7) concluded that adding organic matter to the soil increases the rate of quintozene de- composition. PCA is produced primarily under anerobic conditions; PCTA is produced under aerobic conditions. Nevertheless the high soil residues found during the present investigation indicate that quintozene is very persistent and breaks down slowly. HCB, QCB, PCA, and PCTA were also found in easily detectable quanti- ties associated with quintozene. As indicated in Table Vol. 10, No. 2, September 1976 69 I B OV 225 V OV 17/210 FIGURE 2. Gas chromatograms of QCB. HCB, PCNB. PCTA, and PC A. TABLE 1. PCNB HCB. QCB, PCA and PCTA residues in greenhouse lettuce soil Belgium- -1969-74 Applied Dose (a.i. g/ M=)' RESIDUES. PPM Srre 1969 1970 1971 1972 1973 1974 Total PCNB HCB QCB PCA PCTA 1.5 0.75 0.25 1.5 0.75 4.75 4.90 0.79 0.19 1.52 0.28 — — 2.92 4.0 4.0 2.00 12.92 5.80 0.31 0.19 0.98 0.74 — 046 — 0.69 — 1.55 1.15 0.06 0.06 0.10 0.11 — — 0.93 — _ 0.93 1.34 0.25 0.24 0.46 0.20 — 0.74 0.74 0.74 0.74 — 2.96 4.40 0.38 0,30 0.88 0.55 — — — 0.93 5 2.5 8.43 0.54 0.12 0.28 0.27 0.09 — 4 4 1.86 1.86 0.93 12.65 3.25 1.18 0.51 3.75 1.20 — 4 4 4 4 2 18.00 5.10 0.98 0.40 2.06 0.37 — — 3 4.5 4.5 1.5 13.5 1.83 0.23 0.41 0.78 0.11 4 4 4 1.6 1.6 0.8 16 5.40 1.62 0.63 1.63 0.28 — 2.25 2.25 4.0 4.0 — . 12.5 6.40 0.41 0.28 0.94 1,08 2 4 4 4 4 _ 18.0 6.80 0.56 0.25 0.55 0.73 — 4 3.6 3.2 3.6 1.56 15.96 8.40 0.98 0.27 0.84 0.92 — — — — 0.93 — 0.93 0.97 0.08 0.06 0.14 0.15 — — 0.93 0.93 1.86 1.48 0.10 O.OC 0.12 0.26 2+2+1 (1962 and 1963) 5.0 0.08 0.11 0.03 0.53 0,11 — 2.8 1.86 1.30 1.30 7.26 0.88 0.32 0.26 0.87 0.35 — — — 0.6 0.6 0.86 2.06 1.50 0.08 0.07 036 0.09 — — 0.4 — 0.4 O.S 5.50 0.42 0,42 1.05 1.48 1964 'tilJan. 74: 2 g/2 y per year 40 4.60 1.04 0.70 1.76 1.37 — — 1.4 1.4 1.4 4.2 1.50 0.30 0.24 0,60 051 22 0.3 0.3 0.3 0.3 0.3 0.56 2.06 0.22 0.06 0.06 0,20 0.17 23 0.3 0.3 0.3 0.3 0.3 0.56 2.06 0.14 0.03 0,05 0,10 0.06 24 0.5 0.5 0.6 0.6 0.5 Average 2.7 0.63 3.03 0.08 0.44 006 0.25 0.66 0.84 0.16 0.47 NOTE; Blank denotes no application. ' Dosage rales arc approximations supplied by growers. 70 Pesticides Monitoring Journal TABLE 2. PCNB, HCB. QCB, PC A. and PCTA residues in soil of wiiloof-chicory forcing beds, Belgium— 1969-74 Applied Dose (a.i. g/m=)i Residues, ppm Site 1969 1970 1971 1972 1973 1974 Total PCNB HCB QCB PCA PCTA 1 _ _ 3 _ 3 0.76 0.15 0.08 0.34 0.04 2 — 20 20 20 20 — 80 25.50 1.31 1.14 4.10 0.49 3 — 8 8 — 8 — 24 4.90 0,29 0.19 1.10 0.07 4 — — 17.2 17.2 — — 34.4 2.35 0,26 0.23 1.60 0.12 5 — 7 7 15 — — 29 21.60 1,85 0.54 5.10 0.67 6 — 8 8 8 8 — 32 9.00 2,25 0.73 5,60 0.87 7 — — 8 — — — 8 0.78 0,29 0,31 1,80 0.12 8 — 12 12 12 — — 36 7.50 0.77 0.38 1,70 0.19 9 — — 6 6 — 12 1.60 0.20 0.20 1.00 0.11 10 NI NI NI NI NI NI NI 0.67 0,20 0.14 0.68 0.03 U NI NI NI NI NI NI NI 2.80 0.21 0,13 0.89 0,07 12 — — — — 5 — 5 3.40 0.45 0,21 1.37 0.14 13 — 8 8 6 6 — 30 2.00 0,34 0,26 1,31 0.07 14 — 16 16 16 16 — 64 10.30 1.10 0,95 0.99 0.36 15 — — — — 10 — 10 6.50 0.74 0.60 5.60 0.53 16 NI NI NI NI NI NI NI 23.60 4,18 1.22 13.60 1.57 17 NI NI NI NI NI NI NI 5.10 0,55 0,39 2,30 0.13 18 15 15 15 15 — 60 18.40 2,84 0,57 6,30 0.41 19 NI NI NI NI NI NI 2 0.85 0,04 0,03 0,14 0.06 20 — — 28 28 — — 56 10.60 1.06 0.74 2,30 0.35 21 — 14 14 14 — — 42 20.40 1,70 094 5,40 0.46 22 NI NI NI NI NI NI NI 6.10 0.95 1.22 0,86 0.28 23 — 5 5 5 5 — 20 2.70 0.61 0.29 2.52 0.09 24 — 5 5 5 — _ 15 3.75 0.22 0.17 1.30 0.08 25 4 4 4 4 — 16 3.25 0.27 0.15 0,51 0.04 26 NI NI NI NI NI NI NI 22.50 0.83 0,23 1,07 0.17 27 NI NI NI NI NI NI NI 1.85 0.25 0.21 0,83 0.07 28 10 10 10 10 — 40 19.50 1.40 0.72 7.90 1.02 29 — 10 10 10 10 — 40 15.80 0.81 0,43 3.50 0.25 30 — 14 14 14 — — 42 12.10 1.28 0,70 7.10 0.58 31 7 7 . — 14 0.25 0.08 0.04 0.14 0.06 32 — 6 6 6 6 — 24 3.95 0.52 038 1.58 0.15 33 — 10 10 10 10 — 40 10.90 062 0,20 2.18 0.16 34 15 15 15 15 — 60 34.30 2,30 0.48 3.00 0.41 35 — 14 14 14 14 — 56 13.40 1.20 0.67 7.10 0.78 36 — 30 30 30 30 5 125 55.60 2.06 0,56 0.80 0.41 37 — 28.5 14.25 14.25 14.25 — 71.25 10.90 0,40 0.24 1.10 0.12 38 — — 14.25 14.25 14.25 — 42.75 2.10 0,13 O.Il 0.32 0.32 39 — _ — 4.30 — 4.30 0,64 0.12 0,11 0.26 0.05 40 14.25 4.30 — 18.55 0.74 0.40 0.25 1.40 0.10 41 — — — — 8.60 — 8.60 11,80 0.81 0.80 2.20 2.61 42 NI NI NI NI NI NI NI 5.40 0,86 0.33 3.90 0.46 43 2.90 — — — 2.90 6.25 0.85 0.58 2.50 1.86 44 — — — 6.2 — — 6.2 13.60 111 1.11 3.05 1.28 45 — — 6.2 — — 6.2 3.10 0.50 0.73 3.22 0.71 46 14 7 7 28 1.51 0.51 0.64 2.58 0.24 47 14 — — 4.15 4.15 — 22,30 3.30 097 0.49 7.90 1.11 48 12 Average 12 0.12 9.25 0,02 0.85 0,02 0.46 0.68 2.83 0.39 0.43 NOTE: Blank denotes no application. NI denotes no information available. ' Dosage rates are approximations supplied by growers. TABLE 3. Survey of PCNB, HCB, QCB, PCA. and PCTA residues in greenhouse lettuce soil, Belgium — 1969-74 Samples Samples containing: PCNB Range, ppm HCB QCB PCTA PCA Range, ppm 3 0.0— 0.5 6 8 3 , 0.0—0.1 4 0.5— 1.0 3 2 7 5 0.1—0.2 5 1.0— 1.5 2 7 3 I 0.2—0.3 1 1.5— 2.0 6 3 2 2 0.3—0.5 2.0— 3.0 1 3 '} 4 0.5—0.7 4 3.0— 5.0 3 1 3 6 0.7—1.0 6 5.0— 7.0 2 — 4 1 1.0—1.5 1 7.0—10.0 I — — 3 1.5—2.0 — — _ 1 2.0—3.0 — — — 1 3.0—5.0 5.0—7.0 NOTE: Blank denotes no samples in the range indicated. Vol. 10, No. 2, September 1976 TABLE 4. Survey of PCNB. HCB, QCB. PCA, and PCTA residues in soil of wiiloof-chicorv forcing beds, Belgium— 1969-74 Samples containing PCNB Samples containing: Range, ppm HCB QCB PCTA PCA Range, ppm 2 0.0— 0.5 3 3 12 _ 0.0— 0.1 6 0.5— 1.0 5 8 11 1 0.1— 0.2 4 1.0— 2.0 8 10 3 2 0.2— 0.3 4 2.0— 3 0 4 8 10 2 0.3— 0.5 7 3.0— 5.0 6 8 3 3 0.5— 0.7 7 5.0—10,0 9 7 3 — 0.7— 1.0 8 10.0—15.0 7 4 3 8 1.0— 1.5 3 15.0—20.0 2 — 2 4 1.5— 2.0 5 20.0—30,0 3 _ 1 7 2.0- 3.0 1 30,0—40,0 1 — — 7 3.0— 5.0 1 50.O— 60.0 — — — 5 5.0— 7.0 4 7.0—10.0 — — — 1 10.0—15.0 NOTE: Blank denotes no samples in the range indicated. 71 TABLE 5. PC\'B, HCB, QCB, PCA, and PCTA residues in soil and in Iclliice grown in tlial soil. Belgium — 1969-74 Residues PPM Son. Lettuce SiTB PCNB HCB QCB PCA PCTA PCNB HCB QCB PCA PCTA 1 4.90 0.79 0.19 1.52 0.28 0,39 < 0.005 ND 0.14 ND 3 1.15 0.06 0.06 0.10 0.11 0 10 ooos ND 0,02 ND 4 1.34 0.25 0.24 0.46 0.20 0.04 <0,005 ND 0.01 ND 5 4.40 0.38 0.30 0.88 0.55 1.51 0018 ND 0,40 ND 6 0.54 0.12 0.28 0.27 0.09 002 < 0.005 ND 0.01 ND 7 3.25 1.18 0,51 3,75 1.20 0,63 0,038 ND 0,63 ND 9 1.83 0.23 0.41 0.78 0.11 0,22 0.010 ND 0,13 ND 10 5.40 0.98 S.40 2 06 0.37 n,83 0.037 ND 0,38 ND II 6.40 0.41 0.28 0.94 1.08 0,61 0 009 ND 0.25 ND 12 6.80 0.56 0.25 0,55 0.73 0,60 0.010 ND 0.24 ND 13 8.40 0.98 0.27 0,84 0,92 0,57 0.010 ND 0,26 ND 14 0.97 0.08 0.06 0.14 0.15 0.75 < 0.005 ND 0 31 ND IS 1.48 0.10 006 0,12 0,26 1.15 < 0,005 ND 0.58 ND 16 0.08 0.11 0.03 0,53 0,11 0,04 ND ND 0.01 ND 17 0.88 0.32 0,26 0,87 0,35 0 03 <0.005 ND 0,03 ND 19 5.50 0.42 0.42 1,05 1.48 0.10 0.008 ND 006 ND 20 4.60 1.04 0.70 1.76 1.37 0,05 0013 ND 0,05 ND 21 1.50 0.30 0,24 0.60 0,51 0,38 ND ND 0.21 ND 22 0.22 0.06 0 06 0,20 0,17 n.28 0,007 ND 0.09 ND 23 0.14 0.03 0,05 0,10 0.06 0,72 0.012 ND 0.18 ND 24 0.63 0.08 0.06 0.66 0.16 0.02 < 0.005 ND 0.02 ND NOTE : ND = not detectable. TABLE 6. PC\B, HCli. QCB, PCA. and PCTA residues in soil and in wirloof-cliieory forced in that soil. Belgium— 1969-74 Residues PPM Son WiTi oof-Chicory SnE PCNB HCB QCB PCA PCTA PCNB HCB QCB PCA PCTA 2 25.50 1.31 1.14 4,10 0.49 0.052 0.030 ND 0,012 ND 3 4.90 0.29 0 19 1,10 0.07 0.016 ND ND ND ND 4 2.35 0.26 0.23 1 60 0.12 0005 ND ND ND ND 8 7.50 0.77 038 1.70 0.19 0.160 0.012 ND ND ND 12 3.40 0.45 0.21 1.37 0.14 0.005 ND ND ND ND 14 10.30 1.10 0.95 0.99 036 0.023 ND ND ND ND 16 23.60 4,18 1,22 13.60 1.57 0.007 0.010 ND 0.015 ND 17 5.10 0.55 0,39 2,30 0.13 0,010 0,008 ND 0.010 ND 36 55.60 2.06 0,56 3.80 0.41 0,330 0.029 ND 0.040 ND 37 10.90 040 0.24 1,10 0.12 0008 0002 ND 0.006 ND 38 2.10 0.13 0,11 0,32 0.32 0,005 ND ND ND ND 39 0.64 0,12 0,11 0.26 0.05 0,005 ND ND ND ND 40 0.74 0.40 0.25 1,40 0,10 0.005 0.007 ND 0.017 ND 41 11.8 0.81 0.80 2 20 2,61 0,036 0.005 ND 0,006 ND 42 5.40 0.86 0,33 3,90 0.46 0.056 0.053 ND 0.100 ND 43 6.25 0.85 0,5S 2.50 1.86 0.026 0.009 ND 0.014 ND 44 13.60 1.11 1,11 3.05 1.28 0.015 0.007 ND 0.022 ND 45 3.10 0.50 0.73 3.22 0.71 0,005 ND ND 0.007 ND 46 1.51 0,51 0.64 2,5S 0.24 0 005 0,003 ND 0.005 ND 47 3.30 0.97 0.49 7,90 1.11 0.013 0.026 ND 0.130 ND 48 0.12 0.02 0.02 0,68 0.39 ND ND ND ND ND NOTE: ND = not delectable. I, average residues (ppm) in letliice soil for the 6-year period were: PCNB, .^03; HCB. 0.44; QCB, 0.25: PCA. 0.84: PCTA. 0.47. Corresponding values in wit- loof-chicory soil listed in Table 2 were: PCNB. 9.25; HCB, 0.85; QCB. 0.46; PCA, 2.8.3; PCTA, 0.43. The average PCA:quinl07.enc ratio was 0.290 in lettuce and 0.305 in witloof-chicory soil. The respective values for the PCT.A:quinlozcne ratios were 0.155 and 0.046. This may indicate that more PCTA is produced during lettuce growing ih.m during witloof-chicory growing, which corresponds to the more aerobic conditions of the lettuce field. The calculated average HCB:quinto- zcnc ratios were 0.145 for lettuce soil and 0.092 for witloof-chicory soil. QCB:quinU)7.ene ratios were 0.082 for lettuce soil and 0.048 for witloof-chicory soil. These HCB and QCB ratios seem, especially for lettuce soils, to be higher than the normal impurity content of the formulations applied, which may be explained by the rapid breakdown of quintozene and the slow formation of QCB from quintozene (7). .Apart from the general aspect of soil contamination which these residues present, there is also the possibility that these chemicals will be taken up by the crops crown on polluted soils. In an earlier work (6) the authors found that the ratio between the quintozene soil resi- due and the amount present in the lettuce crop at time of harvest averaged 1.34 for an early harvest (average head 143 g) and 0,44 for a late harvest (average head 315 g). For HCB these ratios were 0.97 and 0.36. re- spectively. The uptake was somewhat higher for low 72 Pesticides Monitoring Journal quintozene soil residues (0.12-0.44 ppm) than for high ones (5.0-6.1 ppm). For witloof-chicory the uptake factor averaged 0.004, much lower than for lettuce. No QCB or PCTA residues were found in the harvested crops, which confirms previous findings. The average soil: crop quintozene ratio calculated from the results of this study was 0.15 for lettuce and 0.004 for witloof-chicory. The value for lettuce is clearly lower than that found in previous work (6), perhaps in part because crops in the present study were sampled for residue analysis 3-6 months after soil samples had been taken for the same purpose. The confirmed variability in the soihcrop residue ratio for witloof-chicory may reflect the various degrees of cleanup which the plant receives before analysis. The residue level may depend greatly on the presence or absence of small quintozene-carrying soil particles be- tween the closely packed witloof-chicory leaves. LITERATURE CITED (/) Beck, J., and K. E. Hansen. 1974. The degradation of quintozene, pentachlorobenzene, hexachlorobenzene and pentachloroaniline in soil. Pestle. Sci. 5(I):41-48. (2) Crop Protection Advisory Services. 1973. Guide for Disease and Weed Control in Agriculture and Horli- culture. Wageningen, Holland. (3) Dcjonckheere. W., W. Sleurbant. and R. H. Kips. 1974. Pesticide residues in lettuce. II. Winter 1972-1973. Meded. Fac. Landbouww. Rijksuniv. Gent 39(1): 297-300. (4) Dejonckheere, W.. W. Steurbaut. and R. H. Kips. 1974. Quintozene (PCNB) residues in witloof chicory. Para- sitica 30(l):28-36. (5) Dejonckheere. W., W. Steurbaut, and R. H. Kips. 1975. The fate of quintozene (PCNB) on lettuce. Meded. Fac. Landbouww. Rijksuniv. Gent 40(2) : 1033-1038. (6) Dejonckheere, W., W. Steurbaut. and R. H. Kips. 1975. Residues of quintozene, hexachlorobenzene, dichloran and pentachloroaniline in soil and lettuce. Bull. En- viron. Contam. Toxicol. 13(6) :720-729. (7) Dejonckheere. W., J. Willcox, W. Steurbaut, R. H. Kips, J. P. Voets. and ]V. Verstraete. 1975. Changes in the rate of metabolism of quintozene in the soil under varying microbial growth conditions. Meded. Fac. Landbouww. Rikjsuniv. Gent 40(2) :1I87-1197. (8) De Vos, R. H., M. C. ten Noever De Braiiw, and P. D. A. Oltliof. 1974. Residues of pentachloronitrobenzene and related compounds in greenhouse soils. Bull. En- viron. Contam. Toxicol. 1 1 (6) :567-571. (9) Gorbach. S.. and U. Warner. 1967. Pentachloronitro- benzene residues in potatoes. J. Agr. Food. Chem. 15(4):6.';4-656. (10) Heymands. P., and F. Lickens. 1972. Crop Protection in Market Gardening. Vegetable Crop Research Sta- tion, St. Katelijne-Waver, Belgium. (ll)Kow, H. W., and J. D. Farley. 1969. Conversion of pentachloronitrobenzene to pentachloroaniline in soil and the effect of these compounds on soil microorgan- isms. Phytopathology 59(7):64-67. (/-') Kuchar. E. J.. F. O. Geenty, W. P. Griffiths, and R. J. Thomas. 1969. Analytical studies of metabolism of Terrachlor in Beagle dogs, rats and plants. J. Agr. Food. Chem. 17(6) : 1237-1240. {13) Leistra, A/., and J. H. Smelt. 1974. Concentrations of quintozene at different depths in bulb growing soils. Bull. Environ. Contam. Toxicol. 1 1 (3) :241-243. (14) Tilemans. E. 1968. List of Registered Crop Protection Chemicals. Ministry of Agriculture. Brussels, Belgium. (15) Wan.i;, C. H., and F. F. Broadbent. 1973. Effect of soil treatments on losses of two chloronitrobenzene fungi- cides. J. Environ. Quality 2(4) :51 1-515. Vol. 10, No. 2, September 1976 73 APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN AROCLOR 1260 AZINPHOSETHYL (Guihion) AZINPHOSMETHYL BHC (Benzene Hexachloride) CARBOPHENOTHION CHLORDANE DDD DDE DDT DIAZINON DIELDRIN DIMETHOATE DISULFOTON ENDOSULFAN ENDRIN ETHION FENITROTHION HEPTACHLOR HEPTACHLOR EPOXIDE IMIDAN LINDANE MALATHION METHOXYCHLOR METHYL PARATHION METHYL TRITHION MI REX NONACHLOR OXYCHLORDANE PARATHION PCB's ( POLYCHLOR- INATED BIPHENYLS) PHORATE PHOSPHAMIDON RONNEL TDE TOXAPHENE TRIFLURALIN Not less than 95% of l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-endo-«A;o-5,8-dimethanonaphthalene PCB, approximately 60T^ chlorine 0,0-Diethyl SI4-oxo-I,2,3-benzolriazin-3(4H)ylmethyl] phosphorodithioate O.O-Dimethyl S[4-oxo-l,2,3-benzotriazin-3f4H)ylmethyl] phosphorodithioate 1 ,2,3,4,5,6-Hexachlorocyclohexane ( mixture of isomers ) . Commercial product contains several isomers of which aamma is most active as an insecticide. S-[[(;'-Chlorophenyl)thio] methyl] 0,0-diethyl phosphorodithioate l,2,3,5,6,7,8.8-Octachloro-2,3,3a,4,7,7a-hexahydro-4.7-methanoindene. The technical product is a mixture of several compounds including heptachlor, chlordene, and two isomeric forms of chlordane. See TDE. Dichlorodiphenyl dichloro-ethylene (degradation product of DDT) p,p'-DDE: l,l-bichloro-2,2-bis(p-chlororhenyl) ethylene o./i'-DDE: l,l-Dichloro-2-(o-chlorophenyl) -2- (p-chloropheny I) ethylene Main component (p,p'-DDT) : a-Bis(p-chlorophenyl) ;3,/3,;3-trichloroethane. Other isomers are possible and some are present in the commercial product. o,p'-DDT: II,I.l-Trichloro-2-(o-chlorophenyl)-2-(p-chlororhenyl) ethane] 0,0-Diethyl 0-(2-isopropyl 4-methyl-6-pyrimidyl) phosphorothioate Not less than 85% of 1,2.3,4. 10,10-hexachloro-6,7-epoxy-l,4,4a,5,6.7, 8, 8a-octahydro-I,4-('ndo-ejro-5, 8-dimethano- naphthalene 0,0-Dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate 0,0-Diethyl S-2(ethylthio) ethyl phosphorodithioate 6,7,8,9,10.10-Hexachloro-l,5,5a,6,9,9a-hexahydro-6.9-methano-2,4.3-benzodioxathiepin 3-oxide 1,2,3,4, 10, I0-Hexachloro-6.7-epoxy-l, 4,4a, 5,6,7, 8. 8a-octahydro-l,4-endo-endo-5,8-dimethanonaphthalene 0,0,0',0'-Tetraethyl S,S-methylene bisphosphorodlthioate Q,0-Dimethyl 0-(4-nitro-m-tolyl) phosphorothioate 1, 4.5,6,7,8. 8-Heptachloro-3a,4,7,7a-tetrahydro-4,7-fndo-methanoindene 1, 4,5,6,7. 8,8-Hept3chloro 2,3-epoxy-3a.4,7,7a-tetrahydro-4,7-methanoindane O.O-Dimethyl S-phthal-imidomethyl phosphorodithioate Gamma isomer of benzene hexachloride {1,2,3.4,5,6-hexachlorocyclohexane) of 99+% purity S-[l,2-Bis(ethoxycarbonyl) ethyl] 0,0-dimethyl phosphorodithioate l,l,l-Trichloro-2.2-bis(p-meIhoxyphenyl) ethane O.O-Dimethyl O-p-nitrophenyl phosphorothioate O.O-Dimethyl S-(p-chlorophenylthio) methyl phosphorodithioate Dodecachlorooctahydro-l,3,4-metheno-IH-cyclobuta[cd]pentalene 1,2,3,4. 5,6.7, 8-Nonachlor-3a,4,7,7a-tetrahydro-4,7-methanoindan 2,3,4,5,6.6a,7.7-Oclachloro-la,lb,5,5a.6,6a-hexahydro-2.5-methano-2H-indeno(I.2-^)oxirene 0,0-Diethyl-0-p-niirophenyl phosphorothioate Mixtures of chlorinated biphenyl compounds having various percentages of chlorine 0,0-Diethyl S-(cthylthio) methyl phosphorodithioate l-Chloro-diethylcarbamoyl-1-propen-2yl dimethyl phosphate Dimethyl 2,4.5-trichlorophcnyl phosphorothionatc 2,2-Bis (p-chlorophcnyll-KI-dichlorocthanc (including isotners and dchydrochlorination products) Chlorinated camphene ( 67-69% chlorine ) . product is a mixture of polychlor bicyclic terpens with chlorinated camphenes predominating. a,a,a-Trinuoro-2,6-dinitro-N,N-dipropyl-p-toluidinc 74 Pesticides Monitoring Journal ERRATUM Pesticides Monitoring Journal, Volume 10, Number 1, pp. 10-17. In the paper "Nationwide Residues of Organo- chlorines in Starlings, 1974," Acknowledgments should read: Special thanks are extended to the following for their help with starling collections: Donald Dona- hoo, James Elder, Robert Hillen, Harry Kennedy, David Lenhart, John Peterson, and Larry Thomas. Earlene Swann compiled the tables and Pamela Kramer constructed the map. Vol. 10. No. 2, September 1976 ''^ Information for Contributors The Pesticides Monitoriri!; Journal welcomes from all sources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators associated with pesticide monitoring, research, and other programs concerned with pesticides in the environ- ment. Other subscribers work in agriculture, chemical manufacturing, food processing, medicine, public health, and conservation. Articles are grouped under seven headings. Five follow the basic environmental components of the National Pesticide Monitoring Program: Pesticide Residues in People; Pesticide Residues in Water; Pesticide Residues in Soil; Pesticide Residues in Food and Feed; and Pesticide Residues in Fish. Wildlife, and Fstuaries. The sixth is a general heading; the seventh encompasses briefs. Monitoring is defined here as the repeated sampling and analysis of environmental components to obtain reliable estimates of levels of pesticide residues and related compounds in these components and the changes in these levels with time. It can include the recording of residues at a given time and place, or the comparison of residues in different geographic areas. The Journal will publish results of such investigations and data on levels of pesticide residues in all portions of the environment in suflfkient detail to permit interpretations and con- clusions by author and reader alike. Such investigations should be specifically designed and planned for moni- toring purposes. The Journal does not generally publish original research investigations on subjects such as pesticide analytical methods, pesticide metabolism, or field trials (studies in which pesticides are experimen- tally applied to a plot or field and pesticide residue de- pletion rates and movement within the treated plot or field are observed). Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and references. Pesticides ordinarily should be identi- fied by common or generic names approved by national or international scientific societies. Trade names are acceptable for compounds which have no common names. Structural chemical formulas should be used when appropriate. Accuracy, reliability, and limitations of sampling and analytical methods employed must be described thoroughly, indicating procedures and con- trols used, such as recovery experiments at appropriate levels, confirmatory tests, and application of internal standards and interlaboratory checks. The procedure employed should be described in detail. If reference is made to procedures in another paper, crucial points or modifications should be noted. Sensitivity of the method and limits of detection should be given, particularly when very low levels of pesticide residues are being reported. Specific note should be made regarding cor- rection of data for percent recoveries. Numerical data, plot dimensions, and instrument measurements should be reported in metric units. PREPARATION OF MANUSCRIPTS Prepare manuscripts in accord with the CBE Style Manual, third edition. Council of Biological Edi- tors, Committee on Form and Style, American Institute of Biological Sciences. 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GOVERNMENT PRINTING OFFICE: 1976 6ai-e52/l Vol. 10, No. 2, September 1976 77 The Pesticides Monitoring Journal is published quarterly under the auspices of the Federal Working Group on Pest Management (responsible to the Council on Environ- mental Quality) and its Monitoring Panel as a source of information on pesticide levels relative to humans and their environment. The Working Group is comprised of representatives of the U.S. Departments of Agri- culture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; Transportation; and Labor; and the Environmental Protection Agency. The Monitoring Panel consists of representatives of the Agricultural Research Service, Animal and Plant Health Inspection 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. 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Feltz, Geological Survey Address correspondence to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, D.C. 20460 Editor Martha Finan CONTENTS Volume 10 December 1976 Number 3 RESIDUES IN FISH, WILDLIFE. AND ESTUARIES Pcige Chlorinated hydrocarbon and PCB residues in tissues and lice of northern fur seals, 1972 79 David A. Kurtz and Ke Chung Kim Organochlorine pesticide residues in plain chacalacas from south Texas. 1971-72 84 Wayne R. Marion Insecticide residues on stream sediments in Ontario. Canada 87 J. R. W. Miles Chronology of organochlorine compounds in Lake Michigan fish, l929-f,f) 92 William J. Neidermyer and Joseph J. Hickey Preliminary study of the occurrence and distribution of DDT residues in the Jordan watershed. 1971 96 Jacob D. Paz Occurrence of pesticide residues in four streams draining different land-use areas in Pennsylvania. 1969-71 101 John P. Truhlar and Lloyd A. Reed RESIDUES IN SOIL Mercury and 2,4-D levels in wheat and soils from sixteen Stales, 1969 111 J. A. Gowen, G. B. Wiersma. and H. Tai Pesticide levels in hay and soils from nine Stales, 1971 114 J. A. Gowen. G. B. Wiersma, H. Tai, and W. G. Mitchell APPENDIX "7 Information for contributors 1 1 8 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Chlorinated Hydrocarbon and PCB Residues in Tissues and Lice of Northern Fur Seals, 1972 ' David A. Kurtz - and Ke Chung Kim ■'' ABSTRACT DDT, dieldrin. and PCB contents of tissues and the sucking lice of the northern fur seal (Callorhinus ursinus) were studied in samples collected in July 1972 in the Pribilof Islands, Alaska. They included the analyses of two nursing cows and their two newborn pups, three 2-month-old pups, and the sucking lice inhabiting these animals, Antarctophthirus cailor- hini and Proechinophthirus fluctus. The "i-DDT content of fat tissue was 5.2, 5.6, and 63 fig/g (x) for cows, newborns, and 2-month-old pups, respectively. Dieldrin appeared at trace levels. PCB residues (Aroclor 1254) were 5.8, 5.5, and 33 fig/g (x), respectively. The 'S.DDT content of blood was less than 0.01 ixgig for cows and newborns and 4.6 fjLg/g for 2-month-old pups. PCB's were found only in trace amounts in the blood of all animals except one 2-month-old pup which contained 3.4 figlg. Lice contained 0.2-6 percent, respectively, of the 1DDT and PCB's detected. All residues were expressed on a wet- weight basis. Two-month-old pups had far higher residue levels than had cows. A high percentage o/iDDT occurred as the DDE metabolite: 60 percent in cows and newborn pups and 90 percent in 2-month-old pups. Introduction Biological concentrations of pesticide residues in harp, harbor, gray, and ringed seals have been reported on a world-wide basis {1-3, 8-9, 12-15, 21-25), but they are indicators of generally localized pesticide contamination levels since these species are localized. Anas, in fact, has suggested that harbor seals could be used to locate geographical areas where organochlorine and polychlori- nated biphenyl (PCB) concentrations are high (i). ' Paper no. AHOH m the journal series of the Agricultural Experiment Station. University Park. Pa. Work supported in part by Marine Mammal Division. National Manne Fisheries Service. National Oceanic and Atmospheric Adminis- tration. U.S. Department of Commerce. ^Pesticide Research Laboratory and Graduate Study Center. The Pennsylvania State University. University Park. Pa. 16802. Reprints available from this address. 'The Frost Entomological Museum. Department of Entomology. Pennsylvania State University. University Park. Pa. The northern fur seals. Culhirhiniis ursinus, on the other hand, are migratory and have an open ocean habitat. They subsist solely on marine fishes and invertebrates. They spend 4-5 months on the Pribilof Islands in Alaska and the remainder in the northern Pacific Ocean ranging from the Bering Sea to areas off the coasts of California and Japan. Analysis of fur seals would thus be an indicator of pesticide concentrations of the neritic seas. Anas and Wilson have studied pesticide concentrations in 30 fur seals collected on the Pribilof Islands in 1968 and off the California cost in l%9 {4). ilDDT concentra- tions in liver of male and female seals of all ages averaged 0.78 and 0.98 ppm, respectively, they were found in quan- tities of 0.21 ppm and 0.26 ppm, respectively, in samples of brain tissue. Dieldrin was detected in only three liver sam- ples and in no brain samples. PCB's were not detected. In five samples of liver and brains from seals collected in November 1%9 on the Pribilof Islands, Anas and Wilson found 2.21 ppm (x) and 0.20 ppm (x) i:DDT, respectively, no dieldrin, and traces of PCB. In blubber they found 15.9 ppm (x) i DDT, 0.045 ppm (x) dieldrin, and only traces of PCB (5). This paper reports the accumulation of iDDT, dieldrin, and PCB's in tissues and the sucking lice of the northern fur seals, Callorhinus ursinus. Two species of the sucking lice, Antarctophthirus callorhini and Proechitw- phthirus fluctus, are parasitic on the fur seal. The taxonomy, ecology, and population biology of these lice have been studied by one of the authors (17-19). The detection of mercury in the tissues and the sucking lice of these fur seals has also been reported by Kim et al. (20). Materials and Methods Samples of body tissue and the sucking lice were collected from the northern fur seals on St. Paul Island, Alaska, in July 1972. Fat and blood samples were taken from two nursing cows, two newborn pups, and three 2-month-old pups. Subcutaneous fat samples were taken Vol. 10, No. 3. December 1976 79 from the ahdominal region and hlood was taken directly from the heart. Kat was collected as a single small sample. Anas and Worlund have speculated that this method produces less specific residue levels than does the collection of a larger homogenized sample (6). Sucking lice of the species A. callorhini were collected from all five pups and those of the species P. fliatiis were collected from only the 2-month-old pups. All samples were stored in glass vials and kept frozen from the time of collection until analysis. The two pregnant cows were caged away from the rookery for study, and samples were taken from these two nursing cows and two newborn pups in captivity for this study. Blood samples were extracted by vortexing 50 mg with 5 ml hexane four times. Hexane layers were combined, concentrated to I ml, and passed through a small florisil column containing 2.3 g florisil. Lice and fat samples were ground in a Duall tissue grinder, size B. Lice samples generally varied from 8 to 29 mg; for one 2- month-old pup the P. fhwtus sample was 139 mg. Fat samples weighed 200 mg. Each sample was extracted three times with 3 ml acetonitrile each time. The combined acetonitrile layers were extracted once with 5 ml hexane to remove excess fats. To the remainder was added 9 ml water containing I percent sodium sulfate and this solution was then extracted three times with 3 ml hexane. The hexane layers were combined, concen- trated, and passed through a florisil column containing 2.3 g activated florisil. All solvents were from Burdick and Jackson and were used without further purification. The extraction and cleanup methods follow those of the U.S. Environmental Protection Agency (26). Quantitative gas-chromatographic (GC) analysis was accomplished using a 160-cm U column of 1.5 percent SP-2250/1.95 percent SP-2401 on 100/120 Supelcoport packing. A Microtek 220 gas chromatograph was oper- ated at an oven temperature of 2I5°C. the inlet was operated at 240°C. and the detector at 330°C. The flow of nitrogen was 60 ml/min with 20 ml/min detector purge. The electrometer sensitivity was 1.6 x 10" amp ampli- tude full scale. Silicic acid column separations were run on all samples that showed residues greater than trace levels in order to separate PCB compounds from DDT compounds (7). Determinations were confirmed on a 155-cm column of 3 percent DECS on 80/l(X) mesh Chromosorb WHP. This column was operated at 200" C. the inlet was operated at 240°C, and the detector at 330°C. The range of recovery of DDT and metabolites was 55 to 66 percent from seal fat tissue and 56 to 58 percent from blood. The low recoveries from fat tissue were a direct result of an additional partitioning in the extraction steps. Following the original partitioning of the fat with acetonitrile. a second partitioning was performed from the acetonitrile portion with a carefully measured volume of hexane. In this step most of the lipids that were partitioned into the acetonitrile layer then moved into the hexane layer. Concurrently, smaller portions of the DDT metabolites and Aroclor mixtures were partitioned into the hexane layer and were subsequently lost from the recovery as this hexane layer was discarded. Aro- clors were also recovered in a similar range. 47 percent from fat and 40 percent from blood. Other recovery data from this laboratory indicated that these data are consist- ent. Although massive amounts of DDT and metabolites were used for recovery, other data based on much lower added values have shown similar recovery percentages. Results The DDT content in fat tissues of the northern fur seals was approximately equal in cows and their newborn pups: total p,p'-DDT"s were 5.2 /xg/g and 5.6 ^Jiglg, respectively (Table I). Two-month pups selected ran- TABLE I. Pesticide and Aroc lor 1254 content in fat samples of the northern fur seal. Callorhinus ursinus. 1972 Residue. (IG/G WET WEIGHT Seal Aroclor 1254 DlEL- DRIN I'.r'- TDE o.p,'- DDT p.n'- DDE p.p'- TDE p.p'- DDT SUM./'.p'- DDTs Nursing cow #2 Newhorn pup #2 Nursing tow # 1 Newhom pup #1 6,8 3,8 4,7 7,2 0,16 0.12 0.07 TR 0.4 0,2 0 1 0.3 1,5 10 0,6 1,0 3,8 3-3 2,0 3,9 1,0 0,6 04 0 6 2.2 1,4 0,9 1,3 7.0 5.3 3.3 5.8 Mean Cows Pups 0,12 0.06 0.3 0,3 1,1 1,0 2,9 36 0,7 0,6 1.6 14 5.2 5.6 Pup (2 mo 1 #1.1 Pup (2 mo 1 #14 Pup 12 mo 1 #l."i 16 81 ND TR TR TR TR ND 0.6 2.0 TR 98 70 5.1 4.7 3.3 0.1 3,1 3,2 0 1 106 77 5,3 Mean 33 TR TR 0.9 58 2.7 2 1 63 Recovery fROM 0.200 g tat sample (nursing cow #3) Added, ng Recovered. V, I0> 47 2000 51 1500 55 2000 66 2000 60 NOTE: Analyses for alt residues except dicldrin and (j./j'TDE were corrected for recovery. TR * trace (approximately 0,01 /«/gl. N D =■ no detectable residue (< (I 003 /« /g). 80 PiSIRIDlS MoNllORlNG JOURNAL domly, however, had a much higher IDDT content. One sample contained only 5.3 ^g/g iDDT. but the other two had 77 ^tg/g and 106 fjig/g. The average of the three samples was 63 /ng/g- The predominant DDT metabolite was DDE which accounted for approximately 60 percent of the total DDT in cows and newborns and over 90 percent in the two-month pups. The difference in the proportion of these isomers between the cows/ newborns and the pups may have significance, but the sample size was too small to form any solid conclusions. It may also be significant that although small amounts of o.p'-DDT were found, no o.p'-DDE occurred in any samples. PCB's were also found in these samples (Table I). General GC peak patterns were seen for Aroclor 1254 but none appeared for Aroclor 1242 nor Aroclor 1260. Differential metabolism of the PCB compounds was also noted. The quantitative level found in the fat of most samples revealed that the PCB level was approximately equal to that of total p.p'-DDT. The average PCB level in cows was 5.8 fj-^Js.'- the average iDDT level was 5.2 /ig/g. For the newborn, PCB's averaged 5.5 ^g/g and DDT averaged 5.6 /ng/g. Average PCB residue for one pup was 91 fjLg/g: i; DDT averaged 77 /Mg/g. The Aroclor 1254 con- tent of the other two pups was lower than the iDDT content: 16 /ixg/g vs. 106 ^g/g and 1.3 ixgjg vs. 5.3 /xg/g. In a recent study by Jones et al. (16) the blubber from one newborn fasted harp seal taken from the Gulf of St. Lawrence in 1973 contained amounts of biocide (1.47 ppm iDDT and 1.80 ppm PCB's) similar to those in pups who were 8-14 days old: 1.21 ppm SDDT and 0.9 ppm PCB's, respectively. The pups' mothers contained 4.41 ppm iDDT and 6.1 ppm PCB's. As in fur seals, the biocides passed the placental barrier, though in smaller amounts. Dieldrin occurred in almost all samples in trace or very low amounts. Levels of DDT and PCB's in the blood of these animals (Table 2) were much lower than in the fat. Absolute levels of DDT metabolites were not detectable in the cows and newborn, eliminating comparisons. The 2- month-old pups had low iDDT values, with a mean of 4.6 /u.g/g. In two samples iDDT was 1-3 percent of that in the fat. In the third sample results were anomalous. PCB's occurred in blood samples only at a trace level. This suggests that, like DDT, PCB's in the blood do not exceed 3 percent of the PCB's in fat. Lice inhabiting the bodies of the seals were analyzed; results appear in Table 3. DDT appeared in the low ppm range in lice on the 2-month-old pups. Total p.p'-DDT's averaged 4.4 /^g/g in A. callorhini and 3.6 /j,g/g in P. fliictiis. No quantities greater than trace were found in lice of cows or newborns. This amounts to about 6 percent of that found in fat and twice that in blood. PCB levels in lice were generally about one-fourth of the I DDT levels or in the low ppm range. In the 2-month- old pups PCB's averaged 2.0 yug/g and 0.9 fxg/g for A. callorhini and P. fhutiis. respectively. iDDT and PCB's appeared in equal proportions in A. callorhini and P. fhictiis species. In essentially all cases the level in the A. callorhini species just slightly exceeded that in the P. flue! us species. Correlation coefficients for blood-lice and lice-lice rela- tionships determined for the 2-month pups were all highly positive. Blood loA. callorhini lice for DDE and the sum of p.p'-DDT were 0.93 and 0.92, respectively. Blood to P. fhictus lice for DDE and the sum of p.p'- DDT were both 0.96. The correlations oi A. callorhini to P. fluctiis for PCB's, DDE, and the sum of p,p'- DDT were 0.69, 0.99, and 0.99, respectively. Discussion ami Conclusions The higher 5. DDT and PCB levels of these seals compared with those collected in 1969 (5) indicate that TABLE 2. Pesticide and Arocloi ' 1254 content in blo< od sam, pies of the northern fur seal. Callor hinus ursmus. 1972 Residue. Mg/g WET WEIGHT Seal Aroclor 12.M Diel- drin TDE o.p'- DDT p.p- DDE P.P- TDE p.p'- DDT Sum. p.p'- DDT s Nursing cow #2 Newborn pup #2 Nursing cow #.1 Newborn pup #3 TR TR TR TR 0.02 0.02 0.02 0.02 ND ND ND ND ND ND ND ND ND ND ND TR ND ND ND ND ND ND ND ND ND ND ND ND Pup (2 mo) #13 Pup (2 mo.) #14 Pup 12 mo 1 #I_S TR TR 34 0.07 0.06 005 ND ND ND ND ND ND 2.8 0.6 10 0.2 0.1 0.3 TR TR 0.1 3.0 0.7 10 Mean 0.06 4.5 0.2 4.6 RtCOVERY FROM 0 05 g BLOOD SAMPLE , (NURSING COW #21 Added, ng Recovered. *^ 4000 40 400 58 300 58 400 56 400 57 NOTE: Analyses were corrected for recovery. TR = [race (approximately 0.03 t^lg for DDT isomers and 0.3 («/g for Aroclor 1254). ND = no detectable residue (< 0.01 for DDT isomers and < 0.1 ^/g for PCB). Vol. 10, No. 3. December 1976 81 TABLE 3. PestUidc and Aroclor 1254 content in suckinf> lice samples of the northern fur seal. Callorhinus ursinus, 1972 Pup (2 mo I #M TR TR TR 0.06 ND Lice' ReSIDLiE. /ig/g WET WEK.HT Seal Aroclor I2.'i4 DrEL- o.p'- DBIN DDT P.P'- DDE P.P'- TDE P.P'- DDT Sum, p.p'- DDTs NeuKim pup #2 Newborn pup #3 .Ac .Ac- TR TR TR ND TR ND TR TR ND ND TR TR TR TR Pup (2 mo.) #13 Ac 0.5 TR ND 19 ND TR 1.9 Pf 0.4 TR TR 1.3 0.01 0.01 1.3 Pup ( 2 mo I * I TR ND ND Pf 0,9 0.00 NOTE: Analyses were not corrected for recovery. TR = trace (approximately 0.01 i^/g for DDT isomers and 0.4 f^/g for Aroclor I2.''4i N D = no detectable residue (< 0,003 («/g for DDT isomers and < 0.1 i^lg for PCBl. 'Ac - Antarctophllnnis lallnrhmi and Pf - Profthinophlhiriisllticliis. the levels of pesticide residues have increased in the oceans in the past several years. Woodwell et al. (27) and Cramer [10) have proposed global models for DDT in the biosphere. In these models they discussed the various reservoirs and rates of exchange between them. The shallow seas form the last accessible reservoir before DDT which, adsorbed to organic matter, sinks to the ocean abyss. While differing in some aspects of the models, both authors predicted a maximum DDT con- centration in the shallow seas in 1971-72. Because the northern fur seal spends most of its life in the shallow portion of the northern Pacific Ocean, analysis of this animal could be a good test of the validity of Woodwell and Cramer's global DDT model. Samples in the present study were collected at the proposed peak level and. though very few in number, had higher residues than had eariier analyses. The small sampling and wide variability between samples detract from their value in confirming this theory. Further analysis of fur seals seems warranted. Analyses also indicated that 2-month-old nursing pups had far higher levels than had cows analyzed from the same herd. The diet at this age is predominantly mother's milk (//). which contains as much as 50 percent fat {5). This implies a tremendous potential for containment of DDT, The mother herself feeds princi- pally on small fishes and squids (4) whose biological loading potential is not so great as seal milk. This magnitlcatii>n was not evident in the results of Frank et al, in studying harp seals (/2). On the contrary, thcii data indicateo that the \oung had lower concentra- tions than had adull IVniales. Two age groups of young contained 2.1 ppm (n= 19) and 2,6 ppm (n= 10) IDDT, Adults from that area and year, however, contained 7. 1 ppm (n=l3). In the study of harp seals by Jones et al, similar results were obtained (/6), Several factors could explain the differences in results of the harp seal studies and the present authors' fur seal studies. These include the amount of biocide excreted in the milk and the degradation pathways in the seal. Little is known of the levels of biocide excreted by mother harp or fur seals in milk. Fur seal pups after 2 months of suckling ought to have higher levels than harp seal pups after only 2 weeks of feeding providing that other factors, such as the levels in the milk, amount of milk ingested, and body fat contents of the seal body, are similar. Degradation rates and pathways for these bio- cides in either species are not well known. Harp seals may have a higher rate of DDA formation, which has not been studied, resulting in lower DDT levels than those of fur seals. On the other hand one cannot overiook the possibility that since only two of the three nursed fur seal pups in the present study contained high DDT levels, these could have resulted from feeding from mothers who had unusually high levels themselves. Another major finding of this study is the high percent- age of degradation of the parent DDT molecule to the DDF metabolite. In both cows and newborns. 60 percent of the IDDT in the fat tissues was in the form of DDF, In the nursing seals fully 90 percent of the IDDT in both fat and blood portions was in the form of DDF, Both A. ((illorhini and P. thutiis lice living on 2- monlh sucklings had 95 percent of the IDDT in the DDF form. In haip seals Jones et al. (/A) found that DDE was also the niajoi fal-soliible metabolite of DDT, For example, in fat tissue DDf; content of mothers and their 8-14-day- old pups was 72 percent and 74 pel cent, respectively, of the IDDl' found. 82 Pf.STKTDKS MoNlrORtNO JOLIRNAI Acknowledgments Authors thank Mark Keyes. George Harry, Patrick Kozlof. and other personnel of the Marine Mammal Division. National Marine Fisheries Service, NWFC, NOAA, U. S. Department of Commerce, for their assistance and cooperation. Thanks also go to Ida B. Harris for performing technical analyses. LITERATURE CITED (/) Addison, R. F.. S. R. Kerr. J. Dale, and D. E. Sargeant. 1973. Variation of organochlorine residue levels with age in Gulf of St. Lawrence harp seals (Pagophiliis groentan- diciis). i. Fish. Res. Board Can. 30(5): 596-600. (2) Addison. R. F.. M. E. Zinck. and R. G. Ackman. 1972. Residues of organochlorine pesticides and polychlorinated biphenyls in some commercially produced Canadian ma- rine oils. J. Fish, Res. Board Can. 29(4): 349-355. (i) Anas. R. E. 1974. DDT plus PCB"s in blubber of harbor seals. Pestic. Monit. J. 8(1): 12-14. (4) Anas. R. £.. and A. J. Wilson. Jr. 1970. Organochlorine pesticides in fur seals. Pestic. Monit. J. 3(4): 198-200. (5) Anas. R. E.. and A. J. Wilson. Jr. 1970. Organochlorine pesticides in nursing fur seal pups. Pestic. Monit. J. 4(3): 114-116. (6) Anas. R. E.. and D. D. Wortund. 1975. Comparison between two methods of subsampling blubber of northern fur seals for total DDT plus PCB's. Pestic. Monit. J. 8(4): 261-262. (7) 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): 761-768. (8) Brewerton. H. V. 1969. DDT in fats of Antarctic animals. New Zealand J. Sci. 12: 194-199. (9) Brown. N. J., and A. W. A. Brown. 1970. Biological fate of DDT in a sub-Arctic environment. J. Wildl. Manage. 34(4): 929-940. (10) Cramer. J. 1973. Model of the circulation of DDT on Earth. Atmos. Environ. 7: 241-256. (//) Eddie. B.. W. J. L. Staden. and K. F. Meyer. 1966. Serologic studies and isolation of bedsonia agents from northern fur seals on Pribilof Islands. Am. J. Epidemiol. 84(2): 405-410. (12) Frank. R.. K. Ronald, and H. E. Braun. 1973. Organo- chlorine residues in harp seals (Pagophilus groenlandicus) caught in eastern Canadian waters. J. Fish. Res. Board Can. 30(8): 1053-1063. (13) Gaskin. D. £.. R. Frank. M. Holdrinel. K. Ishida. C. J. Wallon. and M. Smith. 1973. Mercury, DDT, and PCB in harbour seals (Phoca vilulina) from the Bay of Fundy and Gulf of Maine. J. Fish. Res. Board Can. 30(3): 471- 475. (14) George, J. L.. and D. E. H. Frear. 1966. Pesticides in the Antarctic. J. Appl. Ecol. 3 (suppl): 155-167. (15) Holden. A. V.. and K. Marsden. 1967. Organochlorine pesticides in seals and porpoises. Nature 216: 1274-1276. (16) Jones. D.. K. Ronald. D. M. Lavigne. R. Frank. M. Holdrinel. and J. F. Ulhe. 1976. Organochlorine and mercury residues in the harp seal. Sci. Total Environ. 5: 181-195. (17) Kim. K. C. 1971. The sucking lice (Anophira: Echino- phihiriidae) of the northern fur seal; descriptions and morphologic adaptation. Ann. Entomol. Soc. Amer. 64(1): 280-292. (18) Kim. K. C. 1972. Louse populations of the northern fur seal (Callorhinus ursinus). Am. J. Vet. Res. 33(10): 2027- 2036. (19) Kim. K. C. 1975. Ecology and morphological adaptation of the sucking lice on the northern fur seal. Proc. Symp. Biol. Seals. University of Guelph. Canada, 1972. Repp. P.-V. Reun. Conf Int. Explor. Mer. 169: 504-515. (20) Kim. K. C. R. C. Chu. and G. P. Barron. 1974. Mercury in tissues and lice of northern fur seals. Bull. Environ. Contam. Toxicol. 11(3): 281-284. (21) Koeman. J. H.. W. H. M. Peters. C. J. Smil. P. S. TJioe. and J. J. M. DeGoeij. 1972. Persistent Chemicals in Marine Mammals. TNO Nieuws 27: 570-578. (22) Koeman. J. G.. and H. van Genderen. 1966. Some preliminary notes on residues of chlorinated hydrocarbon insecticides in birds and mammals in the Netherlands. J. Appl. Ecol. 3 (suppl): 99-106. (23) Robinson, J.. A. Richardson. A. A'. Crahtree. J. C. Coulson. and G. R. Potts. 1967. Organochlorine residues in marine organisms. Nature 214: 1307-1311. (24) Shaw. S. B. 1971. Chlorinated Hydrocarbon Pesticides in California Sea Otters and Harbor Seals. Calif Fish and Game 57(4): 290-294. (25) Sladen. W. J. L.. C. M. Menzie. and W. L. Reichel. 1966. DDT residues in Adelie penguins and a crabeater seal from Antarctica. Nature 210: 670-673. (26) U.S. Environmental Protection Agency. 1971 . Analysis of Pesticide Residues in Human and Environmental Studies. Perrine Primate Research Laboratory, Perrine. Fla. (27) Woodwell. G. M.. P. P. Craig, and H. A. Johnson. 1971. DDT in the biosphere: where does it go? Science 174: 1101-1107. Vol. 10, No. 3, December 1976 83 Organochlorine Pesticide Residues in Plain Chachalacas from South Texas, 1971-72^ Wayne R. Marion ^ ABSTRACT Plain chachalacas (Ortalis vetula) from the inlensively culli- xateil and sprayed Lower Rio Grande Galley of Texas were analyzed for pesticide residues during 1971 and 1972. Residues of eight organochlorine pesticides and a polychlorinated hiphenyl were identified in fat tissues of specimens collected from four study areas. Chemicals detected in all 24 birds and average residue levels l±SD) in ppm wet weight were: DDT (I.52±4.I2). DDE (2.48±2.09). dieldrin (0.23±0.59). endrin tO.I3±0.52). and Aroclor 1248 (O.I7±0.20). Residue levels varied considerably, but the majority of the fat tissues contained significantly less than I ppm of these chemicals. Because birds of this species feed primarily on unsprayed native fruits rather than on sprayed crops, they adsorb very few pesticides through their diet. Although birds from exposed areas near cultivated fields had generally higher residues than had birds from less exposed areas, these herbivores generally had much lower residues than would most birds living near heavily treated lands. During the present study there was no evidence that plain chachalacas died as a direct result of exposure to agricultural chemicals, nor was there evidence that eggshells of this species have thinned significantly since 1900. Introduction The Lower Rio Grande Valley of Texas is predomi- nantly a semitropical agricultural region with heavy pesticide use. primarily on cotton (/). Within this region, plain chachalacas (Ortalis vcliila) inhabit small, isolated tracts of dense, brushy woodland (."i) and feed primarily on small fruits of native plants (6), The majority of the ' Anicle No, 1173V m Ihc lechnicjl papci series. li;\.is ABiitiilrural l\r>cnmcnl Slaliun. Submitlcd in (>.irlial t'uirillmcnl nl rcquiremcnis lor OocUtutc ol Philosophy, Texas A&M Lnivcrsily. College .Slalion. lex "Wildlife Kcology Program. Sthool of Korcsl Resourees and Conscrvalion. Univcrsil) of Florida. Gainesville, Fla 32611. Rcprinls available from this address. chachalacas live close to cultivated fields which are sprayed intensively with agricultural pesticides. Pesticide residue levels in the birds were determined and com- pared according to the birds" proximity to agricultural activities. Eggshell thinning in some populations of wild birds has been recognized as a problem associated with environ- mental contamination by DDE and related chemicals (9). To determine whether such a pattern exists in chachala- cas, shell thickness of eggs collected during the present study were compared to museum specimens of eggshells collected in South Texas before 1900, Methods Fat tissues of 24 birds collected from four study areas in the Lower Rio Grande Valley were analyzed for organo- chlorine and polychlorinated biphenyl ( PCB) residues. Three of the areas. Anzalduas Dam. McManus Farm, and Santa Ana National Wildlife Refuge, are isolated dense brushland in southern Hidalgo County surrounded by fields under intensive cultivation. The Falcon Dam area, a narrow strip of riparian vegetation adjacent to the Rio Grande in western Starr County, was not closely associated with intensive farming. Of the 24 fat samples analyzed. 10 were from Santa Ana Refuge. 10 from Anzalduas Dam. and 2 each were from McManus Farm and Falcon Dam study areas. For convenience in comparing residue levels, sample collec- tion sites were classified according to proximity and probable exposure to agricultural chemicals, "Central" samples were taken fri>m birds collected more than 400 m from the nearest cultivated llelds. Samples from birds collected nearer the adjacent fields were labeled "periph- eral." Five samples from central and .'i from peripheral 84 I'l SIR 11)1 s M()Nil()KIN(i .lolJRNAl locations were analyzed for each of the larger areas. Santa Ana Refuge and Anzalduas Dam. All samples obtained at McManus Farm and Falcon Dam were considered peripheral. Samples were frozen in 150-ml glass containers and maintained at approximately -18°C. A general pesticide scan for residues of organochlorine pesticides and PCB's was conducted on all fat tissues in laboratories of the Department of Agricultural Analytical Services at Texas A&M University. Analyses were modified slightly from those outlined in Section 211 of a manual by the Food and Drug Administration, U.S. Department of Health. Education, and Welfare {10). Each fat sample was thoroughly homogenized in anhydrous sodium sulfate and extracted several times using petroleum ether. A Buchner funnel containing sharkskin filter paper was used to decant supernatant from these extractions into a suction flask. Fat solution was transferred to a tared beaker using small portions of petroleum ether. Petro- leum ether was evaporated and the beaker was weighed. Lipid residues were partitioned with acetonitriie satu- rated with petroleum ether and cleaned with florisil. The cleaned extract was analyzed for pesticide residues by electron-capture gas chromatography with parameters as described by Reynolds (8). Residue levels are reported in parts per million (ppm) on a whole tissue wet-weight basis. Mean residues for all areas were compared using Duncan's new multiple range test (2). Mean residues in samples obtained at central and peripheral collection sites were also compared using a t-test (7). Chachalaca eggshells collected during this study were air-dried for several months. Eggshell thickness was determined using a Starrett lOlO-m dial gauge calibrated in 0.01-mm units and expressed as the mean of measure- ments made at three points near the waist of the egg. Chachalaca eggshells collected in southern Texas before 1900 and preserved at the Smithsonian Institution — National Museum of Natural History, Washington. D.C.. were similarly measured and the data were statistically compared with those from recent eggshells using a pooled t-test (7). Results and Discussion Eight organochlorine pesticides including BHC, chlor- dane, DDT. DDE, dieldrin, endrin, hexachlorobenzene (HCB), and toxaphene were reported in one or more fat samples from collected birds. A polychlorinated biphenyl (PCB). Aroclor 1248. occurred in birds from all collec- tion areas except Anzalduas Dam. All 24 fat samples contained residues of p.p'-DDT and its major metabolite, p.p'-DDE. Twenty-one samples contained dieldrin; 12 contained Aroclor 1248. Endrin was found in 8 fat samples. HCB in 3, toxaphene in 2, chlordane in I, and benzene hexachloride (BHC) in 1. Mean fat tissue residue levels for 5 major pesticides were generally highest in specimens from Anzalduas, Santa Ana. and McManus Farm, which are closer to agricultural spraying than is Falcon Dam (Table 1). Duncan's new multiple range test revealed no significant differences in residue levels among study areas, except for DDE. Fat in specimens from peripheral areas at Anzalduas Dam and Santa Ana Refuge contained signifi- cantly higher mean residues (P<0.05) of DDE than did fat from birds at Falcon Dam. The small sample size undoubtedly restricted the power of Duncan's test in detecting these differences. At Anzalduas and Santa Ana study areas, birds collected in peripheral locations had generally higher residue levels than had those from central locations. Comparisons of these differences yielded nonsignificant t values (P>0.05) of 1.03. 1.40, 0.77. 1.19, and 1.06 for Aroclor 1248, DDT, DDE, dieldrin, and endrin, respectively. Once again, the highly variable nature of these residue levels and the relatively small sample size severely restricted TABLE 1. Mean residue levels of five pesticides in fat tissues of plain Cluuhalacas. Lower Rio Grande Valley, Texas— 1971-1972. No, Samples Mean Pesticide Residues, ppm WET WEIGHT Studv Area Aroclor 1248 p.p'-DDT p.p-DDE Dieldrin Endrin Falcon Dam ■, O.I4t0.06 (0.10-0.18) O,03±0,O2 (0,01-0,04) 0,07±0,02 (0,05-0,08) 0.00 0,00 Anzalduas Peripheral 0.00 5.4&:8.49 l,89l0,79 0,79:: 1 ,22 0,53±1,13 (0,72-20,53) (0,86-2,861 (0,0-2,86) (0,0-2,55) Central 0.00 0,54t0,51 0,99±0,79 0,03±0 03 0,04!:0,07 (0.09-1,35) (0.17-2.12) (0,0-0.04) (0.0-0,16) Santa Ana Peripheral 0.42*0.13 0.69±0.53 4.25*2.22 0,08i±0,04 0,02*0,04 (0.24-0,58) (0,19-1, .54) (1,78-6,98) (0,04-0,14) (0,0-0,10) Centtal 0,22±0,24 0,39±0,16 3,65±2,65 0,I7±0,I9 0,00 (0,18-0.49) (0,22-0,64) (1,54-8.17) (0.06-0,50) McManus Farm 0,2fe0,0l 0,5ttt0.06 :,77±0,78 0,0.5±0,03 0,00 (0,27-0,29) 10,46-0,54) (2,21-3,32) (0,03-0,0';) Mean O,17±0,20 l,52±4,i: 24fc2,09 02.1±0,59 0,l2tO,52 (0,0-0,58) (0,01-20,53) (0,05-8,171 (0 0-2.86) (0,0-2,551 Vol. 10, No. 3, December 1976 85 the power of this statistical test in detecting these ditTerences. Quantities of pesticides in tissues are gener- alK related to food habits and history of exposure (.?) Chachalacas which were close to cultivated fields were presumably more heavily exposed to agricultural chemi- cals than were birds and vegetation some distance from intensive farming: so. too. was their food supply. Although not statistically significant, residue levels in fat of birds from peripheral locations were higher than those from central locations: but overall, these birds had remarkably low pesticide residue levels. Residue levels in chachalacas were much lower than in ring-necked pheasants [Phasianus colchicus) from highly agricultural areas. Pheasants feed in agricultural fields, creating a direct dietary pathway for pesticides to enter their bodies. In rice-growing areas of the Sacramento Valley, California, fat tissues of ring-necked pheasants contained an average of 123 ppm DDT and its metabo- lites: the maximum level was 5.448 ppm. Mean concen- tration of dieldrin in fat of these birds was 0.8 ppm {4). Even higher levels have been reported for pheasants in California. In 1962, the same investigators reported that fat from four hen pheasants in a treated agricultural area contained 1,2.^6-2,930 ppm DDT, 306-717 ppm DDE. and 0. l-2.'i ppm dieldrin: considerably lower levels were found in birds from untreated areas (i). Chachalaca eggshells are thicker than those of other gallinaceous birds. Sixty-three eggshells collected in southern Texas before 1900 had a mean thickness of 0.57±0.I2 mm; the ranj;e was 0.49-0.74 mm. This was slightly higher than the average thickness (0.5O±0.06 mm. range 0.41-0.66 mm) of 72 eggshells collected during the present study. The difference in eggshell thickness between pre-pesticide eggs and recent ones was not significant (t= 1.87, P>0.05) and there was little evidence to suggest that pesticides caused this slight difference. Acknoniedgments I appreciate the financial assistance of the Caesar Kleberg Research Program in Wildlife Ecology at Texas A&M University. Sincere thanks go to W.H. Kiel, Jr., for his advice and encouragement during this study. 1 am grateful to A.R. Hanks and F.W. Plapp for their assistance in conducting analyses and in interpreting results. E.E. Klass helped to measure eggshell thickness. 1 am also indebted to K.A. Arnold, J.D. Dodd, T.M, Ferguson, and J.G. Teer for their critical review of the manuscript. LITERATURE CITED (/) Burns. J.E. 1974. Organochlorine pesticide and polychlor- inated biphenyl residues in biopsied human adipose tissue— Texas. 1969-72. Pestic. Monit. J. 7(3/4): 122-126. (2) Diimcin. D. B. 1955. Multiple range and multiple F tests. Biometrics 11(1): 1-42. U) Diislnum. E. H.. and L. F. Stickel. 1969. The occurrence and significance of pesticide residues in wild animals. Ann. New York Acad. Sci. 160( I): 162-172. (4) Ki'ilh. J. O.. and E. G. Hunt. 1966. Levels of insecticide residues in fish and wildlife in California. Trans. N. Am. Wildl. Nat. Resour. Conf 31:150-177. (5) Marian. W. R. 1974. Status of the Plain Chachalaca in south Texas. Wilson Bull. 86(3): 200-205. (6) Marion. W. R. 1976. Plain Chachalaca food habits in south Texas. The Auk 93(2):376-379. (7) Oslte. B. 1963. Statistics in Research: Basic Concepts and Techniques for Research Workers. Iowa State Univ. Press. Ames. 583 pp. («) RcxnoULs. L. M. 1969. Polychlorobiphenyls (PCB's) and their interference with pesticide residue analysis. Bull. Environ. Contam. Toxicol. 4(3): 128- 143. (9) SlicU-l. L. F.. and L. J. Rhodes. 1970. The thin eggshell problem. Pages 31-35 in J. W. Gillett, ed. The biological impact of pesticides in the environment. Oregon State Univ. Press. Corvallis. 210 pp. {10) U.S. Dcparlmcnt of Heatlli. Education, and Welfare. Food and Dnif; Adminislralion. 1972. Pesticide analytical manual. Vol. 1. 86 Pesticides MoNiTORiNCi Journal Insecticide Residues on Stream Sediments in Ontario, Canada^ J. R. W. Miles ABSTRACT Insecticide residues on suspended and holtom sediments of streams of Ontario, Canada. Iiave been studied in a tobacco- growing and a vegetable muck area. The proportion of TDE to DDT was <1 in water and >l in bottom sediments. The ratio of TDE to DDT in bottom material increased linearly from the contamination point at stream source to the mouth of Big Creek in Norfolk County, Ontario. Bed load samples contained three to six times greater concentrations of insecti- cides than bottom material. Adsorption of insecticides on suspended sediment decreased in order DDT > TDE > dieldrin > diazinon, which is consistent with the water solubility of these compounds. Introduction Insecticide analyses of environmental water samples are usually performed on the whole unfiltered sample (5). Because the whole water, including sediment, is the environment of fish, crustaceans, and aquatic insects, analysis of the whole-water sample produces data perti- nent to biological significance of insecticides. Whole- water analyses combined with water discharge data also are used to calculate transport of insecticides from a stream to the receiving body of water. However, the state of an insecticide, i.e., whether pure particles, adsorbed on sediment, or dissolved in water, can affect biological action because some organisms prefer to feed on sediments (i) and because insecticides adsorbed on suspended sediment are eventually deposited and be- come part of the bottom material (6). In the study reported here the author has analyzed insecticide pres- ence in whole- water samples, suspended sediments, bed load, and bottom material of streams in Ontario, Can- ada. Methods Water samples were collected in 1 100- ml narrow-neck bottles clamped to an 8-m aluminum pole. Depth integration was achieved by moving the bottle from just below the surface to within 30 cm of the bottom while the bottles were filling with water. Bottles were sealed with tin-foil-lined caps for transport to the laboratory. Contents of two bottles were combined as one sample in a tared 2-liter florence flask (Fig. I) and the weight of flask plus samples was recorded. Walls of the two sample bottles were rinsed with the same 10-ml acetone which was transferred to the florence flask. A second acetone rinse of 7 ml was also transferred to the flask. A 35-mm magnetic stirring bar was inserted, 50 ml 1:1 hexane/benzene was added, and the flask neck was covered with aluminum foil previously rinsed with hexane. The flask was stirred 15 minutes using enough torque that the vortex pulled the extracting solvent completely into the water. The flask was removed and ' Contribution No. 648. Research Institute. Agncullure Canada. University Sub P.O.. London. Ontario, Canada N6A iBT. FIGURE 1. Equipment for extracting insecticide residues from water samples Vol. 10, No 3. December 1976 87 left standing 15 minutes. The separated extract layer was transferred to a 250-ml separatory funnel with a Teflon stopcock by a suction tube adapter fitted into the separatory funnel neck. Three extractions were made using fresh hexane/benzene and the three extracts were combined in the separatory funnel. The lower aqueous layer was discarded. The extract was dried by adding 10 g anhydrous sodium sulfate prerinsed with benzene and hexane and poured from the neck of the separatory funnel through a filter funnel containing glass wool which had been rinsed with hexane into a 500-ml round-bottom flask for concentration on a rotary evaporator. Recoveries of insecticides from fortified distilled water were all >90 percent. SEDIMENT SEPARATION Water samples for sediment separation were collected at the same time and in the same manner as those for whole-water analysis. The sediment was separated by filtration through a Millipore filter apparatus using 4.25- cm-diameter Whatman GF/C fiber glass papers with nominal porosity of 0.45 /xm. Residues were extracted from the filtered sediment with acetone, followed by 1:1 hexane:benzene in a conical flask. Three successive extractions were completed and the combined extracts were dried with anhydrous sodium sulfate before frac- tionation (9). A separate 4-liter sample of water was also taken and filtered through a tared filter paper to obtain the weight of the sediment loading. gas chromatographs were used. All columns were 2 m long by 2 mm ID and operated at. 180°C. Two 1400 models were equipped with 'H electron-capture detec- tors. The column of one model was packed with 5 percent XE60; the other used a liquid phase mixed before coating, 3 percent DC 200/4.5 percent QF-1. The column of the model 1200 was also packed with mixed DC 200/QF-l but this instrument was equipped with 'H electron-capture detector in series with Rb2S04 alkali flame ionization detector. Results and Discussion BOTTOM MATERIAL An earlier article (//) reported that although in water the ratio of TDE to DDT is << 1, in practically all analyses of bottom mud the ratio is >1. This indicates that the process of dechlorination of p. p' -DDT top,p'-TDE was occurring in the bottom material. These findings are consistent with data of Hill and McCarty (7) who report that DDT is degraded more readily under anaerobic than aerobic conditions. If the ratio of TDE to DDT is calculated from the data on bottom mud published earlier (//). there is a steady increase in the ratio from spring through summer to fall. For Muskoka River bottom mud from May through September 1971, the TDE: DDT values were 1.6, 1.9. 1.9, 2.4, and 5.4. Since DDT was banned from use in Bottom material samples were collected using a sampler designed by the author; it consisted of a steel can, 8.5 cm in diameter and 4.5 cm deep, attached to the end of an 8-m aluminum pole. The can was permitted to settle on the bottom of the stream in inverted position. On rotation of 180° the can sampled a 6-cm-deep portion of bottom material. Five samples of mud were taken from near the bank to mid-stream, and combined into one sample. After the standing water was poured off, the mud was mixed in a pyrex glass tray. Three hundred grams of the mixed sample was placed in a 900-ml narrow-neck glass bottle. One hundred ml of acetone was added and the bottle was swirled to mix. Four hundred ml hexane was added and the bottle was stoppered and tumbled end over end for 1 hour. The supernatant liquid was poured into a l-liter separatory funnel, the acetone was removed by several distilled water washes, and the hexane extract was dried with anhydrous Na.SO,. The moisture content of a 50-g sample of the mud was determined so that results could be reported on a dry-weight basis. Bed load samples were taken w ith a Bogardi 13 bed load sampler ( Fig. 2: 2). The sampler was lowered from a bridge to the stream bottom and left in position 4 hours. The fluid sample was filtered and extracted as described above for separation of sediment from water samples. Fractionation of ex- tracts on fiorisil has been described previously (9,/W). GAS CHROMATOORAPHV Two model 1400 and one model 1200 Varian Aerograph FIGURE 2. Bogardi hcd loud sampler 88 Pesticides Monitoring Journal Ontario in 1970 the above data could mean that DDT on eroded soil incorporated in the bottom mud in the spring was gradually converted to TDE by microorganism activity from May through September. Because it requires time for bottom material to move downstream the author sampled a stream for bottom material from source to mouth all in the same day to assess any differences in residue content and ratios. The stream selected was Big Creek in Norfolk County, Ontario, previously described {10. 1 1). Big Creek drains a tobacco-growing area; DDT-contaminated soil averaging about 3.5 ppm IDDT {4) erodes into the upper reaches of the stream. Residues found at the six sampling stations from source to mouth in 1972 are shown in Table I. Dieldrin concentrations increased gradually from source to mouth but there appears to be no regularity in actual DDT concentration in the bottom material of these six stations. However, there is a regular increase in ratio of p. p' -DDE to p.p'-DDT and an even more pronounced increase in ratios of p. p' -TDE to p.p'-DDT from stream source to mouth. Overall change in TDE: DDT from source to mouth is 20 times! The increase in ratio of TDE to DDT can be explained by the longer contact time of adsorbed DDT residues with anaerobic microorganisms as they move from the source down to the mouth, a distance of about 42 km. Since the DDE: DDT ratio also increased steadily from source to mouth one must assume that the bottom material also harbors organisms containing dehydrochlor- inase. A repeat of the above experiment at four locations in 1973 revealed the same trend but the range of values was not quite so dramatic: from source to mouth TDE: DDT ratios were 0.2, 0.4, 0.5, and 0.6. BED LOAD Simultaneous bed load and bottom material samples were taken at monthly intervals from June through October 1973 (Table 2). With one exception, August 14, all residues on bed load samples were much greater than those in the bottom material. In fact, average DDT in the bed load was three times that in the bottom material. Dieldrin was also three times greater and endosulfan was six times greater in the bed load. The bed load is the shifting mass of detritus and sediment which forms the interface between the water and bottom material and provides the environment of benthic organisms. The TABLE I. Insecticide residues on bottom material at six stations from source to mouth of Big Creek, Ontario — 1972 TABLE 2. Insecticide residues on bed toad and bottom material of Big Creek, Norfolk County, Ontario — 1973 Residues, PPB DRY WEIGHT Resi DUE Ratios Sampling Stations ^ DDT D ELDRIN P.p'- TDE P.P'- DDE p.p'- DDT 1 Stream source 23.8 <0.3 0.1 0,2 2 58.5 0.8 0.2 0,2 3 6.9 <0.3 0.8 0.7 4 13.0 06 1.0 0.9 5 26.1 1.3 1.2 10 6 Stream mouth 34.2 1.4 2,0 1,5 Residues, ppb DRY WEIGHT DDT Dieldrin Endosulfan Bottom Bottom Bottom Sampling Bed Mate- Bed Mate- Bed Mate- Date Load rial Lof.D rial Load rial June 26 198 30 6 1,2 1 <0,l July 10 45 26 4 1,3 <1 <0.l Aug, 14 21 27 1 1,7 3 0.7 Sept, 25 100 35 8 1,3 3 0.2 Oct, 2 30 18 7 1,1 1 0.6 Oct 16 62 18 2 0.7 1 0.2 NOTE: Bed Load = shifting mass of detritus and sediment collected with the Bogardi bed load sampler. Bottom Material = more permanent boltom mud. above data would indicate that animals living in the bed load may be exposed to more insecticide than would be suggested by analysis of bottom material alone. The average ratio of TDE to DDT in bottom material was 1.24; in the bed load the ratio was 0.38. This again indicates that the DDT residues in the bottom material have had a longer period under anaerobic conditions, producing more TDE. SUSPENDED SEDIMENT Residues on suspended sediment in Big Creek in 1973 ranged from 8 to 100 percent of the whole-water analyses, as shown in Table 3. Residues in sediment expressed as percent of the whole-water analysis are generally proportional to the sediment load. Although TDE and dieldrin concentrations in water samples were significant, up to 2.0 ng/liter and 2.7 ng/liter, respec- tively, only traces of TDE and dieldrin were found on the sediment. This is consistent with the solubility of the two chemicals, i.e., 3 times and 13 times that of p,p'- DDT (/). In some instances, namely, April 10, May 1, 8, 22, and June 12, the percent of ilDDT on sediment was much less than that of p,p'-DDT or p.p'-DDE (Table 3). This was because TDE, present in the whole- water sample, contributed to i.DDT but no TDE was detected on the sediment. The average value for iDDT expressed as ppm dry weight of sediment is 0.11 ppm. This value is 4.2 times the average ppm in the bottom material samples from Big Creek during the same sampling period. Since DDT residues in the bottom material are only one-fourth those on the sediment one must conclude that considerable dilution with uncontami- nated boltom material occurs upon deposit of sediment and/or the DDT degrades more quickly in the bottom material. Comparable data on residues in sediment as percent of whole-water analyses for three streams in the Holland Marsh, which contains organic soil used for vegetable production, are shown in Table 4. Concentrations in water and mud of this region are much greater than those of Big Creek, as demonstrated by the greater quantities of insecticides on the sediment. These are Vol. 10, No. 3, December 1976 89 TABLE 3. Insecticide residues on suspended sediment of Big Creek, Ontario — 1973 Sediment Residues VDDT P.P' -DDT P-P' -DDE DiELDRIN Sampling Date T)C/LITER % PPM % PPM Vc PPM % PPM March 27 0.0600 68 0.07 68 0.05 67 002 16 <0.0I April 3 0.0825 81 0.19 72 on 97 0.04 29 .0.01 10 00543 63 0.08 89 0.06 97 0.02 ND ND 17 0.0430 90 0.13 100 0.07 76 0.13 ND ND 24 0,0364 45 0.10 40 0.06 88 0.04 ND ND May 1 0.0440 70 0.10 85 0.05 83 005 ND ND 8 00222 51 0.13 85 0.08 48 0.05 ND ND 15 0.0222 33 0.07 36 0.04 60 0.03 ND ND 22 0.0082 29 0.15 33 0.09 63 0.06 ND ND June 12 0,0330 64 0.09 90 0.05 100 0.04 ND ND July 17 0.0082 8 0.06 19 0.06 ND ND 17 0.04 Sepl. 12 0.0182 53 0.17 32 0.05 ND ND ND ND Oct. 9 0 0116 42 0.10 69 0.10 ND NO ND ND NOTE; ND = none detected. TDE was present in whole-water analyses from trace to 2 ng/Iiler hut only traces were detected on suspended sediments Dieldnn after Apnl 3 was present m whole water from 0.7 to 2.7 ng/!iter but only traces were detected on suspended sediment, except July 17, 'Residues expressed as percent of whole-water analysis and as ppm on dry weight of sediment. TABLE 4. Insecticide residues on suspended sediment of streams in Holland Marsh, Ontario — 1973 Sediment Resi dues' V DDT P-P' -DDT o.p' -DDT P.P' -DDE P.P -TDE DIELDRIN Sampling Load. Date tjg/liter r- PPM % PPM % PPM (y PPM % PPM ^ PPM Stream A Mar. 22 0.0044 38 13.4 36 8.6 42 2.3 47 1.8 39 0.7 8 0.5 29 0.0076 75 12.9 79 9.8 72 1.8 73 0.9 40 0.3 13 0.5 Apr. 5 0.0083 89 14.0 90 10.3 % 2.1 75 0.9 77 0.7 42 0.5 12 0.0026 35 11.5 38 8.7 30 1.2 41 0.9 19 0.8 5 0.5 Stream B Mar. 29 0.0028 44 17.9 43 12.4 45 2.4 43 1.3 57 19 8 0.6 Apr. 5 0.0068 47 8.9 48 6.0 49 1.4 46 0.8 42 0.7 11 0.4 12 0.0040 32 4.7 35 3.2 30 0.6 37 0.5 18 0.4 3 0.2 Stream C Mar. 22 0.0148 88 1.5 86 1.0 96 0.2 90 0.1 91 0.3 18 0.1 29 0.0247 85 0.9 96 0.6 93 0.1 78 0.1 57 0.1 10 <0.l Apr. 5 0.0203 79 1.3 86 0.9 95 0.2 67 0.1 35 0 1 9 <0.1 12 0.0142 65 1.2 70 0.8 90 0.1 60 0.1 46 0.2 13 0.1 AVERAGE 62 64 67 M 47 13 'Residues expressed as percent of whole-water analysis and as ppm on dry weight of sediment. much greater than the residues found in the bottom material which contained /?./?'- DDT, /),//- DDE, and /J./V-TDE in parts per bilHon range. This agrees with the above discussion of data from the Big Creek study. The percentages of insecticides on the sediment are again roughly proportional to the sediment load. It is signifi- cant that /),//- DDT, ()./)'- DDT, and /j,/)'-DDE were all >60 percent adsorbed on the sediment, but the more water soluble p,/7'-TDE averaged 47 percent adsorption and dieldrin averaged 13 percent, ranging from 9 to 42 percent. These ranges may appear wide but this was not a controlled laboratory sediment experiment: composi- tion of sediments could vary between sampling dates, greatly affecting adsorption. Since both sediments and insecticides determined in stream samples are allochtho- nous, great variability can be expected. Dia/inon was present in all whole-water samples (£80 ng liter) hut was not detected on any suspended sediment samples. It is soluble to 40 ppm (/_') in water and evidently remains in solution rather than adst)rbing onto the sediments. Four samples reported in Table 4, all from stream A, contained parathion in the whole-water samples ranging from 13 to 19 ng/liter. but no parathion was detected in the sediments. Parathion has a water solubility of 24 ppm (/2) so presumably it would also be in solution and not adsorbed to the sediment. Elhion, which has a solubility of 0.6 ppm in water as determined by this laboratory, was present in three whole-uater samples in quantities as high as 33 ng,'liter. No ethion was detected in the tillered sediment. This author has observed that sonic laboialtiries studying environmental water samples have analyzed only the IHlcred water. .Since plant and animal life are exposed to the whole water including sediment (.?.<^), such an approach is unrealistic. Ihe study of stream sediments reported herein has been performed in considerable 90 Pesticides Muni ioring Journal detail, including separation of sediment-borne insecticide residues from the whole-water samples and separate analyses of suspended sediment, bed load, and bottom material. The study demonstrates that concentrations of insecticide residues on stream sediments vary with the type of sediment and its location in the stream. Even residues of the supposedly recalcitrant DDT are in a state of change, with the ratios of metabolites DDE and TDE varying in proportion to the parent DDT on the different sediments and on the same sediment at different locations upstream or downstream. Acknowledgments GLC analyses were carried out by Patricia Moy and Karin Henning. Thanlily of Wist-onsin. Madison. WiNconsin 5)706. specimens were preserved in glass jars filled with ethyl alcohol. Some specimens had been preserved originally in formalin before being transferred to ethyl alcohol by the museum staff. Authors obtained whole fish when available. From large fish a sample of the epaxial muscle was analyzed. All samples were placed in glass jars with aluminum-foil-lined caps and were frozen until analysis. The following common and scientific names of the six species of fish examined are from the list published by the American Fisheries Society (2): emerald shiner (Notropis atherinoides), fourhorn sculpin (Myoxoce- phcdiis qiiadrkornis). rainbow smelt (Osmerus mordax). kiyi (Coregonus kiyi), bloater (Coregonus hoyi), and alewife {Alo.sa pseudoharengus). Analytical Methods The WARF Institute, Inc., in Madison, Wis., used gas chromatography to analyze all samples for dieldrin, PCB's, DDT, TDE, and DDT. Large samples were homogenized with the aid of a Hobart food chopper. Sniiill samples were snipped finely with tissue scissors. A portion of the sample was weighed into a 150-ml beaker. The sample was ground with about 30 g anhydrous sodium sulfate and dried 48-72 hours. The sample was placed in a 33-by-94-mm Whatman extrac- tion thimble and extracted for 8 hours on a Soxhiet extractor with 70 ml ethyl ether and 170 ml petroleum ether. The solvent was reduced to near dryness on the steam bath and placed in a 40°C oven for 4 hours. The beaker was removed from the oven, contents were desiccated, weighed, and the amount of lipid in the sample was calculated. An aliquot of the sample was cleaned on a standardized florisil column. Typical elutions vsere l.'^O ml .*> percent ethyl ether in petroleum ether, followed by 240 ml \fi percent ethyl ether in petroleum ether. After florisil cleanup the resulting solutions were concentrated on a 5- lO-ml steam hath and made to 2.S ml with hexane. 92 PeSTJCIDES MoNI IORIN(i JOURNAI The first elutions ft'om the florisil were injected on a gas chromatograph to determine the approximate amount of PCB interference. An aliquot of this solution <5 ;ixg DDE and 20 /ng PCB was run through a silicic acid / celite column according to the Armour-Burke method for separating PCB's from DDT and its analogs (/). Each resulting solution was chromatographed and the amounts of the various pesticides were determined. A Barber- Colman model 5400 gas chromatograph with a 4-ft-by-3- mm glass column packed with 5 percent DC-200 on 80/ 100-mesh Gas-Chrom Q was used for the gas chroma- tography. The carrier gas, nitrogen, was maintained at 80 ml/min; the injector, column, and detector temperatures were 215°. 200°, and 245°C, respectively. Recovery rates of PCB (Aroclor 1254), dieldrin, DDE, TDE, and DDT were 60-80, 65-95, 86-96, 80-90, and 75- 95 percent, respectively. The detection limit for dieldrin and DDT analogs was 0.01 ppm; for PCB's, 0.1 ppm. No confirmatory tests were performed. Results and Discussion Because the years of storage in formalin and ethyl alcohol had dehydrated fish tissues, residues are ex- pressed on a lipid basis (Table I). Gibbs et al. reported that formalin, ethyl alcohol, and isopropyl alcohol af- fected the concentrations of heavy metals in specimens of myctophid fish (3). MacGregor (6) reported that formalin had no effect on the residues of DDT and its metabolites and PCB's in specimens of myctophid fish preserved from 1949 to 1972. Authors do not know whether formalin and ethyl alcohol affected the speci- mens used in this study. Reinert (8) has shown that lipid content, size of fish, and season of capture may affect considerably the concentration of chlorinated hydrocar- bons observed in tissue. Although such effects were not controlled in the present analyses, authors believe that the data represent the magnitude of the residue levels present at time of analysis. Dieldrin first appeared in two samples from 1955. No trends in residue levels of dieldrin during subsequent years could be determined. Levels were usually low, ranging from 0.20 to 2.39 ppm (Table 1). Commercial manufacture of PCB's began in the United States in 1929 (5). No PCB's were detected in museum samples until 1949, when the kiyi had 5.17 ppm and the alewife had 4.85 ppm (Table I). Hom et al. found that the deposit of PCB's in marine sediments from the Santa Barbara basin began about 1945 (4). They associated this finding with the rapid increase in PCB use during World War II as electrical-insulating fluids and paint additives, and in a variety of miscellaneous applications which release these compounds into the environment. Presum- ably Lake Michigan began receiving PCB deposits about the same time, although a critical gap in Lake Michigan data from 1943 to 1948 prevents an absolute statement to this effect. Levels of PCB's in Lake Michigan fish show a progres- sive increase from 1949 through 1966. Hom et al. (4) found a similar increase through 1967 in marine sedi- ments. MacGregor (6) found no trend with time in the concentrations of PCB's in a myctophid fish off southern California between 1949 and 1966. Veith (9) established baseline concentrations for 1971 in Lake Michigan fish of 70.80 ppm and 30.00 ppm PCB's (lipid basis) in alewife and bloater, respectively. These concentrations are TABLE I. Concentrations of organochlorines in Lake Michigan fish, 1929-66 Species' Residues, PPM LIPID WEIGHT Percent LlPlD^ PCB: i DDT Ratio Year Dieldrin PCB DDE TDE DDT Emerald shiner 1938 0,26 ND ND ND ND ND Fourhom sculpin 1936 1.69 ND ND ND ND ND 1949 0.11 ND ND ND ND ND 1951 3.66 ND 3.40 8,54 5.19 5,66 0.18 1955 7.02 0,20 4.39 9.31 13.70 5,48 0.15 1%5 1.20 ND 24.88 37,32 43.54 6,22 0.29 1966 2.17 ND 17,43 38.02 0.83 34,25 0,24 Rainbow smelt 1931 0.35 ND ND ND ND ND 1942 0.35 ND ND ND ND ND 1942 0.54 ND ND ND ND ND 1%0 0.34 ND 59.31 11.86 ND ND 5,00 1966 10.03 0.55 12.34 30.91 14.09 11.91 0.22 Kiyi 1949 4.88 ND 5.17 7.31 3.24 3.03 0.38 Bloaler 1929 0.18 ND ND ND ND ND 1%1 3.87 1.09 7,85 4.96 2.31 2,18 0,83 1%5 12.03 0.93 43,% 34.67 29.96 2.89 0,65 1966 14.24 1.34 39.36 38.03 22.44 4.61 0.60 Alewife 1949 23.95 ND 4,85 2.18 1.68 ND 1.26 1951 24.65 ND 1,02 4,14 3.71 ND 0.13 1952 27.76 ND 3,50 6.98 1.64 2.62 0,31 1953 31.27 ND 5.78 6.57 2.54 0,53 0,60 1954 20.39 ND 1.85 6,34 4.07 ND 0.18 1955 10.57 2.39 5.37 13.98 12.12 3,72 0.18 1965 0.13 ND 79.69 25.81 13.07 19,36 1.37 NOTE: ND - not delecled. 'Scientific names of species sampled: emerald shiner. Noiropis atherinoides; fourhom sculpin. Myoxocephalus quadricornis; rainbow smell, Osmerus mordax; kiyi, Coregonus kiyi; bloater, Coregonus hoyi; alewife, Alosa pseudoharengus. 'Results expressed on liquid basis because prolonged storage of museum specimens in formalin and ethyl alcohol dehydrated fish tissues. Vol. 10, No. 3, December 1976 93 slightly lower than the values found in the present study: 79.69 ppm in alewife in 1965. and 39,36 ppm in bloater in 1966 (Table I). Reinert reported increasing levels of PCB"s in Lake Michigan coho salmon (Oncorhynchiis kisuich) and lake trout {Salveliniis niimayciish) from 1972 through 1974, and stable levels in bloaters during the same time period (R. E. Reinert. Great Lakes Fishery Laboratory. U.S. Department of Interior. 1975: personal communication). Thus it appears that the concentrations of PCB's in Lake Michigan fish remain high despite the restriction of sales to closed-system users in 1971 by Monsanto Company. St. Louis. Mo., the sole producer of PCB's in the United States. Among museum specimens, PCB"s were never detected in the absence of DDE. The ratio of PCB's to iDDT should be important in reflecting the trend of concentra- tions of these compounds. Data from the present study show no trend from 1949 through 1966. Values range from 0.13 to 5.00 (Table 1). 19B0 1960 YEAR FIGURE 1 . Trend of "^DDT concentrations in Lake Michigan alewives and bloaters. 1949-71 . DDT and its analogs were first detected in 1949. They appeared in the same specimens in which PCB's were first detected: kiyi, 13.58 ppm; alewife, 3.86 ppm (Table I), and progressively increased to 1965. Hom et al. (4) reported that DDE in marine sediments deposited off the California coast progressively increased from about 1952 through 1967; MacGregor (6) reported increasing DDT metabolites in California myctophid fish from 1949 through 1970; and Peakall (7) reported DDE in the membranes of peregrine falcon eggshells at least as early as 1948. These four independent studies agree in their determination of the time that DDT and its metabolites began accumulating in the environment. That date corresponds closely with the increase in the manufacture and use of DDT during and immediately after Worid War IL However, the critical years of 1946 and 1947 are not represented in the samples of these four studies. Establishing the presence of DDE in these two years is important to the phenomenon of eggshell thinning attrib- uted to the presence of DDE (5). Data for alewives and bloaters (Figure I) indicate that the concentration of IDDT in Lake Michigan fish peaked in 1965. These data and results from the Great Lakes Fishery Laboratory suggest that residues have been decreasing since the late 1960's. R. E. Reinert reports a continued decrease of IDDT through 1974 in Lake Michigan bloaters, coho salmon, and lake trout (personal communication: see previous allusion). AcknowU'dgrywnts This project was funded in part by the Office of Sea Grant, National Oceanic and Atmospheric Administra- tion, Department of Commerce, through an institutional grant to the University of Wisconsin. Authors arc grateful to R, M. Bailey. Curator of Fishes, Museum of Zoology. University of Michigan, and F. A. Iwen, Museum of Zoology, University of Wisconsin, for providing specimens for this study. We also thank R. E. Reinert for unpublished data and other assistance. LITERATURE CITED (/) Armtiiir. J. A., and J. A. Burke. 1970. Method for separating polychlorinated hiphenyls from DDT and Its analogs. J. Ass. Offlc. Anal. Chem. .'i3(4):761-768. (2) Bdilev. R. M.. J. E. Filch. E. S. Herald. E. A. Lcichner. C. C. Lind.wy. C. R. Robins, and W. B. Scott. 1970. A list of common and scientific names of fishes from the United States and Canada. 3rd ed. Amer. Fish. Soc. Spec. Publ. 6. Ann Arbor. Mich. 150 pp. (i) Gihhs. R. H. Jr.. E. Jaroscuich. and H. L. Windom. 1974. Heavy metal concentrations in museum fish speci- mens: effects of preservatives and time. (Science 184 (4!35):47.'!-477. (4) Hom. W.. R. W. Risebrough. A. Soiilar. and D. R. yOiing. 1974. Deposition of DDE and polychlorinated biphenvK in dated sediments of the Santa Barbara basin. Science 184(41421:1197-1199. {?) Hnhhaid. H E I9f>4. Chlorinated hiphenyl and related comp^ni^d^ hi R, E. Kirk and D. F. Othern. eds. Encyclopedia of Chemical I'echnologv .'i:289. Second rev. ed. ■ (61 MiK (iregor. ./. ,S'. 1974. Changes in the amount and prop»irtions of DDT and its mclabolilcs. DDE and DDI), in the marine environment off soul hern California. 1949-72. Fishery Bull. 72(2):27.S-293. (71 I'cakall. /) li 1974. DDE: its presence in peregrine eggs in 1948. Science 18.3(4 125): 67.3-674. (i^l Reinert, R. E. 1970. Pesticide concentrations in Great Lakes llsh. Pestic. Monit. .1. .3(4): 23.3-240 94 PlSIKIDLS MONIIORING JOURNAL (9) Veith, G. P. 1975. Baseline concentrations of polychlori- (/O) Tail, H. D. 1972. Progress in Sport Fishery Research nated biphenyls and DDT in Lake Michigan fish, 1971. 1971. Great Lakes Fishery Laboratory, U.S. Department Pestic. Monit. J. 9(l):21-29. of Interior, pp. 86-120. Vol. 10, No. 3, December 1976 95 Preliminary Study of the Occurrence and Distribution of DDT Residues in the Jordan Watershed, 197P Jacob D. Paz^ ABSTRACT Dam obtained from the Jordan watershed in 1971 revealed the presence of DDT and its metabolites at various levels along the food chain. Detectable levels of IDDT in water of the Jordan River and two fish ponds ranged from 0.019 to 0.500 ppb, which is '/lo to '/sou the ma.ximiim level permitted in water by the U.S. Government. Mean residue in phytoplank- ton was 0.906 fxg/g: in zooplankton the mean was 6.49 uglg. IDDT residue in fish of the Jordan watershed averaged 0.37 mglkg in carp. 2.59 mglkg in benith. and 3.34 mglkg in sardines. Introduction This study investigated the presence of DDT residues in the Jordan watershed. No previous studies have been conducted on DDT and its residues in that body of water. The area of the Jordan watershed is 2,730 km^. Its major components are the Jordan River and its tributaries: the Dan. the Snir, and the Hermon Rivers. The water level is sustained by spring and effluent discharges as well as by runoff. Most of the 100.000 inhabitants of the watershed live in villages and towns, where they are employed in agricul- ture and industry. The watershed discharges 9- 10 7m' of water annually into the Sea of Galilee (Lake Kinneret). This includes approximately 1.4 10' m' of domestic sewerage effluent, ?.4 10 'm' of tisn pond effluent, and 1.4 10 "m' drainage from agricultural fields (7). ' &ibmilled as panial fulfillmcm for Maslcr of Science degree. Deparlmenl of Manne Science. C. W. Pom. Ions Island Universil)'. Brookvillc. N. Y. ' J.^l W, Mlh Sirecl. Nc» York. N Y 10024. Reprints available from Ihi-. address Most of the effluents flow directly into the Sea of Galilee. The Hula Valley in northern Israel, which was once a swamp, is also drained by the Jordan River. This valley is intensely cultivated and has received extensive applications of DDT and other pesticides. Runoff and wind are mechanisms by which various pesticide resi- dues likely find their way to the Jordan River. Sampling Samples were collected at the three sites labeled in Figure 1: two fish ponds in Dafna. northern Israel, near the source of the Dan River; the Huri bridge at the southern end of the Hula Valley; and a spot 500 feet from the tip of the Jordan River before it enters the Sea of Galilee. SITE 1 Surface water samples were collected at the edge of each pond and 30 feet within the ponds. Subsamples were placed in l-liter polyethylene bottles. Phytoplankton was collected with No. 63 mesh nets and refrigerated in 1-liter bottles. Carp (Cypriniix carpio) were caught in nets within 25 feet of the ponds" edges. SITES 2 AND 3 Water samples were collected at the edge of the river and midriver. Presumably the current provided good mixing. One liter of water consisting of three subsamples was placed in a bottle. Phytoplankton was collected midriver and at the edge of the river with No. 63 mesh nets, and refrigerated in bottles. Zooplankton was caught midriver and at the bank with No. 230 mesh nets. Samples were refrigerated in 1-liter bottles. 96 Pesticides Monitoring Journal FIGURE 1. Sites in Jordan watershed sampled for DDT residue. 1971 Benith (Barbus longiceps) and sardines (Acanthobrama terrae-saiutae) which inhabit the Jordan River were caught by the net and refrigerated at 4°C. Zooplankton — The sample was filtered through Whatman No. 4 filter paper, dried under silica gel, and weighed. Zooplankton was ground mechanically. Extraction was carried out with 10 ml hexane. The sample was filtered and stored for further cleanup. Fish — The extraction procedure followed the Extraction of Lean Tissue with Hexane recommended in the Guide to the Analysis of Pesticide Residues (9). Ten to twenty g tissue from the midbellies of fish was placed in a homogenizer with 10 g sand-washed acid and anhydrous NajSO^. This was ground to a fine powder. The sample was extracted with 50 ml hexane in a 250-ml beaker on a steam bath of 50°C and subsequently vacuum-filtered. The sample was re-extracted three times with 20 ml hexane and transferred to 100 ml in a volumetric flask. The volume was adjusted to 100 ml with hexane to compensate for loss from evaporation. The volumetric flask with its contents was placed at 4°C for 1 hour to precipitate the bulk of the fat. For further cleanup 25 ml of extract was taken (2). CLEANUP Liquid partition was followed as described by de Faubert Maunder et al (2). To remove traces of fatty acids which could interfere with gas chromatography, an activated alumina column was used (/). Alumina was heated for 1 hour at 450°C and cooled in a desiccator. Ten percent water was added. Ten g activated alumina anhydrous hexane was transferred to a chromatographic column in the form of a slurry, which was allowed to settle. A 5-cm layer of anhydrous sodium sulfate was added. The hexane ex- tract was poured completely through and washed three times with 90 ml hexane. The eluate was concentrated to the desired volume by evaporation in a water bath (6). QUANTITATIVE ANALYSIS A model 1200 Varian Aerograph gas chromatograph (GC) with an electron-capture detector and an all-glass column was used for pesticide quantification. Operating conditions were: Analytical Procedures EXTRACTION Water — One liter of water was filtered through Whatman No. 4 filter paper. Samples were extracted with hexane as described in Standard Methods for Examination of Water and Wastewater (8). Phytoplankton — The sample was filtered through fiber glass cloth and ground mechanically. Extraction was carried out with acetonitrile and the sample was re- extracted with 10 ml hexane. The concentration of phytoplankton was determined on a dry-weight basis {4). Column 8 feet long, 1 mm by 3 mm Column Packing 3 percent QF-1 as a liquid support on solid support Varaport No. 39 Carrier Gas N. Initial Pressure 60psi Gas Flow 30 ml/min Vol. 10, No. 3, December 1976 97 Column Temperature Detector Temperature I80°C 225°C TABLE 2. DDT concentrations in pyhtoplanklon of Jordan watershed, Israel — 1971 Residues were reported as IDDT (DDT+ DDE + TDE). Concentration of DDT was determined by a series of standards injected into the GC. Means of the peaks were plotted against the concentration of DDT. No attempts were made to isolate and identify another peak that appeared on the GC. Retention times for the various pesticides were, in minutes: DDE, 4.2; p.p'-DDT, 4,4; TDE, 5.2; o.p'- DDT, 5.5. Results WATER Table I shows pesticide concentrations of DDT residues in water of Dafna fish ponds and the Jordan River at various locations. Quantities ranged from Vio to '/.500 the level permitted by the U.S. Government in a water supply {10). PHYTOPLANKTON Concentrations of i^DDT residue in phytoplankton var- ied from 0.1 to 3.7 /xg/g dry weight (Table 2). SDDT TABLE I. DDT concentrations in water of Jordan River and Daphna fishponds. Israel — 1971 RESIDUES, PPB Sample DDE DDT SDDT Pond 10 1 2 3 0.032 ND 0.032 ND Pond II 4 5 6 7 Mean 0038 0.02 0.073 0.02 0.038 0,02 0.073 0.02 0.026 Jordan Rivf.r H 9 10 II 12 13 Mean 14 \f 16 17 IK 19 20 Mean 0.019 O.JOO 0.032 0.09 0.02 0.024 0.02 0.019 0.500 0.024 0.02 ND ND o.oe 0,076 0.090 0.020 ND ND ND 0.040 0.032 NOTE: See map. ligure I. for -lanipling tiles N D - not JelecleJ (' acetate 1.0 0.0O45 Mcthylmercury dicyandiamide 29.3 0,0061 Methylinercur> quinohnolale 1.0 00O45 Phenylmercury urea 1.0 0.0045 All mercur> compoutids 42.4 0.0068 PHENOX"! HERBICIDES 2.4-D 25.3 0.2705 2,4- DB 1.0 00045 Results Pesticide use records were obtained from farmers for 99 of the 100 sites (Table 2). The phenoxy herbicide 2.4- D was applied to 25 percent of the sites at rates of 0.113 to 0.680 kg/ha., and an undetermined amount was applied to one site as a spot treatment. One wheat grower reported using 2.4- DB, a compound capable of undergo- ing /3-oxidation in many plants to form 2.4- D (2). Mercury compounds were reportedly used as seed treatments on 42 percent of the fields in amounts ranging from 0.005 to 0.01 kg/ha. active ingredient. Mcthylmer- cury dicyandiamide was the most commonly used mer- cury compound, followed by ethylmcrcury p-toluene sulfonamide. The reported use of mercury compounds may have been conservative, because seeds in some cases had been treated prior to purchase and the seed dressings applied were not known. NOTE: Total sites sampled = 90. Application data reported by landowners and/or operators. TABLE 3. Mercury and 2.4-D levels in soil and wheal of 16 Slates. 1969 Residues, ppm dry weight Arithmetic Mean Geometric Mean 95% Confidence Limits Percent of Sites with Residues Number of Samples MERCURY Soil: Mercury compounds used 0.12 0.098 0 080 0 119 0 05-0 29 100 0 24 Mercury compounds not used 0.13 0,105 0,079 0, 1 .39 0,05-0 .36 100 0 24 All soil samples 0.12 0.101 0,086 0,120 0.05-0,36 100,0 48 Wheat Grain: Mercury compounds used 0.27 0.247 0 204 0,300 0,07-0 59 100,0 24 Mercury compounds not used 0.31 0 266 0 212 0,132 0,11-1,06 1000 25 Ml wheat samples 0 29 0 257 0,222 0,2% 0,07-1,06 100,0 49 2.4-D Phenoxy herbicides applied Phenoxy herbicides not applied All soil samples 0.02 0.01 0.01 0.(K)5 0,001 0,001 ' -iOOOl 0002 rOllOl 0,012 0 (W-0 20 200 25 0003 ll,(Xl-0,75 4,2 71 0 tH14 0,00-075 8,3 96 Wheal Grain: Phenoxy herbicides applied Phenoxy hcrtiicidcs noi apphed All wheat samples <0.01 0.001 <0001 0,0(M 0.00-0.05 8,0 25 <0.01 O.tXll <0,0OI 0,IX)2 OIKI-O 12 5 4 74 <0.01 0.001 <0.001 0.002 0,00.0,12 6,0 100 ' DifTcrcnce significant al Ihc 5 percent level as determined by I-tcsl of loglransformcd data. ' Pe\iiciiie application unknown for one site Pesticides Monitoring Journal Mercury levels in soil and grain from sites where mercury compounds had been used were not significantly different from those where no mercury was applied (Table 3). Levels of 2,4- D in soil where phenoxy herbicides had been applied were significantly higher than levels in soil from sites which received no applica- tion (p < 0.05). However, no significant difference was found between levels of 2,4- D in wheat from application sites and those in wheat from nonapplication sites. LITERATURE CITED (/) Hatch. W. R., and W. L. Ott. 1968. Determination of submicrogram quantities of mercury by atomic absorption spectroscopy. Anal. Chem. 40:2085-2087. (2) Melnikov. N. N. 1971. Chemistry of Pesticides. Springer- Verlag. New York. 480 pp. (3) Wiersma. G. B.. P. F. Sand, and R. L. Schutzmann. 1971. Chlorinated hydrocarbon and organophosphate residues in wheat and soil. US DA Agricultural Research Service ARS 81-44. Vol. 10, No. 3, December 1976 113 Pesticide Levels in Hay and Soils from Nine States, 1971 J. A. Gowen, ' G. B. Wiersma. = H. Tai, ^ and W. G. Mitchell ' ABSTRACT In 1971 hay and soil samples were collected in 9 Stales to determine the incidence and levels of pesticide residues in hayfields. Residues were delected in 8 percent of the soil samples and 29 percent of the hay samples. DDT and its metabolites. DDE and TDE. were contained in 2 soil samples and 21 hay samples. Heptachlor epoxide and chlordane were detected in I soil sample, dieldrin in 5 soil samples, and diazinon in 4 hay samples. The present study was undertaken in 1971 because residues of DDT, DDE. TDE, and other chlorinated hydrocarbons were detected in soil and field-collected hay samples in the National Soils Monitoring Program for Pesticides in both 1969 and 1970 (5,11; also Wiersma, Tai. and Sand, 1969: unpublished data). The objective of the present study was to determine pesticide residue levels associated with hay cultivation in nine States during 1971. Introduction Chlorinated hydrocarbons have been the primary con- taminant of animal feed in the past (2). Levels of these and other pesticides in hay. which is a major feed source for meat and dairy animals (7). is a cause for concern. In alfalfa, pesticide residues have been found principally on the leaves and are bound to the plant cuticle {1.2). King et al. (6) found residues of heptachlor and its epoxide to be greater in the crown and roots of alfalfa plants than in the tops, suggesting year-to-year accumu- lation. Windblown contaminated dust, rain-splashed soil, and drift from agricultural applications of insecticides during the growing season have been suggested as possible sources of pesticide residues in this crop {!()). Another source of residues may be the soil in which the alfalfa is grown. Beall and Nash (3) found evidence of DDT, dieldrin. endrin. and heptachlor translocation in alfalfa seedlings grown in five soil types. However, soil contact during harvest was not a major source of heptachlor and its epoxide in alfalfa (6). ' Agronomi%l. Hcolotticiii Monitoring Branch. WH-569. Technical Services Divi. sion. office of Peslicidc Programs. U.S. Environmental Prolcclion Agency. Washington. DC. 2(I4M). ' Chief. Pollutant Pathways Branch. Environmental Monitoring and Support Laboratory. U.S. Environmental Protection Agency. I.as Vegas. Nev ' Supervisory Chemist and Chemist, respectively. Ecological Monitoring Branch. Pesticides Monitoring laboratory . Bay St, Ixjuis. Miss, Materials and Methods Soil and hay samples were collected from sites in nine major hay-producing States (Table 1). Sampling sites were allocated among States and counties in proportion to acreages of hay harvested (9) and were randomly distributed within counties among hayfields of 10 acres or more. A 231-m'-' sampling area was designated in each field. Sixteen soil cores, each .">.! cm in diameter by 7.6 cm in depth, were collected on a uniform grid over each TABLE 1. Sites sampled in nine hay-producing States in 1971 SlAlfc Iowa Kansas Minnesota Missouri Nebraska Ness lork North l>akota South Dakota Wisconsin Hay Soil Hav/Soil Sites Sampled Sites Sampled Si TES Sampled 9 8 8 7 7 7 10 10 10 9 9 9 13 13 13 6 7 6 12 i: i: 10 u 10 II II in 114 Pesticides Monitoring Journai 231-01^ site. The cores were composited and screened and a 2.3-iiter subsampie was packed in a steel can which had been rinsed with isopropy! alcohol. Cuttings of the standing crop of hay were collected in the immediate vicinity of each soil core, air-dried, and thorougly mixed. A 1.4-kg sample was retained for analysis and placed in a plastic bag inside a cloth bag for shipment. The types of hay sampled included alfalfa, 76 percent; mixed hay, 21 percent; clover. 2 percent; and grass, I percent. In addition to the soil and crop samples, pesticide application data for the 1971 crop year, and names of any pesticides known to have been used in the previous 5 years, were obtained for each site wherever possible. Samples were analyzed at the EPA Pesticides Monitor- ing Laboratory, Gulfport, Miss, (now located at Bay St. Louis, Miss.). Detailed analytical procedures are out- lined by Carey et al. (4) for crop samples and Wiersma et al. (//) for soil samples. Because of possible PCB contamination of hay samples by the plastic bags which held them, PCB's were accounted for in analyses but were not considered as part of this investigation. Results Pesticide application data were reported by the landown- ers or operators for 80 of 91 sites. Only 10 percent of the respondents reported using pesticides during the 1971 crop year. The pesticides used were atrazine, chloram- ben, 2,4- D, diazinon, malathion, and methoxychlor. Atrazine was reportedly applied to four fields; 2,4- D to two; and chloramben, diazinon, malathion, and methox- ychlor to one field each. Pesticides were applied to 30 percent of the 80 sites during the 6-year period prior to sampling. All residues are expressed on a dry-weight basis (Tables 2,3). The data were not normally distributed, but tended to fit a log normal distribution. Thus the geometric mean was utilized to provide a better estimate of central tendency. Geometric means were calculated for the variable (x + O.OI), where x is the residue determination. Adjusted geometric means are the calculated geometric means minus 0.01. Arithmetic means are also presented. Of 90 soil samples analyzed, 8 percent contained detect- able levels of pesticides. The compounds indentified were chlordane. o.p'-DDE, p,p'-DDE. o.p'-DDT, p,p'- DDT, p,p'-TDE. dieldrin. and heptachlor epoxide (Ta- ble 1). DDTR (DDE+ DDT+TDE) occurred in two soil samples, heptachlor epoxide and chlordane in one, and dieldrin in five. Organophosphates were not detected in any soil samples analyzed. The pesticides identified in hay, occurring in 29 percent of 87 samples, were p.p'- DDE, <),/)'- DDT, p,p'-DDT, p.p'-TDE, and diazinon (Table 2). DDTR was detected in 21 hay samples; diazinon was detected in four. Discussion On most sites where pesticides were detected, respond- ents claimed that the pesticides in question had not been applied within the six years immediately preceding sampling. Unreported use or spray drift from insecticide applications to other crops might account for some residues in hay and soil. Considering the persistent nature of the organochlorine pesticides (8.11), the resi- dues detected in soil might also have originated from applications prior to 1966. In hay, other possible residue sources are translocation from the soil {3) and volatiliza- tion of the compounds from the soil surface with subsequent reabsorption by the cuticle of the leaves (/.2). TABLE 2. Pesticide residues detected in hayjleld soils of nine States. 1971 Compound Residue Levels, ppm drv weight Adjusted Arithmetic Geometric Mean Mean <0.0I • <0.0I • <0.0I 0,001 0.01 • <0.0I • <0.0I • 0.02 0,001 <0.0I 0.001 <0.0I 0,001 95% Confidence Limits for Adjusted Geometric Mean Sites with Residues. % Chlordane o.p -DDE p.p'-DDE o,p'-DDT p.p-ODT P.P-TDE DDTR Dieidnn Heptachlor Epoxide <0.001-0,002 <0,001 -0,002 <0.001-0,002 NOTE: Total sites sampled ^ 90 Minimum detectable level was 0.01 for all compounds, •-Geometric mean estimate not calculated when less than two positive values were present 0.04 0.02 0.27 0.84 0.37 0.13 1.54 0.12 0,15 I.I 1.1 2.2 I.I I.I I.I 2.2 S.6 1.1 Vol. 10, No. 3. December 1976 115 TABLE 3. Pesticide residues detected in hay from nine States. 1971 COMPOtND /)./) -DDE ,..p -onT P.P-nm p.p-TDE DDTR Diazinon -I96l 1962 1967 1971 1973 1973 1971 1973 TABLE 4. Organochlorine residues in human whole milk, Africa Literature References Gejvall et al. 1972 (IS) Residues, ppb BHC HCB PCBs Sampling Year 1972 TABLE 5. Organochlorine residues in human whole milk, Oceania Nation Residues ppb Literature References VDDT BHC Dieldrin HCB Sampling Year Newton and Greene 1972 (56) Stacey and Thomas 1975 (68) Siyali 1973 (67) Homabrook et al 1972 (29) Australia Australia Australia New Guinea 142.0 78.0 54.0 29.0-95.9 25.0 5.0 5.0 52.5 15.6 1970 1970-1971 1973 1972 Vol. 10, No. 4, March 1977 123 I TABLE 6. OrganocMorine residues in human whole milk, Japan Residues PP» Hefta- PCBs CHLOR LrTERATUu References Prefectuhe VDDT BHC DiELDRIN Epoxide Sampling Year TokutJU el al 1970 (7<) Wakayama 71 0 1050 1970 Nar»fu 1971 t'5l AKhi 20 0-400 0 1970-1971 TakeshiU and Inuyama 1970 (7j| Shimane: fanners 790 1429 0-12.9 1970 nonfarmers 660 2509 0-43.0 1970 Kalo el aJ 1971 134) Kana«awa 19 0-105 0 180-740 0-12.0 1971 1971 Hayuhl 1972 (2<) 24 prefectures: farmers 56 3 92 6 3.7 nonfarmers 63 5 1434 1971 Hayashi 1972 (?5) 24 prefectures 607 125.9 3.7 1971 36 prefectures 62 6 1009 3.4 11 1971-1972 Hayashi 1974 (261 38 prefectures 63 0 105.0 3.4 1 1 1971-1972 1 1\^ 1 1 n'j'\ Nishimolo el al. 1972 (57) Kochi &. Nangoku 30.0 1971-1972 1971 1971 Yamagishi el al. 1972 («) Toyko: colostrum milk 300 440 25.0 41 0 7 0 2.0 Koj.ma el al 1971 (i9) Akita I: farmers -52.0 63.0 <10 1971 nonfarmers 500 55.2 .. H. Musa^o. K. Karino. T. Takijima. I. Fukn- shima. S. Fiijii. T. Taiu>. T. Kobuyashi. O. Kiiriluiru, K. SiiJo. and T. Mulo. 1972. On pesticide residues in foods, first report. Organochlorine pesticide residues Ann. Rep Gumma Prefect. Inst Public Health Cent. Study Environ. Pollul 4:W-86. [24) Hiivashi. M. 1972. Pesticide pollution of mother's milk. J. Jpn. Med. Assoc. 68( 12); i:81- 128:. Q5) Hoyashi. M. 1972. Pollution of mother's milk by organo- chlorine insecticides. Jpn. J. Public Health 1 9(9): 437-441. (26) Hiiyashi. M. 1974. Mother's milk and environmental pollu- tion. J. Pedialr. Pract. 37(9): 1 1 13- 1 1 19. [27] Hcy/ulrick.f. A., and R. Maes. 1969. The excretion of chlorinated hydrocarbon insecticides in human mother's milk. J. Pharm. Belg 24(9-IO):4S9-463. {28) Hidaka. K.. 7. Olw. and K. Fiijiwura. 1972. PCB and organochlorine pesticides in mother's milk. Prog. Med. «2(8):5 19-520. [29) Hornahrook. R.W.. P. G. Dymenl. E. P. Gomes, and J. S. Wiseman. 1972. DDT residues in human milk from New Guinea natives. Med. J. Aust. 25( I): 1297- I3(X). UO) Inoiie. >., S. Abe. H. Esaki. and M. Takamalsii 1973. Polychlorinated biphenyls in human blood. Kurume Med. J. 29(2):8.3-86. (.*/) Iniiyuma. Y.. and T. Takeshiia. 1973. Survey of pesticide residues and PCB's in mother's milk and human adipose tissue. Ann. Rep Shimane Prefect. Inst. Pub. Health Environ. Pollut. 15:37-39. (32) JuszkieH-ivz. T.. T. S:prengier. and T. Radomanski. 1975. Mercury content of human milk. Pol. Tyg. Lek. 30(9):365- 366. (33) Kamala. T. 1972. Hygienic studies on pesticide residues, part 3. Determination of organochlorine pesticide residues in human tissues and other samples. Jpn. J. Hyg. 27(5):439-443. {40) Komarova, L. I. 1970. DDT excretion with the breast milk and its effect on the body of the mother and child. Pediatr. Akush. Hmekol 35(11:19-20 {41) Kanlek. M.. S. Ktibaeki, S. Paradowski. and B. Wierz- clunviecka. 1971. Determination of organic chlorine pesti- cides in human milk. Pediatr. Pol, 46(2): ;83- 188. {42) Kroger. M. 1972. Insecticide residues in human milk. J. Pediatr. 80(3):401-405. (43) Lang. E. P.. F. M. Kiinze. and C S. Pricketl. 1951. Occurrence of DDT in human fat and milk. Arch. Ind. Hyg. 3(3): 245-246. (44) Lofroth. G. 1971. Who cares about DDT? Ecologist l(l7):8-9. {45) Luquet. F. M.. J. Goiirs. J. Casalis. 1974. Contamination of human milk by organochlorine pesticide residues in France. Aliment. Vie 62( l):40-69. (46) Mandroiii, V.. and M. Jordachescu. 1971. Determination of the BHC content in the human organism. Igiena 20(6): 363-364. {47) Malsuda. H.. T. Shimamoto. T. Ilo. and K. Ot>ida. 1971. On the analytical results of organochlorine pesticide resi- dues in mother's milk. Rep. Ehime Prefect. Hyg. Lab. 33:43-48. (48) Matsashima. S. 1972. Pollution of food by agricultural chemicals and the diet. J. Clin Nutr. 40(5):555-563. (49) Mick. D. L.. K. R Long, and P. Bonderman. 1971. Aldrin and dieldrin in the blood of pesticide formulators. Am Ind. Hyg. Assoc. Sept. 72. pp 94-99. (50) Miller. G. J., and J. A. Fox. 1973. Chlorinated hydrocar- bon pesticide residues in Queensland human milk. Med. J. Aust. 2(6):26l-264. (51) Morgan. D. P.. C. C. Roan, and E. H. Pischal. 1972. Transport of DDT. DDE. and dieldrin in human blood. Bull. Environ. Contam. Toxicol. 8(6):32 1-326. (34) Kalo. K.. 7. Yamada. S. Walanabe. Y. Wado. el al. 1971. Analyses of residual pesticides in vegetables, cow's milk and mother's milk. Annu Rep. Kanagawa Prefect. Inst. Public Health 21:85-92. (52) Mori. Y.. K. Ito. K. Sakurai. M. Mori, amd T. Sudo. 1971 . On the results of investigation of milk pollution by pesticide residues. Ann. Rep. Mie Prefect. Inst. Public Health 18:59-68. (35) Kauai. Y.. Y. Hori. Y. Nigawa. I. Yamamolo. M. Kilay- ama. and K. Mori. 1973. On the pollution of mother's milk by pesticides and PCB's in Hokkaido. J. Food Hyg. Soc. Jpn. 14< 3): 302-303. (53) Miisial. C. J.. O. Hiilzinger. V. Zilko. and J. Croekei 1974. Presence of PCB. DDE and DDT in human milk in the provinces of New Brunswick and Nova Scotia. Can- ada. Bull. Environ. Contam. Toxicol. 12(3): 258-267. (36) Knoll. W.. and S. Jayaraman. 1973. Organochlorine pesti- cide residues in human milk. Z. Gesamte Hyg. 19(0:43-45. (37) Knoll. W.. and S. Jayaraman. 1973. On the contamination of human milk with chlorinated hydrocarbons. Nahrung I7(5):599-615. (54) Nagai. /. 1972. Residues of organochlorine pesticides in mother's milk in Yamaguchi Prefecture Ann. Rep. Yama- guchi Prefect. Res. Inst. Public Health 14:93-94. (55) Naraju.T . 1971 . Pollution of cow's milk and human milk by BHC. J. Clin. Nutr 39( l):26-.34. (38) Kmmles. J. A. 1974 Breast milk: a source of more than nulintion for the neonate Clin. Toxicol. 7(l):69-82. (39) Kojima. .S'.. M Sailo. H. Konno. and K Ozowa. 1971. Results of investigation of organochlorine pesticide resi- dues in mother's milk and in blood of the mothers. Rep. Akita Prefect. Inst Public Health 16:65-68. (56) Newton. K. G.. and N. C. Greene. 1972. Organochlorine pesticide residue levels in human milk — Victoria. Aus- tralia—1970. Pestic. Monit. J. 6(l):4-8. (57) Nishimolo. T.. M. U\ela. S. Pane, and K. Okikazawa. 1972 Organochlorine pesticide residues and PCB's in breast milk. Progr. Med 82(9):974-975. 128 Pesticides Monitoring Journal 58) Nishimura. H. 1973. Teratogenic substances. Int. Chem. Eng. 13(4):774-780. 59) Olszyna-Marzys. A. E.. M. De Campos. M. Taghi Farvar. and M. Thomas. 1973. Chlorinated pesticide residues in human milk in Guatemala. Bol. Sanit. Panamer. 74:93-107, 60) Osaka Prefect. 1973. The countermeasures for damages due to agricultural pesticides. 2nd item of 1st clause of Chapter XII. A draft of the plan of Environmental Admin- istration, pp. 392-395. 61) Oura. H.. H. Kobayashi, T. Oura. I. Senda. and K. Kubota. 1972. On the pollution of human milk by PCBs and organochlorine pesticides. J. Jpn. Assoc. Rural Med. 2l(2):30O-30l. 62) Quinb\, G. E.. J. F. Armstrong, and W . F. Durham. 1965. DDT in human milk. 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Shimane Prefect. Inst. Public Health 12:27-28. (74) Tokutsu. K.. T. Koyama. and T. Yokoyama. 1970. Pesti- cide residue in mother's milk and plasma in Wakayama Prefecture. Annu. Rep. Wakayama Prefect. Inst. Public Health 19:59-62. (75) Toltori Prefeclural Hygiene Research Institute. Tottori, Japan. 1971 . Tests and investigations on pesticide residues in mother's milk and blood. Rep. Tottori Prefect. Hyg. Res. Inst. 11:19. (76) Tottori Prefeclural Hygiene Research Institute. Tottori. Japan. 1972. Tests and investigations of pesticide residues in mother's milk. Rep. Tottori Prefect. Hyg. Res. Inst. 12:22. (77) Tuinstra. L. G. M. 1971 . Organochlorine insecticide resi- dues in human milk in the Leiden region. Ned. Melk. Zuiveltijdschr. 25(0:24-32. (78) Unterman. W. M.. and E. Sirghie. 1969. Igiena Buc. I8(4):22l. Ref. in Dairy Sci. Abstr. 32(3): 192 (1970). (79) West. Irma. 1964. Pesticides as contaminants. Arch. Envi- ron. Health 9(5):626-633. (80) Westoo. G. 1974. Changes in the levels of environmental pollutants (Hg, DDT. dieldrin, PCB) in some Swedish foods. Ambio 3(2):79-83. (81) Westoo. G.. and K. Noren. 1968. Nordforsk Biocid— Information 14<10):6-7. (82) Westoo. G..K. Noren. and M. Andersson. 1970. The levels of organochlorine pesticides and polychlorinated biphenyls in margarine, vegetable oils and some foods of animal origin on the Swedish market in 1967-69. Var Foda 22(2- 3):9-3l. (83) Wilson. D. J.. D. J. Locker. C. A. Kitzen. J. T. Watson, and W. Schaffner. 1973. DDT concentrations in human milk. Am. J. Dis. Child. I25(6):8I4-8I7. (84) Yamada. T.. and Y. Sakamoto. 1973. Results of survey of pesticide residues in mother's milk and soil. Hiroshima Prefect. Inst. Prevent. Environ. Pollut. Annu. Rep. 3:57- 58. (85) Yamagishi. T.. K. Takeba. C. Fujimoto. K. Morimoto, and M. Haruta. 1972. On the organochlorine pesticide residues in mother's body and her foetus' body. Rep. Tokyo Pub. 50:44-45. (86) Yamuniishi Prefect. Inst, for Public Health. Yamanashi. Japan. 1972. Results of investigation of mother's milk pollution by organochlorine pesticides. Annu. Rep 'Va- manashi Prefect. Inst. Public Health 15:20. Vol. 10, No. 4, March 1977 129 Insecticide Residues in Human Milk from Arkansas and Mississippi, 1973-74 • Sandra C. Strassman and Frederick W. Kutz ABSTRACT Between September 1973 and February 1974, 57 samples of human milk were collected from women residing in selected areas of Arkansas and Mississippi. Residues of p.p'-DDT, p,p'-DDE. p.p'-TDE. P-BHC. dieldrin. heptachlor epoxide, oxychlordane. and inn^-nonachlor were measured by electron- capture gas chromatography: trace amounts of o.p'-DDT and polychlorinated biphenyls were also detected. Additional ana- lytical procedures were employed to confirm the presence of specific residues. Introduction Residues of certain organochlorine insecticides and their transformation products have been found by many inves- tigators in various human components such as adipose tissue, whole blood and blood serum, urine, feces, and milk. Demonstration of pesticide residues and their me- tabolites in human milk presents a critical health issue from at least two standpoints. First, the residues indicate total body burden of pesticides in the donor mother, providing some measure of lipophilic insecticides stored and accumulating in her body. Second, if the mother breastfeeds the newborn, her milk becomes a major vehicle for exposing the baby to insecticide residues. Exposure to these chemicals begins in utero by transpla- cental passage (/, 7). After birth, exposure may continue through ingestion, respiration, and absorption through the skin and mucous membranes. Since babies are usually kept in protected environs, ingested food probably pre- sents the m^or source of exposure to these pollutants. This paper reports levels of organochlorine pesticide residues and the industrial pollutant, polychlorinated bi- phenyls (PCB's), detected in milk collected from women 'Ecolofical Moniloring Branch. Technical Services Division (WHSftVl. US Env ronmental Prolcclion Agency. Washington. DC 20460. 130 residing in selected counties of Arkansas and Mississippi. All information presented was developed by the National Human Monitoring Program for Pesticides of the U.S. Environmental Protection Agency. This program evalu- ates the exposure to pesticides experienced by the general population of the conterminous United States, and at- tempts to identify changes and trends when they occur. Details of the program have been reported by Yobs (//) and Kutz et al.(5). Collection and Sampling Between September 1973 and February 1974, milk was collected from donors residing in specified counties of Arkansas and Mississippi. All milk was analyzed in May 1975 for selected organochlorine insecticides, their trans- formation products, and PCB's. Since the original intent of this study was to collect human milk for detection of chlorodioxins, possible con- taminants of the herbicide 2,4,5-T (a 2,4,5-trichlorophen- oxyacetic acid derivative), the survey design was limited to the collection of milk from women who probably had been exposed to this pesticide. Consequently, counties selected for the project (Figure I) were those in which rice was grown or which exchanged public services with rice-growing areas of Arkansas and Mississippi where 2,4,S-T was being used or had been used recently. Milk was collected from lactating mothers during their hospitalization after routine delivery or during postpartum examinations, and from members of cooperating LaLeche League chapters. Information received with each milk sample included the donor's age, race, county and State of residence, date of parturition, and any known patholog- ical conditions. Since the object of the study was to reflect the pesticide burden in milk from the general population of the areas, samples were collected only from healthy women with no known occupational exposure to Pesticides Monitoring Journal TABLE 1. Chemicals detectable in human milk' :al Limits of Detectability, PPB FIGURE 1 . Counties in Arkansas and Mississippi selected for sampling human milk for pesticide residue analysis, 1973-74 pesticides. All individuals had established area residency; samples were not taken from transient or new residents. Part of each milk sample was analyzed for organochlorine residues. The remainder is being retained for future chlorodioxin analysis. Approximately one-half ounce of milk was manually expressed by each participant directly into a clean, pesti- cide-free glass bottle. Hind milk, which occurs after several minutes of nursing, was requested because of its high percentage of fat. Samples were immediately frozen and stored until analysis. Chemical Analysis All analyses were performed by a laboratory under con- tract to EPA following methods specified by the National Human Monitoring Program for Pesticides. The labora- tory was required to maintain external quality-assurance standards. Residues were extracted by a modification of the proce- dures described by Curley and Kimbrough (2) and Giuf- frida et al. (i): the lipid was isolated from the milk, pesticides were extracted from the lipid, and the extract was cleaned up. Using the modified Mills-Olney-Gaither procedure {10), analysis was limited to determination of the chlorinated hydrocarbons presented in Table 1 . Vol. 10, No. 4. March 1977 o.p-DDT p.p-DDT o.p-DDE p.p-DDE o.p-TDE p.p'-TDE oBHC tl-BHC y-BHC (lindane) 8-BHC Endnn Aldrin Dieldrin Heptachlor Heptachlor epoude Oxychlordane /rani-Nonachlor Hexachlorobenzcne Mirex Polychlorinated biphenyls 20 20 20 10 20 20 10 20 10 10 20 10 10 10 10 20 20 10 100 1000 Using the modified Mills-Olney-Gaithcr procedure (/O;. After each sample was thawed and homogenized by a supersonic disintegrator, whole milk was weighed into a clean glass centrifuge bottle. Pre-cleaned gljiss wool was added to the centrifuge bottle to adhere to all the coarse precipitate of milk solids formed during the subsequent acetone extraction. Contents of the centrifuge bottle were extracted with acetone three times and pooled in a separatory funnel. Solids were separated from the acetone after each extraction by centrifugation. The remaining coarse milk solids were extracted twice with /i-hexane, and these extracts were combined with acetone extracts in the separatory funnel. The combined «-hexane and acetone extracts were washed three times with 2 percent sodium sulfate, dried through an anhydrous sodium sulfate column, and concentrated in a Kudema- Danish evaporator to approximately 5 ml. The concentrated extract was cleaned up by liquid-liquid acetonitrite partitioning and florisil procedures as described by Thomspon (10). Residues were identified and quantified on a Micro- Tek 220 gas chromatograph equipped with tritium electron- capture detectors using two columns with different resolu- tion characteristics. Column dimensions were 1.5 percent OV- 17/ 1.95 percent QF-1 and 4 percent SE-30/6 percent OV-210. A Coulson electrolytic conductivity detector operated in the chloride mode was used to confirm p.p'- DDT and p,p'-DDE in every fifth sample (9). Results were reported on a whole-milk basis and the percent extractable lipid material was noted for each sample. The 6 percent florisil fraction of each sample was com- posited for confirmation of selected pesticide residues by combined gas chromatography / mass spectrometry (GC- MS) and thin-layer chromatography. Residue data, presented on a whole milk basis, were characterized by calculating the following statistical pa- rameters: 131 i Sample Size — total number of samples ana- lyzed. Percent Positive — percentage of the total number of samples in which a quantifiable residue of a given pesticide was detected. Percent Trace — percentage of the total num- ber of samples in which a residue of a given pesticide was reported but could not be quan- tified. Extreme Values — highest and lowest values detected. Arithmetic Mean — calculated using the stand- ard formula. Mean of Positives — arithmetic mean of resi- dues found at quantifiable levels; reports of zero and trace amounts were excluded. Residues present in trace amounts were identified on two columns; they could not, however, be quantified. In calculating the arithmetic means, only reports of quantifi- able amounts of pesticide residues were considered; re- ports of trace amounts were treated as zero. Where a trace level represented the minimum value, this was indicated. Results and Discussion A demographic summary of the donors of the 57 human milk samples is presented in Table 2. The mean percent extractable lipid is included for each category. Tlie mean age of the 57 mothers was 27 years. Seventeen donors (29.8 percent) were Negroes; 40 (70.2 percent) were Caucasians. Sampling occurred from I to 448 days after delivery; the median postpartum time was 41 days Lipid material extracted from each milk sample ranged fi-om 0.6 to 8.8 percent, with a mean value of 3.0 percent Detected residues of the pesticides and their metabolites presented in Table 3 reflect donors" previous exposure tc the chemicals; residues of PCB's represent exposure tc these industrial chemicals. PCB's were present in trace amounts, below 1 ppm, in every sample. The presence of the compounds was confirmed in a composite of all extracts by combined GC-MS; hexachlorobiphenyls were the major components. All milk samples showed evidence of prior exposure to DDT. TheiDDTequivalent (o,p -DDT + p,p'- DDT + 1.114 [o.p -DDE + p,p'-DDE + o.p'-TDE + p,p'-TDE]) is calculated by adjusting the DDE and TDE transforma- tion products of DDT by a molecular-weight-based con- stant to convert them to an equivalent weight of DDT. Thus the ^^DDT equivalent is a conglomerate figure ex- TABLE 2. Demographic summary of donors sampled for insecticide residues in human milk, Arkansas and Mississippi — 1973-74 Geographic Location No. Samples Mississippi Arlansas Combined Survey Percent Caucasians Percent Negroes Mean Age. Yr. Median No- Mean Extractable Postpartum Days Lipid Material. ? 8 12.5 87.5 29.5 4 2.7 49 796 20.4 26.6 lie 3.0 57 70.2 29.8 27.0 41 3.0 TABLE 3. OrganocMorine pesticide residues in 57 human whole milk samples, Arkansas and Mississippi — 1973-74 Samples with Residues. % Residues, pp^ Positive Trace Arithmetic Mean Mean of Extreme Values Pesticide Minimum Maximum V DDT equivalent* 1000 0 U344 0 344 0.02 2.76 p.p-DDT'^ 100 0 0 0092 0092 0.01 084 P.p -DDE"-" 1000 0 0.227 0.227 0.01 1.72 tf-BHC 368 63.2 0005 0014 trace 0.01 Dieldnn' 28.1 73.9 0004 0012 trace 0,05 Hcptachlor epoiiitje* 35 1 649 0.004 0.012 trace 0.03 Oxychlordanc' 456 54 4 0.005 0.012 trace 0.02 rranj-Nonachlor' 14.1 860 0.001 0.010 (race 0.01 PCBs" 100.0 100.0 trace trace tiace liace ' V DDTequivalcnl = o.p- DDT + p.p'DDT + 1 .1 14 (o.p'-DDE + p.p-DDE + o.p -TDE + p.p-TDE), ■ Rc«due% confirmed by combined gas chromaiography — mass spectrometry, * Confirmation accomplished by Coulson conductivity conductor and thm-layer chromatography. ' Residue levels were below instrument sensitivity and could not be confirmed ■* Presence of PCBs represents exposure to these industnal chemicals 132 Pesticides Monitoring Journal pressing total body burden of these chemicals as DDT. This equivalent, with a mean of 0.344 ppm, represents the insecticide found in the greatest concentration. In the milk analyzed, 73.7 percent of the i D DT equivalent burden was found as DDE. Of the DDT transformation jroducts found in the human milk, p,p'-DDT and p,p'- DDE were apparent at mean levels of 0.092 ppm and 0.227 ppm, respectively. The presence of these metabolites was :onfirmed by Coulson electrolytic conductivity detector, thin-layer chromatography, and combined GC-MS. There was a single observation of p,p'-TDE at 0.02 ppm. Trace quantities of o,p'-DDT were present in all 57 samples; 9,p'-TDE and o,p'-DDE were not detected. The presence of /3-BHC residues indicate exposure to insecticides containing benzene hexachloride. This chemi- cal appeared in at least trace amounts in all milk analyzed at a mean value of 0.005 ppm. The a, y (lindane), and 6 isomers of BHC were not detected. Since aldrin is quickly epoxidized to dieldrin, dieldrin residues signify exposure to either or both of these pesticides. Quantifiable residues of dieldrin were detected in 28. 1 percent of the samples at a mean concentration of 0.004 ppm. Oxychlordane is a major mammalian metabolite of the insecticides chlordane and heptachlor. Along with hep- tachlor epoxide and /rani-nonachlor, which also indicate exposure to heptachlor and chlordane, it was found in quantifiable or trace amounts in every milk sample analyzed. Oxychlordane and heptachlor epoxide were pre- sent at mean levels of 0.005 ppm and 0.004 ppm, respec- tively. The compound fra«j-nonachlor, one of several that comprise technical chlordane and technical heptachlor, was first reported in human adipose tissue in a recent study by Kutz et al. (4). This compound had a mean level of 0.001 ppm in the human milk sampled. Oxychlordane was qual- itatively confirmed by combined GC-MS; levels of hep- tachlor epoxide and /rani-nonachlor were below instru- ment sensitivity and, consequently, could not be con- firmed. To the authors' knowledge, this is the first report of the occurrence of oxychlordane and /ra/js-nonachlor in hu- man milk. Save et al. {8) and Curley and Kimbrough (1.2) have reported residue levels of heptachlor epoxide, diel- drin, BHC, DDT, and PCB's. A cknowledgments Authors gratefully acknowledge the assistance of the following persons with the analyticcd portion of this study: U.S. ENVIRONMENTAL PROTECTION AGENCY G. Wayne Sovocool, Analytical Chemistry Branch, Environmental Toxicology Division, Health Effects Research Laboratory, Re- search Triangle Park, N.C.; Ronald F. Thomas, Chemical and Biological Investiga- tions Branch, Technical Services Division, Beltsville, Md.; Jack Thompson, Quality As- surance Section, Analytical Chemistry Branch, Environmental Toxicology Division, Human Effects Research Laboratory, Re- search Triangle Park, N.C. MICHIGAN DEPARTMENT OF PUBLIC HEALTH Robert L. Welch, Pesticide Epidemiologic Studies Project, Lansing, Mich. LITERATURE CITED (/) Curley. A.. M. F Copeland. and R. D. Kimbrough. 1969. Chlorinated hydrocarbon insecticides in organs of stillborn and blood of newborn babies. Arch. Environ. Health 19(5):628-632. (2) Curley. A., and R. Kimbrough. 1969. Chlorinated hydro- carbon insecticides in plasma and milk of pregnant and lactating women. Arch. Environ. Health 18(2): 156-164. (i) Giuffrida. L.. D. C. Boslwick. and N. F. Ives. 1966. Rapid cleanup techniques for chlorinated pesticide resi- dues in milk, fats, and oils. J. Assoc. Off. Anal. Chem. 49(3):634-638. (4) Kutz. F. W., W. Sovocool. S. Sirassman. and R. G. Lewis. 1977. ;ra;ii-Nonachlor residues in human adipose tissue. Bull. Environ. Contam. Toxicol. I6(l):9-I4. (5) Kutz, F. W., A. R. Yobs, W. G. Johnson, and G. B. Wiersma. 1974. Pesticide residues in adipose tissue of the general population of the United States, FY 1970 survey. Bull. Soc. Pharmacol. Environ. Pathol. 2(3):4-10. (6) Morgan. D. P . and C. D. Roan. 1971. Absorption, storage, and metabolic conversion of ingested DDT and DDT metabolites in man. Arch. Environ. Health 22(3):309-3l5. (7) O'Leary. J. A.. J. E. Davies. W . F. Edmundson. and G. A. Reich. 1970. Transplacental passage of pesticides. Am. J. Obstet. Gynecol. 107(l):65-68. (8) Savage. E. P.. J. D. Tessari. J W . Matberg. W. H. Wheeler, and J. R. Bagby. 1973. Organochlorine pesticide residues and polychlorinated biphenyls in human milk, Colorado— 1971-72. Pestic. Monit. J. 7(l):l-5. (9) Su. G. C. and H. A. Price. 1973. Element specific gas chromatographic analyses of organochlorine pesticides in the presence of PCB's by selective cancellation of interfer- ing peaks. J. Agric. Food Chem. 21(6): 1099-1 102. (10) Thompson. J. F (ed.). 1972. Analysis of Pesticide Resi- dues in Human and Environmental Samples. Prepared by EPA Environmental Toxicology Division. Research Trian- gle Park, N.C. (//) Yobs. A. R 1971. The National Human Monitoring Pro- gram for Pesticides. Pestic. Monit. J. 5(l):44-46. Vol. 10, No. 4, March 1977 133 RESIDUES IN FOOD AND FEED Pesticide and Other Chemical Residues in Total Diet Samples (X) D. D. Manske and R. D. Johnson ' ABSTRACT Sime 1964 the Food and Dnin Administrulion Tolcd Did sliidv has reported residues of pesticides and other chemicals in- gested in the diet of a young adidt male, statistically the Nation's largest eater. During the tenth year of the study, pesticide residues remained at the relatively low levels previ- ously reported. Thirty market baskets were collected in 30 cities which ranged in population from less than 50.000 to 1.000.000 or more. Averages and ranges of residues are reported from August 1973 through July 1974 by food class. Individual items in the dairy- and meat composites in four market baskets were analyzed for pesticides: results are included. Data for lead, cadmium, selenium, mercury, arsenic, and zinc are also in- cluded. Results of recovery studies within various classes of residues are also presented. Introduction The Food and Drug Administration Total Diet Program {10). sometimes called the Market Basket study, began with a program intended for surveillance of fission prod- ucts from atmospheric tests of thermonuclear weapons in May I%1. The program was quickly extended to pesti- cides and certain nutnenis IIO). Although some changes have been made in sampling frequency, areas sampled, analytical methods used, and types of residues sought, the program has continued in essentially the same form to the present. A market basket of food representing the basic 2-week diet of a 16- to 19-year-old male, statistically the Nation's largest eater, is collected in each of several geo- graphic areas. The various foods are prepared in the man- ner in which they would normally be served and eaten. Foods in each of 12 broad classes are composited into a slurry and analyzed for the presence of organochlorinc pesticides, organophosphorous pesticides, carbaryl, her- bicides, certain metals, and polychlorinated biphenyls (PCB's). Melhodoiogy includes atomic absorption spec- troscopy, fluorometry. gas chromatography, thin-layer chromatography, and established extraction and cleanup I Kan%as Cily Field OITlcc Uboralory. Foiul and Drug AdminiMration. US nepail mcnl of Health. Kducalion. and Welfare. Kansas City. Mo. MKlh 134 techniques. Conditions, techniques, and limits of quantita- tion have been described in previous reports of the series U-6. 13-15. 19. Also: H. K. Hundley and J. C. Under- wood, Food and Drug Administration. 1970: personal communication). Amounts and types of residues found from June 1964 through July 1973 have also been described in earlier reports (7-9, II, 12, 15-18). The present report presents results obtained from August 1973 through July 1974. Samples were collected in 30 different grocery mar- kets in 30 different cities. Results During this reporting period 1.613 residues of 42 different compounds were found in the 360 composites examined. In the previous reporting period. 1.729 residues of 40 ditTerent compounds had been found. The 42 different residues found are listed in decreasing order of frequency in Table I. In Table 2. the frequency of occurrence of these residues is broken down according to food class. Table 3 gives the levels of the chemical residues by food class. The average stated in Table 3 is based on 30 composites examined; any trace residues have not been included in calculating the average. For this reason, an average value reported as "T" can be well below the detection limits of the method for that compound. Ihe most common residues and their maximum levels are disucssed below for each of the 12 classes of food composites. No findings have been corrected for recover- ies obtained in recovery experiments. A summary of recovery studies appears in Table 4. DAIKI I'KODUCTS Organochlorinc compounds were the most frequently found residues in dairy products. The most common oiganiK-hlorines were dieldrin. ().(X).SO ppm; BHC. 0.0030 ppni; DDi:. OOIO ppm: and heplachlor epoxide. 0.0020 ppm. Oiher oiganochlonne residues present were DDT, lindane, TDE, methoxychlor, HCB, and PC P. Zinc, Pesticides Monitoring Journal ranging from 4.0 to 8.6 ppm. was found in all 30 compos- ites. Selenium, cadmium, and lead were occasionally found in this food class. No organophosphorous residues were detected. MEAT, F:SH. and POULTRY Nine organochlorine compounds occurred in varying combinations in all 30 composites. The most common were DDE. 0,038 ppm; dieldrin, 0.033 ppm; DDT, 0.020 ppm; BHC. 0.0070 ppm; TDE, 0.005 ppm; and hepta- chlor epoxide, 0.0040 ppm. Other residues were lindane, PCB, HCB, ronnel, diazinon. and ethion. Mercury, se- lenium, and zinc, ranging from trace to 0.04 ppm. 0.1 to 0,4 ppm, and 21.0 to 35.5 ppm, respectively, were found in all 30 composites. Cadmium, arsenic, and lead were also found. GRAIN AND CEREAL PRODUCTS Malathion, ranging from 0.004 to 0.054 ppm, was found in all 30 composites. Selenium and zinc, ranging from 0.10 to 0.40 ppm and 5.9 to 10.1 ppm, respectively, were found in all 30 composites. Other residues included diazinon, BHC, DDT, PCP, chlordane. heptachlor. cadmium, and lead. POTATOES Zinc, ranging from 1,8 to 7.5 ppm, was found in all 30 composites. Of the ten organochlorine residues which appeared in this composite, the most common were CIPC, 0.467 ppm; dieldrin, 0.007 ppm; and DDE, 0.012 ppm. Other residues were endosulfan. DDT, TCNB, TDE, heptachlor epoxide, diazinon, HCB, PCNB. cad- mium, lead, selenium, and mercury. LEAFY VEGETABLF.S Organophosphates were the most frequently detected pesticide residues in leafy vegetables. The most common were diazinon. 0.015 ppm; parathion. 0.022 ppm; and methyl parathion. 0.008 ppm. All 30 composites contained zinc ranging from 0.8 to 4.1 ppm. Cadmium, ranging from 0.01 to 0.14 ppm, was found in 28 composites, and lead, ranging from 0.03 to 0.40 ppm. was found in 20 compos- ites. Less frequently occurring residues were endosulfan. DDE. malathion. selenium, dieldrin. perthane, DDT, DCPA. botran. nitrofen, lindane, and mercury. LEGUME VEGETABLES Zinc and lead, ranging from 5.0 to 14.5 ppm and 0.10 to 1.30 ppm. respectively, were found in all 30 composites. Other residues were cadmium, selenium. HCB. and car- baryl. ROOT VEGETABLES Zinc, ranging from 1.4 to 5,0 ppm. was found in all 30 Vol. 10. No. 4. March 1977 composites. Twenty-four composites contained cadmium with a maximum level of 0.31 ppm, and 22 composites contained lead with a maximum level of 0.30 ppm. Other residues were selenium, arsenic, DDE. lindane, diazinon, TDE, HCB, parathion. and PCP. GARDEN FRUITS The most common pesticide residues in this composite were dieldrin. 0.015 ppm; lindane, 0.004 ppm; BHC, 0.005 ppm; diazinon, 0.003 ppm; and leptophos, 0.090 ppm. Thirty composites contained zinc ranging from 2.1 to 4.8 ppm. Other residues were cadmium, lead, selen- ium, DDE, DDT, arsenic, endosulfan, parathion. car- baryl, perthane. and toxaphene, FRLHTS The nonmetallic residues most frequently encountered in fruits were carbaryl. 0.10 ppm; orthophenylphenol, 0.20 ppm; and ethion, 0.012 ppm. Zinc, ranging from 0.1 to 3.0 ppm, was found in all 30 composites. Other residues were lead, cadmium, selenium, dieldrin, diazinon, mercury, arsenic, parathion, botran, dicofol, aldrin, and phosalone. OILS. FATS, AND SHORTENING The most common residues were malathion, 0.115 ppm, and PCA, 0.050 ppm. Zinc, ranging from 3.6 to 8.4 ppm, was found in all 30 composites. Other residues were cadmium, lead, selenium, dieldrin, DDE, BHC, DDT, lindane. TDE, HCB, parathion, TCNB, PCNB, and captan SUGARS AND ADJUNCTS The most frequently found organochlorine residues were lindane, 0.008 ppm; BHC. 0.002 ppm; and PCP. 0.033 ppm. Thirty composites contained zinc ranging from 1.5 ppm to 6.4 ppm. Other residues included cadmium, lead, selenium, mercury, malathion, diazinon, PCB, and ortho- phenylphenol. BEVERAGES No organochlorine or organophosphates were found in any of the 30 beverage composites examined. Zinc, ranging from 0.3 to 1.3 ppm, was found in all 30 compos- ites. Other metallic residues were cadmium, lead, and selenium. Discussion Of the 360 composites examined, organochlorine residues were found in 172, or 48 percent. Corresponding findings from previous years were 52 percent, 1972-73; 54 percent, 1971-72; and 61.4 percent, 1970-71. Organophosphorus residues in the current reporting period were found in 100 composites, or 28 percent. Corresponding findings in 135 i previous years were 31. 27.8. and 21.4 percent, respec- tively. Carbaryl occurred in eight composites during this report- ing period: four of these findings were at trace levels. This is below the 12 findings in the previous reporting period. Orthophenyiphenol. which is detected by the method used for carbaryl, was found in five composites: two of these findings represented trace levels. Only one compos- ite revealed orthophenyiphenol in the previous reporting period. No chlorophenoxy acid herbicides appeared in this re- porting period. Pentachlorophenol. which is detected by the method used for chlorophenoxy acids, was found 10 times. Seven of these findings occurred in Composite XI, sugars and adjuncts. Analysis of the individual commodi- ties in this composite showed the source of the pentachlo- rophenols to be candy bars. Zinc appeared in all composites ranging fiom 0.1 to 35.5 ppm. The second most commonly occurring metal, cad- mium, was found in all 12 food classes. It occurred in 21 1 of the 360 composites examined at levels ranging from 0.01 to 0.31 ppm. Lead and selenium were also found m all 12 food classes. The highest of the 180 findings of lead was 1.30 ppm, and the highest of the 97 findings of selenium was 0.40 ppm. Mercury occurred in 34 compos- ites: meat, fish, and poultry contributed 30 of those findings. The highest mercury residue was 0.04 ppm. The individual commodity analysis for chlorinated, organ- ophosphate. and PCP residues on food groups I (dairy) and II (meats) that began last reporting period was continued on four samples of this period's 30 Total Diet samples. Composites 1 and II were selected because they had had the most significant occurrence of chlorinated residues in previous analyses. Individual commodity anal- ysis results are shown for dairy products in Table 5 and for meat, fish, and poultry in Table 6. Three items from the dairy group, namely, buttermilk, skim milk, and nonfat dry milk, and one item from the meat group, shrimp, are not shown because they contained no resi- dues. Recovery studies were conducted for all classes of chemi- cals sought throughout the entire year (Table 4). Kach recovery experiment consisted of a single determination for the unfortified food composite and a single determina- tion for Ihc fortified sample Because these were per- formed simultaneously, the fortification level occasionally was below the level present in the sample. In other cases, not enough recoveries were run to permit statistical evaluation. These data are not reported. At very low fiirtification levels, recoveries may range from 0 to 200 percent. As the fortification level is raised, however, recovery improves. Recovery data indicate that individual, low-level residues reported may vary from the so-called true value but the overall findings are useful in appraising the national residue picture. LITERATURE CITED (/) Association of Official Analytical Chemisl.s. 1975. Official Methods of Analysis, 12th ed. Washington, DC. Sections 2.'^. 012-25. 01. V (2) Association of Official Analytical Chemists. 1975. Official Methods of Analysis, 12th ed. Washington, DC. Sections 25.026-25.030. (i) Association of Official Analytical Chemists. 1975. Official Methods of Analysis, 12th ed. Washington, D.C. Sections 25.065-25.070. (4) Association of Official Analytical Chemists. 1975. Official Methods of Analysis, 12th ed. Washington, DC. Sections 25.103-25.105. (5) Association of Official Analytical Chemists. 1975. Official Methods of Analysis, 12th ed. Washington, DC. Sections 25.117-25.120. (6) Association of Official Analytical Chemists. 1975. Official Methods of Analysis, 12th ed. Washington, DC. Sections 25.143-25.147. (7) Corneliiissen. P. E. 1969. Pesticide residues in total diet samples (IV). Pestic. Monit. J. 2(4):140-152. (S) Corneliussen, P. E. 1970. Pesticide residues in total diet samples (V). Pestic. Monit. J. 4(.1):89- 105. (9) Corneliussen, P.E. 1972. Pesticide residues in total diet samples (VI). Pestic. Monit. J. 5(4):313-330. {10) Dnnjian. RE., 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. (//) Dugt>an. R E., H C Barn, and L. }. Johnson. 1966. Pesticide residues in total diet samples. Science 151 (3706): 101- 104. (/2) DugKan, R £.. H C. Barry, and L. Y. Johnson, 1967. Pesticide residues in total diet samples (II). Pestic. Monit, J. 1(2):2-12. (IS) Finocchiaro. J.M., and W. R. Benson. 1965. Thin-layer chromatographic determination of carbaryl (Sevin) in some foiKis J. Assoc. Offic. Anal. Chem. 48(4):7.36-738. [14) Food and Drni; Administration. 1971. Pesticide Analytical Manual, Vol. 1 and II. U.S. Department of Health, Education, and Welfare. (/,'«) Johnson. R.D., and D. D. Manske. 1975. Pesticide resi- dues in total diet samples (IX). Pestic. Monit. J 9(4):157- 169. (/6) Manske. D.D., and P. E. Corneliussen. 1974. Pesticide residues in total diet samples (VII). Pestic Monit. J. 8(2):1I(V124, (17) Manske. I) I) . and R. P. Johnson. 1975. Pesticide 136 Pesticides Monitoring Journal residues in total diet samples (VIII), Pestic. Monit. J. (19) Porter. M. L.. R. J. Gajan. and J. A. Burke. 1969. 9(2):94-105. Acetonitrile extraction and determination of carbaryl in fruits and vegetables. J. Assoc. Offic. Anal. Chem. 18) Martin, R.J.. and R. E. Duggan. 1968. Pesticide residues 52(1): 177-181. in total diet samples (III). Pestic. Monit. J. 1(4): 11-20. TABLE 1. Chemical residues found in food composites. August 1973-JuIy 1974 No. Positive Composites No CoMPosiTiES With Residues Chemical With Residues Reported As Trace ' Range, ppm ZINC 360 0 0,I-3!>,.S CADMIUM 211 0 001-0,31 LEAD 180 ■ 0 0.02-1.30 SELENIUM 97 34 0,0.1-0,40 DIELDRIN 93 17 0.0006-0.0330 Nol less than SS'/r of 1 .2.3.4. IO.IO-hexachloro-6.7-cpoxy-l .4.4a. 5.6.7.8.8a-oclahydro-1.4-endo-exo- 5 .8-dimethanonaphlhalene DDE I.I-dichloro-2.2-bis (p-chlorophenyll ethylene lall isomers are included in reponings) BHC 1.2.3.4.5.6-hexachlorocyclohexane. mixed isomers except gamma DDT I.I.I-tnchloro-2.2-bis (p-chlorophenyl) ethane (isomers other than p.p' also included in reponings) MALATHION diethylmercaptosuccinate. S-ester with 0.0-dimeIhyl phosphorodilhioalc LINDANE 1 .2.3.4.5.6-hexachlorocyclohexane. 99% or more gamma isomer DIAZINON 0.0-diethyl o-(2-isopropyl-6-methyl-4-pynmidyl) phosphorothioale HEPTACHLOR EPOXIDE i.4.5.6.7.8.8-heptachloro-2.3-cpoxy-3a.4.7.7a-tetrahydro-4.7-endo-methanoindan TDE I .l-dichloro-2.2-bis (p-chlorophenyl) ethane (isomers other than p.p' also included in reponings) MERCURY ARSENIC (As,0,) ENDOSULFAN 6.7.8.9.IO.IO-hexachloro-I.-S.5a.6.9.9a-hexahydro-6.9-methano-2.4.3-benzodioxathiepin 3-oxide (re- portjngs include isomers I. il. and the sulfate) HCB hexachloro benzene PARATHION 0.0-diethyl O-p-nitrophenyl phosphorothioate PCB (polychlonnated biphenyls) calculated as Aroclor with varied chlorine content CIPC isopropyl n-(3-chlorophenyl) carbamate PCA pentachloroaniline PCP pentachlorophenol CARBARYL l-naphthyl methyl carbamate TCNB l.2.4.5-(etrachloro-3-nitrobenzene METHOXYCHLOR 1 .1 . l-lnchloro-2.2-bis (p-methoxyphenyl) ethane METHYL PARATHION O.O-dimethyl O-p-nitrophenyl phosphorothioate PCNB pentachloronitrobenzene ETHION O.O.O'.O'-letraethyl S.S'-methylene bisphosphorodithioate ORTHOPHENYLPHENOL 2-hydroxydiphenyl LEPTOPHOS 0-(2.5-dichloro-4-bromophenyl)-0-melhylphenyl phosphorothioate 76 54 53 52 50 46 3 34 18 17 17 17 14 12 10 10 8 8 7 7 7 6 5 5 20 0,0006-0,0380 12 0 0004-0 0070 15 0,002-0,020 6 0,003-0, 115 18 00003-00120 20 0,0007-00270 19 0,0005-0,0040 23 0,001-0,005 17 0,01-0,04 2 0,03-0,60 10 0,003-0,012 8 0,0003-0,0070 10 0,003-0022 13 0050 0 0 005-0 467 1 0,004-0,050 0 0010-0033 4 0,05-0, 50 2 0,001-0,284 2 0 0O4-0OO9 6 0,008 4 0 002-0 005 3 0,003-0,012 2 0,05-020 1 0,013-0,090 {Continued next page) Vol. 10, No. 4, March 1977 137 TABLE I (cont'd.). Chemical residues found in food composites, August 1973— July 1974 Nn PnsfTi\t CoMPo^rTES No CoMPosiTiFS With RtsiDUFs With Rfsidufs Re win PERTHANE l.t-djchloro-2.2his (p-eihylphcnyll ethane BOTRAN 2.6-Jichlon>-4-nitriuniline TOXAPHENE chlonruicd camphene cuniainmg 67 lo 69^ chlorine DCPAiDACTHALf 2,3.5.fc-lclrachloroierephthalic acid dimethyl ester DICOFOHKEI THANEt 4.4'-dichloro-n-(inchloromethyl» bcnzhydrol Al.DRlN Not less than 95'^r of I .:.3.4.10.lO-he\achloro- 1.4.4a.-S.8.8a-hcxahydro-l.4-endo-exo-5.»-dimelhan- onaphihalene CAPTAN N-((inchloromethyl)ihio] -4-cycIohexene-I.2-dicarbo«imidc CH LOR DANE iTcchnicah Cis and trans isomers of l.2.4.5.6.7.8.8-oclachloro-:^a.4.7.7a-teirahydro-4.7-methanoin- dane plus approximately 50^ related compounds HKFTAt HLOR l,4,5,6.7.8.8-heptak;hloro-3a.4.7.7a-tetrdhydro-4.7-endo-methanoindcnc PHOSALONK O.O-dicthyl S-(6Lhlon>-2-t»xohenzoxa2olin-3-yl) methyl phosphorodithioate RONNEL O.O-dimcthvl (()-2.4.5-irichlorophenyl) phosphorothioale NITROFEN 2.4-dichlorophcnyl-p-nitrophenyl ether \'t Tbacf ' RAN(,t . PPM 0 O.OJO-2.28 0 0006-0 067 2 0 163 0 0003-0013 1 0010 0 0001 0 0 178 1 T 0 0004 0 0 171 0 0001 0 0039 ' Chemicals delectable hy the specific analytical methodology can be connrmcd qualitatively but are not quantifiable in concentrations below the limit of quantitation. Limit of quanlitalion varies Arsenic Kndosulfan H( B P.irjlhion P( B (IPC PC A P( P Carbary I TCNB Mcthoxychlor Methyl Puraihion PCNB Ethion Onhuphenylphcnoi Ixptophos Ptrihiinc* Bolran' liixuphcne DC PA 30 30 30 30 30 30 30 30 4 21 29 29 28 8 24 23 4 9 II 13 20 30 tt 26 10 30 30 s 3 s 3 ■> 29 30 9 3 17 27 30 9 4 7 •> 29 27 1 6 10 29 1 30 » 1 4 1 30 .30 30 24 12 6 8 9 5 3 3 2 3 2 4 9 4 16 3 30 III K II (Conliniifd iifxi puna 138 Pesticides Monitoring Journal TABLE 2 (cont'd). Occurrence frequency of chemical residues hy food class, August 1973 — July 1974 Fm)0 Cl ASS' Nl MHhK (11 ()( ( I RRl NC hS XI XII Dicofo) 2 Aldnn I Cap tan 1 Chlordane I Heplachlor 1 Phosalonc 1 Ronnel 1 Nilrofen 1 ' See Table 3 for descriplions of food classes. Table 3. Levels of chemical residues found — by food class in SO composites. August 1973 — July 1974 ResrouES. ppm I. Dairy Products ZINC Average 5.5 Positive Composiles Total Number 30 Number Reponed as Trace 0 Range 4.0-8.6 BHC Aveiage 0.0008 Positive Composiles Total Number 29 Number Reponed as Trace 2 Range 0,0004-0 0030 DIELDRIN Average 00016 Positive Composites Total Number 29 Number Reported as Trace 3 Range 00006-0 0050 DDE Average 0.0015 Positive Composites Total Number 27 Number Reported as Trace 9 Range 0.0006-00100 HEPTACHLOR EPOXIDE Average 0.0004 Positive Composites Total Number T> Number Reported as Trace 10 Range 0 (KKIS-O 0020 DDT Average 0.0003 Positive Composites Total Number 10 Number Reported as Trace 8 Range 0 003-0 006 LINDANE Average 0.0002 Positive Composiles Total Number 10 Number Reported as Trace 6 Range 0.0003-0.0028 SELENIUM Average T Positive Composites Total Number 10 Number Reponed as Trace 9 Range 0.07 TDE Average T Positive Composites Total Number 8 Number Reponed as Trace 8 Range T METHOXYCHLOR Average 0.001 Positive Composiles Total Number 7 Number Reponed as Trace 2 Range 0.004-0.03 CADMIUM Average 0.01 Positive Composites Total Number 4 Number Reponed as Trace 0 Range 001-0 14 LEAD Average 0.01 Positive Composites Total Number 4 Number Rept>rted as Trace 0 Range 0 04-0 0* HCB Average T Positive Composites Total Number 3 Number Reponed as Trace 1 Range 0.0003-0.0006 PCP Average T Positive Composites Total Number 1 Number Reponed as Trace 0 Range 0.010 II. MtAT. Fish. And Poultry DDE Average 0.0085 Positive Composites Total Number 30 Number Reponed as Trace 0 Range 0.002-0,038 DIELDRIN Average 0,0056 Positive Composiles Total Number 30 Number Reponed as Trace 0 Range 0.002-O.033 TDE Average 0.002 Positive Composites Total Number 25 Number Reponed as Trace II Range 0.001-0.005 HEPTACHLOR EPOXIDE Average 0.001 Positive Composites Total Number 22 Number Reponed as Trace 8 Range 000I-O0O4 (Continued next page) Vol. 10, No. 4, March 1977 139 TABLE 3 (cont'd.). Levels of chemical residues found— by food class in 30 composites, August 1973-^uly 1974 Residues, ppm II Mi-M. KiSH. Asn Pol I iB^ MERCURY Aven^ 001 Rjsitivc Compmtlcs ToUl Number 30 Number Reported as Trace 1) Range 001-0 04 SELENIUM Average o:o I\)si(ivc Composilcs Tolal Number 30 Number Reponed as Trace 0 Range 0 10-0 40 ZINC Average 28.0 E\)sillve Composites Total Number 30 Number Reptincd as Trace 0 Range 21.0-35.5 DDT Average 0006 Posibve Composites Total Number 29 Number Reponed as Trace 0 Range 0 002-0 020 BHC Average OOOII Posibve Composites ToUl Number 27 Number Reported as Trace 1 Range 00004-0 0070 DIAZINON Average 00001 Positive Composites Tolal Number 6 Number Reported as Trace 3 Range 0 0007-OOOIO HCB Average T Posiove Composites Tolal Number 4 Number Reported as Trace 2 Range 0 0003-0 0006 CADMIUM Average 0 02 Positive Composites Total Number 21 Number Reported as Trace 0 Range 0 01-0 06 LINDANE Average 00010 Positive Composites Total Number 19 Number Reponed as Trace 3 Range 0 0004-0 0120 PCB Average 0 002 Positive Composites Total Number 13 Number Reponed as Trace 12 Range 0 050 ARSENIC Average 006 Positive Composites Total Number 10 Number Reponed as Trace 1 Range 0 03-0 6 LEAD Average 0 02 Positive Composites Total Number 9 Number Reponed as Trace 0 Range 0,03-0 10 ETHION Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range flOOl RONNEL Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0 0010 III Grain And Cereal Products MALATHION Average 0020 Positive Composites Total Number 30 Number Reported as Trace 0 Range 0 004-0 054 SELENIUM Average 0 24 Positive Composites Total Number 30 Number Reported as Trace 0 Range 0 10-0 40 ZINC Average 8.1 Positive Composites Total Number 30 Number Reponed as Trace 0 Range 5.9-10 1 CADMIUM Average 0.03 Positive Composites Total Number 29 Number Reported as Trace 0 Range 0 02-0 05 DDT Average T Positive Composiles Tolal Number 1 Number Reported as Trace 1 Range T DIAZINON Average 0 002 Positive Comper Reponed as Trace 5 Range T DIAZINON Average OOOI Positive Composites Total Number 3 Number Reported as Trace 2 Range 0.027 HEPTACHLOR EPOXIDE Average T Positive Composites Total Number 2 Number Reponed as Trace 1 Range 0002 DDE Average 0.001 Positive Composites Total Number 9 Number Reponed as Trace 3 Range 0 002-0.01: DIELDRIN Average 0.001 Positive Composites Total Number 9 Number Reponed as Trace 3 Range 0 002-0 007 DDT Average 0.001 Positive Composites Total Number 8 Number Reponed as Trace 4 Range 0 00.5-0 008 ENDOSULFAN Average 0.001 Positive Composites Total Number 6 Number Reponed as Trace 3 Range 0 005-0 016 TDE Average T Positive Composites Total Number 2 Number Reponed as Trace 2 Range T HCB Average T Positive Composites Total Number 1 Number Reponed as Trace 0 Range 0.004 MERCURY Average T Positive Composites Total Number 1 Number Reponed as Trace 1 Range T PCNB Average Posiiive Composites Total Number Number Reported as Trace Range I 0 0.005 V Leafy Vegetables ZINC Average 2.4 Positive Composites Total Number 30 Number Reponed as Trace 0 Range 0.8-4.1 CADMIUM Average 0.04 Positive Composites Total Number 28 Number Reponed as Trace 0 Range 001-0 14 PARATHION Average 0.002 Posmve Composites Total Number M Number Reponed as Trace 6 Range 0.004-0.022 LEAD Average 0.10 Positive Composites Total Number 20 Number Reponed as Trace 0 Range 0.03-04 DIAZINON Average 0.002 Positive Composites Total Number 17 Number Reponed as Trace _s Range 0001-00 SELENIUM Average T Positive Composites Total Number 3 Number Reponed as Trace 3 Range T (Continued next page) Vol. 10, No. 4, March 1977 141 TABLE 3 (cont'd.). Levels of chemical residues found— by Jooti class in 30 composites. August 1973— July 1974 Residues, ppm V L^A^•^ Vtot lABL ts ENDOSUl FAN Average 0.001 Pt>siti*e Composiles Touil Numher 8 Number Rcponed as Trace 4 Riinge 0 no Mini: METHYL PARATHION Average T Positive Composites Total Number 7 Number Reported as Trace 6 Range 0.008 DDE Average T Positive Composites Total Number 4 Number Rep^irted as Trace 1 Range OOOJ-OOOS MALATHION Average T Positive Composites Total Number 4 Number Repi^rted as Trace 2 R*inge 0.00.">-0.006 DIELDRIN Average T Positive Composites lotal Number 3 Number Reported as Trace 3 Range T PERTH ANE Average Positive Comptisiies Tola! Number Number Reported as Trace Range 0.13 3 0 0.03-2.; DC PA Average 0.001 Positive Composites Total Number 2 Number Reported as Trace 0 Range 0.003-0,013 BOTRAN Average T Positive Composites Total Number 1 Number Reported as Trace n Range 0 008 DDT Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.015 LINDANE Average T Positive Composites Total Number 1 Number Reponed as Trace 1 Range T MERCURY Average T Positive Composites Total Number 1 Number Reponed as Trace 1 Range T NITROFEN Average 0.001 Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.039 VI. Legume Vegetables LEAD Average Positive Composites Total Number Number Reponed as Trace Range ZINC Average Pbsitivc Composites Total Number Number Reported as Trace Range CADMIUM Average Positive Composites Total Number Number Rcpi>rted as Trace Range 0.28 30 0 0,10-1,30 8.5 30 0 5,0-14,5 0 O.OI-O.IO SELENIUM Average T Positive Composites Total Number 5 Number Reported as Trace 4 Range 005 CARBARYL Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.5 HCB Average T Positive Composites Total Number 1 Number Reported as Trace 1 Range T VII. Root Vegetables ZINC Average Kisitivc Comptmtcs Total Number Number Reponed as Trace Range t ADMIUM Average Pt>Mtivc Composites Total Number Number Reponed as Trace Range LEAD Average Positive Ctimpovites Total Numbei Number Reponed a\ Trace Rjngc 2.8 30 0 1.4-5.0 0.03 24 0 0.01-4)31 0 0.03-41.30 DDE Average T Positive Composites Total Number 7 Numbei Reponed as Trace 4 Range 0-00.3-fl.no LINDANE Average T Positive Composites Total Number 3 Number Reponed as I race 1 Range 0(X).3-0.00 PARATHION Average T Positive Composites Total Numbei 3 Numbei Reponed as Trace 3 Range T (Continued next page) 142 Pesticides Monitoring Journal TABLE 3 (cont'd.). Levels of chemical residues found — by food class in 30 composites, August 1973 — July 1974 Residues, ppm VH. Rooi Vk.i iahi is SELENIUM Average T Positive Composiles Total Number 3 Number Reponed as Trace 3 Range T ARSENIC Average T Positive Composites Total Number 2 Number Reported as Trace 0 Range 0 03-0.1 DIAZINON Average T Positive Composites Total Number 1 Number Reported as Trace 1 Range T HCB Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.002 PCP Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.01 TDE Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.004 VIII. Garden Fruits ZINC Average 3.0 Positive Composites Total Number 30 Number Reported as Trace 0 Range 2 M8 LEAD Average 0.14 Positive Composites Total Number 26 Number Reponed as Trace 0 Range 0.06-0.60 CADMIUM Average 0.02 Positive Composites Total Number 23 Number Reported as Trace 0 Range 0,01-0,10 DIAZINON Average T Positive Composites Total Number 5 Number Reponed as Trace 2 Range 0,002-0,003 LEPTOPHOS Average 0,005 Positive Composites Total Number 5 Number Reported as Trace 1 Range 0,013-0,090 ENDOSULFAN Average T Positive Composites Total Number 3 Number Reported as Trace 3 Range T TOXAPHENE Average 0.0O5 Positive Composites Total Number 3 Number Reptmed as Trace 2 Range 0.163 DDE Average T Positive Composites Total Number 2 Number Reported as Trace 2 Range T SELENIUM Average T Positive Composites Total Number 2 Number Reported as Trace 2 Range T DIELDRIN Average 0.002 Positive Composites Total Number 17 Number Reported as Trace 4 Range 0002-001 BHC Average 0.0003 Positive Composites Total Number 6 Number Reported as Trace 3 Range 0.0009-0.00 LINDANE Average T Positive Composites Total Number 6 Number Reported as Trace 4 Range 0,002-0,004 ARSENIC Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.04 CARBARYL Average T Positive Composites Total Number 1 Number Reponed as Trace 1 Range T DDT Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.01 1 PARATHION Average T Positive Composites Total Number 1 Number Reported as Trace 0 Range 0.006 PERTHANE Average 0.001 Positive Composites Total Number 1 Number Reponed as Trace 0 Range 0.031 (Continued next page) Vol. 10, No. 4, March 1977 143 TABLE 3 (cont'd.). Levels of chemical residues found— -by food class in 30 composites, August 1973— July 1974 Residues, ppm IX. Fruits ZINC Average Rosilive Composilcs Total Number Number Rep*»rteU as Trace Rartge CARBARYL Average Rjsilivc Comp«^iIes Total Number Number Rcponcd as Irace Range ARSENIC Average Positive Composites Total Number Number Reported as Trace Range ETHION Average Positive Composites Total Number Number Reported as Trace Range ORTHOPHENYLPHENOL Average Positive Composites Total Number Number Reported as Trace Range CADMIUM Average Positive Composites Total Number Number Reported as Trace Range BOTRAN Average Positive Composites Iota! Number Number Reported as Trace Range DICOFOL Average Positive Composites Tola! Number Number Reported as Trace Range I.I 30 0 0.1-3.0 0.01 6 3 O.O.S-0 10 0.02 I 0 03-0 20 O.OOI 5 3 0005^012 0 02 4 I 0 05-0 20 T 3 0 0 01-0 06 0.002 0 (I iK)f^l 067 T 1 0 01 LEAD Average Positive Composites Total Number Number Reported as Trace Range DIELDRIN Average Positive Composites Total Number Number Reported as Trace Range ALDRIN Average Positive Composites Total Number Number Reported as Trace Range DIAZINON Average Positive Composites Total Number Number Reported as Trace Range MERCURY Average Positive Composites Total Number Number Reported as Trace Range PARATHION Average Positive Composites Total Number Number Reported as Trace Range PHOSALONE Average Positive Composites Total Number Number Reported as Trace Range SELENIUM Average Positive Composites Total Number Number Reported as Trace Range 0.10 23 0 0.04-0,44 0 0,001 I 0, 0.003 I 0 Ot(03 0.006 I 0 0 171 X Oils. Fats. And Shortening ZINC Average Positive Composites Total Number Number Rcpt>rtcd as Trace Range CADMILlM Average Positive Composites Total Number Number Reported as Trace Range MALATHION Average Positive Composites Tola! Number Number Reported as Trace Range PC A Average Pk>\ilive ( omp«)MicN lolal Number Number Rep*Mtcd as liacc Range 5.1 30 0 3 6-8.4 002 24 0 0 01-0 07 0.01.5 16 4 001 1-0 IIS 0 DIM 10 I (HH)4-0 050 BHC Average Positive Composites Total Number Number Reported as Trace Range DDT Average Positive Composites lotal Number Number Reported as Trace Range DIELDRIN Average Positive Composites Total Number Number Reported as Trace Range SI LHNIL'M Average l*osiiive Composites 1 otal Number Number Repi>rled as Trace Range T 4 3 0 003 0 001 T 3 0tK)4 T 1 0,05 (Continued next pane) 144 Pesticides Moniioring Journal TABLE 3 (cont'd.). Levels of chemical residues found — by food class in 30 composites. August 1973 — July 1974 Residues, ppm X Oils. Fats. And Shortening LEAD Average 0.03 Positive Composites Total Number 8 Number Reported as Trace 0 Range 0.03-0,40 HCB Average T Positive Composites Total Number 7 Number Reported as Trace 4 Range 0,001-0.007 PCNB Average T Positive Composites Total Number 6 Number Reported as Trace 4 Range 0.0O2-O.0O5 TDE Average Positive Composites Total Number Number Reported as Trace Range CAPTAN Average Positive Composites Total Number Number Reported as Trace Range 2 2 T 0.006 I 0 0.178 DDE Average T Positive Composites Total Number 2 Number Reported as Trace 1 Range 0.004 LINDANE Average T Positive Composites Total Number 2 Number Reported as Trace I Range 0.002 TCNB Average T Positive Composites Total Number 2 Number Reported as Trace 2 Range T PARATHION Average T Positive Composites Total Number 1 Number Reported as Trace I Range T XI, Sugars And Adjuncts ZINC Average 3.0 Positive Composites Total Number 30 Number Reported as Trace 0 Range 1.5-6.4 CADMIUM Average 0.01 Positive Composites Total Number 12 Number Reported as Trace 0 Range 001-0 09 LINDANE Average T Positive Composites Total Number II Number Reported as Trace 2 Range 0OOI-O.0O3 BHC Average 0.0003 Positive Composites Total Number 9 Number Reported as Trace 3 Range 0,0008-0.0020 DIAZINON Average T Postbve Composites Total Number 1 Number Reported as Trace 0 Range 0.002 MERCURY Average T Positive Composites Total Number 1 Number Reported as Trace 1 Range T LEAD Average 0.03 Positive Composites Total Number 9 Number Reported as Trace 0 Range 0.06-0.2 PCP Average 0.004 Positive Composites Total Number 7 Number Reported as Trace 0 Range 0.010-0.03 MALATHION Average 0.002 Positive Composites Total Number 3 Number Reported as Trace 0 Range 0.003-0 04 SELENIUM Average T Positive Composites Total Number 3 Number Reported as Trace 3 Range T ORTHOPHENYLPHENOL Average T Positive Composites Total Number 1 Number Reported as Trace 1 Range T PCB Average T Positive Composites Total Number 1 Number Reported as Trace 1 Range T XII Beverages ZINC Average 0.6 Positive Composites Total Number 30 Number Reported as Trace 0 Range 0.3- LEAD Average 0.01 Positive Composites Total Number 5 Number Reponed as Trace 0 Range 0,03-0.1 (Continued next page) Vol. 10, No. 4, March 1977 145 TABLE 3 (cont'd.). Levels of chemical residues found — by food class in 30 composites. August l973^July 1974 Residues, ppm XII BE^ER'kf.LS CADMIUM Average T Posiuve Composilc\ ToUl Number 6 Number Reported as Trace 0 Range 001-003 SELENIUM Average Positive Composites Total Number Number Reported as Trace Range NOTE: T = trace see Table I footnote I TABLE 4. Recovery data on residues found in total diet samples. August 1973— July 1974 REStDUE Type or Food COMF^SITES Spike Levei . PPM Range oe Blank Level, ppm ' Range of Total FoL'ND. ppm ' No. of Recovery Studies Cadmium Fatty Nonfatty OJO 0.10 0-0.042 (0.1 161 0-0.139 (0023) 0 075-0 160 in III) 0 03 1-0 2.36 (0 119) 30 60 Fatty Nonfatty 020 0.20 0-0 088 (0.035) 0-0.896 (0 200) 0 122-0 316 (0 219) O022-) 512 (0 2871 30 60 SeleniL Fatly Nonfatty 020 0.20 0-0.28 (0.0887) 0-0.40 (0.040) 0 10 -0 50 (0 2431 0 13 -0 58 (02121 30 60 Zinc Fatty Nonfatty Fatty 5.0 5.0 25.0 3 78-10.72 (5 75) 0.35-12.7 (3.67) 24.0-35.5 (294) 8.22 -12.84 (10 6) 4 94 -16 5 (8 62) 45 I -63 6 (52.9) 19 60 Mercury Fatly Nonfatty Falty Nonfatty 0.06 0.06 0.03 0.03 0-0030 (0007) 0-0 008 |0(K)3) 0-0 00 1 T (K) (X)3 10 001) 0 039-0 105 10 067) 0 048-0 078 (0 0621 0 ()27-0 03-3 (0 0301 0 028-0 041 (0 035) 6 16 Carbaryl Nonfatty o: 0-0 20 (0.18) 60 Orthophcnylphenol Nonfatty 0.4 0-0.40 (0.29) Fatty Nonfatty 0.02 0-02 0-0019 (0 007) 0-0 023 10 012) 7 14 2.4-DB Fatty Nonfatty 002 0.02 0-0026 10 012) 0 004-0 032 (0 017) 2. 4.D Fatty Nonfatty 002 002 0-0 017 (0011) 0-0020 (0.016) 6 14 Fatly Nonfatty 0.02 002 0 004-0 02: (0 013) 0-0 025 (0015) Methyl Panthion Falty Nonfatty 0 005 0.005 0-0.015 (00002) (l-ll(H)34 1(1 oo:'^! 0-0 tK)50 (0(10331 CIPC Fatty Nonfatty O.OS 0.05 0,027-0 046 10035) 0.033-0 059 (0.047) 5 10 (Continued next page) 146 Pesticides Monitoring Journal TABLE 4 (cont'd.). Recovery data on residues found in total diet samples, August 1973— July 1974 Type of Food Composites Spike Ltvn . PPM RAN(.f OF Blank Lj veu PPM ' RaN(.i or T(HAl Found, PPM ' No. OF Recovery Studies Daclhal Fatly Nonfatly 0.005 0005 00023-0 Q050 1000361 00033-OOOM (000.501 5 10 Phcsalone Fally Nonfatly 0.05 0.03 0-0.1706 (0.017) 0 022-0 053 (0.038) 0.03Ofl.2l2 (0067) 5 10 PCNB Fatty Nonfatly 0.003 0003 0-0 0041 (00009) 0 00OI8-OOO.56 (0 0028) 00022-0 0034 (0 0028) ' Numbers in parentheses represent average residue levels. TABLE 5. Pesticide residues in individual commodities of dairy composite of four market basket samples, August 1973 — July 1974 ' COMI HODITY ' Whole Fluid Evaporated Cottage Processed Natural Residue FOUN D Milk (4) MILK (4) Ice Cream (4) Cheese (4) Cheese (4) Cheese (4) Butter (4) Uf Milk (3) Resi dues . ppm BHC Times Found 3 3 3 -> 4 4 4 ppm Range T T-0 002 T-O.OOl T-0 002 0.003-0 008 0.004-0016 0 009-0 021 DDE Times Found 4 2 3 3 4 4 4 1 ppm Range T-0.003 T T-O.OlO T-0 002 T-0 045 T-00.50 0006-0 042 ooo: DIELDRIN Times Found 2 3 4 2 3 4 4 ppm Range T-0 002 0002-0 003 T-0004 T 0003-0018 0005-0 009 0016-0 050 HEPTACHLOR EPOXI IDE Times Found 2 2 1 3 4 3 ppm Range T T-OOOl T T-0 003 T-0 008 0-003-0 011 TDE Times Found 1 1 2 ppm Range T 0005 T DDT Times Found 1 2 3 2 ppm Range T 0005-0 007 TO 012 TO 009 METHOXYCHLOR Times Found 1 -> ■) 1 1 ppm Range 0.027 TOO 15 0005-0038 0076 0 154 PCB Times Found 1 ppm Range T LINDANE Times Found 1 1 1 ppm Range 0001 0003 0002 ■ Buttemnilk. skim milk, and nonfat dry milk not shown because no residues were found ■ Numbers in parentheses are numbers of replicates. Vol. 10, No. 4, March 1977 147 ^ ■a o bU -J < ^ a Z J ? < > oS ? X 5 < 0 OJ oc *- !« ^ £ < T s a UJ ^ uj oe W lU OQ > 2 ____ ^ it i/i z !^ 2 ^ x« u. >• H I ^ 5 u . z ^ I ^ ; 2 0 ^2 o «5 = z Z K ^ L 0. Ll. - ul Q ? z QC ^ u z U ^ z c o < CQ ^ ^ "^ ce i£ £§ U ? - 0 Z X ^ Om •- ^ < -. 0 M ■ o — o oil S — O r--, O 8 § 8 S 8 - d — d = 88 ! &>■ = - DC C ^ I Sqi- Q G. U (- E r i, ^IJ ,41 ^-U CJoj '7tl c C 2 z 148 Pesticides Monitoring Journal RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Organochlorine Pesticide and Polxchlorinated Biphenxl Residues in Selected Fauna from a New Jersey Salt Marsh— 1967 vs. 1973^ Erwin E. Klaas^ and Andre A. Belisle' ABSTRACT More than a half milhon pounds of DDT were applied to control mosquitoes in salt marsh estuaries of Cape May County, New Jersey, from 1946 to 1966. The use of DDT was discontinued in the County after 1966. In 1967. mean concen- trations of DDT and metabolites ranged from 0.63 to 9.05 ppm in aquatic fauna, but by 1973 mean residue levels had de- creased 84 to 99 percent among nine species. DDE was still present at reduced levels in nearly all samples in 1973, hut other DDT isomers had mostly disappeared. Dieldrin was detected only in clapper rails, and residue levels decreased during the period. Mean concentrations of PCB's increqsed in the clapper rail, remained the same in the fiddler crab and mud snail, and decreased in the sheepshead minnow, mummichog. striped killifish, and salt marsh snail. Small amounts of mirex, toxaphene, cis-chlordane (and/or Irzns-nonachlor), oxychlordane, and HCB were detected in a few specimens. Introduction A narrow band of salt marshes with numerous estuaries and well-defined drainage systems extends along the eastern and southern coast of New Jersey. These marshes are important nursery areas for estuarine fauna, but because of their location near the large metropolitan areas of New York City. Philadelphia, and Baltimore, they are affected by real estate development and environmental pollution. Cape May County, just southwest of Atlantic City, has over 50.000 acres of salt marsh bordering the Atlantic Ocean and Delaware Bay. This seashore County has been a popular summer resort for a century or more. After World War II. more people than ever before were attracted to the area and State and local governments ' Patuxeni Wildlife Research Center. Fish and Wildlife Service. US Department of Interior, Laurel. Md, 30811 -Iowa Cooperative Wildlife Research Unit. Iowa State University. Ames. Iowa tried to reduce the mosquito population to provide a more habitable environment for residents and vacationers, and to control the spread of mosquito-borne diseases. DDT was first used in Cape May County in 1946 and was used for mosquito control until 1966. when it was re- placed by organophosphates. chiefly malathion, fenthion (Baytex), and more recently. Abate. In September 1%7, Hurricane Doria hit the coast of New Jersey, causing high storm tides and killing clapper rails. Several hundred birds were found dead along causeways in Cape May County, and an estimated 2,000 or more died in the marshes. Biologists at the Patuxent Wildlife Research Center, U.S. Department of Interior — Fish and Wildlife Service, obtained 43 dead rails from six localities (Fig. I). Concurrently, fish and invertebrates were col- lected from these locations and were frozen and stored. Sampling was repeated at the same localities in 1973. The two groups of samples collected 7 years apart, the first having been a year after use of DDT was discontinued in Cape May County, were then analyzed by the same procedures. This paper reports residue levels of organochlorine pesti- cides and polychlorinated biphenyls (PCB's) detected in these samples and compares findings of 1%7 and 1973. The history of pesticide spraying for mosquito control in Cape May County is reviewed as it pertains to residue levels. History of Pesticide Use for Mosquito Control The history of pesticide use on mosquitoes in Cape May County was obtained from the Proceedings of Annual Meetings of the New Jersey State Mosquito Extermina- tion Association (9, 13-15. 17, 18, 21) and from unpub- lished daily work records in the files of the Cape May County Extermination Commission. Vol. 10, No. 4, March 1977 149 CAPE MAY COUNTY NEW JERSEY 9^ COLLECTING aiTBS Tape may city SALT MARSHES FIGURE I. Aerial spra\ zones and fauna collection sites in salt marshes oj Cape May County, New Jersey Ditching, draining, and other methods of water control were the principal means of limiting mosquitoes in Cape May County before 1946. Small quantities of fuel oil and pyrethrum were applied as larvacides. In 1946. the County acquired an aert)sol fog unit for control of adult mosqui- toes. This machine was used to apply a 5 percent DDT emulsion in fuel oil along the streets of resort communi- ties bordering the Atlantic Ocean in the summer of 1946 il8). The amounts of pesticide used in 1946-47 are un- known. In 1948 the mosquito control program included fog. mist, and spray work with DDT. TDE. and pyreth- rum; total quantity used was 19,450 gallons. The marshes just west of Sea isle City received an e.\penmental aerial application June 15. 1948(2/1 By 1949. DDT was the prmcipul chemical used for mosquito control in New Jersey (9). it was usually applied as a 5 percent emulsion in oil or as a wettable powder Kor adult mosquito control. DDT was applied at 0.1 lb/acre; as a larvacide it was applied in early spring at 1-2 lb/acre in restricted areas. Statewide, oil was second in importance to DDT. and pyrethrum larvacide was third. The amount of DDi used in Cape May County in 1949 had risen tt) 25.465 gallons of emulsion applied from the ground. 1.050 gallons from the air. and 6.000 pounds of DDT dust applied from the ground (17). Neither oil nor pyrethrum was used extensively after 1946. Aerial spraying, supported by State funds, was begun on a wide scale in 1949. Areas to be sprayed included a band 2.000 feet wide which began at Cape May Point and continued west of the Atlantic seashore resort towns up to and including Ocean City. A similar band extended just east of the Garden State Parkway. Another band ex- tended along the shore of Delaware Bay (Fig. 1). These bands were divided into 29 zones of known acreage to facilitate aerial application. A wide perimeter around the inland town of Woodbine was sprayed regularly from the air. Aerial sprays were applied from heights of 50-75 feet at a rate of O.I lb of technical DDT in 1 quart of petroleum solvent per acre of ground surface (13-15). These formula- tion and application rates for aerial and most ground spraying of DDT were continued through 1966. DDT emulsion was sometimes applied as a larvacide in re- stricted areas at rates of 0.3 lb/acre (13). About half of all DDT applied between 1950 and 1966 was sprayed from the air; the remainder was dispersed from the ground through aerosol fog machines, truck- and tractor-mounted tank sprayers, and hand sprayers. The total amount of active DDT applied in Cape May County from 1949 to 1966. assuming the formulation rate (0.4 lb/gal) remained the same for all years, was estimated to be 614.970 lb. Yearly amounts increased steadily from 1.926 lb in 1949 to a high of 58.515 lb in 1963 (Table 1). Malathion and fenthion began to replace DDT in 1964 and by 1966 DDT use had declined to 33.186 lb. About 8-10 percent of all DDT applied after 1955 was in dust or pellet forms. Pellets contained either 5 or 10 percent active DDT and were usually applied at rates of 10 or 20 lb/acre (1.0 lb DDT), in the early I960's pellets were used extensively as a larvacide. After 1966. malathion became the principal chemical for mosquito control in Cape May County, although small amounts had been used earlier. Fenthion was also used in pellet form in some areas. Use of malathion and fenthion was essentially discontinued about 1971. Abate was first used in 1969. and by 1973 it was the only chemical in widespread use for mosquito control. Table 2 summarizes the amount of DDT applied 1950-66 as emulsion to each of the six zones from which biotic samples were collected (Fig. 1). These zones, named after the largest nearby town, are Ocean City. Sea isle City, Avalon, I'alermo. Ocean View, and Swainton; they cor- respond to 6 of the 21 aerial spray zones designated on daily wiirk records and maps of the County Mosquito l-^xtermination Commission. The remaining 15 zones have been grouped into Atlantic Shore and Bay Shore areas for the puipose of this summars . I'he Atlantic Shore area includes five aerial spray zones along the Atlantic shore from Swainton and Stone Harbor to Cape Mas and one 150 PiSTICIDKS MONITORINC. JOURNAL TABLE 1. Active DDT applied each year as emulsion. pellets, or dust in Cape May County. New Jersey, by County Mosquito Extermination Commission — 1949-66' Year Pounds V(AR Pounds 1949 1.926 1959 43.897 19'iO 8.861 1960 53,658 I9?l 18.189 1961 51.206 1952 19.587 1962 45,920 1953 22.853 1963 58.515 1954 26.117 1964 56,634 1955 24,267 1'65 45.941 1956 29.018 l'-66 33.186 1957 37.531 195« 37.654 T )TA1. 614.970 Total area sprayed was 46.638 acres. TABLE 2. Active DDT applied as emulsion in different areas of Cape May County, New Jersey — 1950-66 Zone Acres Pounds Pounds/ Acre Ocean Cily 3.000 57.103 19 0 Sea Isle Ciiv 1,500 34.4S6 23,(1 Avalon 2,900 43,582 15 0 Palermo 2,100 14.510 69 Ocean View 1,180 7,%1 68 Swam ton 960 4.854 5 1 Atlantic Shore 13.631 192.676 14,1 Bay Shore 21.367 208.975 98 Total 46.6.38 564.147 12 1 zone northwest of Palermo. The Bay Shore area includes nine aerial spray zones on the Delaware Bay shore. WootJhine. and most of the rural areas, roads, and municipalities west of the Garden State Parkway. The Atlantic Shore and Bay Shore areas are included in this summary to complete the spraying data for the entire County. It is possible that residues were transported to the six sampling zones from the Atlantic Shore or Bay Shore areas by wind drift, tidal action, and water shed runoff. Daily work records of aerial and ground applications included the spray site and the amount of emulsion dispersed at each location. Generally, each spraying location itemized on the work sheets could be assigned to one of the eight zones listed in Table 2 and shown in Figure 1. Quantity of DDT applied in pellet form is not included in Table 2 because exact locations where pellets were used could not always be determined. Because most DDT used ir operations was dispersed in rough estimates of the total lb/; the 17-year period could be r varied from 5.1 lb/acre in the acre at Sea Isle City with a i Spraying was generally hea\ ocean. Annually, the rate of County averaged 0.7 lb/acre a^ in 1950 to I.I lb/acre in 1963. both aerial and ground Mnes of known acreage, ere applied in each zone in lade (Table 2). The rates Swainton zone to 23 0 lb/ lean of 12.1 for all zones, ier in zones nearest the application for the entire id ranged from 0.2 lb/acre This brief history of pesticide use in Cape May County Vol. 10, No. 4, March 1977 does not include pesticides applied on private lawns or gardens, agriculture lands, golf courses, or military bases. Truck crops are the chief agricultural products and most of the cropland is in the western part of the County. More extensive areas of cropland are found in counties to the west and north, and chemicals applied there may have eventually entered estuanes in Cape May County through runoff. Military bases cooperated with the County's mos- quito program by furnishing some chemicals to be sprayed on military land, but it is not known how extensively these authorities may have sprayed on their own. Some larger communities along the Atlantic shore owned aerosol fog machines and applied limited amounts of chemicals. Undoubtedly, the County Mosquito Exter- mination Commission was the largest user of pesticides in Cape May County and dispersed the bulk of organochlo- rines entering the local environment during 1946-66. Sample Collection and Preparation Biotic samples were obtained at six of the spraying zones in Cape May County marshes in 1967 and 1973 (Fig. I) during September 19-23. Collecting points were Ocean City: north side of New Jersey State Highway 23, and 0.5 mile west of State Highway 56; Sea Isle City: west of Highway 19 at the end of 30th Street: Avalon: south side of Highway I. and I mile west of Highway 30: Palermo: east side of Garden State Parkway. 2 miles south of Highway 23; Ocean View: south side of Highway 25, 0.2 mile east of Garden State Parkway; Swainton: south side of Highway I, 0.5 mile east of Garden State Parkway, Scientific and vernacular names of animal species in the study are listed in Table 3, Scientific and vernacular names of plants appear in the text. Cape May County marshes are typical cordgrass {Spar- tina alternifloral salt marshes. The taller (4-6 ft) dense saltmarsh cordgrass occurred as a narrow band along tidal creeks; the shorter (< I ft) sparse cordgrass covered the remainder of the marsh. The height of vegetation ap- peared to be correlated with the degree of tidal inunda- tion; short grass was subject to less frequent inundation than was tall grass. Marshes averaged about 3 miles wide in the area where samples were collected and were divided into an inland side and an ocean side by a meandering channel, the inlercoastal waterway. Ocean City, Sea Isle City, and Avalon are on the ocean side of the marsh; Palermo. Ocean View, and Swainton are on the inland side. In 1967, 40 dead clapper rails were picked up along highway causeways after the hurricane September 17. One rail was shot at the Palermo site September 2. one was found dead at Palermo August 15 immediately fol- lowing an aerial application of malathion. and one was shot at the Sea Isle City site September 2. In 1973, all 151 TABLE 3. Organisms analyzed for orgunmhiorinc resUliies in Cape May County. New Jersey— 1967 vs. 1973 Common and Self niii re Names Clapper Rail Shccpshcad Minnow Mumnii*;hog Sinpcd KiHifish Grass Shnmp Kiddlcr Crah Blue Cnih Rihhcd Mussel Penw inkle Mud Snail Salt Marsh Snail Meadow Grasshopper Hilllui tonfiirnslris C\prtnidiin iiini-n remove moisture. I'his mixture was transferred to a paper thimble and extracted with hexane for about 7 hours. Paper thimbles were pre-exiracled for 7 hours in methylene chloride lo remove background peaks. Cleanup was ac- complished b\ column chromatography; the concentrated extract was placed on a tlorisil column and eliiled with The isomer /)./)'-TDE occurred in all fish samples from both l%7 and 1973. but among the invertebrates, its incidence decreased from 82 percent in 1967 to 42 percent in 1973. Among clapper rail samples the incidence de- creased even more dramatically: from 63 percent to 4 percent. The lower incidence of /),/)'-TDF, and /),/)'-DDT in rails v\as not unexpected because birds evidently metabolize />./> -DDT readily into /),/)'-DDE and p.p'- JDE. and there is a greater propensity for storage of DDF than IDF in bird tissue {1.2). .Also, the rail samples 1.52 Pesticides Monitoring Journal were analyzed as individuals whereas fish and inverte- brates were analyzed as pooled samples in which each sample contained five or more individuals. The isomers o.p'-DDT and ().;?'-TDE were found in 71 percent of the invertebrate samples of mussels, mud snails, and salt marsh snails in 1967. but were not found in any samples in 1973. These isomers are not often detected in wildlife specimens although technical grade DDT con- tains up to 30 percent o.p'-DDT {19. 261. Lamont (19) found (),/?' isomers in brown pelican {Pt'liccinn.<0.05). Decreases in IDDT varied from 84 to 99 percent of 1967 levels. Mean residues of i.DDT observed in 1967 ranged from 0.63 ppm in the periwinkle to 9.05 ppm in the mummi- chog. Each of the three species of fish contained higher mean residue levels than did any other species sampled. Residues of 1 DDT averaged 3.36 ppm in clapper rails in 1967. Clapper rails feed principally on fiddler crabs in which DDT averaged 1.33 ppm in 1967. In 1973. DDT residues had dropped to 0.54 ppm in rails and 0.13 ppm in fiddler crabs. No significant differences (/7<0.05) in resi- dues were detected between male and female rails or between adults and immatures. In an acute toxicity study by Van Velzen and Kreitzer (25) clapper rails were highly tolerant of DDT, and the authors concluded that expo- sure to this pesticide in marshes probably does not cause death among adult rails. Ferrigno (7) observed production crashes in clapper rail populations in Cape May County in 1959 and 1%5. Hatching success remained low from 1965 to 1969 but began to increase in 1970 (F. Ferrigno. Sr.. Slate of New Jersey Department of Environmental Protection, 1973: personal communication). Peak years in hatching success were 1958, 1962. and 1972. Population studies were not conducted before the DDT era. so it would be interesting to document long-term rail popula- tion trends to see whether similar production crashes occur after the DDT era. Mean and maximum residues of DDT in fish (Table 5) TABLE 4. Chlorinated hydrocarbon residues in carcasses of the clapper rail (Rallus longirostris) /rom si.x localities in Cape May County, New Jersey — 7967 and 1973 Residues, ppm wet weight 1967 1973 Mean' Range Mean' Range Ocean 1 ClTV P./) -DDE 1.8 0,55-5, 3 0,49 0,20-1,2 n.p-TDE 0,10 ND-0,28 ND — /i.n'DDT ND _ ND _ Dieldnn 0.14 ND-0,23 0,04 ND-0,19 PCBs <0.5 _ 044 <0, 5-1.1 Carcass wl. g 130.3 67,2-185,0 219,4 177,5-255,0 Percent lipid 4 1 2,4-7,1 8,1 2,1-17 1 No- samples 7 4 Sea Isle City P.p-DDE 2.7 1,1-7,0 0,60 0,31-0,77 n.p-TDE o.:."! ND-I 9 ND _ P.r-DDT 0.14 ND-1,1 ND — Dieldnn ND — ND — PCBs <0,.'i — 0,70 <0, 5-2,0 Carcass wl, g 148 2 120,0-170,3 203 0 182,0-256.5 Percent lipid 3.5 1,9-6,5 8,7 5,1-12.9 No samples 8 4 AVALON p.p'DDE 30 2,1-4,0 0,89 0,33-3,4 p.p-TDE 0.10 ND-0 25 ND — P.p -DDT 0.04 ND-0,17 ND — Dieldrin 0,04 ND-0 18 002 ND-0,11 PCBs <0..'< 0,83 <0,5-3.4 Carcass wl. g 127.6 94, .3-1490 206,7 164,0-2.54.0 Percent lipid i.O 3,9-8,1 11,7 4,9-16,0 No samples 7 6 Paiermo p.p'DDE 63 25-15 0,78 0,33-1 9 p.p-TDE 088 ND-2 3 ND — /.,;.-DDT 0,81 ND-3,0 ND — Dieldrin 0.08 ND-0,22 0,02 ND-0,10 PCBs <0.5 — 1,3 0.73-2,5 Carcass wt. g 144.4 77,4-214.2 202,8 177,5-243.5 Percent lipid .5 1 2.6-9.3 14,6 9,5-20,9 No samples 7 6 OCEA^ 1 View P.P-DDE 3.4 1,4-11.0 0.20 0,18-0,21 P.P-TDE 0.26 N D-0,90 ND — n.p-DDT 0.23 ND-0,4« ND — Dieldrin 0.08 ND-0,18 ND — PCBs <0.5 0,55 <0,.5-0.93 Carcass wl. g 15 1.8 74,9-184,3 181 5 167,0-196,0 Percent lipi J 4,0 2,0-8,1 .V6 5,6-5 7 No. samples 7 1 SWAI NTON p./) -DDE 3.4 0,78-8,8 0,54 0,31-1 6 P.p-TDE 0.18 ND-0 68 0,03 ND-0,17 p.p-DDT 0.15 ND-I, 6 ND — Dieldnn 0.03 ND-O.ll ND — PCBs <0.5 — 0,14 ND-0.5 Carcass wt. g 153.1 90,0-1867 174,1 65.0-263.0 Percent lipid 5.0 2,5-7,1 8,2 2.8-14,2 No samples 7 5 Note: Three samples from 1973 coniained mirex; Ocean City, 0.16 ppm. Sea Isle Cily. 0 39 ppm: Avalon. 0.15 ppm. The same sample from Avalon also coniained 0 12 ppm oxychlordane. N D = noi detected. ' Mean values for chemical residues are geometnc means; mean values for carcass weigh! and percent lipid are arithmetic means. Vol. 10. No. 4, March 1977 153 TABLE 5. Chlorinated hydrocarbon residues in pooled samples of fish from Cape May County. New Jersey — 1967 and 1973 Residues, ppm wet weight LOCAIITY Year n' weight, g upid p./i-DDE /j./>TDE p.p'DDT PCBs * SheepSHEAD minnows {CvpnniJon vanegotiis) Ocean Cily Sea Isle Cily Avalon Palermo Ocean View Swainlon 1%7 1973 l%7 1973 l%7 1973 l%7 l%7 1973 1973 56 168 88 121 41 273 46 40 103 88 23.8 2003 86 0 160 8 42 4 279 06 30 9 34 1 129 82 ino 56 3-8 4 3 4 8 54 5 7 4 0 4 2 4 8 4 1 4 3 1 5 0 12 17 0 38 0 44 006 1 5 0 45 0 07 0 10 4.0 055 IS 0.53 2.8 0.06 12 2.2 0.06 0 18 2 0 ND 4 2 ND 12 ND 5 5 0 55 ND ND 060 0 16 1.1 0 13 0.91 0.18 1.5 4 3 0 18 0.14 Striped killifish lFiinJnln\ mujain) Ocean Cily Sea Isle City Avalon Palenno Ocean View Swajnton 1973 1%7 1973 1973 1973 1%7 1973 1967 1973 28 30 19 17 40 14 29 9 3 6 9 4 31 9 35 0 31 3 18 3 75 4 105 3 9 2 8 2 5 3 0 2 0 3 1 2 1 0 14 2 3 0 15 0 05 0 19 0 55 006 040 006 052 92 0 15 004 007 18 004 0 55 004 ND 9 5 ND ND ND 0 55 ND 008 ND 0.17 2.8 022 0 17 0 19 23 0.14 041 020 MuMMICHOGS iFiindiilns helentt ltlu\t Ocean City Sea Isle City Avalon Palermo Ocean View Swamlon 1%7 1973 1%7 1973' 1%7 1973 l%7 1973 1%7 1973 1967 1973' 20 73 30 3 40 21 60 40 18 21 64 69 73 2 38 0 18 5 80 2 48 7 46 3 45 6 79 2 29 6 889 15 71 2 7 0 29 4 2 46 3 5 49 2.6 3 4 29 3 8 2 3 3 2 3 0 2 0 0 10 10 022 1 3 006 10 021 2 3 008 0 45 0 09 36 0 33 99 009 3 2 005 11 008 5 5 003 0 39 004 4 8 ND 16 ND 13 ND 17 ND ND ND 0.83 0 12 15 023 20 0 18 1.3 0 19 3 5 023 Mlmmichogs [F itndttltis heteroclilus) Ocean Cily Sea Isle City Avalon Palenno Ocean View Swainton l%7 1973 1%7 1973' 1%7 1973 1%7 1973 1%7 1973 1967 1973' 20 73 30 3 40 21 60 40 18 21 64 69 73 2 380 18 5 80 2 48 7 46 3 45 6 79 2 29 6 889 15 71 4 6 3 5 49 2 6 3 4 29 3 8 2 3 3 2 3 0 2 0 0 10 10 0 22 1 3 0 06 10 0 21 2 3 008 0 45 009 3.6 0,33 99 009 3 2 0 05 11 008 5.5 003 0 39 004 4 8 ND 12 0 02 1 6 ND 13 ND 1 7 ND ND ND 0.83 0 12 27 0 29 15 0 23 20 0 18 1,3 0 19 3,5 0,23 NOTE: ND = not delected 'n = number of mdividual fish in the pooled sample KI.02 ppm ( (i-chlordane or fffln.(-nonachlor detected in sample. ^.01 ppm c(5-chlordane or fra/j.v-nonachlor detected in sample. collected in 1%7 are high compared with residues re- ported in an extensive summary by Edwards (6) for marine and freshwater fish. A pooled sample of the sheepshead minnow and another of mummichog from Long Island in 1966 contained 0.94 ppm and 1.24 ppm XDDT, respectively (27). Veith reported mean DDT residues in 13 species of fish from Lake Michigan that ranged from 0.9 to 7.1 ppm (26). Fish from the Delaware River in New Jersey, analyzed as part of the National Pesticide Monitoring Program, had some of the highest mean residues of 1 DDT recorded on the Atlantic Coast; average levels reached 4.S ppm in 1968 (10. II). It is likely that New Jersey fish developed increased tolerance to DDT and its analogs after 20 years of continued DDT use in their habitat. Residues in 1967 samples, however, were much lower than those observed in genetically resistant mosquitofish (G umhti.sUi ctffmis) in Texas which had average 1 DDT residues greater than 50 ppm on a whole-body basis (5). Odum et al. (22) found that fiddler crabs that had fed on detritus containing approximately 10 ppm DDT residues developed poor coordination after 5 days, and residues in the claw muscles of these crabs averaged 0.885 ppm after 10 days. Residues in whole bodies of crabs from New Jersey in 1967 averaged 1.33 ppm, and ranged as high as 4.13 in one sample. The crabs were alive when collected 154 Pesticides Monitoring Journal TABLE 6. Chlorinaled hydrocarbon residues in pooled samples of invertebrates from Cape Mav County. New Jersey —1967 and 1973 Residues, ppm wet weight Sample Percent WEIGHT. G LIPID p.r'-DDE p./i-TDE ,)./) -IDE p.p-ODT n.p-DDl Fiddler crab iUia ptinnax) 1973' I967' 1973 1%7 1973 1967 1973 1%7 1973 l%7 1973 33.78 17.40 115 93 41 13 70 37 26.47 40.57 II 75 105.63 46 40 133 15 0.9 0.7 0,9 I 4 11 0.8 0.5 08 0.8 18 06 0,12 36 Oil 0.41 0.06 13 076 1.9 0.06 0 28 0 03 009 027 004 0 19 0 05 0 14 ND 0.19 ND 0.06 ND ND ND ND ND ND ND ND ND ND ND ND ND 032 ND 0 10 001 004 ND 0.29 ND 0,07 ND ND ND ND ND ND ND ND ND ND ND ND 0.13 0.09 0.11 0.17 0.10 0.23 0.27 0.25 0.27 0.11 0,16 Ribbed Mussel (Geukensia demissa) 1967 1973 1967 1973 1973 1%7 1973 1967 1973 1%7 1973 55.75 91 36 62 54 107,97 101 .59 25,19 83.98 54.95 56.05 66 92 37 03 08 04 0 3 0 2 02 07 0.2 0.6 0.5 02 0 3 0.27 0,02 0 37 001 002 0 94 006 0,20 002 0,02 0 03 0 .36 001 0 51 001 ND 1 5 0,03 0,24 ND ND ND 0 07 ND 0,09 ND ND 0,23 ND 0.05 ND ND ND 2 3 ND 3.6 ND ND 90 0.02 1.6 ND ND ND 047 ND 0.73 ND ND 1.2 ND 020 ND ND ND 0 17 ND 0 05 ND 0 10 0 36 0 22 0 27 0 02 0 10 0 24 Periwinkle {Litiorina linorea) 1973 1973 1%7 1973 1973 1973 1973 2.75 55.33 1.34 64.89 25.47 8.87 4.08 1.1 1.4 1.5 2.6 0.9 ND 004 0 14 002 002 004 0 04 ND ND 0 31 ND ND ND ND ND ND ND ND ND ND ND ND ND 0 18 ND ND ND ND ND ND ND ND ND ND ND ND ND 0 72 0,14 0 15 029 0 30 Mud snail iltyanassa ohsolela) 1967' 1973' 1967 1973 1967 1973 1973 1973 1973 4,69 30.51 10.68 66.91 5.51 53.20 39.15 59.38 35.72 0 2 0.2 2.1 0.8 0.4 1.3 0.9 0.9 1.0 0 30 005 1 6 0 14 0 05 0 03 004 004 003 0 77 0 02 4 3 0 07 ND 003 0 02 ND ND 0 13 ND 082 ND ND ND ND ND ND 0 47 ND 085 ND ND ND ND ND ND 0,07 ND 0,02 ND ND ND ND ND ND 0 07 006 0 13 0 06 0 i: 0 14 0 16 0 34 002 Salt marsh snail ^Metamptis hidetiuints) 1967 1973 1%7 1973 1%7 1973 1967 1973 1967 1973 l%7 1973 6.79 29.16 17.19 43.23 16.85 29.73 27,25 25.89 12.42 37.99 28 30 37 71 1.3 0.7 \.l 0.6 1.3 0.4 1.8 0.8 1.7 0.6 10 04 046 006 I 0 001 006 ND : 0 0 02 0 76 001 0.05 <001 0 04 2 5 001 0 20 ND 5 0 0 02 1 1 ND 0 06 ND 0 10 ND 021 ND ND ND 0 45 ND 008 ND ND ND 2.4 ND 2.9 ND 0.30 ND 5,0 ND 3,5 ND 0 13 ND 0 16 ND 028 ND ND ND 041 ND 0,14 ND ND ND 0 07 ND 0 08 006 0 07 0 06 1 4 006 0.34 0 13 006 006 Grass Shrimp {Palaenntnvie\ sp i 1973 1973 1967 1973 39.47 180.30 3.97 7 81 1.0 0.5 0.5 0 5 0 02 0 02 ND ND noi ND ND ND ND ND ND ND NOTE: ND = not delected ' 0-13 ppm oxychlordanc present in sample. ' 0.04 ppm toxaphene present m sample. ^ 0,02 ppm HCB detected in samples ' 0,02 ppm (/5 levels of 0 05 or less Its^o-lailed. Wilcoxen iwo-sample lesll but behavior was not recorded. Crabs collected in 1973 behaved normally and were not sluggish or awkward when DDT residues ranged from 0.03 to 0.76 ppm. Residue levels in the mollusks collected in 1%7 were generally higher than levels reported by Edwards (6) for a wide variety of related species except oysters. The maxi- mum IDDT residues reported in eastern oysters (Crcis- sostreu virf;inica) collected in the New Jersey waters of Delaware Bay June 1966 — June 1972 was 0.272 ppm, and most residues in these extensive samples were less than half this amount (3). Concentrations in the oysters decreased during the 1966-72 collection period. Woodwell et al. (27) reported 0.26 ppm IDDT in mud snails and 0.44 ppm IDDT in the hard clam (Mercenaria menen- iiria) from Long Island. New York, in 1966 when DDT use was curtailed there. Concentrations of DDT and its metabolites were low in six species of shellfish collected in Long Island waters during 1%8-I970; only a few values were greater than 0.22 ppm (8). Although residue levels varied at the six localities in New Jersey, simple correlation coefficients between IDDT residues and amounts of DDT sprayed for mosquito control at these localities were low and statistically non- significant (/5>0.05). However, residue levels of IDDT were consistently higher in all species at Palermo and Sea Isle City. The Sea Isle City zone was sprayed more than the other localities during the 17 years of recorded DDT usage (Table 2). but Palermo was sprayed less than either Ocean City or Avalon. Foehrenbach {8) was able to correlate pesticide concentrations in shellfish with land use in the watersheds surrounding his collecting stations. It is possible that other pesticide use in the Palermo watershed contributed to concentrations in the biota there. Another explanation is that DDT sprayed from the air drifted with prevailing offshore breezes toward Pal- ermo from Sea Isle City and Ocean City. Because of the widespread coverage of DDT spraying in Cape May County and the short distances involved, further interpre- tation of observed differences in residue levels between localities is pointless. PCB's were the second most common residue found. They occurred in 93 percent of all samples. Significant changes in concentrations occurred between 1967 and 1973 (Table 8). but the pattern was not so consistent in all species as it was for IDDT. Residues decreased in all three species of fish and in the salt marsh snail. A large increase in residues occurred in clapper rails but mean levels remained low. Changes in other species were not significant. Dieldrin was not found in fish and invertebrates but did occur in 37 percent of the rail carcasses in 1967. Only 1 1 percent of the rails collected in 1973 contained dieldrin. Dieldrin apparently was never used for mosquito control in Cape May County but, until banned in 1974. it had been used widely in the United States as an insecticide. Clapper rails feed primarily on fiddler crabs but occasion- ally take small fish and snails. The absence of dieldrin in any of these species may mean that rails obtained the chemical from salt marsh organisms not included in this study, or that rails can concentrate dieldrin in their tissues from residue levels in their food supply that are below detection limits of the present study. All other organochlorines were either absent or occurred in small quantities in only a few samples (see footnotes. Tables 4-6). The infrequent occurrence and low concen- tration of other organochlorines indicate that the use of these persistent insecticides has not increased appreciably as a result of the cessation of DDT use. The lull which followed 20 years of intensive spraying of DDT for mosquito control in Cape May County has been marked by rather rapid decreases in occurrence and con- centration of IDDT in aquatic fauna. More information is needed for species in higher trophic levels such as fish- eating birds and carnivorous fish, but these forms should also begin to show decreased residue levels. Reproduction in the osprey {Pandion Italiaeiiis ) in Cape May County had been seriously depressed for several years, but it began to improve slightly in 1974 (12). However, heron eggs col- 156 Pesticides Monitorinc; Journal lected in Cape May County in 1972 still contained rather high residue levels (23). Acknowledgments Authors gratefully acknowledge the important contribu- tion of Fred A. Ferrigno, Sr., who aided in planning the study, assisted in collecting all the organisms in both 1967 and 1973. and reviewed the manuscript. We thank Aldeen Van Velzen who assisted in collecting in 1967 and Lee Widjeskog who assisted in 1973. Judy A. Hansen was very helpful in providing the data on spraying and we appreciate her cooperation. We also thank E. H. Dust- man and Lucille Stickel for reviewing the manuscript. LITERATURE CITED (1) Bailey. S.. P. J. Bunyan. B. D. Rennison, and A. Taylor. 1969. The metabolism of I,I-Di(p-chlorophenyl-2.2,2- trichloroethane and I,l-Di(p-chlorophenyl)-2.2-dichloroe- thane in the pigeon. Toxicol. Appl. Pharmacol. 14(/):l3-22. (2) Bailey, S.. P. J. Bunyan. B. D. Rennison. and A. Taylor. 1969. The metabolism of l,l-Di(p-chlorophenyl)-2.2-dichlo- roethyiene and 1 ,l-Di(p-chlorophenyl)-2-chloroethylene in the pigeon. Toxicol. Appl. Pharmacol. l4 of n./'-DDD and o./) -1)1)1 in brown pelican egg> and mallard ducks. Bull. Environ. Contam. Toxicol. 5(3):23l-236. (20) Moisiimiiro. F . I97J Microhial degradation of pesticides. Pages 129-154 m M. A. Q. Khan and J. P Bcderka. Jr.. eds. Survival in Toxic Knvironments Academic Press. Inc.. New York (2/) Miilltcrn. T. /). 1949. A review for New Jersey for 1948. Proc 36th .Annii, Meet. N. J, Mosg, Kxterm. Assoc: 187- 144 C:) OJiini. U\ E.. C. M. WoodwvU. anil C. E WiirsUr. 1969. DDT residues absorbed from organic detritus b\ fiddler crabs. Science I64:,S76-.S77. {23) Ohicmlort: H .M . E. E. Klaus, ami T. E. Kaiser. 1973. Hnvironmental pollution in relation to estuarine birds. Pages 53-81 m M. A. Q. Khan and J. P. Bederka. Jr.. eds. Survival in Toxic Environments Academic Press, Inc.. New York (2-/I .Sokal. R R . and E J Rohlf. 1969. Biometry. W. H. Freeman and Co . San Francisco 776 pp. (2.^) Ian Vel:cn. A., and J . E. Krfii:cr. 1975. The toxicity of />./>-DDT to the clapper rail. J. Wildl. Manage. 39(2):305- 309. (26) V'eitli. G . [>. 1975. Baseline concentrations of polychlori- naled biphenyls and DDT in Lake Michigan fish. 1971. Pestic. Monit J. 9(11:21-29 (27) Woodwell. G. M.. C. F. Warstvr.Jr.. and P. A. Isaacson. 1967. DDT residues in an East Coast estuary: a case ot biological concentration of a persistent insecticide. Science l.S6(3776):821-824. 158 Pesticides Monitoring Journal GENERAL Monitoring Agricultural Insecticides in the Cooperative Cotton Pest Management Program in Arizona, 1971 — First-Year Study ^ Donald W. Woodham. ^ Hugh F. Robinson.' Robert G. Reeves.' Charles A Bond.^ and Harry Richardson-' ABSTRACT A couniy-wide pest management program was initialed in Pinal County. Ariz., in 1971 to improve ecologically, economically, and socially the system for protecting cotton from insect pests. Included in this program was a plan to determine the environ- mental impact of any resulting pesticide load in the environ- ment. Monitoring studies were developed for the assay of insecticide residues in soil, sediment, water, and biological materials. This report presents results of the first year's study and analytical methodology used to achieve those results. Introduction A county-wide cotton pest management program was initiated in Pinal County. Ariz., in 1971 as a cooperative endeavor of the U.S. Department of Agriculture — Animal and Plant Health Inspection Service (USDA-APHIS). Cooperative Extension Service and the University of Arizona Department of Entomology. The main objective of this pilot study was to establish a more ecologically, economically, and socially acceptable system for protect- ing cotton from insect pests. During the first year of the study various aspects of this pest management program were organized and executed, including an environmental impact analysis program. This report concerns results obtained from that program. Both biotic (birds, snakes, lizards, frogs, fish) and abiotic (soil, sediment, water) samples were collected and ana- ' U.S. Department of Agriculture — Animal and Plant Health Inspection Service. Plant Protection and Quarantine Programs. Brownsville. Tex. ' USDA. APHIS. PPQ. Staff Officer. New Pest Detection and Survey Staff. 659 Federal Center BIdg . Hyatlsville, Md 20782 Reprints available from this address " USDA. APHIS. PPQ. Sacramento. Calif ' USDA. APHIS. PPQ. Chemist. Gypsy Moth Laboratory. Otis Air Force Base. Mass. ' USDA. APHIS. PPQ. Chemist. Environmental Monitoring Laboratory. Gulfporl. Miss lyzed for pesticide residues to determine what impact, if any. the application of currently used pesticides has on the environment. Sampling Procedures The sample collection and analysis programs were de- signed to obtain comparisons of residues within and outside the projest areas before treatment and after har- vest. The effects of pesticide treatments on pond water and aquatic life were also determined by collecting sam- ples of water, sediment, and aquatic organisms from ponds near the cotton sites. Biotic samples included birds, toads and trogs, snakes, lizards, aquatic and terrestrial insects, and fish, i.e.. min- nows. Abiotic samples were pond water, pond sediment, and soil from cottonfields. Cottonfields in the Pest Management Program were se- lected to provide at least one site in each cotton-growing area of Rnal County, further restricted to areas near or adjacent to permanent or semipermanent water supplies. Sites outside the program were chosen for their locations near selected cotton sites. Insecticide treatment informa- tion was obtained from each sampling site when available (Table I). Random soil samples were collected within and outside program areas utilizing a core sampling device described previously by Woodham et al. (5). All soil was compos- ited, screened, weighed, stored, and shipped according to those procedures. Sediment samples svere collected randomly with an Eck- man dredge, composited, subsampled, stored, and shipped according to Woodham (5). Approximately 10 drags of the dredge were required for each sample; great care was taken to collect all possible fine and coarse sedi- ment and silt material. Vol. 10, No. 4, March 1977 159 TABLF 1 Pesticide irealnwm informiuion. Pituil County. Arizona— 1^7 1 Applica- tion Actual amount/ Site Date Pesticide ACRE lA v:? Slrohane methyl paralhion l/}gal 2A 7;M Hlhsl pardlhioamelh\l parathion 1/3 gal 7/24 Klh\l paralhion melh\i paralhiun Ipt 7/30 Hlhvi parathion mclhvl parathion 1-1/2 pi 8/05 Ethvt parathion meth\l parathion 1-1/2 pt Ki: Kth>l parathionmclhyt parathion Ipt (i:n Ethyl parathion methyl parathion 1-1 : pt 3A NA — 4A _ NA — 5A 7/M Oimcthoate NA (K06 Malathion NA «,n Kth\l parathion NA 8(2: Methyl parathion toxaphcne NA 6A 7/25 ScMn-molasses 21b 7/30 Sevin-molasscs 21b 8/04 Sevin-molasses 2 1b 8/11 Sevin-molasses 2 1b 8/21 Methyl parathion toxaphene Iqt 8 27 Methyl parathion 3-1/4 qt Toxaphene 1-1/2 qt 7A 7/16 Methyl parathion toxaphene 1-1/2 pt 7/25 Methyl parathion lt>\aphene 1-1/2 pt m2 Methyl par-ilhiun toxaphene 1/2 gal *im Methy 1 parathiontoxaphene 1/3 gal 812 Fthyl-methyl parathion Ipi Hndrin Ipt gflh Methyl parathiontoxaphene 1/3 gal 827 Methyl parathiontoxaphene 1/3 gal 9/11 Rlhyl-methyl parathion ipt Ethyl parathion- toxaphene 1/3 gal 9/14 Ethyl-methyl parathion 1/6 gal Endrin Iqt 823 Ethyl-methyl parathion 1/6 gal 8A 7/17 Ethyl parathion Iqt Toxaphene Iqt 7/28 Ethyl-methyl parathion Ipt 8/22 Ethyl-methyl parathion/toxaphene 1/3 gal 9/01 Ethyl parathion/toxaphene 1/3 gal 9A 7/26 Ethyl parathion/methyl parathion 1/3 gal 7/30 Ethyl parathion/methyl parathion 1/3 gal 8/07 Methyl parathion/toxaphene 1/3 gal 8/10 Methyl parathion/toxaphene 1/3 gal 815 Methyl parathion/toxaphene 1/3 gal 825 Methyl parathion/toxaphene Iqt 829 Methyl parathion/toxaphene Iqt lOA — NA — NA = not available. Random water samples were collected from tailwater ponds, irrigation ditches, or canals as near as possible to the corresponding sediment sampling sites. By varying the depth of the dredge except for bottom samples, a repre- sentative gallon of pond water was collected and stored in sealed gallon glass bottles. Birds, mammals, lizards, frogs, toads and snakes were collected by shooting with either a .22 caliber rifle with birdshot or a 12-gauge shotgun, within the various sam- pling sites. Minnows and other fish were caught in a small-mesh minnow seine. Water beetles were collected from sediment samples and grasshoppers were caught in the fields with hand nets. Crickets and some ants were gathered by hand; the remaining ants were collected with an aspirator sampling device. Soil, sediment and water samples were stored at approxi- mately 40° F in a refrigerator pending shipment to the US DA Environmental Quality Laboratory. Brownsville. Tex. Biological samples were stored at 0' F pending airmail shipment in styrofoam biomailers with dry ice. Once sam- 160 pies were received in the laboratory, they were im- mediately unpacked; biological samples were stored again in a 0°F freezer, and soil, sediment, and water were stored at 40°C pending residue analysis. Preparation of Samples EXTRACTION Representative 300-g soil samples were extracted with 600 ml of a 3: 1 (v/v) hexane-isopropyl alcohol solvent mixture in half-gallon Mason jars on a concentric rotator for 4 hours as described previously by Stevens et al. (4). After rotation, 300 ml of the extract was filtered into 1000-ml separatory funnels where the alchohol was removed by wiLshing three times with equal volumes of distilled water. The hexane extract was dried by filtering through a layer of anhydrous granular sodium sulfate into amber sample bottles. The bottles were sealed and refrigerated pending gas-chromatographic (GC) analysis. Soil extracts did not normally require cleanup before analysis. Sediment samples were prepared and stored as soil sam- ples had been, except that 250 g anhydrous granular sodium sulfate was added to absorb excess water. As usual, sediment samples contained excessive amounts of sulfur which interfere with analyses for organophosphate and chlorinated hydrocarbon residues. These samples were treated utilizing the sulfur removal procedure of Schultzmann et al. U). Water samples were extracted by shaking representative 500-g subsamples in 1000-ml separatory funnels three times with fresh 100-ml portions of nanograde (Mallinck- rodt. Inc.) dichloromethane. The organic layers were filtered through a layer of granular anhydrous sodium sulfate to remove entrained water into 500-ml Erienmeyer flasks. One ml of a 0.01 percent Nujol in hexane solution and glass beads were added and the solvent was evapo- rated through Snyder columns to approximately 5 ml on a warm water bath: 40^-50" C. One hundred ml nanograde hexane was added through the Snyder columns and the solvent was again evaporated to approximately 5 ml. The concentrated extracts were transferred to 15-ml graduated centrifuge tubes which were stoppered; the volume was adjusted to 12.5 ml with nanograde hexane. Samples were refrigerated pending GC analysis. Water samples did not normally require cleanup before residue analysis. Larger biological samples such as rabbits, birds, lizards, snakes, and fish were prepared according to the proce- dure used by Woodham et al. (7). Samples were thor- oughly ground in a Hobail food grinder; then representa- tive 25-g subsamples were weighed into 10(R)-ml Waring blendor jars with 150 ml of a 3:1 mixture of nanograde hexane: isopropyl alcohol and blended at low speed for 2 minutes. The macerated materials were transferred into hiilf-gallon Mason jars with 250 ml of the hexane: isopro- Pesticides Monitoring Journal pyl alchohol mixture and the jars were sealed and rotated concentrically 4 hours. Extracts were filtered through glass wool into 1000-ml separatory funnels where the alchohol was removed with three successive washings of equal volumes of distilled water; the aqueous layers were discarded. Hexane extracts were filtered through layers of anhydrous granular sodium sulfate into graduated cylin- ders where 100-ml aliquots were collected. The aliquots were transferred into amber sample bottles, sealed, and refrigerated pending cleanup. Smaller biological samples, mainly insects, weighing 25 g or less were weighed and transferred into micro-blendor cups with 50-ml nanograde isopropyl alchohol and blended for 2 minutes at high speed. The macerates were sealed into quart Mason jars with 150 ml nanograde hexane and rotated concentrically 4 hours at 30 rpm. Extracts were filtered into 500-ml separatory funnels where all alcohol and water were removed by three successive washings with equal portions of distilled water. Extracts were dried and refrigerated. Cl.EANUP Biological sample extracts were cleaned by liquidrliquid partitioning between two immiscible organic solvents, hexaneiacetonitrile, to remove fats and oils. The proce- dure, described previously by Woodham et al. (5). in- volved transfer of 10-g aliquots of the extracts into 125-ml Erlenmeyer flasks and concentrating to approximately 25 ml on a warm water bath using a gentle stream of dry air to facilitate evaporation of the solvent. The concentrated extracts were diluted to exactly 50 ml with nanograde hexane and transferred into 250-ml separatory funnels and partitioned three times with 100-ml portions of nanograde acetonitrile saturated with hexane. The hexane layers were discarded and the combined acetonitrile layers were collected in 500-ml separatory funnels and washed once with 20 ml nanograde hexane saturated with acetonitrile to remove any trace of fats or oils. The acetonitrile fraction was divided into equal portions for further pro- cessing. For organophosphates, one portion of the acetonitrile fraction was transferred to 250-ml Erienmeyer flasks, 1 ml of 0.01 percent solution of Nujol in hexane and glass beads were added, and the solvent was evaporated to approximately 5 ml on hotplates through Snyder columns. The concentrated extracts were transferred to 15-ml grad- uated centrifuge tubes where the volume was adjusted to exactly 12.5 ml with nanograde acetonitrile. The stop- pered tubes were refrigerated pending GC analysis. For chlorinated hydrocarbons, the remaining portion was transferred into 250-ml Erlenmeyer flasks, glass beads and I ml of a 0.01 percent Nujol in hexane solution were added, and the solvent was evaporated to approximately 10 ml on hotplates through Snyder columns. The flasks were cooled and 100 ml hexane was added through the Snyder columns and the evaporation procedure described previously was repeated on a hot water bath. This step was repeated two additional times, and the flasks were sealed and refrigerated pending florisil cleanup. FLORISIL CLEANUP Florisil chromatographic cleanup columns have been de- scribed previously (5). Only two fractions were collected from the columns in the present study because organo- phosphate residue analyses were conducted on the parti- tioned samples. Aliquots from the extraction procedure were transferred into the hexane prewashed columns and eluted with 100 ml nanograde hexane, then with 100 ml 15 percent diethyl ether in hexane; each eluate was collected in separate 250-ml Erlenmeyer flasks. The solvent was evaporated and stored as described previously (5). The less polar pesticide residues such as lindane, heptachlor, aldrin, DDE, TDE, DDT, and toxaphene were contained in the first fraction; the second fraction contained the more polar residues such as dieldrin, endrin, and heptachlor epoxide. G as-Chromatographic A nalysis Analysts used MT-220 gas chromatographs equipped with Ni-63 high-temperature electron-capture detectors and a Melpar Flame Photometric Detector (FPD). The FPD detector was designed to operate simultaneously in the sulfur (394 mu) and the phosphorous (526 mu) modes. Operating parameters were: Columns: 6-ft-by-'/j-in. -glass packed with 3 percent DC-200 on 100/200-mesh Gas-Chrom Q; 3 percent OV-1 on 80/IOO-mesh Chromo- sorb-W; 5 percent QF-1 on 100/120-mesh Gas-Chrom Q; and 1 1 percent mixture of 1.95 percent QF-I : 1.5 percent OV- 17 on 80/IOO-mesh Gas-Chrom Q. A 3 percent DC-200 column as described in (/) was also used for the FPD analysis of organophosphate residues. Temperatures (isothermal): Columns: 200° C Injector: 250° C Detectors EC 300P C FPD 200° C Gas flow rates: Nitrogen (carrier) 80 ml/min Air 40 ml/min Hydrogen 75 ml/min Oxygen 20 ml/min Recorder chart speed was 30 in./hr; sensitivity was ad- justed to obtain approximately half full-scale deflection of the recorder pen with a 0.05-ng injection of aldrin on the electron-capture detectors and 1.50 ng of ethyl parathion Vol. 10, No. 4, March 1977 161 on the FPD detector. Calculations were based on peak heights obtained from analytical standards compared with identical peaks in the samples. Lower limit of sensitivity was 0.01 ppm for organophosphates and chlorinated hy- drocarKm pesticides except in water, whose lower limit was 0.0 1 ppb. Toxaphene was analyzed using the GC method of Haw- thorne and Dawsey (US DA Environmental Monitoring LaKiratory. Gulfport. Miss., 1972: personal communica- tion). Extraction, cleanup, and other processing steps were identical to those used for the organochlorine and organophosphate pesticide residues. The quantitation pro- cedure involved comparing heights of the four major peaks in a toxaphene standard with heights of those peaks in the environmental samples. Gas-chromatographic oper- ating parameters were identical to those described previ- ously for organochlorine and organophosphate pesticides on the 3 percent DC-2(X) column. When minor peaks interfered with the four major peaks of toxaphene, as few as two such peaks could be used for accurate quantita- tion. The lower limit of sensitivity of toxaphene was 0.05 ppm except for water, whose limit was 0.05 ppb. Doubtful pesticide peaks were confirmed by several methods described in previous publications: thin-layer chromatography, Schutzmann et al. (2); partitioning coef- ficients (/^-values). Bowman and Beroza (/): chemical means. Woodham, et al. (4); and multiple column meth- ods. Peaks which were not at least twice the interference level were rejected. Recovery A series of control samples extracted, purified, and analyzed in identical manner as the unknowns, was in- cluded with each group of samples. These controls in- cluded a solvent check, nonfortified sample and a sample fortified with known amounts of the suspected pesticides. These controls were necessary in order to monitor possi- ble contamination of solvents, determine residues in non- fortified sample material, and determine extraction and analytical efficiency of the entire procedure. No interfer- ing peaks were detected in the solvents; pesticide peaks detected in unfortified samples were deducted from those in fortified samples to obtain recovery percentages. Aver- age recovery values are listed in Table 2. Results and Discussion Table 3 present' residue data for the soil samples col- lected within and outside the program areas, before pesticide trcalmenis began and after harvest. The organo- phosphate. ethyl parathion. was detected in trace amounts, 0.13 ppm and 0.03 ppm. in soil from sites 2A and 3A. respectively, within the program area after harvest. No organophosphate residues were detected in soil collected before the pesticide treatments or in soil 162 outside the program area. Residues of ethyl parathion were detected in soil from sites IB, 2B, 3B, 5B. 7B, and 8B at harvest outside program areas. Residues in soil from these sites apparently resulted from direct pesticide application to cotton crops. Organochlorine pesticides were detected in all soils before pesticide treatments and after harvest, within and outside program areas. Before pesticide application, residues ranged from 0.29 to 1.43 ppm /'■A'-RDE. 0.11 to 1.49 ppm p.p'-DDT, and <0.05 to 3.94 ppm toxaphene in soil from sites within the program area. After harvest, residues ranged from 0.21 to 0.76 ppm p.p- DDE. 0.1 1 to 1.33 ppm p.p'-DDT. and 1.18 to 5.18 ppm toxaphene in the soil. Outside the program area, the same organochlorine pesti- cide residues were detected, ranging from 0.50 to 1.82 ppm p.p-DDE. 0.25 to 1.53 ppm p.p' -DDT, and <0.05 to 2.68 ppm toxaphene in pretreatment soil. At harvest, organochlorine pesticide residues ranged from 0.33 to 1.24 ppm /), /'-DDE, 0.31 to 0.86 ppm /),p- DDT, and 2.41 to 4.04 ppm toxaphene in soil collected outside the program area. The decline in p,p'-DDE residues was apparently due to cultivation practices on the various sites. Residue data for pesticides in biological samples are given in Table 4. Ethyl parathion residues ranged from 0.03 ppm in a frog sample collected before treatment within the program area and a rabbit sample collected before treatment outside the treatment area to 1.24 ppm in a sample of minnows collected before treatment within the program area. Organochlorine pesticide residues were detected in all biological samples, predominantly p.p'-DDT and other isomers of DDE. DDT. and TDE. Residue patterns were similar among samples from inside and outside program areas although concentrations were generally lower in samples from outside the program. Various pretreatment samples collected inside program areas had residues of heptachlor epoxide. <0. 01-0. 06 ppm; /3-BHC. <0.01-0.05 ppm; dieldrin. <0.01-0.55 ppm; o.p'- DDE. <0.01-l.52 ppm; /),/)■- DDE. 0.03-45.52 ppm; o.p'- TDE. <0.01-0.60 ppm;p,/5TDE. <0.01-1.73 ppm; o.p'- DDT. <0.01-0.17 ppm; and p.p'-DDT. <0. 01-2. 36 ppm. Residues in post-treatment samples produced generally the same pattern of pesticides, but at generally lower levels. Pretreatment samples collected outside program areas showed residues of /i-BHC, <0. 01-0. 47 ppm; heptachlor epoxide. <0. 01-0. 07 ppm; dieldrin. <0. 01-4. 68 ppm; o.p'-DDE. <0.0I-0.31 ppm; p.p'-DDE. 0.02-57.62 ppm; o.p'-TDE. <0.0I-0.16 ppm; p.p'-TDE. <0. 01-1. 36 ppm; <>./>'-DDT. <0. 01-0. 31 ppm; and p.p'-DDT. <0. 01-2. 12 ppm. in such varied samples as frogs, toads, lizards, birds, and fish. Post-treatment samples from outside program areas generally produced similar residue patterns with lower concentrations; some exceptions occurred, how- Pesticides Monitoring Journal ever, such as an increase in p,p'- DDE residues to a range soil inside and outside program areas. The ncrease in of 0.04-76.30 ppm in post-treatment bird samples. residues outside program areas was apparently due to pest cide treatments during 1971. No toxaphene residue Residues of pesticides used during the 1971 growing were detected in sediment, water, or biological samples season in the Arizona Cotton Pest Management Program inside or outside the program areas which indicates that did not accumulate, except for toxaphene in soil samples. this chlorinated camphene is not transferTed to the biolog- An increase Df toxaphene residues was noted in harvest jcal food chain TABLE 2. Average pesticide recoveries from fortified environmental sample materials. Pinal Count w. Arizona— -1971 Recovery. % Ethyl z 0 , z Hepta Para- >j Mala- > 2 z IX o a- y Hepta- Al- CHLOR O.p'- p.p'- DlEL- En- o.p'- p.p'- o.p- p.p'- TOXA- Sample THION fe S THION St I BHC BHC CHLOR DRIN Epox- DDE DDE DRIN DRIN TDE TDE DDT DDT PHENE Material Si S^ £ IDE Soil 102.2 96.4 1015 100.6 107 3 910 89 0 84 1 89 4 94,8 79,7 910 910 91.0 910 910 91.0 910 910 Sediment 93.0 800 86.0 90.0 89.0 85.5 94.2 86 1 80 8 91 1 85 5 85.5 85,5 79.4 77.0 85.5 87.7 88,6 85.5 Water 89.8 91.3 892 78.9 99.6 936 92 4 930 899 946 95.6 93 5 93 1 95.9 950 93 4 92 9 93 5 936 Lizards and Snakes 88.4 854 82.6 82.6 74.1 100.0 970 1009 1035 829 71.5 82.9 829 %8 86.0 80.5 83.3 80.8 82.9 Frogs. Toads and Polliwogs 95.8 884 83 4 97.8 96.3 100.0 970 1012 95 1 1012 76 0 760 %.8 968 76.0 76.0 760 76.0 980 Birds. Nestlings anc Eggs 935 94.8 970 93.6 95 2 1000 75 6 864 690 85,8 93,2 890 85.8 919 823 923 887 92 9 85 8 Fish and Freshwate r Clams 86 4 960 846 60.8 72.6 100.0 789 72,7 58,4 81,4 100,2 100 2 78 9 763 1048 109 1 915 95 5 1002 Insects 95.7 103.3 106.3 101.8 99.8 100.0 100.5 88.6 76.2 100.5 936 88 9 %.5 102 7 104 0 98 7 1010 97 0 95.7 TABLE 3 Pesticide residues in soil from pest management area. Pinal County, Arizona- -1971 Sampling Residues, ppm Ethyl DlEL- o.p- P.P- o.p'. p.p- o.p- p.p- Site Date' Parathion* DRIN DDE DDE IDE TDE DDT DDT Toxaphene Program Sites lA 7/13 <0.0I ,/. -DDT Program Samples Frogs AND TOA DS lA 7/13 Frogs 0.03 0.01 < 0.01 002 002 7,01 0 01 0.04 0.01 0,05 IttM Frogs <00l <001 <0.0I 002 <0,01 9 1-5 .0 01 <0.01 <0.01 0 .30 10/14 Toads <0.01 <001 <001 <0,01 <0,0I 1 93 ■0 01 <00l <0.01 0 10 2A \an Toads <001 <001 CO, 01 <001 -;0 01 1,43 cOOl <0.01 <0.01 0.20 4A 7/20 Frogs <001 <0,01 0.01 0,01 0,04 6 76 0 02 0.21 0.07 0.39 l(VI2 Frogs <0.01 <00l <001 eOOl .-001 17,60 c 0 0 1 <0.0I <0.0I 1.47 7/20 Toads <0.01 0,02 0 06 0,10 0,12 45 52 0 60 1.01 0.32 2. 50 1012 Toads <0.0I <0.01 <001 <001 -.0,01 i: 39 ■ 0 1)1 .;001 <001 1 46 5A 7/13 Frogs <0.01 <00l <00l <0-OI 0 01 4 19 1)01 002 <001 1)02 IOI8 Frogs <0.01 <001 <0,01 eOOl •001 24 «4 ■ 0 0 1 .;0.0l <0.01 0,99 6A 1(V19 Toads <0.0I <0.01 <001 <0,0I <001 4 59 ■0 01 <0.0I <0.0I 0,51 7A 7/12 Toads <0,01 0.01 0,02 0,01 009 ».34 0 10 0.22 0 17 0,53 KVLS Toads <0.01 <0.01 <0,01 <0,01 <(),01 3 05 ■ 0 01 .-0,01 <0.01 0 63 1(V1S Frogs <0.01 <0.01 .;0,01 <0,01 ■:0 0l 27 01 ■ 1) 1)1 ■ 0 01 ■;o.Ol 0 26 8A 7/20 Frogs <0,01 <0,0I <0,01 0,03 0,03 4 61 0 03 0 1)6 0.05 0 3K 1(V20 Toads <0.01 <00l <001 <0 01 ■ 0 01 0 29 • 1) 0 1 <0.0I <0.0I 003 9A 10^20 Toads cOOl <001 <0 01 <00l • 001 0 9K ■ 001 <0.0I <0.01 0 32 lOA 7/18 Toads <0,0I 0.05 003 0.55 0 12 37 62 0 24 0.84 036 2-36 IW2I Toads <0.01 <00l <00l <001 tOOl 11 i: ■ 0 01 cOOl <0.01 4,44 Fish lA 10/21 Frogs RtSIDUES PPM s Li MM Hi 1-1 A- ( Ml OR Sm Da II Sami' 1 Ms II HIM 1 \HM MIo*.' /I BH( Fr.Aii.i DlCLDRI^ . ,;.DDE , .r'DDF -. /I TDE p.p -TDE ,../. DDT P.p-Dirr NONPROCRAM Samples Hrocs ami Toads IB 7 11 Toads <0.0I 0.02 0.01 4,68 0,02 27,20 0.02 025 0,(M 1 12 ID 1 ' Tiiads <0.01 <0.0I <00l <0.0l <0.0I 3.66 <0.0I <0,0I <0.0I 1,15 III n Krogs <0.0I <0.0I <0.01 <0.0I <0.01 5.35 <0.01 <0.0I <0.0I 0.32 :b IIVM Frogs <0.01 <0.0I <0.0I <0.0I <0.0I 7.93 <0.0I <0.01 <0.0I 0.29 lan Toads <0.0I <0.0I vcs <0.01 <0.0I <0.01 <0.01 <0.01 0 80 cOOl .0,01 <0.01 <0,01 lOB 10/02 Loggerhead Shrike <0.0I Li/ards <0.0I 0.02 <0.0I <0I1I 0 01 4«,92 <0.0I 0.03 <0.0I 0.06 111 1 3 Li/^irils <0.0I <0.0I <0.0I <00l ' (Mil 18 17 <0.0I <0.0I <0.0I <0.0I III 11 Li/ards <0.0I <0.0I <0.0I <0.0I ■..0,01 0.86 <0.0I <0.0I <0.01 <0.0I Mi 7 23 Li/ards <0.0I <0.01 <0.0I <0.0I <0.0I 0.12 <0.0I <0.01 <0.0I <0,01 7 23 Lizards <0.OI 0.01 <0.0I <0.0I <0.0I 0.02 <00l <0,0I <00l ■fOOl 7/23 Lizards -BHC - 0.01 ppm. Vol. 10, No. 4, March 1977 167 BRIEF DDT Residues in Air in the Mississippi Delta, 1975^ Robert D. Arthur, Jimmie D. Cain, and Ben F. Barrentine' ABSTRACT In a previous publication ihc aiilliors reporlcd an 88 percent decrease in IDDT (DDT plus nielaholities) in air between 1972 and 1974 in the Mississippi Delta. This period was the first two years after the use of DDT nas banned in the United States. The present report shows an additional 3f> percent decrease in \DDT levels in air between 1974 and 197^. Thus in the past three years IDDT in air has det reused by 92 percent, a much more rapid decrease than had been expected. Introduction For the past several years, pesticide levels in air in the Mississippi Delta have been measured to determine sea- sonal and yearly trends. Arthur et al. (/) reported pesti- cide levels in the Delta lor 1972-74. The authois observed an 84 percent decrease in 1 DDT (DDT plus metabolites) residues between 1972 and 197.'', the first year ;ifter the ban on DDT use in the United States. A 26 percent decrease in i. DDT in aii was reported between 197.1 and 1974. Sampling; and Analysis Air samples were taken weekly in Stoneville, Miss., located in the middle of the most intensive cotton-growing area of the State. A Misco Model 88 air pesticide sampler was used with ethylene glycol as the trapping agent. A timer was set so that the sampler would operate 4.29 mi- nutes every hour for seven days, making a total collecting ' f^per No 32%. MrsMsMppi AtEncultiiral jnd horc-lr^ I \pcrimcnl Sliitiiin. Missis- Mppi Stale. MtsN SiuJn rinanceil hy II S hnvironmcnral Protection Agency Contract WI-I0-I16W \ pidcmiolonic Studies l*rognim. Technical Services Oivision. Office of Pesticide Programs ' Dqiarlmenl of Biochemistry , Mississippr Slate l.niversity . Mississippi Slate. Miss lV7h2 Repnnts usailahle fiom this addiess time of 12 hours a week. Approximately 7m 'air was sam- pled each week. Analytical procedures and instrument parameters were described previously {/). Results and Discussion Monthly arithmetic and geometric means of 1 DDT in air from 1972 through 197.*^ are presented in Table I. The arithmetic mean in 197.^ was 7,6 ng/m' compared to 11.9 ng/m ' in 1974, and the geometric mean in 1975 was 5. 1 ng/ m' compared to 8.1 ng/m' in 1974. This represents a 36 percent decrease in the arithmetic mean of DDT and a 37 percent decrease in the geometric mean of 1 DDT during the year. Since January 1, 1973, the date on which DDI was banned, arithmetic and geometric means of IDDT in air have decreased 92 percent and 85 percent, respectively. So far some DDT has been found each month in the air from the Delta. The lowest monthly value was 1.3 ng/m 'in December 1975. Since IDDT has decreased so rapidly, it is extremely important to continue monitoring air in the Mississippi Delta in order to determine at what point DDT will no longer be detected. In light of these findings, and as more data on the disap- pearance of DDT from the environment are obtained, authors believe that certain reported characteristics of DDT should be re-evaluated, particularly its extreme stability and'or lack of biodegradabilits in the environ- ment. Illl RAI LIRE CITED (/) .4rlhur. K /).. J. I). Cain, and B. h Harrentine. 1976. .'\lmosphcric levels of pesticides in the Mississippi Delia Bull l-nviion Conlani loxicol 15(2): i:!4- 1.'»4. 168 Pesticides Moniioring Johrnai APPENDIX Chemical Names of Compounds Discussed in This Issue ' ^BATE ALDRIN AROCLOR 3HC (BENZENE HEXACHLO- RIDE) tarbaryl :hlordane DDD DDE DIELDRIN DIMETHOATE ENDRIN ETHION FENTHION HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE MALATHION MIREX NONACHLOR OXYCHLORDANE PARATHION PCBS (POLYCHLORINATED Bl- PHENYLS) SEVIN STROBANE 2.4,'i-T TDE TOXAPHENE TRITHION See temefos Not less than 95% of I.2,3.4.l0.10-hexai:hloro-l .4.4a.5,8.8a-hexahydro-l.4-f'n/<'-<'t"-5.S-dimcthanonaphthalene A mixture of chlorinated terphenyK 1 .2.3.4.5.6-HexachIorocyclohexane (mixture of isomers). Commercial product contams several isomers of which nanimtt is most active as an insecticide. I-Naphthyl N-methylcarbamate 1.2.3..*>.6.7.8.8-Octachloro-2.3.3a.4.7.7a-hexahvdro-4,7-methanomdene The technical product is a mixture of several compounds including heptachlor, chlordene. and two isomenc forms of chlordane See TDE Dichlorodiphenyl dichloro-ethylene (degradation product of DDT) p.p'-DDB: l.t-Dichloro-2.2-bis(/)-chlorophenyl) ethylene w,/?'-DDE: lJ-Dichloro-2-(((-chlorophenyl)-2-(;j-chlorophenyl)ethylenc Main component (/),p'-DDT): (r-Bis(/j-chlorophcnyl) /J ji,/J-trichlortiethane. Other isomers are possible and some are present m the commercial product. o.p' -DDT: [l.l.l-Trichloro-2-((>-chlorophenyl)-2-(;>-chlorophenyI) ethane) Not less than 85% of 1 .2.3.4.IO,K)-hexachloro-6.7-cpoxy-l.4.4a,5.6.7.8.8a-oclahydro-l .4,mAMi.i -.'i.B-dimelhanonaphlhalcnc O.O- Dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate l.2.3,4,IO.U)-Hexachloro-6,7-epoxy-l.4,4a.5.6.7.8,Ka-octahydro-1.4-cn(/«-<'iii/ii-5,8-dimcthanonaphthalcnc O.O.O'.O'-Tetraethyl S.S'-mcthyicnc bisphtisphoroUilhioate O.O -Dimethyl 0-|3-methyl-4-{methylthiol phenyllphosphorothioate l,4.5.6.7.8.8-Heptachlor-3a.4.7,7a-tetrahydro-4.7-r?i(A)-methanoindene l.4,.S.6.7.8.8-Heptachloro 2.3-epoxy-3a.4.7,7a-tetrahydro-4,7-methanoindane Gamma isomer of benzene hexachlonde (1.2.3,4.5.6-hexachlorocyclohexane) of 99+% purity S-[l.2-Bis(ethoxycarbonyl)ethyl] O.O-dimethyl phosphorodilhioate Dodccachloroociahydro-t,3.4-metheno-2H-cyclobuta|cd)pentalene l.2.3.4..S.6.7.8,8-Nonachloro-3a.4.7.7a-tetrahydro-4.7-methanoindan 2,3.4,5.6.6a.7.7-Octachloro-la.lb.V5a.(>.6a-hexahydro-2..S-mcthano-2H-indenQ(l.2-/J)oxirene O.O- Diethyl 0-/7-nitrophenyl phosphorothioate Mixtures of chlorinated biphenyl compounds having various percentages of chlorine See carbaryl. Polychlorinates of camphene. pinene. and related terpenes (2.4.5-Trichlorophenoxy) acetic acid 2.2-Bis(/>-chlorophenyl)-l.l-dichloroethane Chlonnated camphene (67-69% chlorine) Product is a mixture of polychlor bicyclic terpenes with chlonnatcd camphenes predominating. 5 -((y7-Chlorophenylthio)methy DO. O -diethyl phosphorodilhioate Does not include chemicals listed only in tables of paper by Manske/Johnson Vol. !0, No. 4, March 1977 169 Acknowledgment The Editorial Advisory Board wishes to thank the following persons for their valuable assistance in re- viewing papers submitted for publication in Volume 10 of the Pesticides Monitoring Journal: U.S. DEPARTMENT OF AGRICULTURE Daniel R. Embody George F. Fries Kenneth R. Hill -Philip C. Kearney Edwin A. Woolson U.S. ENVIRONMENTAL AGENCY Philip A. Butler Frederick W. Kutz PROTECTION U.S. DEPARTMENT OF HEALTH, EDUCA- TION, AND WELFARE Paul E. Corneliussen Sidney Williams George Yip Anne R. Yobs U.S. DEPARTMENT OF INTERIOR Donald F. Goerlitz 170 Pesticides Monitoring Journal SUBJECT AND AUTHOR INDEXES Volume 10, June 1976— March 1977 Preface Primary headings in the subject index include pesticide compounds, media in which pesticide residues are moni- tored, and major concepts related to the monitoring of pesticides in the environment. Pesticide compounds are listed by common names; trade names are used for those which have no common names. Secondary headings cross-reference the primary head- ings. For a paper which discusses five or more organo- chlorines the compounds are grouped by class under media and concept headings but each compound apjjears individually under the primary headings for pesticide compounds. In the author index all information on a paper appears in the senior author's citations: associate authors, title of the paper, and volume, issue, and pages where the article was pubbshed. Names of associate authors are cross- referenced as minor headings, but the reader is referred to the senior author's entry for the paper's complete cita- tion. Vol. 10, No. 4, March 1977 171 SUBJECT INDEX Abate, see Temefos Air DDT I0(4I:1NI Aldrin Factors Influencing Residues I0(3):I0I-II0 Food and Feed I0(2):4|.43 Sediment Soil ' V aler Wildlife I0(4):I34I4« 10(41: 130.133 t IO(l):24-29 IO(2):6l-67 10(3):10I-1I0 10(3):IOI-1IO IO(l):24-29 IO(2):6l-67 IO(3):IOI-IIO I0( 0:24-29 IO(2):6l-67 I0(3):I0I-II0 Aroclor Factors Influencing Residues I0(3|:84.86 Wildlife IO(3):79-83 IO(3):84-86 Arsenic Factors Influencing Residues IO(2):54-60 Food and Feed 10(4):C Soil I0(2):34-60 AxinphoMthyl Sediment IO(2):61-67 Water 10(21:61-57 Wildlife IO(2):6l-67 Azlnphosmcthyl Sediment 10(21:61-67 Water 10(2):6l-67 Wildlife ia(2):6l-67 B BHC/Lindane Factors InHuencmg Residues 10(1) 10-17 ia(3):IOI-IIO Food and Feed IO(l):l8-23 I0(2):35-40 IO(2):41-43 III|4):I34-I3K I0|4):I2|-1N 10(4): 130- 133 IO(l):24-29 IO(2):6l-67 10(3)101-110 10(3): 101-1 10 10(0:24-29 IO(2):61-67 10(3): 101-110 10(0:10-17 10(0:24-29 IO(2):61-67 I0(3):I0I-II0 Humans Sediment Soil Water Wildlife Bolran Food 10(4): 134- 148 Cadmium Food 10(4): 1 34- 148 CapUn Food 10(4): 134-148 Carbaryl Food 10(4): 134-148 Carboptienotliion Sediment IO(2):6l-67 Water 10(2):6l-67 Wildlife 10(21:61-67 Chlordane Factors Influencing Residues 10(21:54-60 10(31:101-110 Food and Feed IO(2):4l-43 Sediment 10(4): 134- 148 It 10(0:24-29 IO(2):6l-67 10(3)101-110 10(21:54-60 10(3): 101-110 10(3,: 1 14-1 16 Water Wildlife 10(0:24-29 IO(2):61-67 10(3): 101-1 10 10(0:24-29 IO(2):61-67 10(3)101-110 CIPC Food and Feed I0(4):I34-I48 Crufomate Sediment 172 IO(2):6I-67 IO(2):61-67 D 2,4-D Food and Feed 10(3):111-1I3 Soil I0(3):II1-II3 Dactliai'' Food and Feed 10(41:134-148 DCPA Food 10(4):I34-148 DDD, see TDE DDE Factors Influencing Residues 10(0:2-3 10(0:10-17 10(21:44-53 I0(2):54-60 10(3):84-86 10(3):87.91 10(3)101-110 Food and Feed 10(0:18-23 IO(2):4l-43 10(31:114-116 10(41:134-148 I0(4):12l-I29 10(41:130-133 It 10(0:24-29 10(21:61-67 I0(3):87.9I 10(3)101-110 Pesticides Monitoring Journal Humans Sediment Soil 100:54-60 10(3): 101-1:0 10(31:114-115 10(11:24-29 10(21:61-67 10(l):2-3 I0(l):10-17 10ed 10(0:18-23 10(41:134-148 Dieldrin Factors Influencing Residues 10(11:10-17 10(21:44-53 10(21:54-60 10(31:84-86 10(31:87-91 10(31:101-110 Food and Feed 10(2):35-40 IO(2):41-43 ]()|4):134-I48 Humanj 10(41:121-129 10(41:130-133 Sediment 10(11:24-29 10(21:51-67 10(31:87-91 10(31:101-110 Water Wildlife 10(21:54-60 10(3):I01-II0 10(3): 114-116 10(11:24-29 10(2):51-67 10(3): 101-110 10(1):I0-I7 10(0:24-29 10(21:44-53 10(21:61-67 IO(3):79-83 10(31:84-86 10(31:92-95 10(3):101-II0 10(41:149-158 Dimethoate Sediment 10(21:51-67 Water 10(2):51-57 Wildlife 10(2):51-67 Disulfoton Sediment 10(2): 10(2): Wildlife 10(21 61-67 61-67 61-67 Endosulfan Food Sedimeni 10(4)134-148 i( 10(21:61-67 I0(3):87-91 10(21:61-67 10(21:61-67 Endrin Factors Influencing Residues 10(21:54-50 10(31:84-86 10(31:101-110 Food and Feed 10(21:35-40 Humans Sediment Soil 10(21:41-43 10(4): 130-133 It 10(2):61-67 10(31:101-110 10(21:54-60 10(31:101-110 10(2):61-67 I0(3):10I-II0 173 IO(2);6l-67 10(3):84-86 10(31. 1011 10 Etiiion Food ar J Peed 10(2):4l-43 10)41:134-148 Sediment IO(2):6l-67 10(:i;61-67 Wildlife l(X21:61-67 Ethyl Parathion Food and Feed 10(2):41.43 Factors Influencing Residues Age DDT 10(3):96-100 organochlurines IO(2):44-53 10(3): 101-110 Environmenlal. Geogra al, and Locational arsenic 10(2):54-60 DDE 10(31:87-91 DDT IO(2):61-67 10(31:87-91 djeldnn 10(31:87-91 organochlonnes 10(11:10-17 10(21:44-53 10(21:54-60 10(3)184-86 PCBs 10(21:61-67 TDE 10(3):87.91 Farming Practices and Land Use organochlonnes 10(21:54-60 10(31:101-110 quintozene 10(21:68-73 Physical Characteristics of Pesticide temefos 10(11:4-6 Seasonal and Temporal DDT 10(41:168 mercury 10(11:7-9 organochlorines 10(11:10-17 l(K21:44-53 temefos 10(11:4-6 Sex organochlorines 10(21:44-53 Species DDE 10(l):2-3 DDT IO(l):2-3 mercury IO(l);7-9 174 organiKhlorincs 10(21:44-53 I0(3):IUI-I10 Trophic Level DDT 10(31:96-100 mercury 10(l):7-9 Weight DDT 10(31:96-100 Fenitrothion Sediment 10(21:61-67 Water 10(21:61-67 Wildlife l(K2l:6l-67 Food and Feed Fodder DDE 10(31:114-116 DDT 10(31:114-115 DDTR 10(31:114-116 diazinon 10(31:114-116 organophosphales 10(21:41-43 TDE 10(31:114-116 Total Diet arsenic 1(K41:134-148 malathion 10(11:18-23 metals 10(41:134-148 organochlonnes 10(0:18-23 10(41:134-148 organophosphales 10(41:134-148 Vegetables and Grains BHC/lindane 10(21:35-40 2,4- D 10(31:111-113 DDTR 10(21:35-40 dieldrin 10(21:35-40 endnn 10(2):3S-40 HCB 10(21:68-73 mercury 10(31:111-113 PC A 10(21:58-73 PCTA IO(2):68-73 QCB 10(21:68-73 quintozene 10(21:68-73 H HCB Factors Influencing Residues 10(11:10-17 Food and Feed 10)21:68-73 10(41:134-148 10(21:58-73 Wildlife Heptachlor Factors Influencing Residues 10(21:54-60 Food and Feed 10(21:41-43 10(41:134-148 Humans 10(41:130-133 Sediment 10(21:61-67 Soil 10(21:54-60 Water 10(l):24-29 10(2):61-57 Wildlife 10(0:24-29 10(21:61-67 Heptachlor Epoxide Factors Influencing Residues 10)0:10-17 IO)2):54-50 10(31:101-110 Food and Feed 10(21:41-43 Humans Soil 10(41:134-148 10(41:121-129 10(41:130-133 10(2):61-67 10(31:101-110 IO(2);54-60 10(3): 101-110 10(31:114-116 10(0:24-29 10(21:61-67 10(31:101-110 10(11:10-17 10(2):61-67 10(31:101-110 Humans Blood organochlorines 10(41:121-129 Milk organochlorines 10(41:121-129 10(41:130-133 Imidan Sediment llK21:6l-67 10(21:61-67 10(21:61-67 10)0:10-17 KeKhane " , see Dicofol Pesticides Monitoring Journal Lead Food 10(41:134-148 Leptophos Food 10(41:134-148 M Malathion Food and Feed 10(11:18-23 IO(2):41-43 l(X41:134.148 Sediment 10(21:61-67 Water 10(21:61-67 Wildlife 10(21:61-67 Mercury Factors Influencing Residues 10(11:7-9 Food and Feed 10(31:111-113 Soil 10(41:134-148 10(31:111-113 10(1)7-9 VIethoxychlor Food 10(4)134-148 Sediment 10(21:61-67 Water IO(2):6l-67 Wildlife 10(21:61-67 Methyl Parathion Food and Feed 10(21:41-43 10(21:61-67 10(21:61-67 Methyl Trithion Sediment 10(21:61-67 Water 10(21:61-67 Wildlife 10(21:61-67 Mi rex Humans N Nitrofen Food and Feed H1(4|,134 148 Nonachlor Humans 11*4) 1311-133 Vol. 10, No. 4, March 1977 O Orthophenylphenol Food 10(41:134-148 Oxychlordane Factors Influencing Residues 10(11:10-17 10121:44-53 Humans 10(41:130-133 Wildlife 10(1):10-I7 10(21:44- .S3 Parathion Food Sediment PCA Food Soil 10(41 134148 It 10(2)61-67 10(2)61-67 IO(2):6l-67 10(21:68-73 10(41:134-148 10(21:68-73 PCB's (see also Aroclor) Humans 10(4): 121- 129 10(41: I3()- 133 Factors Influencing Residues 10(1)10-17 10(21:44-53 10(21:61-67 Food and Feed 10(21:41-43 10(41:134-148 Sediment Water 10(216167 10(2)61-67 Wildlife 10(1)10-17 10(21:44-53 10(21:61-67 10(3)92-95 10(41 149 158 PCNB, see Quintozene PCP Food PCTA Food Soil 10(21:68-73 10(2)68-73 Pentachloroaniline, see PCA Pentachlorobenzene, see QCB Pentachlorothioanisole, see PCTA Perthane" Food Phorate Food and Feed 10(2):4l-43 Sediment 10(21:61-67 Water 10(21:61-67 Wildlife 10(21:61-67 Phosalone FiKid Phosphamidon SedimenI 10(21:61-67 Water 10(21:61-67 Wildlife 10(21:61-67 Q QCB Food 10(21:68-73 10(2)68-73 Quintozene Degradation 10(21:68-73 Factors Influencing Residues 10(2)68-73 Food and Feed 10(2)68-73 10141 134-IJ8 R Ronnel Food 10(41:134-148 10(21:61-67 Sediment Lakes and Ponds organochlonnes 10(21 61-67 10(41.159-167 organophosphales 10(21:61-67 l(K4l:159. 167 175 Rivcrv and Streams diazinon l(X3):87.9l organochlonnci 10(11:24.29 I0(3):87-9I lOtJIlOlllO Selenium l-t-Xid Soil Croplands 2,4- D 10(3|:11ML1 HCB 10(2l:6S-73 mercury 10(31 111-113 organochlonncs 10(3)101-110 10(31:114.116 10(41: 1'^<)-1(,7 organophosphales 10(4): 15». 167 PC A 10(2)68.73 PCTA I0(2):6«.73 OCB 10(21:6873 quin(ozene 10(21:68.73 Foresls organochlonncs 10(31:101-110 Residential Areas organochlonnes 10(31:101-110 Urban arsenic 10(21:54-60 organochlonnes 10(21:54-60 Food 10(4): 134. 148 TDE Factors Influencing Residues 10(11:10.17 10(21:44-53 10(21 54-60 I0«3l 87.91 10(3): 101. 110 Food and Feed 10(21:41.43 10(31:114.116 10(4)134.148 Human 10(4)121. 129 10(4):13(H33 Sediment 10(11:24-29 10(2) 61.67 10(3187.91 10(3) 101-110 UK 2 1 54-60 10(3) 101-110 10(31 114. 116 UKl):24-29 1(K2):61.67 10(1):11)-17 10(1)2429 10(2| 44-53 10(21:6167 10(31:79.83 10(31:92.95 10(31:96.100 (0(41:149. 15K Tedion, see Tetradifon Temefos Factors Influencing Residues IO(l):4-6 Wildlife 10(11:4.6 Tetradifon Food and Feed 10(11:1823 Toxaphene Factors Influencing Residues 10(21:54-60 Food and Feed 10(21:41.43 10(41:134. 148 Soil 10(21:54-60 Trifluralin Food and Feed 10(21:41.43 Trithion Food and Feed 10(21:4143 w Water (see also Sediment) Canals and Ditches organochlonnes 10(41 159.167 organophosphates 10(4) 1S9-I67 Lakes and Ponds organochlonnes 10(2)61.67 H)l4i ISM-ihT organophosphates 10(21:61-67 10(4):1S9.|67 Rivers and Streams diazinon 10(31:87.91 organiKhlonnes 11X1)24-29 10(31:101. 110 Wildlife Amphibians orgiintxhionnes IIK4) 159. 167 organophosphates 10(41 159-167 Aquatic organochlonnes 10(31:101-110 Birds mercury 10(11:7.9 organochlonnes 10(1)10-17 1(X 31:84-86 10(4): 149-158 10(41:159-167 organophosphates 10(41:159-167 Ducks DDE 10(11:2-3 DDT 10(11:2-3 mercury 10(11:7.9 organochlonnes 10(41:159.167 organophosphates 10(41:159.167 Fish DDE 10(31:96-100 DDT 10(31:96.100 organochlonnes 10(31:92.95 10(31:101110 10(41:149.158 10(41:159.157 organophosphates 10(41:159-167 TDE 10(3)96-100 Invertebrates otTganochlonnes 10(41:159-167 organophosphates 10(4)159167 Mammals organochlonnes 10(21:44.53 10(31:79-83 Plankton DDE 10(31:%. 100 DDT 10(31:96.100 organochlonnes 10(21:61.67 organophosphates 10(21:61.67 TDE 10(31:96-100 Reptiles organochlorines 10(41:159-167 organophosphates 10(41:159.167 Shellflsh organochlonnes UK 11:24- 29 10(41:149.158 temefos 10(11:4-6 Zinc 1(X4|:I34I48 176 Pesticides Monitoring Journal AUTHOR INDEX Arthur. Robert D , Cain, Jimmie D , and Barrentine. Ben F. DDT air in the Mississippi Delu. 1975. 10(4): 168 residues in Lemesch. C, see Polishuk. Z. W. B Barrentine. Ben F.. see Arthur. Robert D. Belisle, Andre A,, see Klaas, Erwin E. Bond. Charles A., see Woodham. Donald W. Cain. Jimmie D.. see Arthur. Robert D Carev. Ann E . Wiersma, G Bruce, and Tai, Han. Pesticide residues in urban soils from 14 United Stales cities. 1970 I0<2):54-60 Carrasco. J. M . Cunat. P . Martinez. M.. and Primo. E. Pesticide residues in total diet samples, Spain— 1971-72. IO(l):18-23 Chun. Michael, see Tanita. Russell. Clark, Donald R., Jr , and Prouty, Richard M Organochlorine residues in three bal speaes from four localities in Maryland and West Virginia, 1973. IO(2):44-53 Cucos, SiMi. see Polishuk. Z, W, Cunat. P.. see Carrasco, J. M. M Maciolek. John, see Tanita. Russell. Manske, D D., and Johnson. R. D Pesticide and other chemical residues in total diet samples (XI 10(41:134-148 Marion, Wavne R Organochlorine pesticide residues in plain chachalacas from south Texas. 1971-72 IO(3):g4-86 Martinez. M , see Carrasco, J M Miles, J. R. W. Insecticide residues on stream sediments in Ontario. Canada. I0(3):87-9I Mitchell, W. G . see Gowen, J. A Mitchell, W G., see Yang. H. S C N Neidermver. William J,, and Hickey. Joseph J Chronology of organochlorine compounds in Lake Michigan fish. 1929-66. l(X3):92-95 o D Ohlendorf, Harry M . see Stendell, Rev C. E)ejonckheere. W., Steurbaut, W. and Kips, R. H. Residues of quiniozene, its contaminants and metabolities in soil, lettuce, and witloof-chicory, Belgium — 1969-74, l(X2):68-73 E Elder, James B., see Stendell, Rey C. Paz. Jacob D. Preliminary study of the occurrence and distribution of DDT residues in the Jordan watershed. 1971 I(X3):96-I00 Polishuk. Z W . Ron. M . Wassermann. M.. Cucos. Simi. Wassermann, Dora, and Lemesch, C. Organochlorine compounds in human blood plasma and milk, 10(4): 12 11 29 Primo, E., see Carrasco, J M Prouty, Richard M., see Clark. Donald R. FiTZPATRicK. George, and Sutherland, Donald J. Uptake of the mosquito larvicide lemcfos by the salt marsh snail. New Jersey — 1973-74, IO(l):4-6 Glooschenko. W. a,, Strachan, W, M, J,, and Sampson, R, C, J, Distribution of pesticides and polychlorinated biphenyls in water, sediments, and seslon of the Upper Great Lakes— 1974 10(2):6l-67 Gowen, J, A,, Wiersma, G, B, and Tai, H, Mercury and 2,4-D levels in wheat and soils from sixteen Stales, 1969 10(3): 1 1 1-1 13 Gowen, J A , Wiersma, G B . Tai. H . and Mitchell. W, G. Pesticide levels in hay and soils from nine States. 1971 10(31:114-116 H HicKEY. Joseph J., see Neidermver. William J. Reed. Lloyd A . see Truhlar. John F. Reeves. Robert G., see Woodham. Donald W. Richardson, Harry, see Woodham. Donald W. Robinson. Hugh F.. see Woodham. Donald W. Ron. M.. see Polishuk, Z. W. Sampson, R. C. J . see Glooschenko, W. A. Stendell. Rev C , Ohlendorf, Harry M . Klaas. Erwin E.. and Elder. James B Mercury in eggs of aquatic birds. Lake Si. Clair— 1973 I0(l):7-9 Steurbaut. W . see Dejonckheere. W Strachan. W, M. J., see Glooschenko. W. A. Strassman. Sandra C. and Kutz. Frederick W. Insecticide residues in human milk from Arkansas and Mississippi. 10(4): 130- 133 Sutherland. Donald J,, see Fitzpatrick. George. Suzuki. M., Yamato, Y.. and Watanabe. T. Organochlorine insecticide residues in vegetables of the Kitakyushu Distiict. Japan— 1971-74. IO(2):35-40 Johnson. Jerry M.. see Tanita. Russell. Johnson, R D . see Manske. D. D. Kim. Ke Chung, see Kurtz. Davtd A. Kips. R. H,. see Dejonckheere. W. Klaas. Erwin E.. and Belisle. Andre A. Organochlorine pesticide and polychlor- inated biphenyl residues in selected fauna from a New Jersey salt marsh — 1967 vs. 1973, 10(4): 149- 158 Klaas. Erwin E , see SYendell. Rey C. Kurtz, David A., and Kim. Ke Chung. Chlorinated hydrocarbon and PCS residues in tissues and lice of northern fur seals. 1972. IO(3):79-83 Kutz, Frederick W.. see Strassman, Sandra C. Tai, H.. see Carey. Ann E. Tai, H.. see Gowen J. A. Tanita. Russell. Johnson, Jerry M . Chun, Michael, and Maciolek, John. Organochlorine pesticides in the Hawaii Kai Marina. 1970-74. 10(0:24-29 Truhlar. John F.. and Reed. Lloyd A. Occurrence of pesticide residues in four streams draining different land-use areas in Pennsylvania, 1969-71. 10(2): 101- 110 w Wassermann, Dora, see Polishuk. Z. W. Wassermann, M.. see Polishuk. Z. W. Vol. 10, No. 4, March 1977 177 Watanabe, T.. s« Suzuki. M. ihc cooperative collon pest managcmeni program in Arizona. 1971— firsl-yca WHiTt. Donald H Nationwide residues of organochlonncs in starlings. 1974. study UX4|:I59-I67 I0(l):10-17 WHrrE. Donald H Residues of DDT and DDE in livers of waterfowl, nonheasl- ern Uuisiana— 1970-71 10(1 1;2-3 -y WlEBSMA. O B . sec Carlv. Ann E. • WiLRSMA. G B . see GowEN. J A Wi.«SM».0 B see Yang. H S C Yamato. Y . see Slizuki, M^ ^^„ W«,DHAM Donald W. Robinson. Hugh F. Reeves. Robert G. Bono. Yang. H S C. Wiersma. G B. and Mitchell. W G. Organochlonne pest.cid Charles A,, and Rir hardson. Harrv Monilonng agricultural insecticides in residues in sugarbeel pulps and molasses from 16 States. 1971, 10(21:41-43 178 Pesticides Monitoring Journal I Information for Contributors rhe Pesticides Monitoring Journal welcomes from all iources qualified data and interpretative information on aesticide monitoring. The publication is distributed jrincipally to scientists, technicians, and administrators issociated with pesticide monitoring, research, and )ther programs concerned with pesticides in the environ- nent. Other subscribers work in agriculture, chemical nanufacturing. food processing, medicine, public health, ind conservation. \rticles are grouped under seven headings. Five follow he basic environmental components of the National 'esticide Monitoring Program: Pesticide Residues in 'eople; Pesticide Residues in Water; Pesticide Residues n Soil: Pesticide Residues in Food and Feed; and 'esticide Residues in Fish, Wildlife, and Estuaries. The ixth is a general heading; the seventh encompasses •riefs. vionitoring is defined here as the repeated sampling and nalysis of environmental components to obtain reliable ;stimates of levels of pesticide residues and related ompounds in these components and the changes in hese levels with time. It can include the recording of esidues at a given time and place, or the comparison of esidues in different geographic areas. The Journal will lublish results of such investigations and data on levels if pesticide residues in all portions of the environment n sufficient detail to permit interpretations and con- lusions by author and reader alike. Such investigations hould be specifically designed and planned for moni- oring purposes. The Journal does not generally publish iriginal research investigations on subjects such as jesticide analytical methods, pesticide metabolism, or ield trials (studies in which pesticides are experimen- ally applied to a plot or field and pesticide residue de- )letion rates and movement within the treated plot or ield are observed). Authors are responsible for the accuracy and validity if their data and interpretations, including tables, charts, ind references. Pesticides ordinarily should be identi- ied by common or generic names approved by national )r international scientific societies. Trade names are icceptable for compounds which have no common lames. Structural chemical formulas should be used vhen appropriate. 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Requests for microfilm and correspondence on editorial matters should be addressed to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U.S. Environmental Protection Agency Washington, D.C. 20460 For questions concerning GPO subscriptions and back issues write; Superintendent of Documents U.S. Government Printing Office Washington, D.C. 20402 1X0 O us GOVRRNMENT PRINTING OKHCE: 1977— 7:0-23fi/3 Pesticides Monitoring Journal CONTENTS Volume 1 1 June 1977 Number Page PESTICIDES IN PEOPLE /)/>7 ciml DDE in /he hlood cinil Jicl of Eskimii chililren from Hooper Bay. Alaska 1 William F. Serat, Min K. Lee, Alherl J. Van Loon. Donald C. Mengle, James Ferguson, John M Burks, and Thomas R. Bender RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury, arsenic, lead, cadmium and selenium residues in fish, 1971-73 — National Pesticide Monilorini; Proi>r(im 5 David F. Walsh. Bernard L. Berger, and Jerry R. Bean Nationwide residues of mercury, lead, cadmium, arsenic, and selenium in slarlinf-s. 1973 35 Donald H. While. Jerry R. Bean, and Jerry R. Longcore Residues of organochlorines and heavy metals in tissues and eggs of brown pelicans. 1969-73 40 Lawrence J. Blus, Burkett S. Neely, Jr., Thair G. Lamonl. and Bernard Mulhem BRIEF Blood levels of chlorinated hydrocarbon residues in the population of a continen- tal town in Croatia O'umoslavia) 54 Elsa Reiner. Blanka Kraulhacker. Mannko .Slipccvic. and Zlata Stefanac APPENDIX 56 HKRAIUM Information for Contributors - 57 58 PESTICIDES IN PEOPLE DDT and DDE in the Blood and Diet of Eskimo Children from Hooper Bay, Alaska^ William F. Serat. Min K. Lee, Albert J. Van Loon, Donald C. Mengle, James Ferguson,- John M. Burks, ' and Thomas R. Bender' ABSTRACT An analysis of the levels of DDT and DDE in the blood of some Alaskan Eskimo children and in the fat of some local marine mammals taken for food suggests that the children's pesticide burden is only modestly lower than that of other American children. Authors suggest that some other food source, perhaps packaged food, supplies a portion of the dieluiy chlorohydrocurhon pesticide. Introduction Marine mammals from virtually all waters contain chlori- nated hydrocarbon contaminants in their tissues, reflect- ing the ubiquitous distribution of agricultural and indus- trial chemicals (2.3.7.8.15). Highest levels of DDT have been reported in migratory seals from Canadian waters of the North Atlantic, from the North Sea, and from the Baltic Sea (8). Except for nonmigratory harbor seals (/), the pesticide and its metabolites are generally less promi- nent in the tissues of mammals from Antarctic and Pacific waters. Although perhaps less dependent on aquatic food sources now than in the past, native populations of western coastal Alaska still derive a substantial portion of their diet from the sea. Thus in the absence of any other substantial contact with DDT, levels of the pesticide and its metabolites in tissues of Alaskan Natives likely reflect the marine component of their diet. Children and adolescents in these. Eskimo populations have lived in the era of worldwide contamination by chlorohydrocarbons. Although a portion of any body burden of DDT-type materials may well have been re- ceived through the placenta or from breast milk (4.5.10). such sources would be difficult to evaluate in the presence of a contaminated marine diet for all but the very young. This paper reports results of a study undertaken to determine whether blood levels of DDT and DDE in Eskimo children of western Alaska are near those of children from other segments of the American population. Alaskan seals and waterfowl which are used as food were also examined for chlorohydrocarbons. Methods BLOOD SAMPLES In May 1972, serum and heparinized whole blood were collected from 40 Eskimo children in Hooper Bay. Thirty- eight sera with 25 matching whole blood samples, and two single whole blood samples were available. They were ^elected from a listing of 204 specimens which had been collected for other purposes. This list representing neariy every school child in the village, kindergarten through ninth grade, was stratified by grade level and sex. A technique of substitution was used so that no specimens finally selected were from children in the same household. The donors" ages ranged from 6 to 17 years; there were 20 males and 20 females. ' Study supported by contract with Epidemiologic Studies Program. Human Effects Monitoring Branch, Technical Services Division. Office of Pesticide Programs. U.S. Environmental Protection Agency. Washington. D.C. * Epidemiologic Studies Program. California State Department of Health. 2151 Berkeley Way. Berkeley. Calif. 94704. Reprints available from this address. ' Bureau of Epidemiology. Center for Disease Control. Public Health Service. U.S- Department of Health. Education, and Welfare. Anchorage. Alaska. Currently Fellow in Cardiology, Department of Medicine. Duke University. Durham. N C ' Chief. Alaska Activity. Bureau of Epidemiology. Center for Disease Control. Public Health Service. US, Department of Health. Education, and Welfare. Anchor;ige. Alaska, Aliquots of 2.0 ml whole blood or sera were extracted with 6.0 ml hexane on a slow rotary mixer. Nanograde (Mallinkrodt) hexane was used in the extraction and as a rinse for all glassware. Pesticide residues in the extracts were quantitated by gas chromatography using electron-capture detectors. Two 6- ft-by-'/4-in. pyrex glass columns allowed separation of residues. One contained 1.5 percent OV-17/1.95 percent QF-1 on 100/120 mesh Chromosorb WHP, and the other Vol. 11, No. 1, .Iune 1977 contained 5 percent OVOIO on SO/ KM) mesh Supelcoport. Columns were maintained at 190° C. inlets at 215° C. and detectors at 210° C. Detectors were operated in the pulsed mode, with 10 percent methane in argon carrier gas at 80 ml/min. Pesticide residue standards were more than 99 percent pure. Recoveries of residues undergoing the analytical regimen were greater than 90 percent and the reliable sensitivity of detection was ().(H)1 ppm for ft.p'-lWE and 0.002 ppm for p.p'-DDV. Measured residue levels in blood and food source samples were not corrected for recovery values. FOOD SOURCE SAMPLES In May 1974. animals which residents had hunted and killed for food near Hooper Bay were tested. Single samples of seal meat, seal fat. and sea duck meat, all components of the native diet, were cleaned by a modifi- cation of the procedure of Stanley and Le Favoure {12). Following digestion in a mixture of perchloric-acetic acids and extraction with hexane, fats in the extracts were destroyed in large part by treatment with 0.5 mi concen- trated HjSOj in a graduated centrifuge tube. After centrif- ugation. the DDT-DDF. residues were quantified by pro- cedures described above. The limit of sensitivity was 0.(X)1 ppm DDK and 0.002 ppm 1)1)1 . Neither the diges- tion mixture nor the HjSOj contained extractable interfer- ing material. In April 197.5. five additional samples of seal oil from hunted species were obtained from food caches in villages 150 miles south of Hooper Bay. Following three extrac- tions with 20 volumes of acetonitrile the extracts were chromatographed. interfering peaks appeared, so the ace- tonitrile extracts were mixed with six volumes of water and then extracted with hexane. Acceptable quantitation of chlorohydrcKarbons could be made from the hexane solution with minimal interference after reacting with concentrated H^SO^. Chromatographic columns were sim- ilar to those used to quanlitale residues extracted from blood. One column was prepared with 5 percent ()V-210 on 1(X)/I20 mesh Gas-Chrom Q and the other with 1.5 percent OV-17/1.95 percent QF-I on 80/l(K) mesh Gas- Chrom Q. The former column operated at 183° C with the carrier gas at 95 ml/min and the lalter operated at 200° C under a gas flow of 80 ml/min Reliable sensitivities were 0.001 ppm for DDE and 0.(X)2 ppm for DDT. Polychlorinated biphenyl compounds (PCB's) are re- ported to be as ubiquitous as DDT-type materials. I'oi this reason extraneous gas-chromatographic peaks in the extract of seal fat were compared with peaks obtained in chromatographing the PC B compound. Aroclor 1242. No correlation could be made between unidentified peaks from the seal fat extract .ind six prominent peaks from a chromatogram of the KB. Therefore, authors cannot report the presence of any such contaminant m I he t,il sample at the sensitivity level of 0.2 ppm for nonmetabo- lized material by the methods used. Aroclor 1254 chromatographed on 1.5 percent OV-17/1.95 percent QF-I on Gas-Chrom Q presented one major peak, from a total of ten, which had a retention time of 6.4 minutes in contrast to 5.0 minutes for p.p'-DDE. Thus there is no discernible nonmetabolized PCS (Aroclor 1254) in lipids from the seals indigenous to the coast of western Alaska, determined at a sensitivity of 0 2 ppm. Results 1)1)1 DDI Table I summarizes results of analyses of DDE in serum. Pesticide levels in the whole blood samples were, in every case where matching serum levels were available for comparison, lower than serum levels by a factor which would relate to the dilution of serum by red blood cells. DDT levels in serum were beneath the limits of reliable detection (().(M)2 ppm) in 29 of the 38 samples and ranged from 0.002 to 0.003 ppm in the remaining nine sera. TABLE 1. Serum levels of p.p'-DDE in children of Hooper Bay. Alaska— 1972 p.p'-DDE Levels, ppm Total Male Female Ages 6-1 1 yr Male Female Ages 12- 17 yr Male Female 1)1)1 DDF IN FOOD-SOURCE SAMPLES Pesticide levels in the single samples of seal fat, seal meat, and sea duck meat ranged from undetectable levels in seal meat to 0.110 ppm DDE and 0.020 ppm DDT in seal fat (Table 2). The highest residue in samples of seal oil was 0.8(lb:0.01 ppm DDE ( lable 3). Discussion A study reported in 1961 (6), preceding the present study by at least 1 1 years, indicated that DDT-related com- pounds were virtually absent in the natural dietary com- lABl.K 2. Levels of p.p'-DDE and p.p'-DDT in three food source samples. Hooper Bay, Alaska — 1974 NLfMBFR Mean Range 38 0,011 0.005-O022 19 0.011 000.'>-0.022 19 0.011 00070016 18 O.OII n ()os-aoi8 9 0.010 0 (M»^ (1 018 9 0012 0 (KWO 016 20 O.OII 0,007-0022 10 0.012 0,008-0,022 10 0010 0,007-0,014 Plsticioe Level, ppm Weight Basis Fat Basis Percent Fat Sample p.p'-ont p.p'-DOJ p.p'-onf. p.p'-ODX Seal fal -Seal meat Sea duck meal 0 105 Nl) 0 (XM 0 019 ND ND 0 no ND 0,17 0 020 ND ND ')<. 5 0 4 2,4 NOTE: NO - no resiJue\ could be Uctccicd within limils of reliable sensiiiviiy. 1*1 SI U IIM S MONI lORINC. JoHKNAl TABLE 3. Levels of chlomhyjnxarhon residues in seal oil, western Alaska — 1975 Residues, ppm Collection Location /J./i'-DDE «.p'-DDT p./j'-DDT Kuskokwim Bay near Kwigillingok (Spotted seal) 0,805:0 01 0,02±0.02 O.29±0.02 (Bearded seaj. baby mukjuk) o.3:±aoi 0.02±0.02 0.23±0.02 Kuskokwim Bay near Kongiganok 0, 19±0.0I 0.02±0.02 0.02±a02 Kipnuk 0.36±0,0I 0,02±0.02 0,I3±0.02 Newtok 0.5I±0.DI O.02±0,02 0 282:0.02 ponents of Alaska Natives. In addition the body fat levels of chlorohydrocarbons described for Natives were sub- stantially lower than those of the general population. It might be assumed, on the basis of average values from a number of measurements, that p.p'-DDT levels in fat were some 450 times higher than in serum and that p.p'- DDE levels were some 400 times higher. Therefore, with reported mean levels of 0.8±0.I0 ppm DDT and 2.Q±0.4I ppm DDE in fat tissue, an approximate serum level of 0.002 ppm DDT and 0.005 ppm DDE might have been expected. Such estimated serum concentrations of the compounds for the study of 1961 (6) are similar to concentrations found now for the children and adoles- cents from Hooper Bay. This comparison suggests that the body burden of these materials has remained relatively stable regardless of the route of exposure, and authors have no indication of recent local usage of any pesticide. Table 4 shows that chlorohydrocarbon levels in the serum of children of Hooper Bay are similar or only modestly lower than in children from most other areas {9.1 1 .13.14). Children in South Carolina (9). especially black children, have dem- onstrated relatively high mean serum DDE and DDT levels, and reference adult populations had even higher levels. The absence of chlorohydrocarbons in dietary samples reported in the previous Alaskan study (6) is in contrast to findings here, although differences in analytical tech- niques and corresponding sensitivities in measurements may well account for this. TABLE 4. Mean serum levels of chlorohydrocarbons in different populations of five States ORTED Studies' AoE. yR Chiorohvdrocarbon. ppm Rep DDE DDT Hooper Bay Alaska 6-17 0 01 1 <0002 South Carolina (»l Whites (v9 0 0246 00066 Blacks 6-9 0.0552 0,0185 Whites Adults 0.0285 0,0112 Blacks Adults 0.1222 0.0263 Florida (//) _ 0.0157 0,0042 Idaho (Ml 3-10 00079 0,0021 11-15 0.0130 0 0030 16-20 0,0149 00030 Utah i;j| <2I 0,0134 0,0036 >2I 0,0209 0,0066 'Numbers in parentheses represent literature references cited in present study. The levels of residues in seal fat. in seal oil. and in sea duck meat found in the present study are notably lower than those in fat of seals taken off eastern Scotland (5.5 ppm DDE and 7.8 ppm DDT), northern and western Scotland (3.4 and 3.8 ppm). and Cabot Strait (5.9 and 5.5 ppm) and Magdalene Island (1.2 ppm and 0.36 ppm) in the Gulf of Saint Lawrence. Canada {8). Furthermore, the levels found in this study do not approach those reported in fat samples of nonmigratory harbor seals from some regions of the eastern North Pacific Ocean (/). Geometric means of IDDT and PCBs were 611 ppm in seals from Puget Sound and 1 1 ppm in seals from Pribilof Islands. Data on the levels of DDE in various tissues from immature males and nursing pups of the northern fur seal from the Pribilof Islands or the coast of Washington (2.3) indicate that fat levels of the compound are seven times as high as those in liver. The immature males would thus be expected to contain some 5 ppm DDE in their fat. a value in keeping with those found in seals from North Atlantic waters. If generally representative, the relatively low levels of chlorohydrocarbons found in the fat and oil samples reported here suggest that lower dietary exposures, at least from an indigenous meat supply, should prevail for Eskimos of western Alaska. This assumption is not borne out by levels of DDE and DDT in serum from the children of Hooper Bay. Environmental levels of the chemically stable compound. DDT. in that locale should not be affected by a recent moratorium on its use. since its introduction into the region would have been largely windborne and in notably smaller quantity than if it had been used in local agriculture. It is possible that prepack- aged food available to many Alaska Natives, especially in school lunch programs, is a source of the chlorohydrocar- bons in the children's blood. Modest dietary exposure and body burdens of the chlorohydrocarbons appear to have been maintained during the past decade or longer. LITERATURE CITED (/) Anas. R. E. 1974. DDT plus PCBs in blubber of harbor seals. Pestic. Monit. J. 8(1):12-14. (2) Anus. R. E.. and A. J. WiLson. Jr. 1970. Organochlorine pesticides in fur seals. Pestic. Monit. J. 3(4):I98-2(X). (J) Anus. R. £.. and A. J. Wihon, Jr. 1970. Organochlorine pesticides in nursing fur seal pups. Pestic. Monit. J. 4<3):l 14-116. (4) Curley. A.. M. F. Copeland. and R. D. Kiinhrough. 1969. Chlorinated hydrocarbon insecticides in organs of stillborn and blood of newborn babies. Arch. Environ. Health l9(5):628-632. (5) Curley. A., and R. Kimhrough. 1969. Chlorinated hydro- carbon insecticides in plasma and milk of pregnant and lactating women. Arch. Environ. Health 18(2): 156- 164. (6) Durhum. W. F.. J. F. Armstrong. W. M. Upholt. and C. Heller. 1961 . Insecticide content of diet and body fat of Alaskan natives. Science 134(3493):I880-1881. Vol. II. No. I.June 1977 (7) Hohlvn. A. V. 1972. Monitoring organochlorine contami- nation of the marine environment by the analysis of residues in seals, in marine population and sea life. Fishing News (Books) Ltd.. London, pp 226-272. (S) Hohlen. A. F.. and K. MursJen. 1967. Organochlorine pesticides in seals and porpoises. Nature 216(5122): 1274- 1276. (9) Keil. J. E., W. Weston III. C. B. Loadholl, S. H. Sandifer. and J. J. Colcoloiifih. 1972. DDT and DDE residues in blood from children. South Carolina. 1970. Pestic. Monit. J. 6(1):!-.^ (/()) O'Leury. J. A.. J. E. Davis, W. F. Edmondsons, and G. A. Reich. 1970. Transplacental passage of pesticides. Am. J. Obstet. Gynecol. l07(l):65-68. (//) Riidi)m\l^i, J. L.. W. B. Deicliinann, A. A. Rcy. and T. Merkin. 1971 . Human pesticide blood levels as a measure of body burden and pesticide exposure. Toxicol. Appl. Pharmacol. 20(2): 175-185. (/2) Slanley. R. L.. and H. T. Le Favoare. 1965. Rapid digestion and cleanup of animal tissues for pesticide resi- due analysis. J. Assoc. Off. Agric. Chem. 48(3):666-667. UJ) Warniik. S. L. 1972. Organochlorine pesticide levels in human serum and adipose tissue, Utah — fiscal years 1967- 71. Pestic. Monit. J. 6(1):9-13. {14) Waison. M.. W. W. Benson, and J. Gahica. 1970. Serum organochlorine pesticide levels in people in southern Idaho. Pestic. Monit. J. 4(2):47-50. {.15) Wolnnm. A. A., and A. J. Wilson. Jr. 1970. Occurrence of pesticides in whales. Pestic. Monit. J. 4(1):8-10. I'l SI u 11)1 s MoNi roRiNG Journal RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury, Arsenic, Lead, Cadmium, and Selenium Residues in Fish, 1971-73 — National Pesticide Monitoring Program David F. Walsh,' Bernard L. Berger,^ and Jerry R. Bean' ABSTRACT As part of the National Pesticide Monitoring Program, the Fish and Wildlife Service, U.S. Department of Interior, analyzed selected fish samples from 100 monitoring stations for residues of mercury, arsenic, lead, cadmium, or selenium in 1971-73. At most stations, detectable residues of all metals were present in more than 95 percent of the composite samples. Fishes with mercury residues exceeding 0.5 mglkg wet weight in the whole fish were mainly predators. Fishes with residues of arsenic, lead, cadmium, and selenium exceeding 0.5 mglkg included predatory and nonpredatory species. The number of composite samples in which residues of these elements exceeded 0.5 mgl kg decreased from 1971 to 1973, whereas the percentage of samples with detectable residues increased slightly. Only se- lected samples were analyzed in 1973; therefore, these figures should be used only cautiously as trend data. Species of fish collected varied considerably between geographic regions but were similar from year to year within each region. Introduction The Fish and Wildlife Service (FWS) has contributed to the National Pesticide Monitoring Program by determin- ing residues of various pollutants in fish. Authors have analyzed for organochlorines since 1967, mercury since 1969, and lead, cadmium, selenium, and the metaioid arsenic since 1971. Results of analyses were published for organochlorines through 1969 {4,6) and for mercury through 1970 (5). The present report presents results of analyses of heavy metals conducted on fishes collected 1971-73 at 100 stations throughout the United States (Fig. 1). On the basis of 1971 and 1972 results from 100 stations only, selected samples were analyzed for metals in 1973: caution should be exercised in interpreting these data. Except for Redhorse and fishes collected in Hawaii, ' Fish and Wildlife Service, U.S. DepanmenI of Inlenor. 17 Executive Park Drive. N.E.. Atlanta, Ga. 30329. ^ Division of Population Regulation. Fish and Wildlife Service. U.S. Department of Interior. 1717 H Street. N.W., Malomic BIdg.. Rm. 527. Washington. DC ' Denver Wildlife Research Center, Fish and Wildlife Service, U.S. Department of Interior. Bldg 16. Denver Federal Center. Denver. Colo. common names of fishes used throughout this report are those designated by the American Fisheries Society (/). Redhorse is used to designate unidentified members of the genus Moxostoina. Fishes from the Hawaiian streams were Tilapia (Tilapia mossambica). Cuban limia (Limia viiiata), and Chinese catfish (Clarias fuscus). Methods FISH COLLECTIONS Fish were collected by FWS biologists, personnel of State fish and game agencies, and local commercial fishermen. Collection gear included a variety of nets and traps, hook and line, and electrofishing equipment. The use of chemi- cal collecting agents was not permitted. As in previous reports (1,7) three composites of three species, each consisting of two to five adult fish, were to be collected at each of the stations from September to November, In the Hawaiian stations up to 26 fish were analyzed. Sample collections included a replicate for each species in 1971, but for only one of the three species from each station in 1972 and 1973, After length and weight of the fish had been determined, each composite was wrapped in foil, frozen, and shipped to the analytical laboratory for prepa- ration and residue analyses. Localities of collection, spe- cies, size, and number offish appear in Tables 1-3. LABORATORY METHODS 1971 — Two subsamples were taken from ground whole body composites: a 1-g sample for mercury and a 15-g sample for arsenic, cadmium, and lead. Mercury determi- nations followed the procedures of Okuno et al. {13). Arsenic was measured by the Jarrell-Ash procedure (7) with the following modifications: a 1:1 (v/v) mixture of concentrated sulfuric acid (H.2SO4) and nitric acid (HNOJ was used to digest the 15-g samples, no perchloric acid was added during digestion, and the final volume was adjusted to 60 ml with distilled water. A subsample of the Vol. II, No. 1, June 1977 Pesticides Moniiorinii Journal digest representing 2.5 g of sample was analyzed by atomic absorption. The digest from the arsenic procedure was also used for determining the presence of lead and cadmium. A sub- sample representing 10 g of sample was placed in a beaker and adjusted to 60 ml with distilled water, three drops of 1 percent (v/v) thymol blue were added, and the pH was adjusted to 5-6 with aqueous solutions of NaOH and HjSOj. This solution was transferred to a 250-ml separa- tory funnel, 10 ml of a I percent aqueous solution of a chelator (diethyldithiocarbamic acid, sodium salt) was added, the funnel was shaken for 2 minutes, and the extract was allowed to stand for 10 minutes. A 10-ml portion of water-saturated methyl isobutyl ketone (MIBK) was added, and the funnel was shaken for 2 minutes to extract the metals into the MIBK. The aqueous solution was drawn off, discarded, and the MIBK was collected in a 16-by-125-mm culture tube. This solution was aspirated into the flame of an atomic absorption spectrophotometer. Recoveries of the metals were determined from the analy- ses of fish samples fortified at different levels with each metal. The overall mean from triplicate analyses for arsenic at three levels (0.1, 0.25, 0.5 ppm) was 82 percent with a standard deviation of 9.3 percent. The mean and standard deviations for lead (0.1, 1,5 ppm) and cadmium (0.05, 0.25, 0.5 ppm) were 109 percerit ± 21.0 percent and 99 percent ± 17.7 percent, respectively. 1972 — Homogenized samples for mercury determinations were dried in a microwave oven for 15 minutes before combustion, but were otherwise analyzed as described for 1971. For lead and cadmium, 1-g subsamples of ground whole-body composites were dried in a beaker on a hot- plate, charred with infrared lamps, and ashed in a muffle furnace at 50ff'C for 4 hours. After cooling, the residue was dissolved in 1 ml concentrated HNO,,, then heated until dry and white. To the cooled residue, I ml of concentrated HNO;, was added, then diluted to 20 ml with water. The solution was warmed on a hotplate, cooled, and adjusted to a pH of 3 ± 0.2. then quantitatively transferred to a 125-ml separatory funnel with 2 ml water. A 1-ml portion of a 1 percent (w/v) aqueous solution of ammonium pynrolidine-dithiodi-carbamate was added to the funnel and mixed. After 2 minutes. 10 ml of MIBK was added, the funnel was shaken for 1 minute, solvents were allowed to separate, and the lower aqueous layer was drawn off and discarded. A 10-ml solution of 5 percent HNO;, was added to the funnel and shaken for 30 seconds. Solvents were allowed to separate, and the lower aqueous layer was collected. This sample solution was analyzed for both lead and cadmium, using a carbon rod atomizer on an absorption spectrophotometer. Arsenic and selenium residues were determined in sepa- rate 1-g subsamples of the ground whole-body compos- ites. Analyses for both followed the Jarrell-Ash (7) proce- dure with the following modifications: samples were placed in a Chromel wire sample holder and the holder was hung on the hook of a ground glass stopper placed in a 2-liter combustion flask containing 20 ml of 25 percent hydrochloric acid (HCl) solution for arsenic determina- tions, or 20 ml of a 1:1 (v/v) mixture of 50 percent HCl and 25 percent H2SO4 for selenium determinations. Flasks were flushed with oxygen, stoppered, and the contents were ignited with an infrared igniter. After combustion, flasks were allowed to stand 1 hour in order for the acid solution to entrain combustion products. For the arsenic determination, the sample solution was transferred to a 100-ml pear-shaped flask and 20 ml of 40 percent (w/v) hydroxylamine hydrochloride was added; after the solution had been allowed to equilibrate for 15 minutes. 1 ml of a 6 percent aqueous solution of potas- sium iodide was added. After another 15 minutes, 2 ml of a 40 percent SnClj solution was added and allowed to stand another 15 minutes; a Teflon-covered magnetic stirring bar was dropped into the flask and the flask was connected to an arsine generator. The solution was stirred briefly, 1 g of 20 mesh zinc was added and mixed for 2 minutes, and the generated arsine was swept with helium into the burner of an atomic absorption spectrophotome- ter. Selenium sample solutions were decanted from the com- bustion flasks and rinsed with 20 ml acid (50 percent HCl and 25 percent H2SOJ. A 10-ml portion of this solution (0.25 g sample equivalent) was placed in a pear-shaped flask with 30 ml of the HCI-H2SO4 acid mixture and I ml of stannous chloride (SnClj). A stirring bar was placed in this flask and the generator was connected as in the procedure for arsenic analysis. A magnetic stirrer was placed under the flask and 2 g of 20 mesh zinc was added; after 15 seconds of stirring, the hydrogen selenide gener- ated was swept into the burner of the atomic absorption spectrophotometer. Mercury recovery studies were made to compare mi- crowave drying with the former P2O5 procedure for drying samples. Analysis of each of three samples using both drying procedures showed no significant differences (P = 0.55). Recoveries of lead and cadmium were determined by fortifying samples at varying levels ranging from 0. 1 to I ppm for lead, and 0.01 to 0.1 ppm for cadmium. The overall mean recovery and standard deviation for lead was 90 percent ± 11.6 percent and 100 percent ± 13.6 percent for cadmium. For arsenic, the overall recovery from samples fortified with levels ranging from 0.05 to 0.3 ppm was 91 percent ± 18 percent. Selenium was deter- mined by the procedure of Church and Robison (i). Recoveries of selenium by the procedure averaged 100 percent with a standard deviation of 15 percent. 1973 — Mercury, lead, and cadmium were determined as in 1972. Arsenic was determined as in 1972, except that the Vol. II. No. I.June 1977 zinc used in generating arsine was 2(H)-40() mesh in a slurry of distilled water ( 10 g zinc to 20 ml distilled water). and an elcctrodeless discharge lamp (EDL) and power supply v^eie used in place of the hollow cathode lamp. Selenium was measured as described for 1972. but the light source was an EDL. llhrKCTION LIMITS ANnSTANDARnS The limits of detection of the metals in the composite fish samples vseie the same in all 3 years. Expressed as mg/kg wet vseight, detection levels of each metal were mercury, 0.01; arsenic. 0.05: lead. 0.10; cadmium. 0.05: and selen- ium. 0.05. Analyses for metal residues were conducted on subsamples of composites prepared as described by Hen- derson et al. for laboratory C (6). During all analyses, standard solutions of each metal were used for quantification and reagent blanks were used to detect possible contamination. Results of the initial run and of the in-house rerun by DWRC varied by less than one order of magnitude. For this reason and for a degree of brevity, rerun results are not presented. The National Academy of Sciences recommends that to protect fish and predatory aquatic organisms, total mer- cury burdens in these organisms should not exceed 0.5 mg/kg net weight {12). For the present purposes, authors have considered that any level exceeding 0.5 mg/kg in whole body components is a high level at which mercury, arsenic, lead, cadmium, or selenium would harm fish. To show annual trends for these elements in all fish, each residue value from the initial analyses was placed into at least one of the following categories: composites ana- lyzed, composites with residues, composites with residues at or below detectable levels, composites with residues between detectable levels and 0.5 mg/kg. or composites with residues above 0.5 mg/kg (Table 4). CROSSCHKCK ANALYSES In cross-check analyses, total mercury was determined by the techniques described by the Joint Mercury Residues Panel {10) and modified as described by Henderson et al. (5). Arsenic and selenium residues were determined as described in the eleventh {8) and twelfth (9) editions, respectively, of the methods book of the Association of Official Analytical Chemists. Lead and cadmium residues were determined as follows: to a 12.5-g sample portion. 5 ml of 10 percent magnesium nitrate was added, the samples were then dried and charred on a hotplate and ashed overnight at 500^0. The samples were wetted with nitric acid, dried on a hotplate, and ashed again at 500°C for 20 minutes. After the sample had cooled, 2 ml concentrated HCL and 15 ml H.,0 were added. Samples were boiled and stored in 50-ml volumetric flasks. Final determinations were made with a Perkin-Elmer model 303 spectrophotometer. PRKSKNTATION OF RESULTS The Denver Wildlife Research Center (DWRC) was con- tracted to conduct the initial analyses and the Wisconsin Alumni Research Foundation (WARF) was contracted to conduct cross-check analyses on selected samples. Also. DWRC conducted a methods check by repeating the analyses on several samples for all 3 years. Samples for cross-checking were selected according to results of initial analysis or the history of high residues at a particular station. A level of 0.5 mg/kg or greater was the criterion generally applied for selection. Mercury, arsenic, lead, and cadmium were analyzed in the samples from 1971. and selenium was added in 1972. In 1973, the rising costs of analytical work precluded the measurement of all metals. Therefore, only selected samples were analyzed for mercury, arsenic, lead, and cadmium, but all samples were analyzed for selenium residues to provide data for 2 consecutive years, 1972 and 1973. The initial and the cross-check data for 1971-73 are presented in Tables 1-3. Results Mercury residues were present in all samples of fish collected (Tables 1-3). Of the 100 stations sampled, 25 in 1971, 12 in 1972. and II in 1973 yielded composites in which mercury concentrations exceeded 0.5 mg/kg. Hen- derson et al. (5) reported composites exceeding 0.5 mg/kg from 9 stations in 1969 and 20 in 1970. Only stations 1-50 were sampled in 1969. These data indicate a general increase of mercury contamination from 1969 to 1971 and a decrease from 1971 to 1973. Henderson et al. (5) also pointed out that certain predator fishes such as bass, perch, and squawfish had the highest mercury residues. Of 12 species in the present study in which mean residues exceeded 0.5 mg/kg during any of the 3 years, 7 were predators: chain pickerel, whit; perch, smallmouth bass, largemouth bass, whitebass. sauger. and Northern squawfish; and 5 could be considered nonpreda- tor, i.e.. nonpiscivorous: bowfin. carp, yellow and brown bullhead, and channel catfish. Residues of mercury, arsenic, and selenium were gener- ally present in more than 90 percent of samples in the present study (Table 4); lead was detected in 56 percent and cadmium in 76 percent of the 584 composites ana- lyzed in 1971. Arsenic residues (Tables 1-3) were generally lower than those of mercury; concentrations in mg/kg ranged up to 3.40 in 1971, 1.70 in 1972. and 1.24 in 1973. Residues in excess of 0.5 mg/kg were detected in composites from eight stations during the 3 years. Unlike mercury resi- dues, arsenic residues above 0.5 mg/kg were not confined to the predatory fishes. Lead residues above 0.5 mg/kg were present in fish from 16 stations in 1971. 34 stations in 1972. and 10 stations in Pesticides Monitoring Journal 1973 (Tables 1-3). The highest concentrations in mg/tcg were detected in fish from the Hawaiian streams: 1 .4 in 1971. 5.2 in 1972. and 1.4 in 1973. Like arsenic residues, lead residues above 0.5 mg/kg were not confined to the predatory fishes. Composites with cadmium residues above 0.5 mg/kg were few in 1971 (less than 1 percent) and 1972 (4 percent), and. of the 75 selected samples analyzed in 1973, none exceeded 0.5 mg/kg (Table 4). This suggests a decrease in the level of detectable residues of this metal, particularly since authors biased these results by selecting the samples to be analyzed during 1973 from stations at which resi- dues in some samples exceed 0.5 mg/kg during 1972. Like lead and arsenic, cadmium residues above 0.5 mg/kg are not restricted to the predatory fishes. Cadmium is an extremely dangerous metal that accumulates readily in fish, has chronic effects, and is considered a threat to fishery resources (/2). The selenium analyses conducted only in 1972 and 1973 showed residues in essentially all samples (Table 4). Residues exceeding 0.5 mg/kg were distributed equally between predatory and nonpredatory fishes. Naturally occurring selenium has been detected in various environ- mental segments, but the biological significance of selen- ium residues is unknown (/2). Excessive levels of metals, greater than 0.5 mg/kg, were found in some fish from most river systems, but such high levels apparently occurred more frequently in certain stations than in others. Of the 1 1 stations with excessive mercury levels in 1973, 6 were from the Atlantic coastal streams (one each on the Stillwater and Kennebec Rivers, Maine; Merrimac River, Mass.: Pee Dee River, S. C; Savannah and Altamaha Rivers, Ga.): 1 on the Gulf coastal streams (Tombigbee River, Ala.); 1 on the Missis- sippi River system (Little River, Minn.): 3 on the Colum- bia River system ( 1 on the Willamette and 2 on the Columbia River). Of those 1 1 stations, 6 exceeded 0.5 mg/ kg during 1972 and 1973 and 3 (Kennebec River, Maine; Savannah River, Ga.; Tombigbee River, Ala.) had resi- dues that exceeded 0.5 mg/kg during all the years re- ported. McKim. who was quoted in a paper by Olson et al. (/4). exposed brook trout to methyl-mercuric chloride and determined residues in muscle tissue to be within 90- 100 percent of those in the whole body. This suggests that not only should the fish and their predators be protected, but that fish from some rivers should not be consumed by humans. Olson et al. (/4) exposed fathead minnows [Pimcphales promelas) to concentrations of methylmercury ranging from 0.018 to 0.247 mg/liter. After 48 weeks, analysis of whole body samples showed mean residues ranging from 1.47 to 10.9 mg/kg total mercury. For the most part, these residues exceed levels of the present study. However, fish from the control water of Olson's experiment, in which no methylmercury was added and residues averaged <0.01 ppm, had mean residues of 0.21 mg/kg (95 percent confi- dence interval, 0.17 to 0.25 mg/kg): water used in the experiment was unfiltered water from Lake Superior. In 1973, residues in samples from Lake Superior, Bayfield, Wis., ranged from 0.09 to 0.40 mg/kg. Olson et al. (14) point out the potential significance of low concentrations of mercury in natural waters. In a biochemical evaluation of methylmercuric chloride, Christensen (2) showed only a decrease in glutamic oxaloacetic transaminase (GOT) activity (L-aspartate: 2-oxoglutarate aminotranslerase, EC 2.6. 1.1.) in brook trout embryos, and a decrease in weight and an increase in GOT activity in alevins. He further concluded that the concentrations used ( 1 .03 fj-gjliter) in the study would be unsafe for the species if exposure were extended from egg through adult. These laboratory studies combined with residue data in the present study suggest that the health of many species collected is in danger. Arsenic levels exceeding 0.5 mg/kg were found in fish from five stations (Tombigbee River, Ala.; Lake Michigan: Lake Superior; Red River, Okla.): those from the Great Lakes had high residues more frequently than the others. A study by the National Academy of Sciences and National Academy of Engineering showed residues up to 1(X) mg/kg in shellfish; sea water normally contains 2 to 3 fg /liter (12). Authors point out that acute effects of arsenic have been investigated, but little is known about sublethal chronic effects except that arsenic is readily accumulated by marine organisms (12). Geographic distribution of high levels of lead appears to have decreased between 1972 and 1973. For instance, of the 14 stations located from the Stillwater River, Maine, south to the Pee Dee River (Northern Atlantic coastal streams), 9 exceeded 0.5 mg/kg in 1972 and 4 exceeded 1.0 mg/kg in 1973. Only 5 of the 14 stations had concen- trations exceeding 0.5 mg/kg and none had composites with residues above 1.0 mg/kg. On the Mississippi River system in 1972, 13 of 35 stations had composites with residues above 0.5 mg/kg; 6 of those exceeded 1.0 mg/kg and 1 exceeded 5.0 mg/kg. In 1973, only I station. Des Moines River. Iowa, exceeded 0.5 mg/kg. This trend generally prevailed where excessive lead residues were found in 1972. There are. however, two stations that do not follow this encouraging trend. In 1973, fish from the Columbia River at Grand Coulee, Wash., and Manoa Stream. Hawaii, had composites with residues of 1.0 mg/ kg and 1.4 mg/kg, respectively. The former represents an increase and the latter represents only a slight decrease. The source of these residues should be investigated. As indicated earlier, results of the in-house methods check by DWRC corresponded closely with the study each year; data are not included in this report. The in- house methods check represents the quality control of the laboratory and shows that the data presented are accurate Vol. II. No. I, June 1977 and can be interpreted within the limits of the methods used. Validity of the present findings is further enhanced by the fact that the cross-check data are from another laboratory which used slight K different techniques, yet agree closely with data here. Kurthermore. examination of the results between replicated samples at one station also indicates that the residues are representative of environ- mental levels. NAS and NAE have stated. ". . . at present, it is not possible to predict accurately the amount of total metal in any environment that may be lethal, biologically active or contributorv to toxicity . . ." (12). Authors submit that the data presented in this program are indicative of environmental levels of arsenic, lead, cadmium, and water with a wide variation in such characteristics as hardness and pH, and that criteria should be established for each metal and water. For an update on the effects of pollution on fish, authors recommend an excellent review by McKim et al. (//) which includes chemical and biological methodology used, the effects of water quality, pesticides, industrial pollutants, including metals, and domestic and radioactive wastes. Residues in river fish analyzed in the present study are based on wet weight, whole fish. The concentrations of residues in the edible portions would probably be lower. Acknowledgments Authors thank the biologists of the Fish and Wildlife Service. State agencies, and universities, and the many commercial fishermen who assisted in collecting fish samples for this study. LITERATURE CITED (/) American Fisheries Society 1970. A list of common and scientific names of fishes from the United States and Canada. Spec. Publ. No. 6. Washington. D. C. 149 pp. (2) Chrisiensen. G. M. 1975. Biochemical effects of methyl- mercuric chloride, cadmium chloride and lead nitrate on embryos and alevlns of the brook trout. Sahelimis fonlin- alis. Toxicol. Appl. Pharmacol. 32:191-197. 0) Cliiirrh. M. R.. timl W. H. Rohi.son. 1974. A rapid, routine absorption spectrometry method for the determination of selenium at sub-microgram IcvoK in animal tissue. Int. J. F-.nviron. Anal. Chem. 3( 1):. 12.3- .1.11 . (4) Henderson. C. A. /«,(,'//,v, unJ W. L. Ji>hn.\on. 1971. Organochlorine insecticide residues in fish — fall 1969 (Na- tional Pesticide Monitoring Program). Pestic. Monit. J. 5(1):1-11. (.5) Henderson. C A. Ini,'lis. anil W. L. Johnson. 1972. Mercury residues in fish. 1969-1970 — National Pesticide Monitoring Program. Pestic. Monit. J. 6<.1): 144-159. (6) Henderson. C. W. L. Johnson, and A. Inglis. 1969. Organochlorine insecticide residues in fish (National Pesti- cide Monitoring Program). Pestic. Monit. J. 3(3): 145-171. (7) ///t,'/i Sensilivily Arsenic Delerminalion hy Atomic Absorp- tion. 1971. Jarrell-Ash Applications t,aboratory, Jarrell- Ash. Co., Waltham. Mass. 5 pp. mimeograph. («) Horwitz. W., ed. 1970. Official methods of analysis. Ilth ed. Association of Official Analytical Chemists. Washing- ton. D.C. 1015 pp. (9) Horwitz. W.. ed. 1975. Official methods of analysis. 12th ed. Association of Official Analytical Chemists, Washing- ton. DC. 1094 pp. (10) Joint Merciir\ Residues Panel Report. 1961 . Analyst 86 (I026):608-614. (//) McKim. J. M.. D. A. Benoit. K. E. Biesinf,'er. W. A. Branfis. and R. E. Siefert. 1975. Effects of pollution on freshwater fish. J. Water Pollut. Control Fed. 47(6): 1711- 1768. (12) National Academy of Sciences, National Academy of Enf;ineerin!>. 1972. Section III — Freshwater aquatic life and wildlife, and Section IV — Marine aquatic life and wildlife. Pages 106-296 in Water Quality Criteria. Ecologi- cal Research Series. EPA-R3-73-033 March 1973. NAS. Washington. D.C. (13) Okuno. I.. R. A. Wilson, and R. E. White. 1972. Determi- nation of mercury in biological samples by Hameless atomic absorption after combustion and mercury-silver amalgamation. J. Assoc. Offic. Anal. Chem. 5.'>( !):96-!00. (14) Olson, a. F.. D. I. Mount. V. M. Snarski. and T. W. Thorslund. 1975. Mercury residues in fathead minnows, Pimephales promelas Rafin.. chronically exposed to meth- ylmercury in water. Bull. Environ. Contam. Toxicol. 1 4< 2): 129-1.34. 10 RkSTICIDI S MONIIORINCI JOLIRNAl TABLE 1. Concentrations of mercury, arsenic, lead, and cadmium in whole fish. 1971 — National Pesticide Monitoring Program Species No. - Fish Average Size Residues, mg/kg WET weight Station Number and Location Length, in. Weight, lb Mercury Arsenic Lead Cadmium Atlantic Coast Streams 1. Stitlwaler River White sucker 5 12 5 (1,8 0.20 <0.05 0.26 <0.05 Old Town. Maine White sucker (R) 5 12 5 0,8 0.28 <0.05 ND <0.05 Yellow perch 5 7.5 0.2 0.32 <0.05 ND <0.05 Yellow perch (R) 5 7 9 0.2 0.32 <0.05 0.26 0.05 Chain pickerel 5 15 1 0,7 0.35 (0.45) <0.D5 «0.05) 0.16 «0.2) <0.5 (<0.05) Chain pickerel (Rl 5 15.0 07 0.39 <0.05 ND ND 51. Kennebec River White sucker 5 12.7 0.8 0.18 <0.05 ND <0.05 Hinckley. Maine White sucker (R) 5 13,8 09 0.18 0.05 ND ND Yellow perch 5 10.3 0.5 0.50 (083) <0.05 (<0.05) ND (0.4) <0.05 «0.05) Yellow perch (R) 5 9,1 0.3 O.SO <0.05 ND ND Smatlmouth bass 5 13 11 11 0.46 <0.05 0.21 ND Small mouth bass (R) " 14,4 14 1.20 (1.88) <0.05 (<0.05) ND (0.5) <0.05 (<0.05) 52. Lake Champlain Pumpkmseed 5 7.3 0.4 0.12 0.10 ND <0.05 Burlington. VI (0.23) (0.08) (0.4) (<0.05) Pumpkinseed (R) 5 6.9 0,3 0 18 <0.05 0.78 ND Yellow perch 5 8.9 0,3 0.37 (0.31) <0.05 «0.05) 0.57 (0.7) <0.05 (0.06) Yellow perch (R) 5 10.0 0,4 0.31 <0.05 ND ND Chain pickerel 3 16,2 1,0 0.39 0.05 0.13 <0.05 Chain pickerel (R) 2 138 07 0.34 <0.05 0.11 <0.05 ^i. Merrimac River While sucker 5 12,0 0 7 0.15 <0.05 0.36 <0.05 Lowell. Mass. White sucker (R) 5 III 0,5 0.46 <0.05 0.36 <0.05 Pumpkinseed 5 6 2 0 2 0.38 <0.05 0.24 ND Pumpkinseed (Rl 5 4,4 0.1 0.42 <0.05 0.16 ND Yellow perch 5 10,7 0,6 0.14 <0.05 ND ND Yellow perch (R) 5 10,7 (1,6 0,42 <0.05 ND ND 2. Conneclicut River White catfish 5 12,1 (18 0,17 0.04 0.41 0.14 Windsor Locks, Conn. White catnsh (R) 5 129 11 0.21 0.06 0.51 0,17 Yellow perch 5 8,8 0,3 0.25 <0.05 0.20 <0.05 Yellow perch (R) 5 10 0 0.6 0.20 <0.05 0.12 <0.05 While perch 4 8,6 0.4 0.38 <0.05 0.23 0.39 While perch (Rl 4 10.0 0.6 0.44 0.05 0.15 <0.05 3. Hudson River Goldfish 5 9.4 0.8 0.06 Oil 1.30 0.12 Poughkeepsie. N.Y. Goldfish (Rl 5 9.9 0.8 0.19 0.08 0.52 0.15 Pumpkinseed 5 6.1 0.1 0.13 0.07 ND <0.05 Pumpkinseed (R) 5 6.0 0.2 0.07 0.05 0.12 <0.05 Largemouth bass 5 10.9 0,9 0.19 <0.05 ND <0.05 Largemouth bass (Rl 5 10.8 0,9 0.10 0.05 ND <0.05 54. Raritan River Golden shiner 5 7.6 0 2 0.12 0.10 0.13 <0.05 Highland Park. N.J. Golden shiner (Rl 6 6.3 0,1 0.26 0.10 ND <0.05 While sucker 5 13 4 1,2 0.11 0.08 0.32 0.10 White sucker (Rl 5 12.3 10 0.18 <0.05 0.24 0.05 White perch 5 9.7 0.7 0.34 0.08 0.16 <0.05 White perch (Rl 5 9,6 06 0.32 0.07 ND <0.05 4. Delaware River While sucker 5 14.6 1,3 0.06 0.06 0.51 0.06 Camden, N.J. White sucker (Rl 5 13 9 1,2 0.06 0.05 0.54 <0.05 Brown bullhead 5 117 0,8 0.12 0.06 0.38 <0,05 Brown bullhead (Rl 5 10,9 0,7 0.04 (0.05) 0.06 (0.06) 0.36 (0.45) <0.05 (<0.05) While perch 5 9.5 0,5 0.25 0.06 0.78 <0.05 While perch (R) 5 9.8 0,6 0.20 <0.05 0.47 <0.05 5. Susquehanna River Carp 4 18.0 3,0 0.12 0.09 0.12 ND Conowingo Dam. Md. Carp (R) 4 18.9 3,3 0.05 0.20 ND 0.10 Channel catfish 5 15.2 1,1 0.04 0.07 0.14 <0.05 Channel calfish (R) 5 15.4 1,3 0.02 0.06 0.17 <0.05 Yellow perch 5 8.6 0,3 0.08 0.06 ND <0.05 Yellow perch (R) 5 8.4 0.3 0.10 0.08 ND <0.05 6. Potomac River Carp 5 17.2 2.6 0.26 0.13 0.11 0.08 Little Falls, Md. Carp (R) 5 15.7 2,0 0.19 0.11 0.21 O.ll Redhorse' 5 13.5 1,0 0.18 <0.05 ND 0.06 Redhorse (Rl 5 14.7 1,2 0.15 0.06 ND 0.09 Smallmouth bass 5 14.1 1,4 0.32 <0.05 ND ND Smallmouth bass (R) 4 10.2 0,5 0.14 <0.05 ND 0.05 55. James River Redhorse sucker 1 16.5 1,8 0.15 0.05 ND ND Richmond. Va. Redhorse sucker (Rl 2 16.0 1.6 0.10 <0.05 ND 0.23 Channel calfish 2 21.5 3.6 0.23 <0.05 ND 0.05 Channel catfish (Rl 2 17.0 1.4 0.11 <0.05 ND ND Largemouth bass 5 11.6 0.9 0.24 <0.05 ND ND I Jircemoulh bass ( Rl 5 8.6 0.3 0,23 <0.05 ND ND {Continued next page) Vol. 11, No. I.June 1977 11 TABLE I (cont'd.). Coiuenlrulions of mercury, arsenic, lead, and cadmium in whole fish. 1971 — National Pesticide Monitoring Program Average Size Residues, mo/kg wet weight No. Fish Station Number and Location Species Length, in. Weight, lb Mercury Arsenic Lead Cadmium 7. Roanoke River Rcdhorsc 4 Id 7 2.5 0.13 <0.05 ND ND Roanoke Rapids. N.C Redhore (Rl 4 19 8 2.9 0.12 <0.05 ND 0,17 Brown bullhead 3 9.7 0.3 0.06 <0.05 ND ND Largcmouth bass 5 10 5 0.7 0.14 0.10 ND 0,06 Larigenunith hass