BOSTON PUBLIC LIBRARY GOVSBAiMENT QOCU^tKTS UEPARTMtWT L- Ftb 16 2000 j " O O J PESTICIDES MONITORING JOURNAL JUNE 1981 VOLUME 15 NUMBEI PEMJAA (15) 1-75 (I^A^^/i^J?^/?)^ rnEy, /^.Q . j^A 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. The Pesticides Monitoring Journal is published by the Management Support Division in the Office of Toxic Substances, 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 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 Allan R. Isensee, Science and Education Administration — Agricultural Research Herman R. Feltz, Geological Survey Address correspondence to: PaulFuschini (TS-793) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, D.C. 20460 Editor Roberta B. Maltese CONTENTS Volume 15 June 1981 Number 1 Page FISH, WILDLIFE, AND ESTUARIES Polychlorinated Biphenyls and Other Organic Chemical Residues in Fish from Major United Slates Watersheds Near the Great Lakes, 1978 1 Oilman D. Veith, Douglas W, Kuehl, Edward N. Leonard, Kenneth Welch, and Glenn Pratt Organochlorine Pesticide Residues in Some Indian Wild Birds 9 Bhupendra S. Kaphalia, Mirza M. Husain, Tejeshwar D. Seth, Ashwini Kumar, and Coimbatore R. Krishna Murti Cadmium, Lead, Mercury, Arsenic, and Selenium Concentrations in Freshwater Fish, 1976-77 — National Pesticide Monitoring Program 14 Thomas W. May and Gerald L. McKinney FOOD AND FEED Pesticide, Heavy Metal, and Other Chemical Residues in Infant and Toddler Total Diet Samples— (ID— August 1975-July 1976 39 Roger D. Johnson, Dennis D. Manske, Dallas H. New, and David S. Podrebarac Organochlorine Pesticides and PCBs in Cod-Liver Oil of Baltic Origin, 1971-80 51 Jerzy Falandysz Pesticide, Metal, and Other Chemical Residues in Adult Total Diet Samples — {XII) —August 1975-July 1976 54 Roger D. Johnson, Dennis D. Manske, and David S. Podrebarac APPENDIX ^ 70 ERRATUM 72 MEETING NOTICE 73 Information for Contributors 74 FISH, WILDLIFE, AND ESTUARIES Polychlorinated Biphenyls and Other Organic Chemical Residues in Fish from Major United States Watersheds Near the Great Lakes, 1978 Oilman D. Veith/ Douglas W. Kuehl," Edward N. Leonard,' Kenneth Welch," and Glenn Pratt* ABSTRACT wenty-six composite samples of fish were collected during 978 from United States watersheds near the Great Lakes nd analyzed for polychlorinated biphenyls (PCBs) and dated organic chemicals. PCB mixtures resembling Aroclor 254 were found in all samples, and mixtures resembling 'roclor 1242 (or 1016) were found in 77 percent of the vnples. Total PCB concentrations in the whole-fish com- osite samples ranged from 0.13 to 14.6 ppm; 65 percent of le samples contained > 2 ppm PCBs. DDT and its metab- Hles were also found in all samples. ZDDT concentration 'as 1.66 ppm, and 81 percent of the samples contained : 1.0 ppm ZDDT. Chlordane ranged from < 0.007 to 2.57 pm in 38 percent of the samples. Hexachlorobenzene was jund in 65 percent of the samples, ranging from <^0.005 ) 0.447 ppm. Other chemicals identified by gas chroma- Jgraphy/mass spectrometry included petroleum hydro- ^rbons and chlorobenzenes, chlorostyrenes, chlorophenols, nd chlorinated aliphatic compounds. Fish from the Ashta- ula River (Ohio), Rocky River (Ohio), and Wabash River ndiana) contained extremely complex residues of chlori- ated and other organic chemicals. Introduction a 1976, authors extended their gas-liquid chromatogra- hy/mass spectrometry (GLC/MS) exploratory studies f organic chemical residues in Great Lakes fish to in- lude residues in fish from major United States rivers M the purpose of tabulating polychlorinated biphenyls PCBs) and other xenobiotic chemicals accumulating in ^e aquatic environment. A previous work (6) showed lat the types and concentrations of chemical residues 1 fish varied immensely among rivers in the same area f the country. Fish in some rivers in eastern Michigan nd Ohio contain PCB residues almost exclusively. U.S. Environmental Protection Agency. Environmental Research Lab- ratory, 5201 Congdon Boulevard, Duluth, MN 55804 U.S. Environmental Protection Agency, National Pollutant Discharge Umination System (NPDES) Permits Branch-Region V, 230 S. Dear- 3'n, Chicago. IL 60605 whereas fish from the Ashtabula River nearby in Ohio contain at least 19 major chlorinated chemicals in addi- tion to PCBs. Fish from rivers a few miles apart differ in hexachlorobenzene (HCB) residues by a factor of al- most 3,000. The wide variation in both the types and amounts of chemicals in different waters suggests that it is not cost- effective to apply trend-monitoring programs to the problem of determining the extent of contamination by toxic chemicals. Trend monitoring requires a predeter- mined list of chemicals to monitor, precise methods for measuring small differences in concentration, and, to minimize biological variability, a fairly rigid sampling protocol with respect to species and size. In contrast, the initial problem regarding toxic industrial chemicals is the identification of every major chemical component of residues from hundreds of industrial areas. Such areas may not have diverse fish populations because of the contamination. Finally, order-of-magnitude estimates of residue concentrations by GLC/MS may be used to di- rect enforcement-related field studies to "hot-spots" for more intensive studies. A previous work (6) indicated that taking composite samples of any fish near the mouth of a river provides a convenient, enriched sample of bioaccumulable chemi- cals being discharged into the entire watershed and ex- cludes the bulk of the less persistent, nonaccumulable chemicals attributable to natural products and sanitary wastes. Because the accumulation of chemicals in fish species varies considerably less than the concentration of chemicals in rivers and areas of rivers, composite samples also provide adequate estimates of relative con- centrations in the sampling areas. This paper presents the results of exploratory studies of chemicals in fish from rivers in Minnesota, Wisconsin, Indiana, Michigan, Ohio, and New York (Figure 1). OL. 15, No. 1, June 1981 1 ■> 1976 SAMPLES • 1978 SAMPLES FIGURE 1. Map of U.S. EPA Region V showing siles where fish samples were collected for GLC/MS analyst bioacciimiilating hazardous organic chemical residues Materials and Methods COLLECTION OF FISH The areas that were sampled for detailed GLC/MS analyses in 1976 and the 26 sampling areas for the pres- ent study (1978) are shown in Figure 1. Table 1 gives a brief description of the 1978 sampling locations. State and federal field personnel used nets and other conventional apparatus to collect fish. Sampling areas included known problem areas disclosed by previous studies as well as rivers for which little data were avail- able. Where possible, samples were collected near mouths of rivers or confluence of major tributaries. Sample areas are designated as general areas of rivers rather than exact locations because of the migratory nature of many fish and the tendency of bioaccumulable chemicals to contaminate large areas near the discharge. Samples were wrapped in solvent-rinsed aluminum foil, frozen, and shipped with dry ice to the Environmental Research Laboratory in Duluth, Minnesota. PREPARATION OF SAMPLES The procedures for preparation and analysis of samples have been described previously (6). Composite whole- fish samples were homogenized with a Hobart t grinder. Subsamples weighing 20 g were extracted Soxhlet extractor with a 1:1 mixture of hexane methylene chloride. Following Florisil column clea samples were analyzed by electron-capture (EC) flame-ionization (FI) GLC and multiple-ion-dete( (MID) GLC/MS. GLC analysis provided measurement of PCBs, F DDE, and 2DDT, as well as information on the ( plexity of the residue with respect to other nonf organic chemicals. MID GLC/MS was used to qu tate cis- and /ran.r-chlordane, cis- and trans-nona-d heptachlor epoxide, and oxychlordane. A procec blank was performed with every fifth sample. Dupli analyses of several samples gave results within 4 pei for both EC GLC and MID GLC/MS. Recovery I laboratory-raised fathead minnows spiked with 1 PCB and 50 ppb pesticides was >92 percent for ' compound. A second subsample (100 g) of each fish was Sox extracted in a 1:1 mixture of hexane and meth) chloride, cleaned by gel-permeation chromatogn (2), and qualitatively analyzed by full mass r Pesticides Monitoring Join * g s H o 2 a &• d X CL. u E o 0- D. J ft. i 12 z S o 2 Sg" CO m dS: U 5 0»- « m » "* c^ » o • i/^ r- oi ^D V V m •— r~ 'i' ^- »o ■— _ rJ ^ r-; rn r^ o o o o o o o o o o o o o O 00 u^ ^C ^ ^^ m in O (N ^ 0\ O; \C ^ rj —* fi (N ^' (S \0 ^C >/^ ID y^, -^ 2 V V V <^ - "V IQ o fi !S s d d d d d l-" 1-H 6 00 (S m ■* O O (S (S is d d d d d ^ d ,_ o l/^ \D oo r- VO r% q w-i ri r- m r- «-i **i o o tt r* n o o en m d o o o o o »-; V 00 <-i •- O O 00 o V V en 3 1-5 u « VI >* u a> c D. I- u u tn rj «N ■ s 4t u u ■d c la 5 _a O 41 > o a t c *« Xi « ^ c ? Jl rt ^ i-' r^ O s c uT 0. u u £i c a; u u S s" > "E. XJ 2 .°1 £ ^ &> s o s o •S 3 O <3- s<2 2 2 02 en 2 e 3 O 2 .s S 2 2 ■so § °ii 3 £ I .2 S S § o ° ^ " I . u uT uT Pi J- > « « _, •i K ;5 ;5 5 C C o U E E - 3 3 2 -a o n 4h ^ ,t cu (n S S O o -.a 2 1 is O JO z d * >- o z q « z n II s z 15, No. 1, JraE 1981 (m/z 50-550) scanning GLC/MS. Again, procedural blanks were performed with every fifth sample, and spiking experiments showed >90 percent recovery. ANALYSES The GLC/MS analyses were performed on a Finnigan 4000 mass spectrometer interfaced to an INCOS data system. Instrument parameters and operating conditions follow : Column; glass, capillary, 30-m long by 0.25-mm (ID), coated with SE-30 Temperature. °C: column programmed from 100 to 225° at 4°/ minute (with a 20-minute hold) ion source 280 Carrier gas: helium flowing at 30 cm/second Mass scan: 50-550/2 seconds Electron energy: 70 eV Emission: 350 mA MID GLC/MS analyses were also performed on the above equipment, with the same temperature program- ming, followed by a 20-minute hold. The mass spec- trometer was computer-controlled to monitor six ions for equal time during a 2-second period. The six ions were m/z 373 for chlordane, m/z 409 for nonachlor, m/z 272 for heptachlor, m/z 355 for heptachlor epox- ide, m/z 387 for oxychlordane, and m/z 442 for de- fluorotriphenylphosphene (DFTPP). DFTPP was used as an internal standard for MID quan- tification. Each extract was spiked with DFTPP to give a concentration of 10 ng/jiJ. Two standards of the chlor- dane components of 5 ng/ju,l and 20 ng//J each were used as samples after each set of five fish samples. Quan- tification was based on a lO-ng/^al solution with standard INCOS software. The quantified standards gave values within 4 percent of expected values. The limit of de- tectability was 0.50 ppb wet weight. Ion source was operated as above with an emission of 350 mA. Results and Discussion PCBs were found in all 26 samples at concentrations ranging from <0.1 ppm in fish from the upper reaches of Cattaragaus Creek, New York, to 14.6 ppm in fish from the Raisin River, Michigan. Aroclor 1254 consti- tuted over 50 percent of the total PCB residues in the majority of the samples. Aroclor 1016/1242 was found in 20 of the 26 samples at concentrations ranging from <0.1 to 9.83 ppm in Raisin River fish. These results are consistent with the authors' previous study of 58 sam- ples, in which Aroclor 1016/1242 was present in 77 percent of the samples (6). Fish from the Fox River (Wisconsin), Raisin River (Michigan), and Ashtabula and Greater Miami Rivers (Ohio) remain heavily contaminated with PCBs. Twelve other samples contained PCB residues >2 ppm. Al- though PCB concentration in the edible portion o: fish is expected to be lower than that in the whole the present data suggest that 65 percent of the fish pies would pose significant hazards to animals, su( mink, feeding on the fish (i) . DDT, once the major organochlorine contaminai fish in many U.S. waterways, is a minor contamina the river systems investigated in the present study though DDE was found in all samples, 2DDT coi tration in 81 percent of the samples was below 1.0 the maximum concentration was 1.66 ppm, in Ontario fish. HCB was the next most prevalent organochlorine f in the present study; 65 percent of the samples tained measurable quantities. Although most sar contained <0.05 ppm HCB, Ashtabula River fish tained 0.447 ppm. The authors' previous work (6 vealed concentrations of 3.14 ppm HCB in fish fron Ashtabula River in 1976. The apparent decline m£ the result of sampling variability or of pollution-a ment measures taken since the 1976 discovery. The that fish analyzed in the present study were coll upstream from the alleged discharge (3) into the tabula River may also be significant. An ongoing investigation is a direct result and a primary bene this type of biomonitoring, because areas of highest lamination are identified for more intensive stuu minimum cost. Chlordane and components of technical chlordane I found in 38 percent of the samples. Although fish I most of the rivers contained <0.05 ppm chlordane! from the Grand River, Michigan, and Rocky I Ohio, contained 2.57 ppm and 2.68 ppm, respect The total nonachlor concentrations in these fish 3.07 ppm and 1.82 ppm, respectively. Heptachloi heptachlor epoxide were found only in fish fron Wabash, Ashtabula, and Huron Rivers and Lake tario. Oxychlordane was present in Rocky River, I Ontario, and Lake Erie fish at a maximum conce) tion of 167 ppb. The coho salmon caught at the n\ of the Cattaragaus Creek, New York, are undouti Lake Erie fish, which would account for the oxyc dane residues. In addition to chemicals quantified by GLC or GLC/MS, the results of exhaustive GLC/MS stud> the fish extracts are summarized in Table 2. The fill organic chemicals identified in Table 2 are aliphati^ aromatic hydrocarbons. Heptadecane, pentadecanei related hydrocarbons are natural products of bsl: algae, as well as the results of petroleum contamini from mixtures such as fuel oil. Present methodology mits only qualitative statements about the sourd^i these compounds, based on FI GLC chromatogii Pesticides Monitoring Joif dinecarboxamide appeared to be as common as adecane in fish from these rivers. iachloroanisole was identified in 15 of the 26 sam- of fish. The authors have observed halogenated 3les in effluents of sewage treatment plants receiv- the respective halogenated phenols (4). Present in- lation suggests that the anisoles arise from methyla- of the corresponding phenols by bacteria. Studies at Environmental Research Laboratory in Duluth (un- ished data) have shown that fish exposed to halo- ited phenols do not produce the anisoles metaboli- '. The presence of pentachloroanisole may therefore ; from the widespread use of pentachlorophenol as a d preservative. Because the bioconcentration factor the methyl derivative of phenols is several orders of nitude greater than that of the phenol, pentachloro- ole as an environmental contaminant is probably the It of selective bioaccumulation of a more persistent ibolite of pentachlorophenol. tachloronorbornene and hexachloronorbornadiene ! found only in the Wabash River fish collected w Terre Haute, Indiana. These two compounds are •mediate chemicals in the production of cyclodiene icides, and their occurrence is linked to manufac- ig sites for these pesticides. These chemicals were ided in Table 2 because they are unique in the lash River, not because of widespread occurrence, ie data confirm the authors' studies of fish from the :r Wabash (6) and suggest a source of contamina- in the vicinity of Terre Haute, Indiana. The only r identification of heptachloronorbornene and hexa- ronorbornadiene in the aquatic environment was irted by the Food and Drug Administration, U.S. artment of Health and Human Services, in fish from Mississippi River below Memphis, Tennessee (5). :x was identified only in Lake Ontario fish. The com- jd was first observed in 1973 and was extensively in- gated by state and federal agencies. Is were identified in all samples and, although the 1-, penta-, and hexachlorobiphenyl homologs were lominant, PCBs containing two or three chlorine IS were found in 19 of the 26 samples. above-mentioned quantitative and qualitative data ent a reasonably comprehensive description of the nical residues that contaminate fish in some major rs. However, these data fail to illustrate adequately leed for improved biomonitoring or analytical meth- development. Fish from many of the rivers contain lue mixtures that are similar to the GLC chromato- 1 of the Maumee River fish presented in Figure 2. chromatogram was obtained by using a 30-m, wall- sd capillary column and an electron-capture detec- Although there are many chemicals in this extract, is, HCB, and natural products account for all peaks in the chromatogram. Therefore, the residues in this area are comparatively simple to work with, and routine GLC methods should be adequate for any surveillance work. In contrast, the Ashtabula, Wabash, and Tittabawassee Rivers contain extremely complex mixtures of bioaccu- mulable chemicals. An electron-capture capillary chro- matogram of extract of fish from the Ashtabula River is shown in Figure 3. Chemicals identified include tetra-, penta-, and hexachlorobutadiene; chlorinated benzenes up to hexachlorobenzene; penta- and hexachlorobutyla- mines; and numerous hexa-, hepta-, and octachlorosty- renes. Despite the identification of almost 100 chemicals in this sample, those identified to date are largely only those in the highest concentrations. A comprehensive study of residues in fish from the Ashtabula and Wabash Rivers is presented elsewhere (3). Even though progress has been made in developing methods for rapid characterization of chemical residues, the long lists of chemicals being published from studies of environmental samples should not lead to the conclu- sion that present methods are thorough or adequate. In many of the rivers the authors have studied during the past four years, chemicals are present that cannot be identified without improved cleanup methods and in- strumental techniques. More important, the number of sample sites studied would have to be increased by an order of magnitude in order to screen even a single sam- ple from industrial areas over the next five years. Major improvements in the current state-of-the-art methods for GLC/ MS screening will have to be made before an ade- quate number of samples can be thoroughly studied. LITERATURE CITED (/) Aulerich, R. J., R. K. Ringer, H. L. Seagran, and W. G. Youatt. 1971. Effects of feeding echo salmon and other Great Lakes fish on mink reproduction. Can. J. Zool. 49(5) :61 1-616. (2) Kiiehl, D. W.. and E. N. Leonard. 1977. Isolation of xenobiotic chemicals from tissue samples by gel permea- tion chromatography. Anal. Chem. 50( 1) : 182-185. (3) Kuehl. D. W.. E. N. Leonard. K. ]. Welch, and G. D. Veith. 1980. Identification of hazardous organic chemi- cals in fish from the Ashtabula River, Ohio, and Wabash River, Indiana. J. Assoc. Off. Anal. Chem. 63(6): 1238-1244. (4) Kuehl. D. W., G. D. Veith, and E. N. Leonard. 1978. Brominated compounds found in waste-treatment efflu- ents and their capacity to bioaccumulate. In Water Chlorination, Vol. 2, Ann Arbor Science Publishers, Inc., Ann Arbor, Mich. pp. 175-192. (5) Spehar, R. L., G. D. Veith, D. L. DeFoe, and B. A. Bergstedt. 1977. A rapid assessment of the toxicity of three chlorinated cyclodiene insecticide intermediates to fathead minnows. National Technical Information Service, Washington, DC, EPA-600/3-77-099. 22 pp. (6) Veith, G. D., D. W. Kuehl, E. N. Leonard, F. A. Puglisi, and A. E. Lemke. 1979. Polychlorinated bi- phenyls and other organic chemical residues in fish from major watersheds of the United States, 1976. Pestic. Monit. J. 13(1) :l-n. 15, No. 1, JtTNE 1981 TABLE 2. Chemical contaminants identified by GLC/MS in fish from United States rivers near the Great Lakesf Chemical Contaminant Wisconsin Fox River River Lake Pepin Wabash Wabash River River (above ( below St. Tittaba- Terre Terre White Joseph Grand wassee Haute) Haute ) River River River River Raisin River Scioto Ashtai' River Rivi i Tridecane Tetradecane Pentadecane Hexadecene Hexadecane Heptadecene Heptadecane Octadecane Nonadecane Eicosane Naphthalene Methylnaphthalene Dimethylnaphthalene Biphenyl Melhylbiphenyl C2-Biphenyl Phenanthrene Fluoranthene Pyrene Fluorene Dibenzofuran Acenaphthalene Methylbenzanthracene Dibenzothiophene Pyridinecarboxamide Terphenyl Phenylnaphthalene Pentachlorobenzene Hexachlorobenzene Peniachloroanisole 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 Penlachlorophenol Pentachlorobenzyl alcohol DDE TDE DDMU DDT Heptachloronorbornene Heptachloronorbornadiene Mirex Photomirex Endrin Monochlorobiphenyl Dichlorobiphenyl Trichlorobipheny! Tetrachlorobiphenyl Pentachlorobiphenyl Hexachlorobiphenyl Heptachlorobiphenyl Octachlorobiphenyl Hexachlorostyrene Heptachlorostyrene Octachlorostyrene Chlordane Nonachlor Heptachlor Heptachlor epoxide Oxychlordane NOTE: 1 = Confirmed by GLC and MS retention time data; 2 = confirmed by MS data; 3 = suggested by MS data. Pesticides Monitoring JctN BLE 2 (cont'd.). Great Great Maumee Miami Miami Catta- San- River Maumee River River Catta- RAGAUS ON Chagrin Rocky CONNEAUT Black Portage dusky (Water- River (MlAMIS- (Eliza- Lake RAGAUS Creek ER River River River River River River VILLE) (COLLEN) burg) BETHiowN) Ontario Creek (Mouth) 2 2 2 2 2 2 1 1 1 1 1 1 I 1 1 1 I 1 1 1 1 1 1 1 2 2 2 2 2 2 2 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 3 1 1 3 1 1 2 3 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ' 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 I 1 1 1 1 1 1 1 1 1 15, No. 1, June 1981 ^.j^-— v-^ 30 MINUTES FIGURE 2. Capillary electron-capture chromatogram of fish extract from Maumee River, Ohio. FIGURE 3. Capillary electron-capture chromatogram of fish extract from Ashtabula River, Ohio. Pesticides Monitoring Jot. 9 Organochlorine Pesticide Residues in Some Indian Wild Birds ' Bhupendra S. Kaphalia, Mirza M. Husain, Tejeshwar D. Seth, Ashwini Kumar, and Coimbatore R. Krishna Murti ABSTRACT sidiies of BHC and DDT were estimated by gas-liquid 'omatographic analysis of tlie internal body organs, depot , and blood plasma of a few species of Indian wild birds itured in and around the urban area of Lucknow. Total IC and y-BHC (lindane) levels were high in breast muscle. ?r, heart, and lung tissues of pigeon, crow, and vulture, npared witli the respective tissues of chicken, cattle egret, i kite. More lindane and total BHC was found in tissues vulture compared with other species. The major part BHC isomers in the brain of birds examined was ac- mted for by a-BHC. Total BHC detected in depot fat of \ws was 29.7 ppm; lesser amounts were found in vulture, e, and cattle egret, respectively. Total DDT levels were ■nparable in the blood plasma of chicken, pigeon, crow, and tie egret, although residues generally showed the follow- order in the tissues examined: chicken < pigeon < cat- egret < crow < kite < vulture. High levels of DDT re delected in depot fat of crow, kite, and vulture (50.8, 0, and 95.3 ppm, respectively). Avian species thus reflect •logical tnagnification of BHC and DDT residues, presum- y due to their food habits. Introduction ganochlorine pesticides and related compounds have :n detected in significant amounts in the environment i in human body tissues (8). Pesticides are dispersed h during their manufacture and by their extensive ! for controlling vector-borne diseases and crop pests. vironmental contamination from persistent organo- orines has been recognized as a threat to wildlife for ire than two decades. Many residues have been found tissues and eggs of birds in Europe and North Amer- (7, 20, 23. 24). Some reports {10) of high mortal- of birds have been attributed to poisoning by organo- orines. The bioconcentration of DDT and other or- lochlorine residues is apparently associated with the 'itat and dietary habits of different species of birds 4, 9, 17, 23). For example, earthworms are the prin- al source of DDT for robins (/). These pesticides er the bodies of earthworms through soil, which is largest reservoir of pesticide residues. iustrial Toxicology Research Centre, Post Box 80, Mahatnia dhi Marg, Lucknow-226001. India Certain species of birds, because of their worldwide dis- tribution, are considered good indicators of environmen- tal pollution by pesticides {16). For example, crows have been used by many workers {11, 15, 18, 21. 22). The present report deals with DDT and BHC residues in wild pigeon {Columha livia), house crow {Corvus splendens), common pariah kite {Milvus migrans), Ben- gal vulture (Gyps bengalensis), and cattle egret (Bubul- cus ibis). Farm-bred chickens were taken for compari- son. Materials and Methods Wild pigeon, crow, kite, vulture, and cattle egret (three birds in each species) were obtained through commer- cial bird trappers during February and March 1980, from the urban area of Lucknow, a major city located 26°52' north and 80°56' east in the Indo-Gangetic plain. It is one of the most populated regions in the world, with a tropical climate. Chickens (average body weight 500 g) were purchased from the State Live Stock Farm, Lucknow. Within 24 hours of capture, birds were sacrificed, blood was collected in heparinized containers, and plasma was separated. Depot fat and internal body organs were excised. The average bird weights were 200, 305, 750, 4200, and 260 g for pigeon, crow, kite, vul- ture, and cattle egret, respectively. ANALYSIS FOR ORGANOCHLORINE PESTICIDE RESIDUES Blood Plasma — One milliliter blood plasma was mixed with 3 ml concentrated formic acid (98 percent pure) and extracted with «-hexane by shaking 1 hour. The n- hexane extract was washed with glass-distilled water and cleaned by concentrated H^SO^ treatment according to Dale et al. (6), as modified in the Arrhenius Labora- tory, Analytical Chemistry, University of Stockholm, Sweden. Body Tissues — Minced tissue (2 g) from body organs was thoroughly homogenized with 7 ml formic acid and transferred to a 50-ml conical flask. The homogenizing tube and pestle were washed twice with 5-ml portions of n-hexane, and the washings were collected in the flask. The homogenate was shaken in a 40 °C water bath for 1 hour and then the solvent layer was withdrawn. 15, No. 1, June 1981 Minced depot fat (0.5 g) was homogenized with 3 ml formic acid and 5 ml n-hexane, transferred to a 50-ml conical flask, and treated as above. The extracts of brain and body fat samples above were partitioned with acetonitrile (saturated with ?i-hexane) to remove fat. Pesticide residues were re-extracted in n-hexane. The solvent extract was passed through a col- umn filled with anhydrous Na^SOj and collected in a round-bottomed flask. The column was washed with 10 ml ;i-hexane and the washings were added to the original filtrate. The solvent extract was evaporated to dryness under reduced pressure and then re-dissolved in 5 ml n-hexane. Fractions (2 ml) were treated with 2 ml fum- ing HoSO^ and centrifuged, and the solvent layer was withdrawn. Pesticide residues were determined by gas-liquid chro- matography (Varian Aerograph Series 2400), using electron-capture detection ( 'H), at the following operat- ing conditions: Carrier gas: Gas pressure: Gas flow: Detector temperature: Injector temperature: Column temperature: Column: pure nitrogen passed through silica gel and molecular sieve to remove moisture and oxygen, respectively 65 psi 40 ml/minute 200 °C 190°C ISO'C glass spiral column, 6 ft < coated with 1.5 percent OV-17 Vb in. ID, -I- 1.95 per- cent OV-210 Residue peaks were identified by thin-layer chromatog- raphy (TLC) on silica gel G-coated glass plates {14) and comparison with reference standards obtained from PolyScience Corp., Niles, Illinois. Further confirmation of the residues was done by chemical methodology and column chromatography (79). Recoveries of BHC isomers, DDT, and DDT metabi (p,/7'-DDE and p,p'-TDE) in the fortified sampli liver, brain, muscles, and body fat were between 7C 94 percent. Sensitivity of the method was about ( ppm for BHC isomers, aldrin, and p,p'-DDE and £ 0.002 ppm for p,p'-DDT. All reagents and chemicals used were high purity were checked for interferences under the experim conditions. Results and Discussion The concentrations of BHC and DDT residues in 1 plasma, brain tissue, and depot fat are summarize Tables 1 and 2. Levels of total BHC, y-BHC (lindi and total DDT in breast muscle, liver, heart, lung, ney, and spleen of birds are shown in Figure 1 values are expressed in terms of whole-tissue wet we results were not corrected for recovery. DDT and BHC and their residues are widely distril in the ecological system. Although BHC residues* excreted rapidly (13), slow accumulation does occ the body tissues and body fat on chronic exposure. '. and derivatives are quite stable and are resistai enzymic action; thus, residues accumulate in biolc tissues. The levels of DDT residues present in the are occasionally taken as an index of contaminatici DDT and DDT metabolites of the local environri The general tendency appears to be that the smalle TABLE 1. Range and geometric mean values of total BHC and y-BHC {lindane) residues in blood plasma, brain depot fat of some wild birds and chickens i Residues, ppm Whole -Tissue Wet Weight T Blood Plas MA Brain Tissue Depot Fat Bird Total BHC LlNDANi: Total BHC Lindane Total BHC Lin < Chicken 0.007 1 0.002 0.014 0.001 0.208 0.1 f 0.006-0.010 = 0.002-0.003 0.008-0.025 0.001-0.002 0.121-0.310 0.075 f (0.008)3 (0.002) (0.016) (0.002) (0.253) (0.18 Pigeon 0.048 0.016 0.316 0.020 — 0.045-0.053 0.015-0.019 0.215-0.607 0.014-0.034 — (0.048) (0.016) (0.355) (0.021) — Crow 0.030 O.OIl 0.246 0.014 21.815 6. 5 0.015-0.062 0.006-0.024 0.213-0.266 0.01O-O.016 15.532-29.726 3.99t 1' (0.035) (0.013) (0.248) (0.014) (22.487) (6.'b Kite 0.060 0.028 0.093 0.012 5.468 2. 1; 1.182 If 0.043-0.094 0.020-0.051 0.030-0.168 0.009-0.019 3.328-12.414 (0.064) (0.031) (0.119) (0.013) (6.567) (3.1 ; Vulture 0.106 0.066 1.132 0.26 12.628 10. ) 0.066-0.143 0.044-0.080 0.759-2.047 0.142-0.683 6.510-19.823 4.951- f (0.112) (0.068) (1.247) (0.335) (13.980) (11.' » Cattle egret 0.004 0.048 0.126 0.053 6.309 4.: ' 0.056-0.075 0.040-O.057 0.032-0.175 0.042-0.080 5.623-7.239 3.567 |( (5.(i h (0.064) (0.048) (0.132) (0.055) (6.344) 1 Geometric mean. « Range. ■ Arithmetic mean. 10 Pesticides Monitoring Jou f LE 2. Range and geometric mean values of DDT and DDT metabolites in blood plasma, brain, and depot fat of some wild birds and chickens Residues, ppm Whole -Tissue Wet Weight 'OUND Blood Plasma Brain Depot Fat Blood Plasma Brain Depot Fat CHICKEN PIGEON DDE 0.002 0.002 0.222 0.004 0.012 0,002-0.003 0.001-0.002 0.190-0.250 0.003-0.006 0.005-0.021 (0.002) (0.002) (0.226) (0.004) (0.014) — FDE 0.002 0.001 0.055 0.001 0.001 — 0.002-0.002 0.001-0.001 0.045-0.083 ND-0.002 ND-0.003 — (0.002) (0.001) (0.059) (0.001) (0.001) — DDT 0.003 0.008 0.272 0.003 — ND-0.007 0.007-0.009 0.236-0.298 0.002-0.007 ND (0.004) (0.008) (0.274) (0.004) — — DDT 0.009 0.011 0.587 0.009 0.013 — 0.005-0.012 0.00 9-0.012 0.55O-O.670 0.005-0.014 0.005-0.023 (0.009) (0.010) (0,590) (0.010) (0.017) — CROW KITE DDE 0.035 0.035 18.595 0.100 0.038 23.108 0.024-O.044 0.025-0.064 15.081-21.069 0.043-0.192 0.026-0.053 4.652-60.00 (0.036) (0.039) (18.798) (0.119) (0.040) (36.287) rDE 0.007 0.003 2.107 0.317 0.019 11.275 0.006-0.010 ND-0.024 1.151-3.530 0.229-O.420 0.014-O.027 2.850-43.886 (0.007) (0.011) (2.327) (0.327) (0.020) (19.391) )DT ND ND 2.107 — — — — — ND-5.024 ND ND ND ND ND (2.289) — — — DDT 0.018 0.004 12.563 0.044 0.003 4.496 0.014-0.024 ND-0.030 4.488-63.421 0.027-O.074 ND-0.027 2.454-8.148 (0.019) (0.018) (24.958) (0.048) (0.009) (5.049) DDT 0.066 0.063 44.486 0.522 0.076 44.986 0.052-0.080 0.031-0.128 31.197-89.713 0.346-0.655 0.075-0.077 10.310-120.115 (0.067) (0.074) (50.788) (0.543) (0.076) (67.014) VULTURE CATTLE EGRET DDE 0.183 0.587 35.070 0.029 0.027 3.014 0.106-0.245 0.298-1.052 20.297-53.948 0.026-0.033 0.018-0.035 2.131-3.049 (0.196) (0.655) (37.878) (0.030) (0.028) (3.110) rDE 0.209 0.386 39.543 0.004 0.004 6.991 0.133-0.317 0.228-1.022 25.197-61.909 0.003-0.006 NID-0.014 2.289-23.478 (0.222) (0.499) (40.736) (0.005) (0.006) (10.710) DDT 0.039 0.095 6.162 0.003 — 3.979 0.023-0.060 0.038-0.229 2.477-15.113 ND-0.006 ND 1.418-7.854 (0.028) (0.122) (7.946) (O.OOJ) — (4.976) DDT 0.479 1.204 87.945 0.041 0.038 17.048 0.292-0.685 0.644-2.535 53.051-143.92 0.037-0.045 0.035-0.045 8.360-36.267 (0.509) (1.416) (95.353) (0.042) (0.039) (20.323) lal the higher the ratio of food consumption per weight, regardless of food habits. Thus, within the ; food habit group, smaller individuals are likely to 5t larger amounts of pesticide residues. Age and ' size of the species are also important in influencing accumulation of pesticide residues. However, food ts and the food-chain concentration mechanism are ; important in determining the total body burden of cide residues. e 1 shows that levels of BHC and lindane present in d plasma, brain tissue, and depot fat of kite and 3 egret are comparable. Relatively high levels of BHC were detected in crow and pigeon brain, as oared with blood plasma levels. Vulture (a carrion- :r) contained 1.25 ppm total BHC and 0.34 ppm ne in the brain, which are many times higher than oncentrations present in other species of birds stud- As high as 29.73 ppm total BHC was recorded : 'age, 22.49 ppm) in crow depot fat. BHC levels in liver, heart, lung, and kidney were gen- erally high in pigeons and crows (Figure 1). Breast muscles and spleen of vulture exhibited relatively high accumulation of BHC. Kite and cattle egret showed gen- erally low concentrations of these compounds in tissue. Compared with other isomers of BHC, lindane accumu- lation was high in the tissues of vulture and cattle egret. However, the a-isomer accounted for the major burden of this compound in brain tissue of all birds studied. A single specimen of pigeon ovary examined in the present study contained 1.21 ppm total BHC and 0.31 ppm lin- dane. Residue levels found in the tissues and blood plasma of chicken were relatively low. Until 1962 (S), carcasses of random samples of birds had been analyzed for aldrin, dieldrin, or DDT. DDE is the primary breakdown product of DDT and is univer- sally distributed; exposure to this compound is essentially a continuous one. Residues of parent compound, DDT, and the metabolite TDE are less frequent. Results of 15, No. 1, June 1981 11 0-600- 5 -2 S 0 too - - O 0 200 - O O O o o =,-^. O400- b (M b "> fs. ro U3 o b •" O O. d- Lung ^jrn^^D Ami Totot H C H e Kidney 3mS^L ■551 1'' i^ji; " -» s n i Total HCH lotal DDT f. Spte«n FIGURE 1. Total BHC, lindane, and lotal DDT in internal body organs of different species of birds. the present study show a positive correlation of E concentration in blood and brain, as well as in bl^ and depot fat, as suggested by several workers (2, Levels of DDT and DDT metabolites in blood plas brain, and depot fat are presented in Table 2, and t DDT levels in the rest of the tissues are given in FiguL, 1 Few samples of lungs, spleen, and depot fat of c showed measurable levels of o,p'-DDT. p,p'-DDT not detected in lung, kidney, and brain tissue of pig and cattle egret. p.p'-TDE was not found in the lung these birds. Relatively high levels of p.p'-DDE were served in different body organs of cattle egret, comp< with those present in other birds examined. More t 70 percent of total DDT was present as p.p'-DDl most body organs of pigeon. An equivalent concer tion of p.p'-DDT and comparatively low levels of i TDE in body organs of crow, and to some ex chicken, indicate that the exposure is rather contini from different environmental sources. Vulture and contained high concentrations of p,p'-DDE and ; TDE, compared with the levels of parent compc (p,p'-DDT). Total DDT levels were 0.59, 20.32, 50.79, 67.10, i 95.35 ppm in depot fat of chicken, cattle egret, ci kite, and vulture, respectively. In other tissues, total J dues of DDT generally occurred in the following oni chicken < pigeon < cattle egret < crow < < vulture. Total DDT detected was 0.01, 0.01, C 0.07, 0.054, and 0.51 ppm in blood plasma and C 0.02, 0.04, 0.07, 0.08, and 1.42 ppm in brain tissu ^ chicken, pigeon, cattle egret, crow, kite, and vulture spectively. The sample of pigeon ovary analyzed > tained 1.01 ppm total DDT. DDT and its metabolites show a consistent biomagni] tion in wild birds, presumably through the food-c' concentration mechanism. Flesh-eating birds had sh higher body burdens of DDT than non-flesh-eating c Thus, birds of the upper trophic zone in the food c show higher bioaccumulation of DDT residues. I levels present in birds are perhaps a reflection of the vironmental status of the habitat and food choice particular avian species. A cknowledgment Authors thank Narayan Singh for technical assista ■ S. H. Mehdi for illustrations, and M. M. Lai for sta i cal analysis. LITERATURE CITED (/) Barker, R. J. 1958. Notes on some ecological elt of DDT sprayed in elms. J. Wildl. Manage. 22(3):p (2) Brown, J. R., and L. Y. Chow. 1975. Comparil study of DDT and its derivatives in human t ( 12 Pesticides Monitoring Jom^ samples in Norfolk County and Holland Marsh, On- tario. Bull. Environ. Contam. Toxicol. 13:483—488. Cramp, S., P. J. Conder, and J. S. Ash. 1964. The risk of bird life from chlorinated hydrocarbon pesti- cides. Royal Soc. Prot. Birds Kept. 1962-July 1963, p. 24. Cramp, S., and P. J. S. OIney. 1966. The sixth report of the joint committee of the British Trust for Orni- thology and the Royal Society for the Protection of Birds on toxic chemicals in collaboration with the Game Research Association. July 1964-December 1966, p. 26. Dale, W. E., T. B. Gaines, and W. J. Hayes, Jr. 1962. Storage and excretion of DDT in starved rats. Toxicol. Appl. Pharmacol. 4(1):89. Dale. W. E., J. W. Miles, and T. B. Gaines. 1970. Quantitative method for determination of DDT and DDT metabolites in blood serum. J. Assoc. Off. Anal. Chem. 53(6): 1287-1292. Eades, J. F. 1966. Pesticide residues in the Irish en- vironments. Nature 210(5036) :650. Edwards, C. A. 1976. Persistent Pesticides in the En- vironment. 2nd ed. CRC Press, Cleveland, Ohio. 170 pp. Henny, C. J. 1977. Birds of prey, DDT and tussock moths in Pacific Northwest. Trans. North Am. Wildl. Nat. Resour. Conf. 42:397^11. Hunt, E. G., and A. I. Bischoif. 1960. Inimical effects on wild life of periodic DDD applications to Clear Lake. Calif. Fish Game 46(1) :91. Ishida, ]., Y. Ogino, and M. Imanaka. 1977. Birds in Relation to Environmental Pollution. Part 4, Organo- chlorine pesticides and PCB in organs. Okayame-ken Kenkyo, Hoken Senta Nempo-1, Japan, pp. 195-197. Jensen, S., L. Renberg, and R. Vaz. 1975. Methods for analysis of DDT and PCB in environmental samples using chromatographic methods. FAO Fish. Tech. Pap. 137:229-236. Koransky, W., J. Portig, H. W. Voliland. and I. Klem- pau. 1964. Elimination of a- and 7-hexachlorohexane and effects of liver microsomal enzymes. Arch. Exptl. Pathol. Pharmakol. 247( l):49-60. (14) Kovacs, M. F., Jr. 1963. Thin layer chromatography for chlorinated pesticide residue analysis. J. Assoc. Off. Agric. Chem. 46(5) :884-893. (15) Malasuyama, E. 1977. Results of environmental pol- lution monitoring using crow as an indicator. Pestic. Abstr. 10(77): 1602. (16) Moore, N. W. 1966. Pesticides in the environment and their effects on wild life. Blackwell, Oxford, UK. p. 311. (17) Moore, N. W., and C. H. Walker. 1964. Organic chlorine insecticide residues in wild birds. Nature (London) 201 (4924) : 1072-1073. (18) Osawa, T., K. Takahashi, Y. Mishima, and M. Mawa- riya. 1978. Residues of organochlorine pesticides and PCB in wild birds, especially in crows. Pestic. Abstr. 1I(78):508. (19) Picer, M.. N. Picer, and M. Ahel. 1978. Chlorinated insecticide and PCB residues in fish and mussels of east coastal waters of the middle and north Adriatic Sea, 1974-75. Pestic. Monit. J. 12(3) : 102-1 12. (20) Robinson, J., and M. Roberts. 1968. Accumulation, distribution and elimination of organochlorine insecti- cides by vertebrates. Soc. Chem. Ind. Monogr. 29: 106-119. (21) Tagaki, F., R. Kaise, and S. Watanabe. 1978. Survey on environmental pollution using crows as an index. Pestic. Abstr. 11 (78): 1029. (22) Takeshiia, T. 1977. Heavy metal content of crow's feathers and organochlorine compound content of their internal organs. Pestic. Abstr. 10(77=) : 1646. (2.?) Turner. J. C, S. R. B. Solly, J. C. M. Mot-krinjnen, and V. Shanks. 1978. Organochlorine, fluorine and heavy metal levels in some birds from New Zealand Estuaries. N.Z. J. Sci. 21(1):99-102. (24) U.S.D.I. Fish and Wildlife Studies. 1963. A review of Fish and Wildlife Service investigations during the cal- endar year. U.S.D.I. Fish Wildl. Serv. Circ. 199 (1964): 129. 15, No. 1, June 1981 13 Cadmium, Lead, Mercury, Arsenic, and Selenium Concentrations in Freshwater Fish, 1976-77 — National Pesticide Monitoring Program Thomas W. May ' and Gerald L. McKinney ' ABSTRACT As pari of the National Pesticide Monitoring Program, the Fish and Wildlife Service, U.S. Department of the Interior, collected freshwater fish during 1976-77 from 98 monitor- ing stations and analyzed them for residues of cadmium, lead, mercury, arsenic, and selenium. Range and geometric mean values in mg/kg wet weight follow: Cd, 0.01-1.04, 0.07; Pb. 0.10-4.92, 0.32; Hg, 0.01-0.84, 0.11; As, 0.05- 2.92, 0.27; Se, 0.05-2.87, 0.56. An arbitrary 85th percentile was calculated for concentrations of each element in fish to identify monitoring stations having fish with higher-than- normal concentrations: Cd. 0.11 mg/kg; Pb, 0.44; Hg, 0.19; As, 0.38; Se, 0.82. Log-transformed mean concentrations in fish from 1976-77 monitoring stations are compared with means from the same stations in 1972 (Cd, Hg, Pb, As, Se) and 1973 (Se) to depict temporal trends in whole-body con- centrations: Cd, significant decline; Pb, no significant differ- ence; Hg, significant decline: As, significant increase: Se, no significant difference. Because of changes in laboratories and analytical procedures, these conclusions should be used cau- tiously as trend information. Production, consumption, and disposal of cadmium, lead, mercury, arsenic, and selenium are discussed as potential environmental sources of the ele- ments to the aquatic environment. Specific environmental sources are suggested for monitoring stations having trace element levels exceeding calculated 85th percentiles. Introduction The National Pesticide Monitoring Program (NPMP) is a Federal program established to monitor nationwide environmental contaminants in air, soil, water, humans, plants, and animals. United States government agencies participating in NPMP are the U.S. Environmental Protection Agency (EPA); Geological Survey, U.S. Department of the Interior; Food and Drug Adminis- tration, U.S. Department of Health and Human Serv- ices; U.S. Department of Agriculture; and Fish and Wildlife Service, U.S. Department of the Interior. The Fish and Wildlife Service (FWS) is responsible for monitoring selected environmental contaminants in 1 Fish and Wildlife Service, U.S. Department of the Interior. Columbia National Fisheries Research Laboratory. Route 1. Columbia, MO 65201 ' U.S. Environmental Protection Agency, Surveillance and Analysis Division. Region VII. 25 Funston Rd., Kansas City, MO 66115 freshwater fish. Although primary emphasis has b placed on organic contaminants, selected trace elemi have been determined intermittently. In 1969, 3 o posite samples, each of a different species and consis of 3 to 5 whole adult fish, were collected from sampling stations and analyzed for mercury (i Cadmium, lead, and arsenic were added to the progn in 1971, and selenium was added in 1972. San collections included a replicate for each species in IS but for only one of three species from each statioi 1972. In 1973, all samples were analyzed for seleni. but only selected samples were analyzed for mercii arsenic, lead, and cadmium. The 1971-73 analyses v conducted by the Denver Wildlife Research Cer FWS (87). Samples were collected from 97 station 1974, but no trace elements were analyzed. San collections were suspended during the 1975 samp year to enable a technical and administrative review fish-monitoring activities. The freshwater fish-monito program was reviewed internally and restructured, responsibility for NPMP in FWS was shifted to Columbia National Fisheries Research Laboraii (CNFRL). In 1976, collection stations were increased from 10( 117 to include a more extensive coverage of the Gi Lakes. Collections were then modified to include di| cate composite samples of a bottom-dwelling species i one composite of a representative predatory specie each station. A list of acceptable bottom-dwellers predator species, listed in order of priority in Tabl was developed. The collections included 146 sam from 52 stations in 1976 and 163 samples from stations in 1977 (Figure 1). The purpose of this re is to present and interpret heavy metals data gatht for the NPMP during 1976-77. Environmental Sources of Heavy Metals Production, consumption, and disposal processes o I result in the transport of trace elements to the aqu i environment. The U.S. EPA has established priors for trace element contamination problems and thif to resources by including 1 3 trace elements on i 14 Pesticides Monitoring Jour' BLE 1. Sequenlial priority for selection of bottom- ding and predator species of fish, as established by the National Pesticide Monitoring Program ' [TOM FEEDERS (commercially or recreationally significant, if ible) Carp (Cyprintis carpio) Common sucker ICaloslomiis commersoni) or other members of the sucker family Channel catfish {Ictalurus punctatiis) or other members of the catfish family Other, with justification iDATORS (should be an important sport fish) Cold water stations: rainbow trout (Salmo gairdneri) , brown trout (Salmo trutta), brook trout (Salvelinits tontinalis) , lake trout {Salvelinus namayciish) Warm-water stations: largemouth bass iMicroptertis salmoides), or other member of the sunfish family, such as crappie {Poxomis sp.), bluegill iLepomis macrochirus) , etc. Cool-water stations: walleye (Srizostedion vitreitm) or other members of the perch family Other, with justification, but must be representative of the drain- age system Dm National Pesticide Monitoring Program, Freshwater Fish Col- on Instructions, internal memorandum issued annually to FWS ional Pesticide SpeciaUsts. priority pollutants chemicals list. In this section, authors attempt to link production-consumption practices asso- ciated with cadmium, lead, mercury, arsenic, and selenium to environmental sources to clarify the ra- tionale for monitoring concentrations of these trace elements in freshwater fish. CADMIUM Cadmium has a close geochemical association with zinc, and natural geochemical sources of cadmium are linked with zinc deposits occurring as massive-sulfide and sulfides in strataform carbonates. Nearly all domestic cadmium is produced as a by-product of zinc concen- trates and imported zinc smelter flue dusts (66). The primary domestic producers of cadmium in 1978 were AMAX Zinc Co.. Inc., Sauget, lOinois; ASARCO Inc., Corpus Christi, Texas, and Denver, Colorado; Bunker Hill Co., Kellogg, Idaho; National Zinc Co., Bartlesville, Oklahoma; New Jersey Zinc Co., Palmerton, Pennsyl- vania; and St. Joe Zinc Co., Monaco, Pennsylvania. A 1976 TREND MONITORING STATION O '977 TREND MONITORING STATION D INACTIVE STATION # = TO OR > THAN 85TH PERCENTILE (SEE TEXT FOR EXPLANATION) o URE 1. Stations sampled for determination of some metals in freshwater fish as part of National Pesticide Moni- toring Program, 1976-77. .. 15. No. 1, June 1981 15 Of the domestic consumption of cadmium, 95 percent is divided into five principal uses: plating, pigments, alloys, batteries, and plastic stabilizers. Electrically or mechanically plated hardware used in vehicles and other equipment accounted for 40-45 percent of domestic cadmium consumption in 1978. The production of red, orange, yellow, and maroon pigments consumed 15 percent of the supply, and most of the rest was used in nickel-cadmium batteries, special-purpose alloys, and compounds providing heat and light stability to plastics, particularly polyvinyl chloride (65). In addition to smelter production of cadium metal, pri- mary producers have emphasized production of various cadmium compounds in recent years (63). Cadmium is used in the manufacture of pesticides for control of moles and plant diseases affecting residential lawns and golf courses (63). Cadmium is released to the environment primarily from four sources: the electroplating industry; the smelting and refining of zinc, lead, and copper; the application of phosphate fertilizer; and surface mine drainage (15. 80). The tendency of cadmium to concentrate in sedi- ments (15) may result in a persistent source of the contaminant to various trophic levels in the aquatic environment. Studies indicate that fish accumulate cadmium from the water and through the food chain; both modes of uptake can be toxic (80). The electroplating industry uses cadmium plating for corrosion protection. Wastewater is generated from countercurrent rinses, rinses following chromating, dumping of the chromating solution, and purging of the plating-recovery loop (82). Plant outlet pipes often lead to municipal sewage treatment plants, where about 50 percent of the cadmium remains with sewage sludge, and the rest is discharged (81). Incineration of sewage sludge volatilizes cadmium, whereas deposition in land- fill areas subjects streams and groundwater to contamina- tion. Snowmelt from the roofs and grounds of plating firms can contain more than 1 ppm cadmium, originat- ing as particulate droplets of plating solutions exhausted from the interiors of the firms by fans and accumulating on the roofs or walls or the ground below the discharge point (55). Perimutter and Lieber (70). who traced the spread of cadmium from a plating plant, found groundwater containing up to 10 ppm cadmium. When zinc ores are roasted, cadmium is volatilized and partly collected as fumes or flue dust. The rest is re- leased to the atmosphere and deposited in the area surrounding the smelter (15). The soil around a smelter facility that had been operating for 80 years was contaminated with cadmium within a radius of at least 10 miles (76). Flue dust returned to the smelter is often stored in waste cinder banks, which are a sou of pollution due to leaching and erosion from r; water (78). Suspended sediments containing up to percent cadmium have been reported in streams fi high runoff areas near copper and zinc smelters (7 Inland smelters and mills generally have extensive ; heaps and tailing ponds along streams for waste dispo Estuarine and river refineries generally dispose of wa directly into the water through outfalls. Phosphate ores used in fertilizer manufacture may c tain from 9 to 130 ppm cadmium (77). Runoff fil agricultural areas where phosphate fertilizers are x could result in substantial cadmium loading to aquatic environment. The primary sources of cadmium contamination dui mining are the emission of particulates and the lead of cadmium from the overburden. Ores are enric by flotation techniques to yield a 40-60 percent i mium metal product. Because the cadmium concen tion in a mine is only a few percent, most of original ore mass becomes tailing waste. As much 18-36 percent of the cadmium may be retained in tailings (15). Mine waters from sulfide ores can con more than 40 ppm cadmium, but levels of 0.1 to 2 j are more common (15). Draining from coal mil areas also poses a threat: Eight bituminous coals f: Kentucky and Pennsylvania had 1-2 ppm cadmium (i. Low concentrations (<0.1 ppm) of cadmium in (j are deceptive, because cadmium is extremely toxic ■( cumulative. Benoit et al. (6), who measured cadm levels in various tissues of brook trout exposed to ( mium in water for up to 38 weeks, reported that kidney accumulated the highest concentration, folio by the liver and gills. Exposed fish placed in f water lost cadmium rapidly from gill tissue but did lose it from either the kidney or liver. In a similar week exposure of rainbow trout to cadmium, madfi Kumada et al. (29), almost no cadmium was lost f the kidney of exposed fish returned to fresh water. LEAD Lead is a major constituent of certain geological for tions, including stratabound deposits, volcanic-sedir tary deposits, replacement deposits, veins, and cor I metamorphic deposits. Lead ore deposits commi contain the sulfide mineral galena (PbS), which is o associated with sphalerite (ZnS), pyrite (FeSj), cha pyrite (CuFeS,), and other sulfur salts (64). Most domestic primary lead production (88 percii originates from the limestone or dolomite stratabct deposits of southeastern Missouri (66). The silver- 1 vein system of Idaho's Coeur d'Alene District pro\ ' 8 percent of domestic primary lead, and the res 16 Pesticides Monitoring Jooh vided by replacement deposits in Colorado (3 per- t) and Utah (1 percent). In 1978, primary lead was Ited and refined at seven U.S. plants (65): four \RCO plants in El Paso, Texas; East Helene, Mon- i; Omaha, Nebraska; and Glover, Missouri; and [AX in Buick, Missouri; St. Joe Minerals in Hercu- ;um, Missouri; and Bunker Hill in Kellogg, Idaho, ause of the relative ease of reclaiming the metal, old ip lead (secondary lead) accounted for 51 percent domestic consumption in 1978. More lead is now duced from secondary sources than from domestic ■,(66). transportation industry is the major end user of 1: 51 percent is consumed in storage batteries and percent in lead alkyl compounds that are used as jline antiknock additives. The electrical industry (8 :ent consumption) has long depended on lead for le coverings where corrosion or moisture problems f exist. Because of its toxicity, lead is no longer i in interior paints and has been largely replaced ;xterior paints by zinc and titanium pigments. Lead nents are still the preferred base material for corro- I protection in structural and highway components percent of total consumption). In the ammunition jstry, lead remains the major metal in shot and ill-caliber bullets (4 percent consumption). The con- iction industry (3 percent consumption) is using ■easing amounts of lead as a sound barrier in parti- is and ceilings, as well as in roofing, piping, flashing, . caulking. Various other industries use lead for many erent purposes and together account for 1 3 percent :onsumption (66). id enters the environment from several sources. The or source of lead emissions (88 percent) is the ibustion of leaded gasoline. Although environmental rictions, initiated in 1972 to control air pollution, e reversed the growth in use of lead antiknock itives, unleaded gasoline accounted for only 33 per- t of the gasoline sold in 1978 (83). The average I content in pooled (leaded and unleaded) gasoline 1972 was 1.2 g/gal. Under cruise conditions, lead ■mitted from automobile exhausts in the form of II particles, most of which are < 1 fi.m in mass Man equivalent diameter (32). Such a small par- : size increases the residence time of lead emitted the atmosphere and, consequently, dispersion from point of emission. The small size of the particles tted is generally characteristic of urban lead aero- , and concentration of lead in ambient air is strongly elated with automobile traffic density (39). Thus, ospheric fallout and surface runoff of lead into : ims and rivers should be most intense where water- I s flow through metropolitan areas. Smelting and mining of lead, zinc, and copper have caused marked environmental contamination problems, even though lead emissions from these sources are small relative to vehicle exhausts. Sediments containing up to 17 percent lead by weight have been found below zinc and copper extractive industries, in streams used for irrigation and drinking water (78). The pollution hazard is greatest where there is erosion of waste cinder banks, tailings, and slag heaps. Although most large smelters are equipped with efficient dust and fume collection systems that claim 98 percent recovery (64), the re- covered flue dusts are sometimes stored in unprotected waste cinder banks, where leaching and erosion by rain- water result (78). Despite efficient stack collection systems, aerial fallout of lead has resulted in severe local contamination. Leaves of post oak (Quercus stcllaia) and shortleaf pine (Pinus echinata) within 0.5 mile of a lead smelter in Missouri contained levels of lead as high as 8,125 and 11,750 ppm (7). Samples of various plant species containing normal lead concen- trations could be obtained only beyond a 20-mile radius from the smelter-mining-milling complex. The deaths of 20 horses prompted the analyses of samples of forage grass in the vicinity of another Missouri smelter, in which concentrations as high as 14,700 ppm lead were reported (7). Lead mines associated with limestone or dolomite stratabound deposits (Missouri's Old and New Lead Belts) must pump out 5,000-7,000 gal/min of ground- water in order to operate. The relatively clear water is typically cycled through the mill and ffotation concen- trators and ends up containing mud, organic flotation agents, and other wastes. This effluent is discharged into valleys formed by dams of coarser mill tailings, and the final effluent is the tailing pond outfall. In the New and Old Lead Belt mining-milling areas, tailing pond outfalls have resulted in the deposition of a dark lead- bearing dolomite mud on stream bottoms; the mud in turn is covered by a gray algal-bacterial slime. Benthic fauna were found to be intolerant of the dolomite mud covering (78) . Other environmental sources of lead are landfills or dumps, fly ash from coal-burning power stations, coal combustion, sewage sludge, and application of pesticides containing lead (47). Small emissions occur from lead oxide manufacturing and fuel oil combustion (39). Coal mining could contribute significant quantities of lead to the environment during flood erosion (78). Upon entering natural waters, most lead is precipitated to the sediment bed as carbonates or hydroxides (80). Laboratory studies have shown that lead compounds can be transformed to tetraalkyllead, but the exact mecha- nism is still unclear. Wood et al. (90) proposed a Type I microbial methylation reaction for lead, where the high I. 15, No. 1, June 1981 17 redox potential of the Pb IV/Pb II redox couple causes Pb IV to act as an attacking electrophile. Subsequent heterolytic cleavage of the Co-C methylcobalamin bond results in the transfer of a carbanion methyl group to the more oxidized form of the element. Jarvie et al. (25), however, were unable to achieve methylation of trimethyllead salts and lead nitrate by this microbial pathway and, instead, proposed a chemical mechanism for conversion of the compounds to tetramethyllead in active anaerobic sediments. Other workers (57) have demonstrated the methylation of lead(II) compounds to tetramethyllead by microorganisms, which suggests other routes of methylation besides the mentioned micro- bial and chemical routes. It is not now known whether lead, like mercury, can accumulate through the food chain as an alkylated entity. Because divalent lead is the principal form accumulated by aquatic animals, the possibility of methylation of ionic lead in vivo can- not be disregarded (80, 53). Tetraalkyllead compounds have been found in various marine tissues (53). MERCURY Mercury has an impressive list of uses encompassing many different types of industry and has almost 3.000 distinct applications (72). The largest end user in the United States is the electrical apparatus industry, which accounts for 42 percent of total consumption and in- cludes the manufacture of mercury batteries and alkaline energy cells, vapor discharge lamps, rectifiers, and switches. The second greatest use (16 percent) is in the electrolytic preparation of caustic soda and chlorine (chloralkali industry), where the continuous-flow mer- cury cathode cell still accounts for about 20 percent of total chloralkali-producing capacity (4). Mercury con- sumption in the United States for chloralkali purposes has been reduced sharply since the 1960's for at least three reasons: a decrease in the number of new mercury cell chloralkali plants, modification of existing plants to reduce mercury losses, and conversion of some plants to the diaphragm process. The paint industry consumes 13 percent of the mercury used in the United States. mostly for mildew proofing (58). Industries manufac- turing industrial control instruments consumed about 8 percent of U.S. mercury supplies in the manufacture of switches, relays, gauges, pump seals, and valves. Other uses, which account for about 15 percent of total mercury consumption, include those in agriculture, den- tistry, general laboratory applications, and pharmaceu- ticals (4). Mercury consumption for pesticide use in agriculture is down sharply from the late 1960's, but a relatively small number of mercury pesticide formula- tions are currently available (5, 58). The U.S. paper and pulp industry no longer uses mercury as a slimacide, but still may be consuming mercury at the combined chloralkali-pulping operations (12). There are two primary ways mercury reaches the aqi< ic environment: pre- 1975 chloralkali operations < pre- 1972 paper-pulping operations. Although the int duction of mercury to the environment from these dustries is now relatively small, stream and lake s{i ments contaminated from discharges 10-15 years i are a persistent mercury source, and methylation anaerobic microbes initiates bioconcentration and f( chain bioaccumulation (12). Seepage from some we disposal areas of closed chloralkali plants continues contaminate streams and reservoirs (56). Higher-th background mercury sediment concentrations have b" found more than 100 miles downstream from a s thetic fiber operation that stopped using mercury years ago (3). Although U.S. mercury consumption and indust mercury loss have been reduced from early 1970 lev mercury contamination associated with increased c and crude oil production may pose future proble Fossil fuels contain from 10 ppb to several ppm n cury, depending on the coal type (12). Inasmuch the United States is preparing for a dramatic intensif tion of coal mining, combustion, and conversion appears likely that an environmental mercury prob will be present for some time to come. Bacteria present in most natural waterways can coni mercury to methylmercury. Ridley et al. proposes Type I microbial methylation reaction for mercury 1 is very similar to that already mentioned for lead ( 90). Most of the mercury in fish exists as methyln cury derived largely from food. Some authors h suggested that water, as well as food, is a major soi of methylmercury in fish (80). ARSENIC Arsenic occurs in association with complex base-mi ores, chiefly those of copper, lead, gold, and to a lei extent, cobalt and tin (60, 66). The element is a mil constituent of those ores and is regarded as a troul some impurity in smelting and refining of base me The recovery of arsenic in residues from fumes, si I mings. and flue dusts involves sophisticated technoll and is costly and relatively inefficient. As a result, refinery incentive for arsenic recovery is closely cc lated with concurrent economics and market conditi i In 1978, all domestic production of arsenic was i fined to the copper smelting-refining complex of American Smelting and Refining Company (ASARC in Tacoma, Washington. Anaconda, another large No western copper smelting company located in Bi' Montana, has arsenic-refining facilities that have mained unused for the past several years. Bee: \ domestic arsenic production is so limited and availab J is so closely tied to prevailing copper prices, the Ur ' 18 Pesticides Monitoring Joub^ ;es historically has met most of its requirements for inical compounds by importation (60). For example, nestic production supplied only 10.5 percent of total ;. arsenic demand in 1973 and about 50 percent in '8 (60, 66). riost all arsenic (97 percent) enters end-product lufacturing in the form of white arsenic or As20:,. ; other 3 percent is in the metallic form and is used an additive in specialized lead and copper alloys, hty-two percent of white arsenic is consumed in the nufacture of agricultural pesticides, such as lead ;nate, calcium arsenate, sodium arsenite, and organic ;nicals that are used as insecticides, herbicides, gicides, algicides, desiccants, and defoliants (60). janoarsenical compounds include cacodylic acid, di- ium methanearsonate (DSMA), monosodium meth- arsonate (MSMA), and sodium cacodylate (5, 60). ; only extensive use of arsenic that is not based on toxicity is in the glass industry, where it is used as a olorizer and as a constituent of opalescent glass and imels. Other small uses (60) are in the paint industry gments), pyrotechnics (constituent of fireworks), irmaceuticals (treatment for skin disorders and :ping sickness), electronics (diodes, transistors, and !rs), and the metals industry (as an additive to rous alloys to increase cast iron strength). ienic enters the aquatic environment by four primary ites: (1) Dissemination by air pollution. Because of complexity, inefficiency, and expense of removing enic from smelter stack gases, the element has be- ne a major air pollution problem in states having elting-refining operations (60). Coal combustion is )ther important source of arsenic to the air. (2) alter solid waste disposal. Because no domestic tallurgical plants, except ASARCO, process commer- 1 arsenic, the disposal of fumes, skimmings, and flue its could constitute a solid waste pollution problem :cting both soil and water. (3) Arsenical pesticides, ntinued use is expected for many years to meet the nand for effective pest control in the face of expand- agricultural production (60, 66). (4) Geologic. ;ause arsenic is found in association with specific ilogic formations of volcanic origin, ground and sur- e waters in some areas of the western United States 'e high arsenic levels (31 ) . ienic occurs in natural waters primarily in the ;nate-arsenite forms (27, 79). Inorganic forms of ;nic can be methylated by various microorganisms, uding fungi, methanogenic bacteria, yeasts, and cellular algae (43). Evidence suggests that arsenic s in the lower oxidation states perform a free-radical ick (homolytic cleavage) on the Co-C bond of hylcobalamin or nucleophilic attack on 5-adenosyl- methionine, as well as on methylcobalamin (49, 90). Fish apparently can biosynthesize organoarsenic com- pounds within the gastrointestinal tract (34, 43). How- ever, the main source of arsenic for fish is primarily organoarsenic compounds that are synthesized at lower stages in the food chain (34). Generally, arsenic is not biomagnified in aquatic food chains. Penrose et al. (44) suggested that organisms at each trophic level convert inorganic arsenic to a detoxified organic form, orga- nisms at the next higher trophic level then rapidly excrete the ingested organic arsenic, precluding food chain bioaccumulation. SELENIUM In 1978, all primary selenium was produced as a by- product from the processing of copper refinery slimes to recover gold, silver, and tellurium. Three copper refineries (AM AX Copper, Inc., Carteret, New Jersey; ASARCO Inc., Amarillo, Texas; and Kennecott Copper Corp., Magna, Utah) accounted for all domestic pro- duction of selenium (62, 66). Secondary production, or recycling, was limited; only about 1 percent of the 1978 consumption was recovered from xerographic and rectifier scrap and chemical waste products. Domestic consumption of selenium decreased steadily from 1974 to 1977 and increased slightly in 1978 (66). Major end uses of selenium in 1978 (66) were in electronic and photocopier components (35 percent), glass manufac- turing (30 percent), and chemicals and pigments (25 percent). The electronics industry used selenium in dry- plate rectifiers for many years, but silicon, germanium, and cadmium have largely replaced it in these applica- tions. The use of metal drums coated with photocon- ducting amorphous selenium in the dry photographic process of xerography has become a major end use of the metal. Selenium has the property of converting light energy directly into electrical energy — a property that has enabled the development of numerous photocell devices, such as photographic exposure meters and solar batteries (41). The glass and ceramics industry adds selenium to glass melt to control final product color. Selenium is used to neutralize green tinting caused by iron impurities, resulting in the manufacture of clear glass. Addition of more selenium to the melt produces a pink-to-ruby red glass. Its use in dark-colored glass in buildings and vehicles to reduce glare and heat transfer is increasing. A large number of selenium compounds have commer- cial uses, ranging from semiconductor research to anti- dandruff agents in shampoos. Much of the selenium consumed by the chemical industry is used to prepare pigments containing selenium. A major class of pigments is the cadmium sulfoselenide compounds, which have superb resistance to sunlight, heat, and chemical attack (41). -. 15, No. 1, June 1981 19 The primary sources of selenium in the environment are geologic and industrial. Selenium closely resembles sulfur chemically, and sulfur or sulfide deposits of bismuth, copper, iron, lead, mercury, silver, and zinc sometimes contain as much as 20 percent selenium (68). Other sulfate minerals, such as barite and jarosite, con- tain selenium, and native sulfur can contain more than 0.1 percent selenium. Other geologic formations con- taining selenium include sandstones, limestones, and shales. Sandstones containing > 100 ppm selenium have been found in Wyoming {17, 91). The Niobrara for- mation, a limestone region of South Dakota, contains > 40 ppm selenium in chalky shales and marls. Phos- phate rocks associated with limestone may contain from 1 to 300 ppm selenium, suggesting the occurrence of selenium in phosphate fertilizers. Of the sedimentary rocks, shales have been mainly responsible for cases of selenium poisoning in animals in the United States. For example, vegetation in some areas of the Pierre Forma- tion near the Missouri River in southern South Dakota has potentially toxic selenium concentrations. These shales are considered highly seleniferous and have selenium levels ranging from 1 to > 30 ppm (41). Industry releases selenium to the environment through combustion of coal and fuel oil, nonferrous smelting and refining processes, metal refining, and glass manu- facturing. Domestic coal averages 3.2 ppm selenium (46). Average selenium concentrations are 1.3 ppm in lignite coal and 2.08 ppm in central and western U.S. coals (42). In one study, about 53 percent of the selenium in coal was emitted to the atmosphere during combustion, either as volatilized selenium or in asso- ciation with fly ash particles too small to be trapped by precipitators (41). Coal combustion accounted for 62 percent of the total industrial emission of selenium in 1970 (41). EPA found that crude oil contained an average of 0.4 ppm selenium (41), and Hashimoto et al. (19) reported averages of 0.92 ppm in raw petroleum and about 1.0 ppm in heavy petroleum. Smelting and refining of nonferrous metals produces slag heaps and tailing dumps containing high concentrations of seleni- um. Thus, solid wastes from metal mining and milling may be a more serious source of selenium pollution than is atmospheric fallout from base metal smelting and refining (41). Selenium emissions are high in glass manufacturing, because the high temperature of the glass melt volatilizes selenium (41). Attempts to correlate atmospheric concentrations of selenium with the location of industrial selenium emis- sions have generally met with only limited success. For example, Traversy et al. (24) found the highest selenium concentrations in precipitation samples at or near highly industrialized locations in the Great Lakes region, and Copeland (10) showed that selenium concentrations in Lake Michigan zooplankton increased near Chicago. In these two situations, the effects of selenium from ind trial emissions appeared to be localized, and nati sources of selenium may generally be more import than anthropogenic ones (41). Ingestion may be the most important mode of selenii uptake by aquatic biota, but more research is neen to confirm this possibility (56). Phillips and Rii (80) concluded that the poor survival of stocked in a highly seleniferous Colorado lake was due to accumulation of excess selenium through the fi chain. Several species of molds and microorganisms i methylate selenium (41). Little is known, howe^ about selenium methylation pathways in the aqux environment. Methods and Materials SAMPLE COLLECTION Fish were collected by FWS biologists, state fish game personnel, and local commercial fishermen, \ used a variety of nonchemical collecting techniq (e.g., trapping, electrofishing, seining). After the ti length and weight of each fish had been determir the sample composites were separately wrapped aluminum foil, frozen, and shipped to CNFRL. Fish from frozen composites were reduced to ice-ci sized blocks with a Hobart Model 5212 food sen band saw. Blocks were passed twice through a l£| (Hobart 1 hp Model 4822) or small (Hobart Vi Model 4612) meat grinder, depending on total c( posite size and weight. Between sample homogen tions, the band saw and disassembled grinder com nents were washed with hot water or steam and rin: with deionized water. About 400-g portions of groij fish were placed in an acid-cleaned glass jar witl Teflon-lined cap and stored in a freezer. In 1976, fro 10-g portions of 83 samples representing 44 stati were sent to the EPA Region VII Laboratory in Kai City for digestion and analysis. All samples colleci in 1977 were prepared and analyzed at CNFRL. DIGESTION AND ANALYSIS OF SAMPLES COLLECTED IN Arsenic, Cadmium, and Lead — Five grams of tha' fish homogenate were placed in 10-in. Technicon dige tubes. Ten milliliters of concentrated HNO, was ad I to each tube, and the sample-acid mixture was heic room temperature for 1 hr to reduce foaming w i heat was applied. Samples were heated on a Techni Model BD-40 block digestor at 150°C for 60 mini and at 250°C for 90 minutes. The gradual incn; from room temperature to 150'^C allowed the sam i to dissolve with little foaming; heating to 250°C ■ required to overcome reflux action at the constric of the digestor tube. Samples were heated to dryit 20 Pesticides Monitoring JoukI lecompose lipid material. If the sample was black n dryness was reached, it was removed from the stor. cooled, treated with an additional 10 ml con- rated HNO,, and returned to a cold digestion block for 90 minutes at 250°C. Subsequent addition of nl portions of acid was continued until the appear- i of a white residue indicated complete digestion, white residue was dissolved with 10 ml 10 percent 0:, at 90°C. Dilution to 50 ml with deionized water Med a final acid matrix of 2 percent HNO,. This :edure allowed simultaneous preparation of up to tissue samples, with only HNO;, as the oxidizing . Unfortunately, the recovery of selenium by this hod was incomplete, precluding the use of selenium I originating from the 1976 samples. I tissue digestates (2 percent HNO,) were analyzed a Jarrell-Ash Model 975 Atomcomp inductively pled argon plasma (ICAP) optical emission spectro- tometer. Samples were introduced in a cross-flow iilizer at 1.4 ml/min by a Gilson eight-channel ip. An autosampler maintained sample flow at 30 ples/hr. Other pertinent ICAP parameters follow: Incident RF power; Reflected RF power: Observation heiglit: Sample argon flow rate: Coolant argon flow rate: l.I kW 20 W 15 mm above load coil 0.5 1/min 18 1/min ection limits for arsenic, cadmium, and lead were i, 0.05, and 0.10 mg/kg, respectively. ■cury — One gram of sample was placed on the cm of a dry BOD bottle; 1 ml each of concentrated ■O^ and HNO, was added, and the bottle was placed water bath at 58°C until the tissue was completely olved (30-60 minutes). The bottle was cooled to ^ in an ice bath, and 1 g KMn04 crystals was added maintain oxidizing conditions. The digestate was ed, loosely capped, and held overnight at room perature (75). cold-vapor atomic absorption method for mercury lysis (75) can be summarized as follows: Each :state was diluted with distilled water to a final ime of 125 ml, and 6 ml sodium chloride-hydrox- nine sulfate solution was added to reduce excess nanganate. After 30 seconds, 5 ml stannous sulfate tion was added and the bottle was immediately ;hed to the aeration apparatus. Mercury vapors were pt into a Plexiglass absorption cell and measured I Coleman MAS-50 mercury analyzer system (26). action limit was 0.02 mg/kg. 5STI0N AND ANALYSIS OF SAMPLES COLLECTED IN 1977 cury, Cadmium, and Lead — Mercury, cadmium, lead residues in fish were oxidized by acid digestion . 15, No. 1, June 1981 in heated, enclosed glass bombs (45-ml acylation tubes, Regis Chemical Co.), which allow oxidation and re- covery of all three meals with a single digestion. Diges- tion tubes were cleaned by successive rinsing with concentrated HNO,, HCI, and ultrapure water (15-18 megohm-cm specific resistivity). Cleaned tubes were oven-dried, cooled, and covered with sheet polyethylene before the sample was introduced. Teflon caps for the tubes were soaked successively for several hours in boiling concentrated HNO3 and HCI, followed by a final rinsing with ultrapure water. Approximately 2 g (±0.01 g) thawed fish homogenate was weighed into tared digestion tubes. Sub-boiling- point, distilled concentrated HNO, (2 ml) and double- distilled HCIO^ (1 ml) were added and the mixture was vortex mixed, capped loosely, and allowed to predigest overnight at room temperature (/). The mixture was vortex mixed again, and the bomb was sealed and placed in a heated aluminum block (65 °C) for 48 hours. The sample was quantitatively transferred and diluted to a final weight of 50 ± 0.01 g with 1 percent HCI. Diluted digestates were stored in cleaned poly- propylene bottles (38) for cadmium and lead analyses or borosilicate test tubes for mercury analysis (14). Mercury was determined by flameless atomic absorp- tion spectrophotometry (AAS) (28). The analytical system was automated with a Technicon Autosampler IV and Proportioning Pump III, with appropriate pump tubes, pulse suppressors, mixing coils, and locally fabricated phase separator (Figure 2). Atomic absorp- tion measurements were made on a Perkin-Elmer Model 305B spectrophotometer, using the 253.7-nm resonance line from an electrodeless discharge lamp. Scale expan- sion up to 10 X was used when appropriate. The detec- tion limit was about 0.01 mg/kg. The absorption cell was constructed from a Pyrex tube about 100 mm long and 6 mm I.D. with quartz end windows. Side arms of 4-mm-O.D. Pyrex were attached near each end of the cell for vapor passage. The cell was heated to 35-40°C with a high-intensity radiant heat projector (Cole- Parmer Dyna Lume Model 3151-6) to prevent con- densation on the end windows. Lead and cadmium were measured with a Perkin-Elmer Model 305B spectrophotometer equipped with an HGA-2100 graphite furnace and an AS-1 autosam- pling system. Table 2 specifies the instrument conditions for measuring each element. A four-point additions procedure to correct for chemical and matrix interfer- ences was performed on each diluted digestate: ( 1 ) Digestate -\- 0.00 ppm Pb; + 0.00 ppm Cd (2) Digestate -f 0.02 ppm Pb; + 0.002 ppm Cd (3) Digestate -f 0.04 ppm Pb; + 0.004 ppm Cd (4) Digestate + 0.06 ppm Pb; -f 0.006 ppm Cd 21 Pulse Suppressors -ff Hydroxylamine Hydrochloride 1.5% Stannous Chloride 10% J D(5 1 SaTiplef Wash H20 FIGURE 2. Flow scheme for automated digestion and determination of mercury. TABLE 2. Instrumental conditions for atomic absorption measurement of cadmium, lead, arsenic, and selenium in freshwater fish from the United States, 1977 Condition Cadmium Lead Arsenic Selenium Wavelength, nm 228.8 283.3 193.7 196.0 Spectral band width, nm 0.7 0.7 0.7 2.0 Temperature ramping no no no no Drying time, °C 90(30) 90(30) — , — (time, seconds) Charring time. °C 400(20) 400(20) — — (time, seconds) Atomization temp.. °C 2200(7) 2300(7) — — (time, seconds) Purge gas and flow Ar(20) Ar(20) Ar Ar (ml/minute) Gas mode normal normal EDL — Source EDL EDL no EDL Background correction Dij^rc DiArc 5 mv no Scale expansion 3X lOx PR I 3X Recorder full scale 10 mv 10 mv — 10 mv AS-1 injection volume 10 Hi 10 Hi none — Tube type uncoated uncoated — — Quaru cell temp., "C — — — 800 Reductant — — 1000 NaBH. Reaction flask volume, ml — — NaBH< 10 Analysis cycle time — — 10 PR II Detection limit, mg/kg 0.01 0.1 0.05 0.05 The average of two injections was used as one additions point. Correlation coefficients (r) below 0.999 for the line of best fit were rejected, and corresponding diges- tates were rerun. point, distilled concentrated HNO^ (5 ml) was ad the flask was loosely covered with sheet polyethyl, and the mixture was predigested overnight at r| temperature. Subboiled HNO, (25 ml) and del distilled HCIO4 (3 ml) were added, and the flask 1 heated on a micro-Kjeldahl rack to drive off Hf After digestion had proceeded through the HCIO4 f ing and reaction stages, additional heat was applie^ drive off the acid. When about 0.5 ml HCIO4 remai- the flasks were removed from the heat, cooled, contents were diluted with 3 percent HCl to volumes of 100 ml. Diluted digestates were store« linear polyethylene bottles before analysis. Predigestion sample preparation for selenium was same as that for arsenic. Following predigestion, 2.' subboiled HNO^ and 1 ml double-distilled HCIO4 1 added and the flask was heated to drive off Hf Digestion was allowed to proceed through HCIO4 1 ing and reaction stages. The HCIO^ reaction stage characterized by an initial foaming with subseq clearing (decoloration) of the digestate. Care was ti to terminate the digestion before HCIO4 was driver ' (88). Cooled digestates were diluted to 100 ml wi I percent HCl and transferred to linear polyethy* bottles. Arsenic and Selenium — For arsenic digestions, approxi- mately 2 g (±0.01 g) thawed fish homogenate was weighed into a tared, 100-ml Kjeldahl flask. Sub-boiling- Arsenic and selenium were analyzed with a PeK Elmer MHS-1 mercury-hydride system in conjunc 1 with a Perkin-Elmer Model 305B spectrophotomiiil 22 Pesticides Monitoring JouBf -ument conditions for measuring the elements are d in Table 2. On the MHS-1 system, a reaction : containing 10 ml diluted digestate was installed 1 polypropylene manifold. Argon was recycled in 3sed circuit through the reaction flask and a heated tz cell. An NaBH4 pellet (Alfa Ventron) was dis- ,ed into the flask and reacted with the digestate to form hydrogen, which reduced the metals to tile arsine and hydrogen selenide. The gas stream led the hydrides into the heated quartz cell where were decomposed and measured. Complete analy- from addition of the digestate to readout on the trophotometer, proceeded automatically for each a. ■ISTICAL TREATMENT vo-way analysis of variance (ANOVA) with sta- i and years as main effects was used to test two hypotheses: (1 ) There was no significant difference letal residue concentrations due to location, and (2) 5 was no effect due to time (1972-73 vs. 1976-77). eneral, stations were confounded by species differ- s across years. The following adjustments were e in the data sets before statistical testing: i) Absolute values were used for all less than ( < ) ita. )) Selenium values for 1972 and 1973 were avail- ile for only 44 of the stations sampled in 1977. tierefore, the two-way ANOVA data set for selen- m consisted of 44 stations and 3 years (1972, 1973, id 1977). ;) The detection limit for cadmium in 1977 sam- es (O.OI ppm) was one-fifth the limit in 1972 and *76 samples (0.05 ppm). Therefore, we adjusted 1 1977 cadmium values <0.05 mg/kg to 0.05, to iminate bias due to differences in detection limits. he two-way ANOVA data set consisted of 82 atching stations and two time periods (1972 vs. )76-77). i) The two-way ANOVA data set for lead and mer- iry also consisted of 82 stations and two time periods 1972 vs. 1976-77). ;) Detection limits for arsenic were 0.05 ppm for le 1972 and 1977 samples and 0.25 ppm for 1976 mples. Because most of the 1977 arsenic concentra- Dns were <0.25 mg/kg, the results of arsenic residue lalyses for the 1976 stations were not included in e two-way ANOVA set; consequently, only 44 atching stations and 2 years (1972 vs. 1977) mained. error sum of squares to estimate variation within /idual samples was obtained from a preliminary way ANOVA with an unbalanced cell size (52). method of weighted squares of means (52) was used to make inferences about main effects. All analyses were performed on log-transformed data [logio (1 -f- cone.)] Results The precision and accuracy of the 1976-77 trend- monitoring analyses were determined by duplicate sample sets and samples containing inorganic spikes. A duplicate sample set is defined as two aliquots of tissue from the same sample composite carried through the entire digestion-analytical procedure. The average difference of duplicate sets was within 25 percent for all elements, except for mercury in 1976 samples (37 percent) and lead in 1977 samples (70 percent). Aver- age recoveries from spiked samples were within 10 percent of the added quantity, except for mercury in 1976, for which average recovery was 64 percent (Table 3a). Analyses of reference materials yielded average values within the specified certification ranges for all elements (Table 3b). TABLE 3. Quality control results of the 1976-77 trend- monitoring analyses a. Recoveries of elements from spiked samples 1976 Mean Mean CONCN., RECOV- CONCN., RECOV- Element « tiO/ML ERY, % S.D. n tIG/ML ERY, % S.D. Cadmium 14 0.1 92 10 7 0.004 106 7 Lead 13 0.1 91 10 8 0.040 102 12 Mercury 6 0.001 64 15 8 0.010 98 12 Arsenic 14 0.1 98 17 17 0.004 94 10 Selenium — — — — 15 0.0O4 101 17 b. Reference materials — 1977 Certified Reference concn. range, material ^ element ^ig/o Mean CONCN., MG/G S.D. NBS cadmium 0.27 ± 0.04 11 0.31 0.02 Bovine liver NBS lead 0.34 ± 0.08 9 0.38 0.05 Bovine liver NBS mercury 0.016 ±0.002 12 0.016 0.005 Bovine liver FDA arsenic 11 ±2 13 10.5 1.37 Cod NBS arsenic 3.3 ±0.4 18 3.27 0.35 Albacore tuna FDA selenium 1.4 ±0.4 13 1.36 0.21 Cod NBS selenium 3.6 ± 0.4 18 3.68 0.40 Albacore tuna NOTE: n ~ number of samples; S.D. = standard deviation; FDA = Food and Drug Administration; NBS = National Bureau of Standards. Locations, species sampled, average size, and trace ele- ment concentrations for 1976-77 trend-monitoring samples are listed in Table 4. Eighty-three samples collected in 1976 were analyzed by the EPA Region VII Laboratory. The 1977 samples (157 samples of 163 collected) were analyzed by CNFRL. The data ranges in mg/kg wet weight were Pb, 0.10-4.92; Hg, 0.01-0.84; Cd, 0.01-1.04; As, 0.05-2.92; and Se, 0.05- 15, No. 1, June 1981 23 2.87. To examine potential temporal trends of trace element concentrations, 1976-77 data for lead, mercury, cadmium, and arsenic were compared with those re- ported by Walsh et al. (87) for the same stations in 1972. Because selenium concentrations were not ported for the 1976 collections, 1977 selenium coni trations were compared with those from the s; stations in 1972 and 1973. TABLE 4. Conccnirntions of cadmium, lead, mercury, arsenic, and selenium in whole-fish samples collected for the Nati Pesticide Monitoring Program, 1976-77 ( Station Number AND Location (FIGURE 1 ) Species ' No. OF Fish Average Size Residues, mg/kg Wet Weight Length, INCHES Weight, LB Cadmium Lead Mercury Arsenic Sele ATLANTIC COASTAL STREAMS 1. Pennobscot River, Old Town, Me. white perch white sucker - 5 5 5 9.8 14.3 14.1 0.5 1.18 1.16 <0 05 <0.05 0.12 0.13 0.23 0.20 <0.25 <0.25 51. Kennebec River, Hinckley. Me. yellow perch white sucker 5 5 5 9.6 14.2 14.5 0.36 1.22 1 22 <0.05 0.06 0.13 0.13 0.34 0.16 <0.25 <0.25 52. Lake Champlain, Burlington, Vt. northern pike brown bullhead 5 5 5 17.8 11.1 10.7 1.48 0.8 0.64 <0.05 <0.05 <0.10 0.34 0.21 0.04 <0.25 <0.25 53. Merrimac River, Lowell, Mass. largemouth bass white sucker 4 5 5 9.7 11.8 12.6 0.48 0.64 0.76 <0.05 0.06 0.21 1.23 <0.02 <0.25 <0.25 2. Connecticut River, Windsor Locks, Conn. white perch white catfish 5 5 5 9.2 11.6 12.1 0.46 0.74 0.88 0.11 0.25 0.16 0.40 1.19 0.79 0.27 0.08 0.12 <0.25 <0.25 <0.25 3. Hudson River, Poughkeepsie, N.Y. largemouth bass goldfish 5 5 5 12.1 11,3 11.1 0.92 1.18 1.08 <0.05 0.20 0.32 0.10 3.07 3.83 0.09 0.05 0.06 <0.25 <0.25 0.68 54. Raritan River, Highland Park, N.J. carp 5 17.3 3.14 <0.05 0.23 0.05 <0.25 4. Delaware River, Camden, N.J. white perch white sucker 5 5 5 7.0 15.4 15.2 0.2 1.7 1.6 0.22 0.20 0.16 1.57 0.98 1.17 0.14 0.12 0.14 0.21 0.10 0.10 M 0.: 0,: 5. Susquehanna River, Conowingo Dam, Md. white perch channel catfish carp 5 6 5 5 6.3 10.7 16.6 16.7 0.1 0.4 1.9 1.9 0.05 0.04 0.02 0.05 0.44 0.19 0.34 0.26 0.10 0.05 0.08 0.11 0.28 <0.05 o.n 0.11 6. Potomac River, Little Falls, Md. largemouth bass carp 5 5 5 12.2 19.0 17.5 1.2 3.9 2.9 <0.01 0.04 0.04 0.15 0.78 0.33 0.20 0.12 0.09 <0.05 0.13 0.16 0.- 0.. 0.. 55. James River, Richmond, Va. smallmouth bass redhorse 5 4 4 9.2 16.0 17.5 0.4 1.8 2.2 0.03 0.81 0.36 0.14 0.32 0.15 0.12 0.25 0.18 0.06 0.10 0.07 0, c: 0. 7. Roanoke River, Roanoke Rapids, N.C. white catfish 5 5 11.1 12.2 0.54 0.86 <0.05 0.16 0.05 <0.25 8. Cape Fear River, Elizabcthtown. N.C. gizzard shad 5 5 13.7 13.3 1.06 0.96 0.08 0.40 0.04 0.26 56. Pee Dee River, Dongola, S.C. white catfish 4 5 15.1 14.7 1.35 1.26 <0.05 0.20 0.45 <0.25 9. Cooper River, Summerton, S.C. striped bass channel catfish 2 5 5 26.0 13.3 13.9 7.3 0.86 0.8 <0.05 0.28 <0.02 <0.25 10. Savannah River, Savannah, Ga. largemouth bass channel catfish white catfish carp 4 3 3 4 10.9 15.1 13.8 14.6 0.83 1.33 1.63 1.83 <0.05 0.08 0.17 <0.10 <0.10 <0.10 0.12 0.06 0.14 <0.25 0.63 1.46 57. 11. Altamaha River, Doctortown, Ga. St. Johns River, Welaka, Fla. brown bullhead channel catfish largemouth bass inactive « 5 3 5 14.6 17.4 15.4 1.56 1.9 2.1 <0.05 <0.05 0.30 0.18 0.14 0.34 <0.25 <0.25 12. St. Lucie Canal, Indiantown, Fla. largemouth bass white catfish channel catfish 5 5 3 15.3 13.4 19.8 2.26 1.24 3.03 <0.05 <0.05 <0.10 0.14 <0.02 0.06 <0.25 <0.50 24 Pesticides Monitoring Joui^ BLE 4. (cont'd.). Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for the National Pesticide Monitoring Program, 1976-77 TATioN Number AND Location (FlGUKEl) Species ' No. OF Fish Average Size Residues, MG/KG Wet Weight Length, inches Weight, LB Cadmium Lead Mercury Arsenic Selenium Androscogin River, Lewislon, Me. yellow perch white sucker 5 5 5 9.3 12.2 12.4 0.38 0.68 0.38 <0.05 <0.05 0.16 0.24 0.20 0.11 <0,25 <0.25 — GULF COAST STREAMS Suwanee River, Old Town, Fla. inactive Apalachicola River, Jim Woodruff Dam, Ala. largemouth bass spotted sucker 5 5 5 14.1 17.5 18.4 1.56 2.38 2.82 0.02 0.02 0.03 0.18 <0.10 0.16 0.11 O.U 0.17 O.U <0.05 0.07 0.23 0.52 0.52 Alabama River, Chrysler, Ala. mixed species^ largemouth bass freshwater drum 3 5 8 13.5 15.9 10.2 1.77 2.3 0.66 0.02 0.03 0.03 0.19 <0.10 0.15 0,16 0,55 0,07 0.13 0.20 0.21 0.34 0.31 0.65 Tombigbee River, Mcintosh, Ala. mixed species ' freshwater drum 4 5 13.9 11.7 2.3 0.78 0.03 0.04 0.20 0.13 0,18 0.50 0.18 0,09 0,44 0,77 Mississippi River, Luling, La. freshwater drum 5 5 5 13.0 14.1 14.3 1.1 1.58 1.58 0.03 0.03 0.02 0.17 0.12 0.17 0.03 0.10 0.12 0.26 0.13 0.18 0.44 0.45 0.67 Brazos River, Richmond, Tex. alligator gar striped mullet striped mullet = gizzard shad 3 5 5 5 18.5 14.1 13.3 9.9 1.0 1.3 1.1 0.4 0.02 0.03 0.02 0.01 <0.10 0.48 0.46 0.65 0.31 0,01 0.02 0,04 0.08 1.48 1.40 0.60 0.24 0.40 0.24 0.26 Colorado River. Wharton, Tex. largemouth bass channel catfish gizzard shad 3 5 5 5 9.4 12.4 13.3 12.2 0.4 0.6 0.8 0.8 0.01 0.06 0.04 0.01 0.10 0.14 <0.10 0.20 0.12 0,03 0,05 0,01 0.05 <0.05 0.07 0.85 0.44 0.30 0.29 0.32 Nueces River, Mathis, Tex. largemouth bass gizzard shad 5 5 5 13.3 11.3 11.3 1.5 0.6 0.7 <0.01 0.03 0.03 <0.10 0.61 0.56 0,18 0,02 0.02 0.21 0.53 0.37 0.29 0.29 0.47 Rio Grande, Brownsville, Tex. channel catfish gizzard shad 3 5 5 12.6 11.6 11.8 0.63 0.56 0.52 — — — — — Rio Grande, Elephant Butte, N.M. not collected ' Rio Grande, Alamosa, Colo. brown trout white sucker 5 5 5 11.18 10.7 10.8 0.62 0.52 0.52 <0.05 <0.05 0.39 0,10 0.03 0.04 <0.25 <0.25 — Pecos River, Red Bluff Lake, Tex. not collected San Antonio River, McFaddin, Tex. channel catfish alligator gar smallmouth bass 3 3 3 19.2 22.9 18.3 4.8 2.2 6.6 0,02 0.17 0.02 0.25 O.U 0.71 0.13 0.28 0.06 <0.05 0.13 0.09 0.41 0.17 0.66 GREAT LAKES DRAINAGE Genessee River, Scottsville, N.Y. St. Lawrence River, Massena, N.Y. Lake Ontario, Port Ontario, N.Y. Lake Erie, Erie, Pa. Lake Huron, Bay Port, Mich. pumpkinseed carp 5 5 5 5,1 15.9 15.5 0.2 2.3 2.2 0.03 0.02 0.03 0.62 0.35 0.23 0.09 0.04 0.04 0.06 0.09 0.14 0.28 0.19 0.37 smallmouth bass white sucker 5 5 12.6 14.1 1.2 1.3 0.01 0.03 0.14 0.41 0.26 0.19 0.67 0.16 0.45 0.31 rock bass channel catfish 5 5 5 8.6 14.1 14.2 0.5 0.9 0.9 0.03 0.02 0.04 0.20 0.22 0.20 0.36 0.07 0.07 0.31 0.10 0.16 0.36 0.30 0.29 yellow perch white sucker 5 5 5 8.6 11.3 11.4 0.4 0.6 0.7 0.03 0.05 0.05 <0.10 0.19 0.16 0.08 0.05 0.05 O.U 0.17 0.17 0.67 0.69 0.50 carp carp* yellow perch 5 5 5 5 18.7 17.1 7.6 7.5 3.72 2.9 0.2 0.2 0.04 0.02 0.02 0.01 0.49 0,22 0.23 0.23 0.23 0.05 0.04 0.03 0.10 0.13 <0.05 <0.05 0.35 0.64 0.44 0.34 15, No. 1, June 1981 25 TABLE 4. (cont'd.). Concentrations of cadiniiiin. lead, mercury, arsenic, and selenium in whole fish samples collected the National Pesticide Monitoring Program. 1976-77 < TATioN Number AND Location (FIGURE 1) Species i No. OF Fish Average Size Residues, MG/KO Wet Weight Length, inches Weight, LB Cadmium Lead Mercury Arsenic Seii 21. Lake Michigan. Sheboygan, Wis. bloater lake trout 5 5 5 4 10.1 10.0 27.5 23.8 0.52 0.56 6.6 4.5 0.01 0.02 <0.01 0.02 0.15 0.15 <0.10 <0.10 0.03 0.04 0.19 0.19 2.92 2.91 1.20 1.33 0, 0. 0. 0 22. Lake Superior, Bayfield, Wis. lake trout lake whitefish 6 3 24.7 20.3 5.0 2.86 0.02 0.05 <0.10 <0.10 0.43 0.03 0.56 0.47 0 0 102. Lake Superior, Keeweenaw Point, Mich. bloater lake trout 5 5 A 10.4 10.3 22.0 0.60 0.60 4.40 0.03 0.30 0.02 0.12 <0.10 <0.10 0.11 0.10 0.10 1.33 1.19 0.39 0 0 0 103. Lake Superior, Whitefish Point, Mich. lake trout lake whitefish 4 5 5 23.9 19.2 19.8 5.1 3.0 2.8 0.02 0.04 0.04 0.14 0.29 0.11 0.26 0.05 0.07 0.43 0.41 0.97 0 0 0 104. Lake Michigan, Beaver Island, Mich. bloater lake trout 4 5 11.3 25.7 0.6 5.9 0.02 <0.01 0.12 <0.10 0.04 0.27 2.41 0.92 0 0 105. Lake Michigan, Saugatuck, Mich. bloater lake trout 5 5 5 11.4 11.3 24.7 0.6 0.6 4.7 0.03 0.01 0.31 <0.10 0.05 0.25 2.30 0.94 0 0 MISSISSIPPI RIVER SYSTEM 67. Allegheny River, Natrona, Pa. walleye silver redhorse golden redhorse 3 5 5 12.4 10.6 13.2 0.63 0.48 0.94 0.07 0.19 0.07 0.26 23. Kanawha River, Winfield, W.Va. black crappie carp brown bullhead 5 5 5 6.3 14.8 9.6 0.14 1.44 0.46 <0.05 <0.10 <0.02 <0.25 68. Wabash River, New Harmony, Ind. largemouth bass carp 5 5 5 10.7 16.8 16.1 0.72 2.7 2.38 0.06 0.18 0.17 0.22 0.10 <0.25 <0.25 24. Ohio River, Marietta, Ohio sauger carp 5 4 13.9 17.2 1.18 2.92 <0.05 0.22 0.26 2.49 0.10 0.05 <0.25 <0.25 69. Ohio River, Cincinnati, Ohio sauger channel catfish smallmouth buffalo 5 5 4 5 3 13.7 11.1 15.5 12.2 13.7 1.04 0.5 1.3 1.08 1.8 <0.05 <0.05 0.10 0.42 0.10 0.04 <0.25 <0.25 70. Ohio River, Metropolis, 111, largemouth bass carp 5 5 5 14.2 16.5 16.2 1.72 2.52 2.12 <0.05 0.18 <0.10 0.25 0.30 0.15 <0.25 <0.25 25. Cumberland River, Clarksville, Tenn. largemouth bass carp spotted sucker 4 5 4 9.8 13.4 12.2 0.52 1.16 0.76 — — — — 71. Tennessee River, Savannah. Tenn. not collected 106. Lake Huron, Alpena, Mich. lake trout white sucker 5 5 6 5 23.4 19.0 16.3 12.7 4.3 2.8 1.9 0.9 <0.01 0.04 0.02 0.02 <0.10 0.39 0.28 0.13 0.23 0.07 0.03 0.02 0.51 0.11 0.10 0.16 0. 0 0 0 107. Lake St. Clair. Mt. Clemens. Mich. walleye carp 5 5 5 20.3 20.4 20.1 2.7 4.5 4.5 0.06 0.15 0.16 0.13 1.83 0.78 0.84 0.60 0.32 0.24 0.13 0.09 0. 0 0 108. Lake Erie, Port Clinton, Ohio walleye carp 5 5 5 15.9 15.9 16.7 1.6 2.5 2.4 <0.01 0.03 0.03 <0.10 0.19 0.21 0.09 0.03 0.04 0.36 0.15 0.21 0, 0. 0 109. Lake Ontario, Roosevelt Beach. N.Y. inactive 110. Lake Ontario, Cape Vincent, N.Y. inactive 72. Wisconsin River, Woodsman, Wis. smallmouth bass carp 5 5 5 12.9 17.2 17.7 1.12 2.3 2.46 0.07 0.23 0.14 <0.2S 26 Pesticides Monitoring Joui ' LE 4. (cont'd.). Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for the National Pesticide Monitoring Program, 1976-77 ATiON Number ND Location (FIGURE 1) Species > Des Moines Rivet, Keosauqua, Iowa Illinois River, Beardstown, 111. Mississippi River, Little Falls, Minn. Mississippi River, Guttenberg, Iowa Mississippi River, Cape Girardeau, Mo. Mississippi River, Memphis, Tenn. Arkansas River, Pine Bluff. Ark. Arkansas River, Keystone Reservoir, Okla. Arkansas River, John Martin Reservoir, Colo. Verdigris River, Oologah, Okla. Canadian River, Eufaula, Okla. White River, DeValls Bluff. Ark. Yazoo River, Redwood, Miss. Red River, Alexandria, La. Red River, Lake Texoma, Okla. Missouri River, Hermann, Mo. Missouri River, Nebraska City, Neb. Missouri River, Garrison Dam, N.D. Missouri River, Great Falls, Mont. Big Horn River, Hardin, Mont. Yellowstone River, Sidney. Mont. James River, Olivet. S.D. North Platte River, Lake McConaughy, Neb. South Platte River, Brule, Neb. carp walleye black crappie carp walleye black bullhead largemouth bass carp white crappie carp smallmouth buffalo bluegill carp largemouth bass carp inactive while bass carp white bass river carpsucker white crappie bigmoulh buffalo black crappie bigmouth buffalo smallmouth buffalo largemouth bass gizzard shad freshwater drum goldeye carp walleye white sucker goldeye longnose sucker redhorse sucker goldeye white sucker sauger carp goldeye carp walleye carp green sunfish carp No AVERAO: E Size Residues, MG/KG Wet Weight OF Fish Length, INCHES Weight, LB Cadmium Lead Mercury Arsenic J Selenium 5 5 3 15.6 15.4 16.5 1.94 1.94 1.53 0.06 1.04 <0.05 0.27 0.41 <0,10 0.07 0.06 <0.25 <0.25 <0.25 — 5 5 5 8.2 14.1 14.2 0.32 1.22 1.40 <0.05 <0.05 0,23 0.32 0,09 0.05 <0.25 <0.25 — 5 5 5 11.1 8.2 7.9 0.5 0.32 0.28 0.06 0.10 0.32 <0.25 — 5 5 5 14.1 19.9 21.3 1.72 3.56 4.48 <0.05 <0.05 0.55 0.30 0.05 0.05 <0.25 <0.25 — 5 5 5 8,7 14.4 15.4 0,24 1.26 1.68 <0.05 0.45 0.13 0.49 0.17 <0.02 <0.25 0.30 — 3 3 17.3 16.4 2.63 2.97 0.02 0.03 <0,10 0,13 0.04 0.05 0.14 0.11 0.25 0.33 5 5 6.3 19.8 0.1 3.78 0.02 0.05 0.27 0.18 0.05 0.07 0.12 0.12 0.23 0.33 5 5 5 13.7 17.9 17,8 1.8 2.1 2.4 <0.01 0.12 0.09 <0.10 0.39 0.44 0,17 0.15 0,21 0.20 <0.05 0.07 0.67 0.54 0,65 5 5 5 12.4 17.8 16.1 0.9 2.5 2.1 0.02 0.54 0.78 0.11 0.75 0.82 0.07 0.09 0.09 0.55 0.08 0.09 0.60 0.50 0.44 5 5 5 13.9 13.0 12.2 1.4 1.1 0.7 <0.01 0.02 0.02 <0.10 0.38 0.38 0.34 0.13 0.06 0.65 0.08 0.16 0.35 0.28 0.38 5 3 3 8.5 15.1 15.5 0.2 1.87 1.87 0.02 0.04 0.04 0.15 0.17 0.24 0.18 0.13 0.14 0.12 0.06 0.12 0.24 0.54 0.41 5 5 5 9.3 15.0 15.5 0.9 2.0 2.2 <0.01 0.02 0.04 0.10 0.10 0.11 0.14 0.04 0.06 0.16 0.10 0.09 0.43 0.41 0.38 5 5 5 17.1 17.3 17.0 2.8 3.14 2.94 0.01 0.02 0.01 0.19 0.12 0.15 0.10 0.13 0.10 <0.05 0.05 <0.05 0.22 0.32 0.35 5 5 5 10.4 10.4 9.9 0.6 0.4 0.3 0.03 0.05 0.05 0.31 1.14 1.44 0.12 0.02 0.02 0.11 0.55 0.61 0.72 0.89 0.86 5 16.3 2.2 0.03 <0.10 0.24 0.06 0.66 5 5 5 12.5 14,8 15.3 0.7 1.7 1.8 0.03 0.06 0.06 2.43 0.75 0.86 0.09 0.03 0.05 <0.05 0.10 0 13 0.73 1.28 1.52 5 5 5 17.3 14.2 14.3 1.64 1.18 1.18 <0.01 0.03 0.03 0.10 0.47 0.30 0.22 0.08 0.07 0.18 0.32 0.23 0.70 0.73 0.73 9 3 5 12.7 16.6 17.1 0.7 1.97 2.36 0.06 0.18 0.44 0.13 0.32 0.14 0.12 0.06 0.15 0.08 0.42 0.10 1.36 0.33 0.29 10 10 10 12.4 14.2 12.5 0.5 1.2 0.8 0.03 0.01 <0.01 0.11 0.10 <0.10 0.19 0.09 0.05 0.06 0.09 0.06 2.87 1.71 1.07 5 5 5 12.7 14.8 20.7 0.58 1.62 3.82 0.02 C.04 0.24 <0.10 <0.10 0.17 0.22 0.12 0.15 0.06 0.16 0.08 1.75 0.88 0.82 5 5 5 14.1 16.1 16.2 0.9 2.0 2.0 0.03 0.05 0.10 0.92 1.95 1.08 0.23 0.07 0.09 <0.05 0.06 0.07 0.82 0.53 0.57 5 5 5 17.2 19.1 20.1 1.6 3.0 3.8 <0.01 0.09 0.08 0.42 0.54 0.94 0.04 0.17 0.10 0.81 0.13 0.20 0.73 0.81 0.63 5 5 5 5.4 10.1 9.6 0.1 0.5 0.4 0.01 0.02 0.02 1.25 0.49 0.53 0.06 0.01 0.02 0.09 0.14 0.05 2.08 2.05 2.53 15, No. 1, June 1981 27 TABLE 4. (cont'd.). Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected the National Pesticide Monitoring Program, 1976-77 £ TATiON Number AND Location (FIGURE 1) Species ^ No. OF Fish Average Size Residues, MO /kg Wet Weight Length, inches Weight, LB Cadmium Lead Mercury Arsenic Sele> 89. Platte River, Louisville, Neb. goldeye river carpsucker 5 5 5 12.8 13.4 14.6 0.7 1.0 1.4 0.03 0.06 0.10 0.97 1.33 1.74 0.10 O.ll 0.12 0.07 0.13 0.07 1.0 1.0 1.1 90. Kansas River, Bonner Springs, Kans. freshwater drum carp 5 5 5 9.3 19.1 19.3 0.34 3.5 3.58 0.02 0.07 <0.01 <0.10 0.16 0.21 0.10 0.13 0.12 0.08 <0.05 0.09 0.8 0.8 1.0 111. Mississippi River, Lake City. Minn. walleye white sucker 5 5 21.1 17.8 3.76 2.56 0.06 0.05 0.25 0.25 0.11 <0.02 <0.25 <0.25 - 112. Mississippi River, Dubuque, Iowa largemouth bass carp 5 5 5 9.6 18.5 17.9 0.48 2.98 2.84 <0.05 <0.05 <0.I0 0.14 0.05 0.04 <0.25 <0.25 - 116. Souris River, International Border, N.D. northern pike 5 19.5 1.66 <0.05 0.37 — <0.25 - HUDSON BAY DRAINAGE 34. Red River, Noyes, Minn. Sanger white sucker 5 5 5 13.1 12.4 13.9 0.62 0.52 1.14 <0.05 0.16 <0.10 <0.10 0.45 0.13 <0.25 <0.25 - COLORADO RIVER SYSTEM -i 35. Green River, Vernal, Utah 36. Colorado River, Imperial Reservoir, Ariz 91. Colorado River, Lake Havasu, Ariz. 92. Colorado River, Lake Mead, Nebr. 93. Colorado River, Lake Powell, Ariz. channel catiish carp channel catfish carp channel catfish carp largemouth bass carp 12.5 13.6 12.5 5 16.8 Not collected 5 14.8 19.0 15.9 0.54 1.3 1.24 1.34 1.84 2.28 1.88 <0.05 <0.10 <0.02 <0.25 <0.05 0.18 <0.02 0.30 5 13.8 1.46 <0.05 0.27 0.14 <0.25 5 13.5 1.1 0.21 0.35 0.15 0.26 5 13.5 1.2 0.22 0.16 0.07 <0.25 94. Gila River, San Carlos Reservoir, Ariz. 114. Bear Creek, Brigham City, Utah 115. Colorado River, Yuma, Colo. not collected channel catfish carp mullet carp largemouth bass 13.3 11.5 14.7 0.9 0.96 1.68 0.09 <0.10 — <0.25 13.5 11.7 12.0 0.99 0.81 1.02 <0.05 <0.05 0.23 0.20 <0,02 0.03 <0.25 <0.25 INTERIOR BASINS 37. Truckee River, Fernley, Nebr. 38. Utah Lake, Provo, Utah 93. Bear River, Preston, Idaho carp Tahoe sucker walleye carp 5 16.1 3.02 0.03 0.26 0.37 0.07 5 8.8 0.34 0.02 0.14 0.39 0.15 5 8.7 0.32 0.02 0.28 0.32 0.19 5 19.8 3.62 , — 5 18.9 3.32 — _ — — 5 18.8 3.24 — — — — inactive CALIFORNIA STREAMS 39. Sacramento River, Sacramento. Calif. 40. San Joaquin River, Los Banos, Calif. 28 largemouth bass goldfish 12.5 12.4 10.2 1.2 1.3 0.7 0.02 0.11 0.06 <0.10 0.19 0.21 0.14 0.19 0.09 0.19 0.23 0.22 0.: 0.; o.< striped bass Sacramento blackiish 13.0 12.3 11.0 0.9 0.8 0.6 <0.01 <0.01 <0.01 <0.10 <0.10 0.12 0.08 0.07 0.16 0.33 0.12 0.09 l.( 1.: Pesticides Monitoring Jour BLE 4. (cont'd.). Concentrations of cadmium, lead, mercury, arsenic, and selenium in whole fish samples collected for the National Pesticide Monitoring Program, 1976-77 Station Number AND Location (FIGURE 1) Species ' No. OF Fish Average Size Residues, mg/kg Wet Weight Length, Weight, INCHES LB Cadmium Lead Mercury Arsenic Selenium COLUMBIA RIVER SYSTEM Snake River, Hagerman, Idaho northern squawtish largescale sucker rainbow trout 5 5 5 5 15.3 13.7 13.5 13.8 1.18 0.92 0.94 1.0 — — — — Snake River, Lewiston, Idaho northern squawfish largescale sucker 5 5 5 15.2 15.4 15.9 1.14 1.28 1.36 <0.05 0.10 0.07 0.10 0.12 0.10 0.31 0.07 0.11 <0.25 0.50 1.11 Salmon River, Riggins, Idalio largescale sucker 5 4 18.2 17.9 1.7 2.1 0.12 0.23 0.19 0.50 Snake River, Ice Harbor, Wash. channel catfish largescale sucker 5 5 5 13.0 14.7 14.8 0.54 1.14 1.12 0.10 0.09 0.07 0.21 0.17 0.11 0.10 0.04 0.05 0.61 <0.25 <0.25 Yakima River, Granger, Wash. black crappie largescale sucker 4 5 5 6.0 11.6 12.1 0.1 0.56 0.66 0.14 <0.05 0.19 0.10 0.05 0.09 0.50 0.61 Willamette River, Oregon City, Oreg. smallmouth bass chiselmouth 3 5 5 9.2 10.2 10.8 0.5 0.4 0.5 <0.05 0.20 0.12 0.85 0.13 <0.02 <0.25 1.15 Columbia River, Booneville Dam, Oreg. northern squawfish largescale sucker 5 5 5 13.5 14.3 12.4 0.9 1.08 0.82 <0.05 0,15 <0.10 <0.10 0.23 0.05 <0.25 0.87 Columbia River, Pasco, Wash. carp 5 5 11.4 11.6 0.66 0.7 <0.05 <0.05 0.34 0.13 <0.02 <0.02 <0.25 0.35 Flathead River, Creston. Mont. northern squawfish longnose sucker 5 4 3 13.6 15.2 12.8 0.74 1.1 1.0 - — — — Columbia River, Grand Coulee, Wash. yellow perch largescale sucker 5 5 5 7.9 16.4 17.3 0.26 1.58 1.74 <0.05 0.33 0.16 2.57 0.03 <0.02 <0.25 0.30 PACIFIC COAST STREAMS Klamath River, yellow perch 5 9.2 0.4 <0.01 <0.10 0.09 <0.05 0.16 Hornbrook, Calif. Klamath sucker 5 12.4 0.7 <0.01 <0.10 0.06 0.11 <0 05 5 12.5 0.7 0.01 0.10 0.03 0.12 0.08 Rogue River, black crappie 5 9.1 0.76 <0.01 <0.10 0.16 <0.05 0.11 Gold Ray Dam, Oreg. Klamath sucker 5 8.7 0.28 0.01 <0.10 0 02 0.11 0.06 5 9.1 0.32 0.01 <0.10 0.03 0.13 0.12 ALASKAN STREAMS Chena River. Fairbanks, Alaska Kenai River, Soldatna, Alaska Artie grayling longnose sucker not collected 5 10.5 0.38 0.02 0.27 0.07 0.05 0.80 5 14.6 1.26 0.03 0.13 0.08 0.17 0.32 HAWAIIAN STREAMS Waikele Stream, Waipahu, Hawaii Manoa Stream, Honolulu, Hawaii Cuban limia 28 1.9 <0.10 0.05 0.38 0.04 0.08 0.77 28 2.4 <0.10 0.05 0.51 0.05 0.10 0.80 Chinese catfish 3 6.9 0.2 0.11 0.80 0.12 0.10 0.43 tilapia 33 6.9 0.23 0.03 2.28 0.02 0.27 0.38 3 6.3 0.2 — — . — — — Cuban limia 36 2.7 <0.10 — — _ — 37 2.7 <0.10 0.03 4.93 0.05 0.49 0.12 mmon names for species from the continental United States follow thr^sc designated in "A list of common and scientific names of fishes m the United States and Canada", American Fisheries Society Special Publication No. 6, 3rd Edition^ 1970. lere two or more rows of data follow a species name, the data represent replicate samples. shes ( — ) =: not analyzed (sample not submitted, or inadequate digestion procedure, e.g.. 1976 Se data). ictive — stations so designated have been temporarily deleted fromverse conditions, etc.). xed species = white catfish, carp, and spotted sucker. xed species — freshwater drum, spotted sucker, and smallmouth buffalo. t collected = personnel were unable to obtain fish samples (e.g., ad the NPMP collection station network. .. 15, No. 1, June 1981 29 As expected, location effects were highly significant (P < 0.001 ) for all five elements (Table 5). Effects due to time were significant for mercury, arsenic, selenium (P < 0.001), and cadmium (P < 0.05), but not for lead (P ^ 0.213). Interactions between main effects were not significant. TABLE 5. Results of two-way analysis of variance (weight- ed squares of means) on concentrations of lead, mercury, cadmium, arsensic, and selenium in freshwater fish, United States, 1976-77 TABLE 6. Mean concentrations of lead, mercury, ci mium, arsenic, and selenium in whole fish ' Source Deorpes OF Sum of Freedom Squares Mean Square Significance Level Lead Stations 81 4.536 0.056 5.905 0.001 Years 1 0.014 0.014 1.553 0.213 Interaction 81 0.661 0.008 0.860 0.791 Error 368 3.490 0.009 Mercury Stations 81 0.367 0.004 3.305 0.001 Years 1 0.023 0.023 16.874 0.001 Interaction 81 0.059 0.0007 0.531 0.999 Error 364 0.499 0.001 Cadmium Stations 81 0.432 0.005 2.196 0.001 Years 1 0.015 0.015 6.434 0.011 Interaction 81 0.126 0.001 0.645 0.991 Error 368 0.894 0.002 Arsenic Stations 43 0.804 0.018 7.875 0.001 Years I 0.051 0.051 21.774 0.001 Interaction 43 0.090 0.002 0.887 0.671 Error 217 0.515 0.002 Selenium Stations 43 2.579 0.60 13.173 0.001 Years 2 0.160 0.080 17.663 0.001 Interaction 86 0.273 0.003 0.698 0.976 Error 352 1.603 0.004 Significant differences in mercury (P < 0.001) and cadmium concentrations (P < 0.05) were observed from 1972 to 1976-77 (Table 6); lead concentrations did not decline significantly, but arsenic concentrations increased significantly (P < 0.001). The two-way ANOVA indicated an effect for selenium due to time (P < 0.001. Table 6). Mean selenium concentrations for 1973 were significantly lower than those for 1972 selenium values (a priori test, 0.001 < P < 0.005). A posteriori comparison (54) of mean selenium levels indicated no significant differences between 1972 and 1977 samples. Because of changes in laboratories, ana- lytical procedures, station, fish species, size and age of fish, etc., these results should be used cautiously as temporal trend information. Discussion The average percent difference between duplicates for cadmium, mercury, arsenic, and selenium was consid- ered acceptable, particularly because some duplicates had elemental concentrations near the detection limit. Recoveries from spiked samples, and reference mate- Mean Concentrations, mg/kg wet weight = Element 1972 Sicnifica: (P) Lead 0.354 (0.322-0.387) 0.338 (0.297-0.380) >0.05 (^ Mercury 0.153 (0.142-0.164) 0.112 (0.099-0.126) <0.001 Cadmium 0.112 (0.098-O.126) 0.085 (0.068-0.102) <0.05 Arsenic 0.127 (0.108-0.146) 0.207 (0.184-0.231) <0.001 Selenium ^ 0.604 (0.567-0.641) 0.576 (0.534-0.619) <0.001 1 Matching stations in years. " Figures in parentheses are 95 percent confidence intervals. =1 The mean concentration (and 95% CI) for selenium in 1973 0.455 (C. 422-0. 488) mg/kg. This was the only element having matcl station data in 1973. The P value (<0.001) results from the two-' ANOVA on all 3 years. rials, indicated satisfactorily accurate recovery of f elements in all years, except for mercury in the spil samples for 1976. The low recovery (64 percent) mercury (Table 3) suggests problems during sami digestion and analysis. Imprecision in lead-quality control data indicates tji measured lead values may not accurately reflect av age levels in fish tissues. The accuracy and precis of lead spike recoveries (91 ± 10 percent and 102 j 12 percent) and National Bureau of Standards refereij material analyses (Table 3) indicate that digestion £i analytical techniques were satisfactory. Nonunifol distribution of lead in fish tissue and authors' inabij to achieve complete homogenization were more lik| the causes of imprecision. For example, in tuna, lead content of epidermis tissue is several thousand tir that in muscle tissue from the same fish (9, 59). Mi of the lead in the epidermis is associated with mui (9). Similarly, rainbow trout (Salmo gairdneri) ac mulate lead in mucus and scales (85, 86). As a res lead digestate concentrations are difficult to correl i with muscle tissue dry weights because of mucosal sli i contamination (89). To approximate normal background ranges for wh( fish trace element concentrations, station means of I transformed individual data values (Table 4) w calculated for each element and arranged in orden increasing concentration. The stations with transfomii mean values exceeding the 85th percentile were t identified (Table 7). The antilog of this 85th percent was arbitrarily used to distinguish stations with h|i metal concentrations. Though the 85th percentile nf not be meaningful biologically, it was considered abn background and potentially worth further study. Autb ) 30 Pesticides Monitoring JourI'^ \BLE 7. Stations from which fish had trace element con- ntration equal to or exceeding the 85th percentile for the 1976-77 trend-monitoring collection 85th Percentile, Stations (in order of increasing EMENT mo/kg CONCENTRATION ) dmium O.U 70, 68, 43, 107, 45, 24, 93, 2, 98, 3, 4, 33, 75, 73, 55, 78 ad 0.44 99. 78. 87, 53, 88, 2, 107, 82, 98, 24, 4. 31. 86, 89, 3, 100 :rcury 0.19 43, 22, 1, 70, 66, 57, 83, 59, 51, 34, 74, 14, 37, 56, 107 senic 0.38 3, 66, 82, 43, 22. 46, 44, 42, 103, 45, 10, 60, 102, 105, 104, 21 enium 0.82 82, 4, 90, 89, 85, 31, 40, 84, 88 tempted to suggest sources that could account for the gher values encountered at these stations. It should recognized that relating specific sources of metals to ;vated concentrations of the elements in freshwater h is speculative. The intent is to provide a metal urce perspective for the drainage basins to help mfy elevated metal concentrations in fish from these eas. .DMlUM idmium concentrations in freshwater fish had a range 0.01-1.04 ppm, a mean of 0.067 ppm, and an 85th rcentile of 0.11 ppm. The decrease in cadmium ncentrations in fish since 1972 (Table 6) parallels dmium metal production and consumption, which clined over the same period (63). NPMP stations which fish had cadmium concentrations equal to or ceeding the 85th percentile (Table 7) are discussed low in relation to possible contaminant sources, lantic Coastal Streams — Fish from four rivers, the mnecticut (station 2), the Hudson (station 3), the ;laware (station 4), and the James (station 55), all ntained mean cadmium concentrations exceeding 0.17 m. Each of these river systems lies in a heavily lustrialized area. A zinc smelting company, which is primary cadmium producer, is on the Lehigh River, a butary of the Delaware. Metal fumes from the lelter's low stacks have killed trees in the Lehigh illey, and river sediments contained 5.4 ppm cadmium 8). The James River receives eflfluents from numerous emical, fertilizer, and other industries (16). from zinc-smelting activity from a primary cadmium producer located on the Ohio River at Monaco, Penn- sylvania. Similarly, a lead-smelting and refining com- plex at East Helena, Montana may be the primary source of cadmium in fish collected at station 33 (Great Falls, Montana. Miesch and Huff'man (76) found cadmium contamination in soil 10 miles from a smelter in Helena Valley. It was estimated that 290 tons of cadmium had been added to the soil within a radius of 1-19 km from the smelter stacks. Superphosphate fertilizers are a suspect source at station 73 (Des Moines River), where high cadmium levels may reflect substantial agricultural runoff. High cadmium fluxes have been reported for the Mississippi River as it flows through mineralized areas in Tennessee, Missouri, and Kentucky (15). Cadmium levels in carp at Cape Girardeau, Missouri (station 75, Mississippi River), are probably the result of numerous sources, A zinc company at Sauget, Illinois (East St. Louis), has discharged waste on the Mississippi flood- plain, forming a black sludge containing 0.1 percent cadmium (78). A large lead-smelting facility at Hercu- laneum, Missouri, has discharged eflluent directly into the river. The smelter's slag piles along the banks of the Mississippi contained from 19 to 250 ppm cadmium, and much slag has been bulldozed into the river (78). In addition, industrial and municipal sewage effluents from St. Louis and phosphate fertilizer runoff" may contribute to the cadmium load at this station. The highest cadmium mean value was in carp from station 78 on the Verdigris River at Oologah, Oklahoma. A zinc company in Bartlesville, Oklahoma, may supply cadmium to the upper Verdigris River area as a result of particulate fallout from smelter stack emissions (55). The 85th percentile value of 0.11 ppm was character- istic of fish from station 70 on the Ohio River and probably reflects the relatively heavy industrialization of the lower river area. Colorado River System — Southwestern Colorado and north-central Utah contain major deposits of lead and zinc ores, and numerous active mines are located there (61). A geologic source of cadmium, as well as mine waste drainage into tributaries of the Colorado River, could account for elevated cadmium levels in fish from Lake Powell, Arizona (station 93). eat Lakes Drainage — Like the Atlantic coastal earns. Lake St. Clair (station 107) is surrounded by iieavily industrialized area. Cadmium residues in fish )m the area ranged from 0.06 to 0.16 ppm, apparently iginating from a number of industrial sources in and ar Detroit, ississippi River System — The 0.22-ppm cadmium level carp from station 24 at Marietta, Ohio, may result Columbia River System — Bottom sediments of the Wil- lamette River and its numerous tributaries have cad- mium concentrations ranging from 0.5 to 1 ppm (73). Concentrations of 2.5 ppm cadmium were found in sediment samples near the river mouth downstream from Portland, Oregon. Uniformity in sediment cadmium con- centrations throughout the Williamette River basin sug- gests a geologic source of the metal. Active lead-zinc- silver mining in the Salmon River basin (station 43) may iL. 15, No. 1, June 1981 31 account for the elevated concentrations in large-scale suckers (23, 21). High cadmium concentrations in fish from Grand Coulee, Washington (station 98), may re- flect industrial waste from Spokane and activities of the Bunker Hill smelting complex at Kellogg, Idaho. Water from the South Fork of the Coeur d'Alene River has contained up to 0.45 ppm cadmium, corresponding to a cadmium transport of 240 lb cadmium/ day (22, 37). The South Fork drains an area where thousands of tons of mine ground tailings of lead-zinc-silver ores were dumped decades ago (15). The Bunker Hill and asso- ciated smelters have tailing ponds extending for over 4 miles in the flood plain of the South Fork of the Coeur d'Alene River (7S). Lead concentrations in freshwater fish (Table 4) ranged from 0.10 to 4.93 ppm and averaged 0.32 ppm. The trend in lead concentrations (Table 6) indicated no sig- nificant change from 1972 to 1976-77. The NPMP sta- tions having concentration means at or above the 85th percentile of 0.44 ppm are discussed below. Atlantic Coastal Streams — Segments of the Atlantic coastal streams where stations 2, 3, 4, and 53 are located contain many different types of industry. Industrial sources of lead could include those from metal finishing, brass manufacturing, lead alkyl manufacturing, primary and secondary lead smelting, coal combustion, and lead oxide manufacturing. River mud in the vicinity of a New Jersey zinc company, located on a tributary of the Dela- ware River, contained 0.13 percent lead {78). The St. Lawrence, New York, area contains a geologic source of lead; the Balmat mine, located there, ranks 18th in domestic output (67). The headwaters of the Hudson River may receive a lead flux from these ore deposits. Great Lakes Drainage — Lake St. Clair (station 107), like the Atlantic coastal streams, is bordered by substan- tial industry and has a well-documented history of pol- lution (13). Lake St. Clair may receive urban lead aerosol fallout from the Detroit area, as well as effluents from numerous Detroit industries. Mississippi River System — The Missouri-Oklahoma- Kansas vicinity is the location of stratabound deposits characteristically containing lead ores (64). Thus, in addition to point industrial sources of lead, the Verdigris River (station 78) and Red River (station 82) may re- ceive lead from geologic origins. Fish residues at station 24 (Ohio River) may be affected by effluents (aerial fallout, tailing erosion, etc.) from a zinc company at Monaca, Pennsylvania. High concentrations at stations 88 and 89 (South Platte River), presumably reflect in- dustrial discharges from Denver. The Pierre Shale of the Great Plains region contains low concentrations of lead and may provide a natural source of lead for statio 31,86, 87, and 88 (69). Columbia River System — Lead residues from fish Grand Coulee, Washington (station 98), may be fluenced by several lead sources affecting Franklin Roosevelt Lake. These are industrial effluents from Sf kane, lead-zinc mining in Pend Oreille, Washingtc natural stratabound deposits in Metaline Falls, Washit ton; and the mining-smelting complex at the South Fc of the Coeur d'Alene River. The Spokane water sup] has had concentrations of copper and zinc above th( allowed by Public Health Drinking Water Standar The source is erosion and leaching of heavy metals fn slag and tailing piles along the South Fork of the Cot d'Alene River (78). Hawaiian Streams — Waikele Stream (station 99) and tributaries total 117 miles in length and drain a 45 square-mile watershed. Diversions for domestic and aj cultural uses and highly permeable soils contribute extreme variations in flows, which ranged from 0.02 13,600 ftVsecond over 24 years. Heavy urban runofl characteristic of the flood flows in the lower reaches the stream. Agricultural and residential use of If arsenate has occurred in the drainage area, and vehi sources of lead are prevalent. The Manoa-Palola stre system (station 100) drains an area of about 9.35 mi characterized by high vehicle density. Air quality d have reflected high levels of lead aerosols and ot vehicle pollutants in the area. Lead arsenate has 8 been applied in the past for agricultural use and tern; control (Lenhart, D. J. 1979. Regional Pesticide Speed ist. Fish and Wildlife Service, U.S. Department of fl Interior, Portland, Oregon, personal communication)! MERCURY Mercury concentrations in fish in 1976-77 (Table ( ranged from 0.01 to 0.84 ppm, and averaged 0.11 pr The decline of mercury levels in freshwater fish si I 1972 (Table 6) is probably due to an overall reduct) of industrial mercury emissions, coupled with a relaii decrease in total domestic mercury consumption o| the same period (65). NPMP monitoring stations ha\' fish with mercury concentrations exceeding the 85th ji centile (0.19 ppm; Table 7) are discussed below. Atlantic Coastal Streams — The Penobscot and Kenneii River stations 1 and 51 have a long history of chlorali; and paper-pulping operations (Haines, T. A. 1979. Ft Research Station Leader, Fish and Wildlife Serv ( Orono, Maine, personal communication). Unfiltcf water samples from various sites in both rivers had tt( mercury levels in 1971 that equaled or exceeded the P (lig/ liter recommended by the National Academy of !i ences Water Quality Criteria (35, 40). U.S Geologjc Survey water quality data (retrieved through STORIH 32 Pesticides Monitoring Jour ' JO substantiated concentrations > 0.2 /^g/ liter; some lues as high as 0.5 ju,g/ liter were reported from the inobscot River in 1978 (74). An old paper industry Hartsville on a tributary to the Pee Dee River (station i), most likely discharged mercury that became en- ipped in sediments years ago. Georgia's Altamaha ver (station 57) was studied intensively in 1970, and srcury residues of 1.0 ppm in largemouth bass were ported by the Georgia Water Control Board (18). A rge pulp processing company is just above this sam- ing site (station 57), at Doctortown, Georgia. ulf Coast Streams — Alabama's Tombigbee River (sta- )n 14) and Alabama River (station 59) both exceeded e 85th percentile of 0.19 ppm. with fish from station having a mean concentration of 0.33 ppm. There ;re two chloralkali plants contaminating the Tombig- e in the early 1970's (12) — one at Mcintosh and the her at river mile 26 (Smith, B. W. 1970. Assistant nief of Fisheries Section. Alabama Game and Fish Dmmission, personal communication). Mercury con- ntrations have been relatively high in fish from the labama River throughout the NPMP samplings (20, '), but the source of mercury has not been identified. reat Lakes Drainage — The Lake St. Clair (station )7) mercury problem originated from chloralkali op- ations at Sarnia, Ontario, and is well documented (12, f). In 1970, mercury concentrations in fillets from four lecies of Lake St. Clair fish exceeded 1 ppm (67). An- her Great Lakes station at which fish had mercury incentrations greater than 0.19 ppm was station 22 on ike Superior. The Ontario Department of Lands and Drests reported mercury concentrations > 0.5 ppm in e muscle of fish from different parts of Lake Superior 1970 (12). The source was presumably chloralkali ants at Marathon and Thunder Bay. The St. Lawrence iver (station 66) was listed by FDA as seriously con- minated in 1970. Mercury cell chloralkali plants are ill operating along the river at Cornwall, New York, id Beauharnois and Shawinigan, Quebec (13). 'ississippi River System — In the Red River (station I), which drains into Lake Winnipeg in Manitoba evince, the 0.28-ppm mercury concentration in fish ceeds the 85th percentile. The source of mercury has )t been identified. Station 70 at Metropolis, Illinois, is rectly downstream from the confluence of the Ken- cky and Ohio Rivers. Two mercury cell chloralkali ants are located at Calvert City, Kentucky, near the outh of the Kentucky River (13). terior Basins — Pre- 1900 gold and silver milling opera- )ns of the Nevada Comstock Lode introduced substan- I amounts of mercury into the Truckee and Carson ver drainage systems; in bottom sediments, total mer- ry concentrations were as high as 20 ppm in 1971 (48). Concentrations in fish (0.50-2.72 ppm) were highest in white bass, a piscivorous species from Lahon- tan Reservoir. Bottom sediments in the Truckee River basin (station 37) contained greater than background mercury concentrations, as a result of ore milling activ- ity in the Washoe Valley (72). Columbia River System — The Columbia River system, including the tributary Yakima, Willamette, Snake, and Salmon Rivers is on the East Pacific Rise, the location of major mercury deposits (cinnabar) in the Western Hemisphere. There are secondary mercury mining op- erations in Washington and Idaho, as well as gold min- ing, where mercury was used to recover gold from its ores by amalgamation (12). In 77 percent of northern squawfish samples from the Salmon River, the axial musculature contained mercury concentrations higher than 0.5 ppm (8). ARSENIC Arsenic concentrations in fish (Table 4) ranged from 0.05 to 2.92 ppm and averaged 0.27 ppm. The increase in arsenic in freshwater fish since 1972 (Table 6) may be the result of dissemination by air pollution, smelter solid waste disposal, and continued use of arsenical pesticides. Contamination sources for arsenic are sug- gested here for the ^ 85th percentile (^ 0.38 ppm) NPMP stations. Atlantic Coastal Streams — No specific industrial source for arsenic in the Hudson River (station 3) is known. Extensive industrialization of the river, however, pre- sumably accounts for high arsenic concentrations in fish. In Georgia and South Carolina, substantial numbers of cotton farms (71) border the Savannah River and its tributaries (station 10). Arsenicals were used exten- sively on cotton from the early 1940's through the mid- dle 1960's in Georgia (Winstead, E. E. 1979. Assistant Commissioner, Georgia Department of Agriculture, Atlanta, personal communication). Agricultural runoff of applied arsenicals would provide a persistent source of arsenic to sediment beds. Gulf Coast Streams — In 1976, the Southern Plains states had more than 5 million acres planted in cotton, com- pared with slightly over 3 million for the Delta states (57). The highest concentration of cotton farms in the Southern Plains occurs along the Rio Grande Valley and western Texas Panhandle. Stations 82 and 60 are located on the Red and Brazos River systems, respectively, that drain these cotton-growing areas. Arsenic acid was the most heavily applied arsenical in 1976 in the Southern Plains, followed by sodium cacodylate and DSMA (57). Great Lakes Drainage — Relatively high arsenic levels have been reported in many areas of Lake Michigan. In the southern portion (stations 21 and 105), sediment )L. 15, No. 1, June 1981 33 concentrations have reached values as high as 30 ppm (50). In the northern portion (station 104), arsenic has accumulated in ferromanganese nodules that exist in the Green Bay area (50). One of the more striking cases of arsenic pollution involves the Ansul Co. of Marinette, Wisconsin (located close to the Menominee River, which empties into Green Bay). That company was a major manufacturer of methanearsonic acid (MAA) and cacodylic acid (CA), both arsenical herbicides (2). The company stored arsenic-contaminated sodium chloride and sodjum sulfate manufacturing by-products in un- protected salt piles on the bank of the river. Precipita- tion runoff from the piles produced levels of > 200 ppm arsenic in river sediments. Groundwater below the piles had total arsenic concentrations in excess of 6,000 ppm. Sediment levels adjacent to the salt piles were 2 percent arsenic by weight. As a result, the Menominee River is responsible for contributing 30-50 tons of arsenic per year to Lake Michigan (2). Marsh (36) concluded that there was a definite accumulation of lead and arsenic in and around Grand Traverse Bay in northeast Lake Michigan. Lead arsenate pesticides, used as orchard spray, accounted for all of the arsenic and about half of the lead buildup. In contrast to Lake Michigan, specific sources of arsenic in Lake Superior (stations 22, 102, and 103) and the St. Lawrence River (station 66) were not readily appar- ent. A nonpoint source affecting all of the Great Lakes was mentioned by Traversy et al. (24), who reported that arsenic levels in precipitation were higher than those in water from the Great Lakes and surrounding rivers. The elevated arsenic precipitation levels were especially prevalent at or near highly industrialized locations such as Toronto, Sarnia, and Hamilton. 1970 to 1977. The arsenic levels in the present repo^ are similar to those found by the Upper Lakes Referenn Group (84). At stations where arsenic seems to 1 higher than background levels — i.e., greater than tl 85th percentile (0.38 ppm) — concentrations in bloate (Coregonus spp.) tended to be about double those lake trout (stations 21, 102, 104, and 105). The ten ency of bloaters to concentrate arsenic is apparent fro other work (II, 84) and may be related to a prima diet of zooplankton, which has been shown to bioco centrate arsenic (80). I Columbia River System — Stations 42-46 had mean i senic residues above the calculated 85th percent] (Table 7). Such a preponderance of "high" stations) a relatively small geographical area gives credence the following four possible sources of arsenic pollution 1. Volcanic eruptions in the central Cascade area dun the Eocene epoch resulted in a large accumulation I volcanic deposits referred to as the Fisher formation, some instances, arsenic and perhaps boron were a p. of the pyroclastic debris that formed the so-called Fish rocks. Arsenic released from Fisher rocks by percolati subsurface water has resulted in arsenic groundwa contamination in some areas of the southern Willame Valley (31). This geologic source of arsenic may present in other areas of the Columbia River system. 2. A copper-smelting facility at Tacoma, Washingt( and the lead-smelting refineries located at Kellogg, Ida (Bunker Hill), and East Helena, Montana, may prov airborne sources of arsenic to the Columbia River si tern. Soil and water pollution are possible through smi er solid waste disposal (78). A mine and copper smelting facility at White Pine, Michigan, is on the Mineral River, which drains into southern Lake Superior. Wash water and smelter runoff flow into Mineral River, as well as uncontrolled erosion from slag piles and tailing pond outfalls (78). Any of these effluents could contain substantial amounts of Arsenic concentrations in whole fish from the Great Lakes have been reported by Lucas et al. (33) and Traversy et al. (24) for the period from 1968 to 1971. Lucas et al., who analyzed 19 fish of 3 species, found a mean of 0.16 ppm arsenic, whereas Traversy et al., who analyzed 43 whole fish samples of 15 species, reported a mean of 0.063 ppm. The present authors report a mean arsenic concentration level of 0.72 ppm for fish from Great Lakes stations, including data from 33 sample composites of 10 different species. Although species, location, and methodology differences cannot be ruled out, the mean differences suggest a significant increase in arsenic concentrations in Great Lakes fish from 34 3. Active mining of copper, lead, and gold may prest mine water and mine tailing disposal problems, becai arsenic is found in association with these base-ma ores. 4. In the headwater regions of the Yakima, monosodi methanearsonate (MSMA) and cacodylic acid are c; rently used for thinning in forestry (Gregory, S. I 1979. Field Station Leader, Columbia National Fisheij Research Laboratory, Fish and Wildlife Service, C vallis, Oregon, personal communication). SELENIUM Concentrations of selenium in fish ranged from 0.05" 2.87 ppm and averaged 0.56 ppm. Stations having m concentration levels exceeding the 85th percentile (C ppm) are discussed below. Atlantic Coastal Streams — Fish from station 4 on I Delaware River at Camden, New Jersey, had cond trations exceeding the 85th percentile, not only i Pesticides Monitoring JovRt enium (0.82 ppm), but also for cadmium and lead. le elevated trace element concentrations in these fish jbably reflect the highly industrialized character of ; Delaware River. 'ssissippi River System — The Big Horn (station 84) d Yellowstone (station 85) River tributaries of the ssouri River are closely associated with Montana's rt Union coal formation and outcroppings of phos- ate beds in Montana and Wyoming (45, 71). Sele- im concentrations in fish from these rivers may result im a geologic source of the element. Selenium sources the aquatic environment at the South Platte River ir Denver (station 88) may be industrial effluents or posits of coal, barite, and sulfur ore (77). Phosphate i outcroppings are located along the Kansas-Missouri rder close to station 90 on the Kansas River (77). enium concentrations in fish from stations 80 and 31 ly also reflect a geologic source of the element, pri- irily sedimentary rocks associated with the Pierre mation. Ufornia Streams — The source of selenium in fish at tion 40 on the San Joaquin River is unknown. Selo- e, a selenium-containing pesticide, was registered for ; on citrus in California in the I960's {41). This terial may have been applied in the San Joaquin itx valley and, if so, could still be a source of sele- im to the aquatic environment. Summary mary sources of the trace elements to the aquatic /ironment follow: dmium: electroplating industry, zinc-lead-copper elting and refining, phosphate fertilizers, sulfide ore- oing activities. ad: combustion of gasoline, lead-zinc-copper smelt- : operations, sulfide ore-mining activities, coal com- ition. :rcury: pre-1975 chloralkali industry, pre-1972 paper- iping operations, synthetic fiber industries, coal com- ition. senic: copper-lead-gold smelting and refining, coal nbustion, smelter solid waste disposal, arsenical pestl- es, geologic. enium: geologic, industrial. ce in the environment, there is evidence that all five :e elements may undergo biologically mediated trans- mation reactions that yield organometallic compounds t are routed through the food chain. Trace element concentrations (mg/kg wet weight) in whole fish in 1976-77 follow: Geometric 85th Metal Range Mean Median Percentile Cadmium 0.01-1,04 0.07 0.05 0,11 Lead 0.10-4.92 0,32 0,19 0,44 Mercury 0.01-0.84 0.11 0.09 0.19 Arsenic 0.05-2.92 0.27 0.25 0.38 Selenium 0.05-2.87 0.56 0.50 0,82 Temporal trends in whole-fish trace element concentra- tions (mg/kg wet weight) from 1972 to 1976-77 were as follows: cadmium, significant decline; lead, no sig- nificant difference; mercury, significant decline; arsenic, significant increase; and selenium, no significant differ- ence (1972 vs. 1977). Ackn owledgm en ts We thank each of the following persons for providing information: Marc Anderson, Water Chemistry Pro- gram, University of Wisconsin, Madison. Wis.; Jim Andreasen, CNFRL Field Research Station Leader, FWS, Victoria, Tex.; Frank M. D'ltri, Institute of Water Research and Department of Fisheries and Wildlife, Michigan State University, E. Lansing, Mich.; Stan Gregory, CNFRL, Field Research Station Leader, FWS, Corvallis, Oreg.; Terry Haines, CNFRL, Field Research Station Leader, Orono. Me.; David Lenhart, ECE Co- ordinator, Region 1, FWS, Portland, Oreg.; Dan Martin, CNFRL, Field Research Station Leader, FWS, Yankton, S.D.; Lawrence W. Nicholson, Great Lakes Fishery Laboratory, FWS, Ann Arbor, Mich,; Mike Saiki, CNFRL, Field Research Station Leader, FWS, Davis, Calif.; Barry W. Smith, Assistant Chief of Fisheries, Alabama Game and Fish Commission, Montgomery, Ala.; Max W. Walker, Environmental Specialist, Georgia Department of Natural Resources, Atlanta, Ga.; Parley Winger, CNFRL, Field Research Station Leader, FWS, Athens, Ga.; E. E. Winstead, Assistant Commissioner, Georgia Department of Agriculture, Atlanta, Ga. We especially thank the FWS biologists, state fish and game personnel, and local commercial fishermen who assisted in the collection of the 1976-77 NPMP fish samples. LITERATURE CITED (/) Adrian, W. J. 1971. 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No. 221, Univ.ii Wyoming, Laramie, Wyo. 64 pp. 38 Pesticides Monitoring Jouw" FOOD AND FEED Pesticide, Heavy Metal, and Other Chemical Residues in Infant and Toddler Total Diet Samples — (11)— August 1975-July 1976 ' Roger D. Johnson, Dennis D. Manske, Dallas H. New, and David S. Podrebarac ABSTRACT Food and Drug Administration, U.S. Department of 'th and Human Services, initiated the Total Diet Study 964 to monitor residues of pesticides and other chemi- ingested in the average diet of the United States' hearli- ■aler, the young adult male. In August 1974, one-third le adult market baskets were replaced with infant and ler market baskets. Averages and ranges of residues for second in a series of infant and toddler baskets, for '1st 1975-July 1976, are reported. Included are results of ■minations for zinc, cadmium, lead, selenium, arsenic, mercury. Results of recovery studies conducted with lounds of each residue type are also presented. Introduction Food and Drug Administration (FDA), U.S. De- ment of Health and Human Services (formerly U.S. artment of Health, Education, and Welfare), has [ monitoring the United States' total diet since 1964 ), 11-17). The program began with surveillance of s for fission products from atmospheric tests of ■nonuclear weapons. Later, the emphasis was di- ;d toward pesticide residues in foods. For several s the program focused on the total diet of the 16- 9-year-oId male, statistically the United States' tiest eater. In August 1974, 10 of the 30 market ets were replaced with the total diet of 6-month-old Its and 2-year-old toddlers. The 10 market baskets collected in 10 cities that ranged in population 1 fewer than 50,000 to one million or more. Is in each of 11 broad classes, as listed in Table 1, prepared separately, composited into a slurry, and >'zed for organochlorine and organophosphorus pes- es, carbaryl, herbicides, metals, and a few industrial licals. Methodologies included atomic absorption troscopy, fluorometry, gas chromatography, thin- TABLE 1. Commodity classes of infant and toddler foods analyzed for pesticides, metals, and other chemical residues, August 1975-July 1976 Key Food Class I Drinking water ' II Whole milk, fresh i III Other dairy and substitutions, infant Other dairy and substitutions, toddler IV Meat, fish, and poultry, infant Meat, fish, and poultry, toddler V Grain and cereal products, infant Grain and cereal products, toddler VI Potatoes ■■ = VII Vegetables, infant Vegetables, toddler VIII Fruit and fruit juice, infant Fruit and fruit juice, toddler IX Oils and fats i. ^ X Sugar and adjuncts, infant Sugar and adjuncts, toddler XI Beverages ^- * I and Drug Administration, Kansas City District Office Labora- L009 Cherry St., Kansas City, MO 64106 NOTE: Use key with Table 3. ^ Because of similarity between infant and toddler diets, single deter- minations for certain classes of food are made and reported for both. - No infant composite for western region. ■^ No infant composite from the north-central, western, and southern regions. * No infant composite from north-central region. layer chromatography, mass spectroscopy, and estab- lished extraction and cleanup techniques (7, 8, 10, 18, 19). Except for the water composite (9), quantitation limits and instrumental conditions were the same as those described for the adult market baskets. Results The infant composites of the present series contained 301 residues of 31 compounds, with 51 residues at the trace level. In comparison, the first infant composites reported last year contained 306 residues of 28 com- pounds; 121 were reported at the trace level. Toddler composites of the present series showed 473 residues of 38 compounds; 76 were present in trace amounts. The first toddler series last year reported 468 residues of 30 compounds with 179 at the trace level. 15, No. 1, June 1981 39 The chemical compounds found, the number of findings, and the range for each are listed in Table 2. TTie fre- quency of occurrence of each compound by food class is presented in Table 3. Table 4 shows the level of every residue found within each food class. The averages given in Table 4 are based on the total number of composites examined for that food class. Trace values were treated as zero in calculating these averages. Table 5 shows the intake of pesticide and industrial chemical residues in terms of /xg/kg body weight/day, and Table 6 shows the intake of six metals in terms of /xg/day (mg/day for zinc). For comparison, the findings for the 1975 fiscal year are also shown. The most common residues and their average levels are discussed below for each of the 1 1 food classes. No findings have been corrected for recoveries. DRINKING WATER Infant and Toddler — -Tap water samples analyzed were taken from the same location as the market basket. The result of a single analysis is that reported for both infant and toddler composites. The water was used to prepare other market basket items requiring dilution or addition of water. Only two metal residues were found: four samples contained zinc averaging 0.170 ppm for the series, and one sample contained cadmium, averaging 0.002 ppm. WHOLE MILK, FRESH Infant and Toddler — This composite was common to both diets. Averages for chlorinated pesticide residues included 0.001 ppm p,p'-DDE; trace a-BHC (hexa- chlorocyclohexane); trace dieldrin; and a trace of heptachlor epoxide. Averages for the three metals found were 6.80 ppm zinc; 0.007 ppm cadmium; and 0.002 ppm selenium. A trace of PCP was detected in one composite. OTHER DAIRY AND SUBSTITUTIONS Infant — The variation in infants' and toddlers' diets be- comes apparent with these composites. Dieldrin was found in four composites averaging trace for the series. Averages of other organochlorines were traces of o-BHC, heptachlor epoxide, methoxychlor, and /?,p'-DDE. A trace of PCP was found in one composite. Averages for metal residues were 5.38 ppm zinc, 0.004 ppm cadmium, and 0.013 ppm lead. Toddler — All 10 composites contained dieldrin, averag- ing 0.003 ppm, and «-BHC, averaging 0.002 ppm. Averages of other pesticide residues included 0.004 ppm p,p'-DDE, 0.001 ppm heptachlor epoxide, and traces of octachlor epoxide, methoxychlor, HCB, and lindane. A trace of PCP was found in one composite. Averages of metal residues included 5.94 ppm zinc, 0.016 ppm selenium, 0.013 ppm cadmium, 0.006 ppm lead, and a trace of mercury. 40 TABLE 2. Chemical and metal residues found in in] and toddler food composites from 10 United States citie August 197 5 -July 1976 Chemical Found No. OF Composites With Residues No. OF Positive Composites With Residues Reported as Trace ' Range, i INFANT Zinc Cadmium Lead Selenium P.p'-DDE 2 Dieldrin Malathion a-BHC Heptachlor epoxide Mercury PCP CIPC Arsenic Dichloran Endosulfan ^ HCB Endrin Lindane Toxaphene Octachlor epoxide TCNB P,P-DDT ' Chlordane Diazinon Methoxychlor Parathion Ethion Fonofos Carbaryl TCTA Perthane 85 59 35 21 17 15 12 9 6 4 4 3 3 3 3 3 2 2 2 2 1 1 1 1 1 1 1 1 1 TODDLER Zinc 100 0 0.100-3i Cadmium 77 0 0.005-0. Lead 35 0 0.050-0. Dieldrin 31 6 O.OOI-O. a-BHC 29 12 0.0006-0. Selenium 27 0 0.020-0, P.P'-DDE = 26 4 0.001-0. Heptachlor epoxide 20 13 0.001-0. Malathion 16 0 0.005-0. Lindane 15 3 0.001-0. HCB 14 8 0.0007-0. Arsenic 11 0 0.030-0. Octachlor epoxide 10 9 0. Mercury 7 0 0.002-0. PCP 6 5 0. CIPC 5 0 0.023-0. PCA 4 0 0.002-0. Pentachlorobenzene 4 1 0.001-0. Toxaphene 4 3 Oj Dichloran 3 0 0.012-0. PCNB 3 0 0.001-0. Diazinon 3 1 0.001-0; 1 Chlordane 3 2 0. Parathion 3 3 T p,p -DDT 2 2 1 0. P,p'-TDE 2 2 1 0. Fonofos 2 0 O.OOI-O. Ronnel 0 0. Endrin 0 0. 2,4-D 0 0. TCNB 0 0. rra/ij-Nonachlor 0 0. PCTA 0 0. TCTA 1 T Ethion 1 T o-PhenylphenoI 1 T Methoxychlor 1 T PCP methvl ether 0 0. ^ Chemicals detected by the specific analytical methodology below limit of quantitation were confirmed qualitatively and reportet i trace (T). The limits of quantitation vary with residues and .-> classes. • Other isomers also included in reporting » Reportings include isomers I and II and sulfate. Pesticides Monitoring Jour» LE 3. Frequency of occurrence of chemical and metal ues, by food class, in infant and toddler food composites rom 10 United States cities — August 1975-July 1976 Food Class ' icAL I II III IV V VI VII vin IX X XI NUMBER OF OCCURRENCES IN INFANT FOODS 4 10 10 10 10 8 10 9 2 7 5 ium 1 4 4 7 10 8 10 6 2 6 1 0 0 1 8 6 6 8 5 0 0 1 Lim 0 1 0 10 10 0 0 0 0 0 0 IDE 0 3 4 5 0 3 2 0 0 0 0 in 0 2 4 6 0 2 0 0 1 0 0 Won 0 0 0 0 10 0 0 0 2 0 0 0 3 5 1 0 0 0 0 0 0 0 chlor epoxide 0 I 3 0 0 0 0 0 2 0 0 ry 0 0 0 2 0 0 1 0 0 1 0 0 1 1 0 1 0 0 1 0 0 0 0 0 0 0 0 3 0 0 0 0 0 ,c 0 0 0 0 3 0 0 0 0 0 0 Iran 0 0 0 0 0 1 0 2 0 0 0 ulfan 0 0 0 0 0 1 1 1 0 0 0 0 0 0 2 0 1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 2 0 0 le 0 0 0 0 2 0 0 0 0 0 0 hene 0 0 0 0 0 0 0 0 2 0 0 ilor epoxide 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 DT 0 0 0 0 0 0 1 0 0 0 0 lane 0 0 0 0 0 0 0 0 1 0 0 on 0 0 0 0 1 0 0 0 0 0 0 xy chlor 0 0 1 0 0 0 0 0 0 0 0 ion 0 0 0 0 0 0 1 0 0 0 0 1 0 0 0 0 0 0 0 1 0 0 0 :is 0 0 0 0 0 0 0 0 1 0 0 71 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 ne 0 0 0 0 0 0 0 1 0 0 0 NUMBER OF OCCURRENCES IN TODDLER FOODS im DE :hlor epoxide lion le ilor epoxide ry hlorobenzene tiene ran on ane ion DT )E >s Jonachlor ylpiienol lychlor ethyl ether 10 10 10 10 10 8 4 9 8 10 8 9 10 10 10 10 0 10 able 1 for key to food classes. 15, No. 1, June 1981 MEAT, FISH, AND POULTRY Infant — These infant composites contained among the highest number of residues. Metals dominated 37 of the 53 residues, with averages of 16.8 ppm zinc, 0.094 ppm selenium, 0.087 ppm lead, 0.023 ppm cadmium, and 0.002 ppm mercury. Of the 16 nonmetals. dieldrin was found in six composites averaging a trace for the series; /7,p'-DDE, averaging 0.003 ppm for the series, was found in five composites; HCB, octachlor epoxide, and a-BHC averaged a trace. Toddler — Ninety-nine residues were found. All 10 com- posites contained residues of p,p'-DDE, ranging from 0.002 to 0.016 ppm. and dieldrin, ranging from 0.001 to 0.003 ppm. Heptachlor epoxide, p,p'-TDE, p,p'- DDT, hexachlorobenzene (HCB), a-BHC, lindane, octachlor epoxide, ronnel, and /ra«j-nonachlor averaged a trace for the series. Average metal residues included 27.5 ppm zinc and 0.180 ppm selenium. Lesser amounts of arsenic, lead, cadmium, and mercury, averaging 0.092, 0.030, 0.010, and 0.006 ppm, respectively, were also found. GRAIN AND CEREAL PRODUCTS Infant — All 10 composites contained malathion, rang- ing from 0.003 to 0.049 ppm and averaging 0.020 ppm. There was one report of diazinon at the 0.010 ppm level, and only traces of lindane and PCP were found. Averages for the metals were 14.6 ppm zinc, 0.189 ppm selenium, 0.046 ppm lead, 0.027 ppm cadmium, and 0.018 ppm arsenic. Toddler — Like the infant composites, these toddler composites all contained malathion residues, ranging from 0.006 to 0.025 ppm and averaging 0.012 ppm. Diazinon, averaging trace amounts, was found in three composites. Averages for the metals found were 10.3 ppm zinc, 0.179 ppm selenium, 0.065 ppm lead, 0.026 ppm cadmium, and 0.008 ppm arsenic. POTATOES Infant — The chlorinated herbicide CIPC was found in three composites, ranging from 0.023 to 0.469 ppm and averaging 0.073 ppm for the series. TCNB averaged 0.003 ppm for the series. Other organo- chlorine pesticides averaging trace amounts included p.p'-UUE, dieldrin, dichloran, endosulfan, TCTA, and HCB. Of the metals found, zinc averaged 2.72 ppm, lead averaged 0.061 ppm, and cadmium averaged 0.048 ppm. Toddler — The chlorinated herbicide CIPC was found in five composites, ranging from 0.023 to 0.469 ppm and averaging 0.156 ppm for the series. TCNB was found in one composite at 0.026 ppm, and dieldrin, lindane, p,p' -DDE, TCTA, and HCB averaged a trace. The metals zinc and cadmium averaged 3.92 41 TABLE 4. Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 Un States cities — August 1975-July 1976 Residvie, PPM Chemical Residue, PPM Chemical Infant Toddler Infant TODDLEK I. WATER DIELDRIN Average Positive composites T 0.003 ZINC Average 0.170 0.170 Total number 4 10 Positive composites Number reported as trace 2 0 Total number 4 4 Range 0.001 0.001-O.C Number reported as trace 0 0 METHOXYCHLOR Range 0.200-0.600 0.200-0.600 Average T T CADMIUM Positive composites Average 0.002 0.002 Total number 1 I Positive composites Number reported as trace 1 1 Total number 1 1 Range T T Number reported as trace 0 0 CADMIUM Range 0.02 0.020 Average 0.004 0.013 Positive composites Total number Number reported as trace Range 4 0 0.005-0.020 7 0 II. WHOLE MILK, FRESH 0.006-O.t ZINC Average 6.80 6.80 u-BHC Average T 0.002 Positive composites Positive composites Total number 10 10 Total number S 10 Number reported as trace Range 0 3.30-28.8 0 3.30-28.8 Number reported as trace Range 4 0.001 0 0.001-0.( a-BHC Average T T p,p'-DDE Average T 0.004 Positive composites Total number 3 3 Positive composites Total number 4 8 Number reported as trace Range 2 0.0006 2 0.0006 Number reported as trace Range 4 T 1 0.001-0.( P,P'-DDE Average 0.001 0.001 LEAD Average 0.013 0.006 Positive composites Total number 3 3 Positive composites Total number 1 1 Number reported as trace Range DIELDRIN 1 0.002-0.005 1 0.002-0.005 Number reported as trace Range PCP Average 0 0.130 0 0.060 Average T T T T Positive composites Total number 2 2 Positive composites Total number 1 1 Number reported as trace Range CADMIUM Average Positive composites Total number 0 0.001 0.007 4 0 0.001 0.007 4 Number reported as trace Range SELENIUM Average Positive composites Total Number reported as trace Range 1 T 1 T 0.016 4 0 0.030-O.t Number reported as trace Range PCP Average Positive composites Total number Number reported as trace Range HEPTACHLOR EPOXIDE Average Positive composites Total number Number reported as trace 0 0.005-0.040 0 0.005-0.040 T I 1 T T I 1 T 1 1 T T 1 1 OCTACHLOR EPOXIDE Average Positive composites Total number Number reported as trace Range MERCURY Average Positive composites Total number T 6 6 T T 1 Range SELENIUM T T Number reported as trace Range HCB Average Positive composites Total number Number reported as trace Range 0 0.002 Average Positive composites Total number Number reported as trace Range 0.002 1 0 0.02 0.002 1 0 0.020 T 5 4 0.0007 LINDANE Average T in. OTHER DAIRY AND SUBSTITUTIONS Positive composites Total number ZINC 1 Average 5.38 5.94 Number reported as trace 0 Positive composites Range 0.002 Total number 10 0 10 0 Number reported as trace IV. MEAT, FISH, AND POULTRY Range HEPTACHLOR EPOXIDE 2.90-8.50 1.60-14.6 ZINC Average T 0.001 Average 16.84 27.52 Positive composites Positive composites Total number 3 8 Total number 10 10 Number reported as Uace 3 3 Number reported as trace 0 0 Range T 0.001-0.003 Range 8.90-36.3 11.3-34. 42 Pesticides Monitoring Joui* .E 4 (cont'd.). Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 United States cities — August 1975-July 1976 Residue, ppm Residue, ppm Chemical Infant Toddler Chemical 4IUM age ive composites ■tal number imber reported as trace inge age ive composites ■tal number imber reported as trace inge [lUM age ive composites tal number imber reported as trace Jige URY age ive composites tal number imber reported as trace nge •RIN age ive composites tal number mber reported as trace nge age ive composites tal number mber reported as trace nge ige ive composites ;al number mber reported as trace nge )E ige ve composites al number mber reported as trace ige ;hlor epoxide Ige ve composites al number mber reported as trace Ige IC Ige ve composites al number mber reported as trace Ige CHLOR EPOXIDE ge ve composites al number mber reported as trace Ige E ge ve composites al number Tiber reported as trace Ige T ge ve composites al number Tiber reported as trace Ige 0.094 0.180 10 0 0.040-0.220 9 0 0.110-0.300 0.087 0.030 8 0 0.050-0.180 3 0 0.050-0.190 0.023 0.010 7 0 0.010-0.100 9 0 0.008-0.020 0.002 0.006 2 0 0.004-0,016 6 0 0.005-0.020 T 0.002 6 4 0.002-0.003 10 1 0.001-0.003 T T 2 2 T 4 2 0.0007-0 .0009 T T 1 1 T 8 7 0.0007 0.003 0.005 5 2 0.002-0.019 10 0 0.002-0.016 T T 2 2 T 4 3 0.004 0.092 7 0 0.060-0.290 T 9 8 0.002 2 1 0.002 Infant TODDLEK LINDANE Average Positive composites Total number Number reported as trace Range RONNEL Average Positive composites Total number Number reported as trace Range rranj-NONACHLOR Average Positive composites Total number Number reported as trace Range 4 3 0.003 1 0 0.002 1 0 0.006 V. GRAIN AND CEREAL PRODUCTS 2 1 0.005 ZINC Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range ARSENIC Average Positive composites Total number Number reported as trace Range MALATHION Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range PCP Average Positive composites Total number Number reported as trace Range LINDANE Average Positive composites Total number Number reported as trace Range DIAZINON Average Positive composites Total number Number reported as trace Range 14.6 10 0 6.8-20.3 0.189 0.027 0.018 3 0 0.040-0.090 0.020 10 0 0.003-0.049 0.046 2 0 0.004 0.001 1 0 0.010 10.29 10 0 6.30-18.9 0.179 10 10 0 0 0.140-0.250 0.080-0.290 0,026 10 10 0 0 0.020-0.050 0.018-O.040 0.008 2 0 0.030-0.050 0.012 10 0 0.006-0.025 0.065 6 0 0.050-O.100 5 0 0.060-0.210 T T 1 1 T 1 1 T 3 1 0.00 1-0.00 J 15, No. 1, June 1981 43 TABLE 4 (cont'd.). Levels of chemical and metal residues, by food class, in infant and toddler food composites froi United States cities — August 1975-July 1976 Residue, ppm Chemical Residue, ppm Chemical Infant Toddler Infant Toddle VI. POTATOES VII. VEGETABLES ZINC Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range LINDANE Average Positive composites Total number Number reported as trace Range P,p'-DDE Average Positive composites Total number Number reported as trace Range DICHLORAN Average Positive composites Total number Number reported as trace Range ENDOSULFAN Average Positive composites Total number Number reported as trace Range CI PC Average Positive composites Total number Number reported as trace Range TCNB Average Positive composites Total number Number reported as trace Range TCTA Average Positive composites Total number Number reported as trace Range HCB Average Positive composites Total number Number reported as trace Range 2.72 0.30-4.30 0.061 3 1 0.001-0.002 T 0 0.006 I 1 T 0.073 3 0 0.023-0.469 0.003 1 0 0.026 1 1 T 3.92 10 0 0.300-8.20 0.078 6 0 0.050-0.120 6 0 0.050-0.350 0.048 0.045 8 0 0.020-0.130 10 0 0.010-0.120 T T 2 1 0.002 2 1 0.002 1 0 0.007 3 1 0.002 0.156 0.023-0.469 0.003 1 0 0.026 1 1 T 1 1 T ZINC Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range CADMIUM 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 p,p'-DDE Average Positive composites Total number Number reported as trace Range P,P'-DDT Average Positive composites Total number Number reported as trace Range ENDOSULFAN Average Positive composites Total number Number reported as trace Range PCP Average Positive composites Total number Number reported as trace Range LINDANE Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range a-BHC Average Positive composites Total number Number reported as trace Range 3.66 10 0 1,80-6.40 0.078 0.060-0.240 0,043 10 0 0.010-0.120 1 0 0.002 1 1 T 2 0 0.002-0.004 1 1 T 0,004 1 0 0,037 3,49 1 1 T 1 0 0,002 1 1 T 2 0 0.002 44 Pesticides Monitoring Jou i LE 4 (cont'd.). Levels of chemical and metal residues, by food class, in infant and toddler food composites from 10 United States cities — August 1975-July 1976 Residue. PPM Chemical Residue, PPM Chemical Infant Toddler Infant Toddler VIII. FRUITS AND FRUIT JUICES MALATHION Average 0.025 0.041 Positive composites rage 0.610 0.870 Total number 2 6 tive composites Number reported as trace 0 0 >tal number 9 9 Range 0.015-0.035 0.005-0.187 umber reported as trace 0 0 TOXAPHENE ange 0.300-1.00 0.200-2,40 Average Positive composites T 0.007 •age 0,066 0.062 Total number 2 4 live composites Number reported as trace 2 3 )tal number 5 5 Range T 0.075 umber reported as trace 0 0 DIELDRIN inge 0.070-0.290 0,080-0,240 Average 0.001 0.001 ISULFAN Positive composites ■age T Total number 1 5 tive composites Number reported as trace 0 3 )tal number 1 Range 0.002 0.002-0.007 umber reported as trace 1 ENDRIN mge T Average 0.006 0.001 HANE Positive composites ■age T Total number 2 1 tive composites Number reported as trace 1 0 )tal number 1 Range 0.011 0.009 jmber reported as trace 1 HEPTACHLOR EPOXIDE inge T Average T 0.001 LORAN Positive composites age 0.001 0.005 Total number 2 2 tive composites Number reported as trace 2 1 )tal number 2 3 Range T 0.007 imber reported as trace 0 0 FONOFOS inge 0.006-0.007 0.012-0,026 Average T T HUM Positive composites Total number 1 2 age 0.007 0.005 Number reported as trace 1 0 Eive composites ttal number 6 4 Range T 0.001-0.002 Jmber reported as trace 0 0 CHLORDANE inge 0.010-0.017 0.010-0.020 Average Positive composites T 0.014 ARYL Total number 1 3 age T Number reported as trace 1 2 tive composites Range T 0.137 ital number 1 Jmber reported as trace 1 p,p'-DDE inge T Average Positive composites Total number T 1 ■age T T Number reported as trace 1 tive composites Range T )tal number 1 1 Jmber reported as trace 1 LEAD mge T T Average Positive composites 0.050 )N Total number 6 age T T Number reported as trace 0 tive composites Range 0,060-0.120 ital number 1 1 HCB Average Positive composites Jmber reported inge as trace 1 T 1 T 0.002 NYLPHENOL Total number 4 age T Number reported as trace 1 tive composites Range 0.001-0.016 )tal number Jmber reported as trace 1 1 PCNB mge T Average 0.001 Positive composites Total number Number reported as trace 3 IX. OILS AND FATS 0 Range PCA 0.001-O.0O5 age 20.3 14.43 Average 0.005 ive composites Positive composites tal number 2 10 Total number 4 imber reported as trace 0 0 Number reported as trace 0 nge 20.2-20.4 10.6-19.2 Range 0.002-0.044 lUM PENTACHLOROBENZENE age 0.074 0.062 Average 0.001 ive composites Positive composites tal number 2 10 Total number 4 imber reported as trace 0 0 Number reported as trace 1 nge 0.067-0.080 0.040-0.110 Range 0.001-0.009 15, No. 1, June 1981 45 TABLE 4 (cont'd.). Levels of chemical and metal residues, by food class, in infant and toddler food composites froi United States cities — August 1975-July 1976 Residue, ppm Chemical Infant SELENIUM Average Positive composites Total number Number reported as trace Range PARATHION Average Positive composites Total number Number reported as trace Range ARSENIC Average Positive composites Total number Number reported as trace Range PCTA Average Positive composites Total number Number reported as trace Range PCP METHYL ETHER Average Positive composites Total number Number reported as trace Range X. SUGAR AND ADJUNCTS ZINC Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range MERCURY Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites Total number Number reported as trace Range PCP Average Positive composites Total number Number reported as trace Range LINDANE Average Positive composites Total number Number reported as trace Range a-BHC Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range 2.73 7 0 0.20-20.7 0.005 6 0 0.007-0.010 0.0006 0 0.006 Toddler 0.011 2 0 0.050-0.060 T 2 2 T 0.003 1 0 0.030 I 0 0.003 1 0 0.002 5.51 10 0 1.50-12.5 0.015 10 0 0.010-0.020 0.004 1 0 0.040 0.007 1 0 0.070 0.001 6 0 0.001-0.003 T 6 3 0.001-O.0O2 0.028 2 0 0.090-0.190 Residue, ppm Chemical Infant Toddle ARSENIC Average Positive composites Total number Number reported as trace Range 2.4-D Average Positive composites Total number Number reported as trace Range 0.004 1 0 0.040 0.002 1 0 0.025 XL BEVERAGES ZINC Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range 0.314 0.180 5 0 0.100-1.00 7 0 0.100-0 0.007 0.002 1 0 0.012 2 0 0.010 0.011 0.007 1 0 0.080 1 0 0.070 NOTE: Average residues are based upon the total number of cc ites examined; trace values were treated as zero. It is quite p that average values reported as T can be well below the detection of the method for that composite. ppm and 0.045 ppm, respectively, and were four^ all 10 composites; lead was found in six compo] averaging 0.078 ppm for the series. VEGETABLES Infant — The highest level for a chlorinated pesh was 0.037 ppm endosulfan found in one compi There were two reports of p.p'-DDE, 0.002 ppmi 0.004 ppm, and trace findings of parathion and j DDT. Average residues of metals included 3.66 zinc, 0.078 ppm lead, 0.043 ppm cadmium, and a of mercury. Toddler — Trace averages were reported for parat dieldrin, lindane, PCP, p.p'-DDE and a-BHC. lead, and cadmium accounted for 26 of the toti residues and averaged 3.49, 0.081, and 0.026 i respectively. FRUITS AND FRUIT JUICES Infant — The chlorinated pesticide Perthane® ana carbamate pesticide carbaryl were found only ir food group, in one composite at the trace level. < 46 Pesticides Monitoring Jot)( LE 5. Intake of pesticide and industrial chemical ndues by infants and toddlers, market basket surveys FY 1975 \s FY 1976 Residue, ^g/kg Body Wt/Day TABLE 6. Dietary intakes of metals by infants and toddlers, FY 1975 vs FY 1976 Infant Toddler FY 75 FY 76 FY 75 FY 76 chlor epoxide hlor L ulfan I ulfan II ulfan sulfate L ryl lane ran il )S )hos le lion xychlor 1 parathion lylphenol ordane ion hloroanisole iilorobenzene ND 0.0153 0.0153 0.1276 T T 0.1276 0.0097 ND 0.0097 ND ND ND ND 0.0228 ND T ND 0.0020 ND ND T 0.0383 ND ND ND ND 0.0044 ND 0.0133 0.2028 T ND ND T T 0.0053 ND 0.0005 0.0073 0.0154 tachlorothioanisole) ND ne ND 3ne lene fonachlor henothion ND T ND 0.2573 ND ND ND ND 0.0249 0.0249 0.0682 T ND 0.0682 0.0001 ND 0.0001 0.001 1 0.0045 0.0368 0.0424 0.0055 ND T T 0.0321 ND ND 0.0053 0.0230 ND T ND T 0.0009 ND 0.0049 0.0865 T ND ND 0.0008 T ND ND ND ND T ND T ND T ND T ND 0.0019 ND ND 0.0502 0.0502 0.1598 0.0064 0.0037 0.1699 0.0057 ND 0.0057 ND ND 0.0078 0.0078 0.0211 ND 0.0047 ND 0.0458 ND ND 0.0067 0.0506 ND ND ND ND 0.0064 0.0033 0.0341 0.1374 ND ND ND T ND 0.0058 ND 0.0007 0.0024 0.0214 ND ND ND T T 0.0467 ND T ND ND 0.0412 0.0412 0.0985 0.0046 0.0018 0.1049 0.0057 ND 0.0057 ND ND ND ND 0.0132 ND ND 0.0100 0.3942 0.0058 ND 0.0030 0.0342 ND ND 0.0007 0.0002 0.0042 ND 0.0096 0.1488 T ND T T 0.0013 0.0064 0.0003 0.0013 0.0007 0.0162 0.0004 ND ND ND 0.0022 0.0127 0.0050 0.0074 ND : ND r= not detected; T =^ Trace (below the limits of quantita- etected and verified, but not quantifiable). ides reported at the trace level included endo- 1, PCP, and ethion. Dichloran was found in two osites and averaged 0.001 ppm for the series. Low- metal residues included zinc, lead, and cadmium, ging 0.610, 0.066, and 0.007 ppm, respectively. ler — Dichloran, found in three composites, ranged 0.012 to 0.026 ppm for a series average of 0.005 Traces of PCP, ethion, and the fungicide o- Residue, jig/day Infant Toddler Metal FY 75 FY 76 FY 75 FY 76 Lead Cadmium Zinc 1 Arsenic - Selenium Mercury 20.79 5.16 5.33 2.76 21.63 0.03 26.94 12.33 8.15 0.42 10.81 0.56 25.61 10.72 8.26 11.10 58.38 0.94 30.12 14.19 9.46 12.28 44.99 0.81 1 Values are mg/day. - Values calculated as arsenic Irioxide (As^O^) . phenylphenol were also reported. Zinc, lead, and cad- mium all averaged below 1.0 ppm. OILS AND FATS Infant — Only two of the 10 market baskets included a separate composite of oils and fats for the infant. Mala- thion, endrin, and dieldrin averaged 0.025, 0.006, and and 0.001 ppm, respectively. Trace averages were re- ported for toxaphene, heptachlor epoxide, and chlor- dane. Fonofos, an organophosphorus pesticide, was found only in this food group, at the trace level. Both com- posites had residues of zinc, 20.2 ppm and 20.4 ppm, and cadmium, 0.067 ppm and 0.080 ppm. Toddler — A total of 71 residues was reported for these 10 composites. The metals accounted for 29 residues and included zinc (average 14.43 ppm), cadmium (average 0.062 ppm), lead, selenium, and arsenic. Three organophosphorus pesticides were reported: malathion in six composites, ranging from 0.005 to 0.187 ppm and averaging 0.041 ppm for the series; parathion traces in two composites; and fonofos in two composites, ranging from 0.001 to 0.002 ppm and averaging trace for the series. Malathion residues averaged highest of the nonmetals and appeared in the most composites. Among the organochlorine com- pounds, toxaphene averaged 0.007 ppm and was reported in four composites. Other organochlorine residues included PCA, dieldrin, pentachlorobenzene, chlordane (average 0.014 ppm), HCB, heptachlor epoxide, PCNB, p.p'-DDE, PCTA, and PCP methyl ether. SUGAR AND ADJUNCTS Infant — Only three metal residues were reported for these infant composites. Zinc was found in seven com- posites, ranging from 0.20 to 20.7 ppm, for a series average of 2.73 ppm. Cadmium was found in six com- 15, No. 1, June 1981 47 posites, ranging from 0.007 to 0.010 ppm and averag- ing 0.005 ppm for the series. One residue of mercury was reported at 0.006 ppm for a series average of 0.0006 ppm. Toddler — In contrast, the toddler composites had 38 residues of nine different compounds: five metals, two chlorinated herbicides, and two organochlorine pesti- cides. Averages of the metals included 5.51 ppm zinc, 0.015 ppm cadmium, 0.028 ppm lead, and 0.004 ppm each for arsenic and selenium. Two composites con- tained herbicides: PCP at 0.07 ppm and 2,4-D at 0.025 ppm. Six residues were reported for each of the chlorinated pesticides, lindane and a-BHC, with ranges 0.001 to 0.003 ppm and 0.001 to 0.002 ppm, respec- tively. BEVERAGES Infant — Only three metal residues were reported for these composites. Zinc was found in five composites, ranging 0.100 to 1.00 ppm, and averaging 0.314 ppm for the series; 0.012 ppm cadmium and 0.080 ppm lead were reported for one composite. Toddler — The metal residues found in these toddler composites were the same as those found in the infant composites. Zinc was found in seven composites, rang- ing from 0.100 to 0.500 ppm, and averaging 0.180 ppm for the series. Cadmium was reported twice at the 0.01 ppm level, and lead was reported once at 0.070 ppm. Discussion INFANT The infant composites contained a total of 301 resi- dues: 207, or 68.7 percent, were metals; 86, or 28.6 percent, were pesticides; and the remaining 2.7 per- cent included seven herbicide residues and one fungi- cide residue. In comparison, a total of 306 residues was reported for the first infant composite series: 199 (65 percent) metals, 99 (32.3 percent) pesticides, five fungicides, one herbicide, and two industrial chemicals. Of the metal residues, zinc, occurring most frequently, was found in 85 composites with the highest level, 36.3 ppm, occurring in the meat-fish-poultry composite. Although 59 cadmium residues were reported, the 35 lead residues, ranging from 0.050 to 0.290 ppm, might be of greater significance. The highest level of lead residues was found in the fruit and fruit juice compos- ites. All but one of the 21 selenium residues were found in the meat-fish-poultry composites. Arsenic was re- ported at low levels in three grain-cereal composites. Six- teen chlorinated pesticide compounds were reported in 69 residues; 43 were found at the trace level. Of these, the most frequently occurring residues were dieldrin and p,/?'-DDE, found mostly in the dairy composites and the meat composites. Endosulfan, found in one ■ table composite at 0.037 ppm, was the chlorii pesticide occurring at the highest level. Malathion, an organophosphorus pesticide, was f in each of the 10 grain and cereal composites, w high value of 0.049 ppm. In addition to 0.010 diazinon found in one composite, single trace ami of three other organophosphorus pesticides wen ported: parathion, ethion, and fonofos. A single of carbaryl, the only carbamate pesticide screened found once in the fruit-fruit juice composite. Only two herbicides were found in the composites, chlorinated herbicide CIPC, which is usually foui potatoes, was reported for three potato compc ranging from 0.023 to 0.469 ppm, and trace amoui PCP were found in four composites. The funj TCNB was reported in one potato composite at i ppm. TODDLER A total of 473 residues was found in the toddler composites. Of these, the six metals accounted foi residues, or 54.3 percent of the total, the 17 chlori pesticides accounted for 164, or 34.6 percent, ani six organophosphorus pesticides were reportec times for 5.4 percent of the total. The remainin; percent included four chlorinated herbicides four times, three chlorinated fungicides found eight t one industrial chemical found four times, an, phenylphenol found once. Zinc, ranging from 0.100 to 34.0 ppm, was foun almost every composite. Cadmium was the second frequently occurring residue, but the range, 0.0( 0.120 ppm, was much lower. Most of the lead dues, with a range of 0.050 to 0.350 ppm, were 1 in the grain, potato, vegetable, and fruit compel All 10 grain composites and nine meat compj contained selenium residues. The meat-fish-pc( composites contained seven of the 11 arsenic res) and six of the seven mercury residues, which have^ traced to the seafood portion of the composite. | Seventeen chlorinated pesticides accounted for or 34.6 percent, of all the residues; these were If predominantly in the dairy and meat-fish-poultry f posites. The most frequently detected chlorinated cide was dieldrin, found in every dairy and mealji poultry composite. a-BHC and DDE were also i) several times in those two composites. The most prevalent organophosphorus pesticidei malathion, found in all 10 grain-cereal composite^ in six oil-fat composites. Other reportable organol phorus pesticides were diazinon, parathion, foil and ronnel, each residue found in either the \\ cereal or the oil-fat composites. The herbicides 48 Pesticides Monitorxno Joofc icides represented a small number of residues. ■ four chlorinated herbicides were reported: CIPC ues, found in five potato composites, ranged from 3 to 0.469 ppm; PCP, 2,4-D, and PC? methyl ■ were scattered throughout the other food groups. t of the eight residues of the three chlorinated icides detected were found in the fat-oil composite. ichlorobenzene, an industrial chemical, was present e toddler diet but was not found in the infant diet; is detected in four oil-fat composites and ranged 0.001 to 0.009 ppm. The fruit-fruit juice com- es contained one residue of the fungicide o- ylphenol at the trace level. ; 7 shows the number of occurrences of each ue type as found in each food class. very studies were done for many of the more non residues. In each case, simultaneous determi- ns were made on an unfortified composite and on mposite fortified with a known level of residue. 5 8 lists the contributions from the unfortified com- 3, and the total amount of residue recovered igh the method. A single determination was made ach reported recovery. In some cases only a few losites were fortified with a particular compound; are presented for information only. In other cases, tempt was made to investigate the recovery of the frequently found residues from a variety of prod- natrices and to provide a basis for a meaningful ation of the methods. The data are presented in :8. A ckttowledgments ors acknowledge the contributions of all staff bers assigned to the Total Diet Section, Food and Administration, Kansas City District Laboratory. ,E 7. Types and number of residues, by food class, >und in infant and toddler total diet samples from 10 United States cities — August 1975-July 1976 Food Class ^ F E I II III IV V VI VII VIII IX X XI INFANT les ides ial chemicals ides 23355343233 — 45536457 — — 1 — 1 1 TODDLER les ides ial cliemicals ides 23565333553 — 48 11 2552 11 2 — — — — — — 2— 1 2 — — TABLE 8. Recovery data on residues found in infant and toddler total diet samples from 10 United Slates cities — August 1975-July 1976 1 1 1 — 1 1 2 — By in Table 1. Range OF Range of Unforti- Total Number Type of Spike fied Residue of Food Level, Composite, Found, Recovery Residue Composite PPM PPM > PPM >■- Studies NONMETALS Oxychlordant ; Fatty 0.003 0.0027-0.0039 2 Nonfatty 0.003 0.0026 1 Heptachlor Fatty 0.003 0.0027-0.0031 2 epoxide Nonfatty 0.003 0.0027 1 Ethion Fatty 0.010 0 -trace 2 Nonfatty 0.010 0.010 1 DCPA Fatly 0.005 0-0.001 0.0045-0.007 4 Nonfatty 0.005 0.00043-0.0064 (0.0043) 8 Methyl Fatty 0.005 0.0011-0.003 2 parathion Nonfatty 0.005 0.0014-0.0053 4 Perthane Fatty 0.010 0.005-0.0094 3 Nonfatty 0.010 0.0009-O.0131 (0.0087) 8 Tetradifon Fatty 0.100 0.065-0.090 2 Fatty 0.020 0.019 1 Nonfatty 0.100 0.048-0.109 4 Nonfatty 0.020 0.016-0.024 2 Endosulfan Fatty 0.010 0.006-0.008 2 sulfate Nonfatty 0.010 0.004-0.013 4 Malathion Fatty 0.005 0.0025-0.0049 2 Nonfatty 0.005 0.0043-0.0056 3 Phosalone Fatly 0.02 0.018 1 Nonfatty 0.02 0.009-0.015 2 Leptofos Fatty 0.05 0.039-0.049 2 Nonfatty 0.05 0.004-0.046 4 PCP Fatty 0.02 0-0.010 0.0007-0.018 4 Falty 0.04 0.020-0.024 3 Nonfatty 0.02 0-0.003 (0.0012) 0.003-0.016 (0.0096) 6 Nonfatty 0.04 0-0.004 0.02S-O.032 3 Picloram Falty 0.10 0-0.075 2 Nonfatty 0.10 0.033 1 2,4-D Fatty 0.04 0-0.042 3 Nonfatty 0.04 0.026-0.039 5 Silvex Fatty 0.04 0.008-0.022 2 Nonfatty 0.04 0.023-0.039 2 MCP Fatty 0.020 0.009-0.011 2 2-methyI- Nonfatty 0.020 0.009-0.013 3 4-chloro- Nonfatty 0.040 0.029-0.036 2 phenoxy- acetic acid 2,4-DB Fatty 0.02 0.014 1 Nonfatty 0.02 0.012-0.017 2 Nonfatty 0.04 0-O.026 2 2,4,5-T Falty 0.02 0-0.002 0.004-0.022 2 Falty 0.04 0.016 1 Nonfatty 0.02 0.007-0.0196 4 Nonfatty 0.04 0.025-0.029 2 Carbaryl Nonfatty 0.20 0.02-0.20 (0.18) 17 o-Phenyl- Nonfatty 0.40 0.08-0.40 16 phenol (0.30) Fonofos Fatty 0.01 0.002-0.004 2 Nonfatty 0.01 0.006-0.008 (0.007) 5 Toxaphene Falty 0.20 0.201-0.240 2 Nonfatty 0.20 O.125-O.204 (0.170) 4 METALS Arsenic Fatly 0.30 0.25-0.30 3 Fatty 0.40 0-0.10 0.34-0.535 (0.462) 5 Nonfatty 0.30 0.17-0.32 3 Nonfatty 0.40 0-0.03 0.24-0.385 (0.313) 12 Cadmium Falty 0.10 0.002-O.086 (0.030) 0.095-0.162 (0.116) 11 Nonfatty 0.10 0-0.371 (0.0195) 0.090-0.162 (0.116) 19 Lead Fatty 0.20 0-0.119 (0.039) 0.099-0.260 (0.187) 11 Nonfatty 0.20 0-0.072 (0.031) 0.084-0.345 (0.196) 19 15, No. 1, June 1981 49 TABLE 8 (cont'd.). Recovery data on residues found in infant and toddler total diet samples from 10 Unted States cities — August 1975-July 1976 Range of Range of Unforti- Total Number Type of Spike fied Residue of Food Level, Composite, Found, Recovery Residue Composite PPM PPM 1 PPM ■■ = Studies Mercury Fatty 0.06 0-0.019 (0.005) 0.047-0.089 (0.069) 7 Nontatty 0.04 0-0.003 (0.001) 0.045-0.056 (0.052) 4 Nonfatty 0.06 0-0.002 (0.0002) 0.065-0.136 (0.079) 13 Selenium Fatty 0.20 0-0.20 (0.07) 0.19-0.45 (0.30) 6 Fatty 0.40 0-0.20 (0.03) 0.26-O.50 (0.39) 5 Nonfatty 0.20 0-0.29 (0.04) 0. 18-0. 56 (0.25) 11 Nonfatty 0.40 0-0.15 (0.034) 0.25-0.54 (0.36) 6 Zinc Fatty 5.0 1.62-19.2 (7.33) 5.95-24.0 (12.2) 6 Fatty 25.0 5.0-30.2 (17.9) 28.5-52.6 (41.7) 5 Nonfatty 10.0 6.3-7.4 (7.0) 14.8-18.2 (16.8) 3 Nonfatty 5.0 0-7.55 (2.67) 4.55-12.6 (7.37) 14 1 Numbers in parentheses represent average residue levels. 2 Values are uncorrected for badtground. LITERATURE CITED (/) Corneliussen, P. E. 1969. Pesticide residues in total diet samples (IV). Pestic. Monit. I. 2(4) :140-152. (2) Corneliussen, P. E. 1970. Pesticide residues in total diet samples (V). Pestic. Monit. J. 4(3):89-105. (3) Corneliussen, P. E. 1972. Pesticide residues in total diet samples (VI). Pestic. Monit. I. 5(4) :313-330. (4) Duggan, R. £., H. C. Barry, and L. Y. Johnson. 1966. Pesticide residues in total diet samples. Science 151 (3706):101-104. (5) Duggan. R. E.. H. C. Barry, and L. Y. Johnson. 1967. Pesticide residues in total diet samples (II). Pestic. Monit. J. 1(2):2-12. (6) Duggan, R. E., and F. J. McFarland. 1967. Assess- ments include raw food and feed commodities, m basket items prepared for consumption, meat sa: taken at slaughter. Pestic. Monit. I. 1(1): 1-5. (7) Finocchiaro, J. M., and W. R. Benson. 1965. layer chromatographic determination of cai (Sevin) in some foods. J. Assoc. Off. Agric. ( 48(4):736-738. (8) Food and Drug Administration. 1971. Pesticide lytical Manual, Vols. I and 11. U.S. Departme Health and Human Services, Washington, D.C. (9) Food and Drug Administration. 1976. Comp! Program Guidance Manual. 7305.002, Part IV, a, 2(a). (10) Himdley, H. K., and J. C. Underwood. 1970. Del nation of total arsenic in total diet samples. J. i Off. Anal. Chem. 53(6) : 1 176-1 178. (//) Johnson, R. D.. and D. D. Manske. 1975. Pes residues in total diet samples (IX). Pestic. Moi 9(4): 157-169. (12) Johnson, R. D., and D. D. Manske. 1977. Pes and other chemical residues in total diet samples Pestic. Monit. J. 1 1(3) :1 16-131. (13) Johnson, R. D., D. D. Manske, D. H. New, and Podrebarac. 1979. Pesticide and other chemical re in infant and toddler total diet samples — (I) — A 1974-July 1975. Pestic. Monit. J. 13(3):87-98. {14) Manske, D. D., and P. E. Corneliussen. 1974. Pes residues in total diet samples (VII). Pestic. Mo 8(2):110-124. (15) Manske, D. D., and R. D. Johnson. 1975. Pes residues in total diet samples (VIII). Pestic. Mo 9(2):94-105. (16) Manske, D. D.. and R. D. Johnson. 1977. Pesticic other chemical residues in total diet samples Pestic. Monit. J. 10(4) : 134-148. (17) Martin, R. J., and R. E. Duggan. 1968. Pesticid( dues in total diet samples (III). Pestic. Moi l(4):ll-20. (18) Official Methods of Analysis. 1975. AOAC, Arli: VA, 1 2th ed., sections 25.026-25.030, 25.065-2 25.103-25.105, 25.117-25.120, 25.143-25.147. (19) Porter, M. L.. R. J. Gajan, and J. A. Burke. Acetonitrile extraction and determination of ca| in fruits and vegetables. J. Assoc. Off. Anal. < 52(1):177-181. 50 Pesticides Monitoring Joup Organochlorine Pesticides and PCBs in Cod-Liver Oil of Baltic Origin, 1971-80 Jerzy Falandysz ' ABSTRACT mocMorine pesticides and polychlorinated biphenyls Bs) in cod-liver oil of Bailie origin were monitored diir- 1971-80. Residues of DDT and its metabolites. PCBs. he.xachlorobenzene were present in all samples. Gen- y, ZDDT residues declined, but the reason for the ne is unknown. Introduction of technical DDT as an insecticide in countries sur- iding the Baltic has been prohibited since 1971. The nochlorine pesticides presently used for agricultural OSes in Poland are toxaphene, methoxychlor. endo- in, and lindane. DDT was widely used in agriculture has been detected at high levels in tissues of Baltic ne mammals, fish, and birds (7). The prohibition [le agricultural use of DDT in Poland was reflected le nearly tenfold reduction of 2DDT residue levels dipose fat of slaughtered animals during the last de (A. Niewiadowska. Veterinary Institute, Pulawy, ), personal communication). However, so far there been no reports showing a decline of 2DDT residue s in animals of the Baltic Sea. Another class of or- chlorine compounds, polychlorinated biphenyls Bs), occurs throughout the Baltic environment. , polychlorinated terphenyls (PCTs) have been d recently in Baltic marine organisms (2, 13, 15). rmation on production and industrial use of PCBs PCTS in countries surrounding the Baltic remains ure. Some quantities of PCBs are produced and able in Poland under the trade name Chlorofen 12). PCBs have also been produced in West nany as Clophen, in the Soviet Union as Sovol, in Czechoslovakia as Delor. This paper presents the ts of analyses of cod-liver oil of Baltic origin for ues of hexachlorobenzene (HCB), 2DDT, and Analytical Methods 3les of cod-liver oil were obtained from a factory dynia. The procedures for isolation and determina- rinary Hygiene Research Station, ul. Kaprow 10, PL 80-316 :k, Poland tion of the organochlorines have been presented else- where (4). Two cleanup processes were used. The oil sample was dissolved in «-hexane; 1 ml n-hexane was used for every 20 mg fat extracted. Twenty mg fat was cleaned with 1 ml of a 1 : 1 mixture of fuming 20-25 percent sulfur dioxide and concentrated sulfuric acid in a screw-capped, Teflon-lined test tube (2, 4, 8). The colorless hexane layer was injected directly into the gas chromatograph. In addition, a 4-ml aliquot of cleaned sample was subjected to alcoholic potassium hydroxide hydrolysis in a screw-capped. Teflon-lined test tube. The test tube was immersed for 15 minutes in the water bath at 50 °C. After cooling, the mixture was shaken with 4 ml distilled water. Following separation, the upper hexane layer was injected into the gas chro- matograph. The residues were quantitated by electron- capture gas chromatography. Instrument parameters and operating conditions follow: Chromatograph: PYE 104 Detector: o^Ni Column: glass, 150 cm long by 4 mm ID packed with a 2:1 mixture of 8 percent QF-1 and 4 percent SF-96 on 100-120 mesh Gas-Chrom Q Temperatures. °C: detector 210 column oven 195 Carrier gas: argon flowing at ml/min PCBs were quantified by comparing sample peaks with that of PCB standard Clophen A 50, which appeared on the gas chromatogram after p,p'-DDE. DDE content was calculated from the total height of the peak with retention time equal to that of standard p,p'-DDE. p,p'- DDT and p,p'-TDE were calculated from the difference in height of peaks with retention times equal to those of p,p'-DDT and p.p'-TDE before and after hydrolysis with alcoholic potassium hydroxide. In recovery experi- ments, the calculated values and standard deviations, in ppm, were as follows: HCB, 0.27 ± 0.015; DDE, 5.8 ± 0.25; TDE, 5.1 ± 0.39; DDT, 1.3 ± 0.14; and PCBs, 11 ± 0.84 (4). Results and Discussion The levels of organochlorine residues in cod-liver oil are presented in Table 1. DDT and its metabolites were present in all samples. DDE levels ranged from 1.1 to 15, No. 1, June 1981 51 TABLE 1. Mean and range ippm) oj chlorinaled hydrocarbons in cod-liver oil of Baltic origin, 1 97 1 -SO n HCB P.P' -DDE P.P -TDE P,P' -DDT SDDT PCBs Year Mean Range Mean Range Mean Range Mean Range Mean Range Mean Range 1971 0.24 4.6 2.3 6.6 13 4.8 1972 0.36 4.2 4.6 8.4 17 9.5 1973 0.28 0.20-0.32 7.2 4.1-9.3 3.7 2.2-4.5 10 8.4-12 22 15-26 5.7 4.3-7.0 1974 0.23 0.10-0.37 5.5 1.3-9.8 2.9 0.69^.8 5.7 2.1-9.4 14 4.0-22 5.9 2.2-9.0 1975 0.23 0.12-0.34 8.3 2.9-17 3.5 1.4-5.4 5.0 2.2-8.5 17 8.9-28 8.6 4.6-13 1976 11 0.30 0.16-0.44 8.3 1.1-24 3.5 1.0-6.5 4.6 1.1-8.9 16 3.3-38 8.6 3.1-16 1977 0.35 0.26-0.54 5.3 3.1-9.3 3.9 3.0-5.0 3.9 3.2-5.9 13 9.8-20 9.6 4.9-16 1978 0.32 0.28-0.41 4.1 4.1-4.2 2.9 2.7-3.1 2 2 1.3-3.0 9.2 8.2-9.8 7.1 5.5-8.5 1979 0.24 4.2 5.2 2.1 11 4.3 1980 0.29 0.28-0.30 3,4 3.0-3.8 1.9 1.3-2.5 1.2 0.59-1.8 6.5 4.9-8.1 5.1 4.7-5.6 NOTE: Mean is arithmetic mean. 24 ppm, TDE from 0.69 to 6.5 ppm, and DDT from 0.59 to 12 ppm; 2DDT levels ranged from 3.3 to 38 ppm. PCBs. resembling Clophen A 50, and HCB were also detected in all samples, at levels ranging from 2.2 to 16 ppm and from 0.10 to 0.54 ppm, respectively. All samples contained at least trace amounts of a- and y-BHC. Because the residues of these isomers were negligible by comparison, they were excluded from the table. It should be pointed out that much higher leveli organochlorines than those noted in Table 1 have found in the livers of some specimens of cod frorr Baltic. For example, the livers of cod taken from Kattegat in 1973 contained PCBs ranging from 4 t ppm and averaging 13 ppm wet weight; livers of taken from the Rivo Fiord in 1975 contained I ranging from 29 to 57 ppm and averaging 38 ppm weight {13. 14). Many papers have been published on organochlorine residues in the liver of cod from the Baltic (/, 5. 6, 8, 10, 11, 13, 14, 16-18), but only several for cod-liver oil (7, 3, 10). The cod-liver oil of Baltic origin is unfit for medical purposes because of its high contamination with DDT and PCBs. The main Polish catches of cod are taken in the southern Baltic (Figure 1, regions 25 and 26) (9). The cod-liver oil produced in the factory in Gdynia, Poland, is manufactured from fresh cod livers. The crude cod-liver oil produced on board the fishing vessels operating in the southern Baltic is also delivered to the factory in Gdynia. After clarification, the crude cod-liver oil is usually mixed with that produced from the previous catch and is stored in a large-capacity tank. For the present study, all samples were taken from oil dispatched from the factory. Those particular lots of oil were taken from the day-by-day production or from the storage tank, mainly mixed oil. The annual production of cod-liver oil in 1975. 1976. and 1977 was 280, 316, and 220 tons, respectively. Table 1 shows that 2DDT may have declined, but that decline cannot be verified because the mean values for organochlorines must be at least corrected by the quantity of oil in the particular lot analyzed — information that was not avail- able to authors. Also, it has been shown (11, 16, 17) that the organochlorine residues in livers of cod from the western Baltic can be correlated to the length of the fish. The lengths of the cod from which livers were obtained for processing in the present study were not uniform. Cod caught in the southern Baltic generally range from 25 to 120 cm long. In 1970, the cod were predominantly 39 to 44 cm long, and in 1971, 45 to 50 cm long (9). The following extreme ranges for 2DDT have I been noted: Levels in cod taken from the souti Baltic in 1970-71 ranged from 14 to 57 ppra« averaged 26 ppm wet weight and 66 ppm lipid W( (6); levels in cod taken from the Sund during ranged from 1.4 to 53 ppm and averaged 8.7 ppm weight and 29 ppm lipid weight (13). FIGURE 1. Baltic Sea, with division of the sampling f according to International Council for the Exploration < t Sea 52 Pesticides Monitoring Jout LITERATURE CITED Falaiidysz, J. 1977. Residues of organochlorine pesti- ticides, polychlorinated biphenyls and he.xachloro- benzene in some cod-liver oils available at Polish market in years 1971-1976 (In Polish). Farm. Pol. 33(6): 35 1-356. Falandysz. J. 1980. Chlorinated hydrocarbons in gulls from the Baltic south coast. Mar. Pollut. Bull. 11(3); 75-80. Falandysz. J., and E. Kcdehka. 1979. Residues of hexa- chlorobenzene, chlorinated diphenylethylenes, and polychlorinated biphenyls in cod-liver oils in the years 1976-1978 (In Polish). Farm. Pol. 35(6) :337-341. Falandysz, J., and I. Stangret. 1979. Use of concen- trated sulphuric acid and alcoholic potassium hydroxide for analysis of residues of organochlorine pesticides, polychlorinated bi- and terphenyls in fish oils and cod-liver oils (In Polish). Farm. Pol. 35( 8) :465-472. Falandysz, J., B. Michalska, J. Trojanowska, and S. Wodecka. 1980. Residues of chlorinated hydrocarbons in Baltic cod liver and in canned cod-liver products (In Polish). Rocz. Panstw. Zakl. Hig. 31 (2) : 163-168. Huscbenheth, E. 197 S. The contamination of fish with chlorinated hydrocarbons (In German). Arch. Fisch Wiss. 24(1-3): 105-1 16. Jensen, S., A. G. Johnels. M. Olssoii. and G. Otter- lind. 1969. DDT and PCB in marine animals from Swedish waters. Nature (London) 224(5216) :247- 250. Jensen. S., A. G. Johnels, M. Olsson, and G. Otterlind. 1972. DDT and PCB in herring and cod from the Baltic, the Kattegat and the Skagerrak. Ambio. Spec. Rep. 72(l):71-85. Kosior, M. 1976. Cod of the Southern Baltic in the years 1969-1972 (In Polish). Pr. Mor. Inst. Ryb. 18 (Ser. A): 183-214. {10) Lipka, E., M. Zarecz, E. Grochowska, and B. Dobo- szynska. 1978. Studies on DDT appearance in Baltic Sea fish. Part II. Determination of DDT and its metabolites in cod liver and cod liver products (In Polish). Bromatol. Chem. Toksykol. 1 1(2) : 171-175. (//) Luckas. B.. M. Berner, and P. Herbert. 1978. The contamination of cod livers from Baltic Sea cod catches with chlorinated hydrocarbons in 1976/77 (In Ger- man). Fischereiforschung 16(2):77-81. (12) Liizak, J., M. Rybak, and D. Zycinski. 1976. Effect of Chlorofen on aqueous organisms and chemical char- acteristics of changes in aqueous medium caused by this substance (In Polish). Rocz. Panstw. Zakl. Hig. 27(5):555-561. (/J) Noren, K., and K. Rosen. 1976. Levels of organo- chlorine pesticides and PCB in fish from Swedish waters (In Swedish). Var Foeda 28(Suppl. l):2-55. (14) Ohiin, B., and R. Vaz. 1978. Methylmercury and PCB levels in fish and mussels caught off the west coast of Sweden in connection with dredging operations (In Swedish). Var Foeda 30(Suppl. l):3-23. (15) Renberg, L., G. Sundstrom, and L. Rcutergardh. 1978. Polychlorinated terphenyls (PCT) in Swedish white- tailed eagles and in grey seals: a preliminary study. Chemosphere 7(6) :477-482. (16) Schneider, R.. and C. Osterroht. 1976. On the chlori- nated hydrocarbon levels in cod livers from the Kiel Bight (Western Baltic). International Council for the Exploration of the Sea. CM. E:31. (17) Schneider, R., and C. Osterroht. 1976/77. Residues of chlorinated hydrocarbons in cod livers from the Kiel Bight in relation to some biological parameters. Meeresforschung 25 ( 3-4) : 105-1 14. (18) Westoo, G., and K. Noren. 1970. Levels of organo- chlorine pesticides and polychlorinated biphenyls in fish caught in Swedish waters or kept for sale in Sweden, 1967-1970 (In Swedish). Var Foeda. 22(9- 10):93-146. 15, No. 1, June 1981 53 Pesticide, Metal, and Other Chemical Residues in Adult Total Diet Samples~(XII)— August 1975-July 1976 ' Roger D, Johnson, Dennis D. Manske, and David S. Podrebarac ABSTRACT This report is the twelfth in the series on the presence of pesticide and other chemical residues in the average diet of the United States' heartiest eater, the young adult male. Twenty market baskets were collected in 20 U.S. cities that ranged in population from < 50,000 to 1 million or more. Composites of 12 food classes were analyzed. Averages and ranges of residues found are reported for August 1975 through July 1976. by food class. In addition to the pesticide and chemical residues, data for lead, cadmium, selenium, mercury, arsenic, and zinc are included. The individual items making up the dairy and meat composites in four market baskets were analyzed separately for pesticide residues, and the results are included. Results of recovery studies of pesti- cides and chemicals within various food classes are also presented. Introduction In 1964, the Food and Drug Administration (FDA), U.S. Department of Health and Human Services (for- merly U.S. Department of Health. Education, and Welfare), initiated a Total Diet Program (7), sometimes called the Market Basket study. Its purpose was to monitor the atmosphere for fission products from at- mospheric tests of thermonuclear weapons in May 1961. Later, the program was e.xpanded to include pesticide residues and certain nutrients. At its inception, the program was primarily concerned with the adult diet, which was defined as a market basket of food representing the basic two-week diet of a 16-to- 19-year-old male, statistically the United States' heartiest eater. Beginning in August 1974. 10 of the 30 market baskets collected per year were changed to repre- sent the basic two-week diet of infants (6-month-old) and toddlers (2-year-old) {13). The market baskets were collected in four different geo- graphic areas, wi'h the specific diet of the particular region determining the composition of the market bas- ket. Foods were prepared for normal home consump- tion, and every food item was then placed into one of the 12 composite classes listed in Table 1. For e food class. 20 composites, one from each market baf were prepared. Each composite, containing foods similar characteristics, was analyzed for certain me residues of organochlorine, organophosphorus, carbamate pesticides, herbicides, and industrial ch cals. Methodologies included atomic absorption spec copy, fluorometry. polarography, gas chromatogra thin-layer chromatography, mass spectroscopy, andei lished extraction and cleanup techniques (8-10, 18, Amounts and types of residues found from June 1 through July 1975 have been tabulated in earliei ports (/-5, 11-17). This report covers the results tained from August 1975 through July 1976 for i market baskets collected in 20 different cities. Re for the 10 infant and toddler market baskets colle during the same period are presented in a sep; report. Results During this reporting period, 1,039 residues of 471 ferent compounds were found in the 240 compc examined. In the previous reporting period, 959 resij of 42 diff'erent compounds were found in the same ii ber of composites. The 47 compounds are listed ii| ^ Food and Drug Administration, Kansas City District Office Labora- tory. 1009 Cherry St.. Kansas City, MO 64106 54 creasi ng order of frequency in Table 2. Table 3 si the frequency of occurrence of each compound by class. and Table 4 shows the levels of every rei found with in each food class. The average value in 1 TABLE 1. Classes of adult food composites analyzet pestici des. metals. and other chemical residues, A I 1975-July 1976 Key Food Class I Dairy products n Meat, fish, and poultry III Grain and cereal products IV Potatoes V Leafy vegetables VI Legume vegetables VII Root vegetables VIII Garden fruits IX Fruits X Oils. fats, and shortening XI Sugar and adjuncts XII Beverages (including drinking water) Pesticides Monitoring Jow[i iLE 2. Chemical and metal residues found in adult ! composites from 20 United States cities — August 1975- July J 976 TABLE 3. Frequency of occurrence, by food class, of pesticides, metals, and other chemical residues in adult food composites from 20 United States cities — August 1975- No. OF No. of Positive Composites with "^ ' -r 1 \j IICIL Po'^" f, . r JND C Composites rH Residues Residues Reported AS Trace • Range, PPM Chemical rn \_l,rt33 - Wl I II III IV V VI VII VIII IX X XI XII 239 170 0 0.100 -76.0 N umber of Occurrences lium 0 0.010 - 0.100 85 0 0.040 - 0.820 Zinc 20 20 20 20 20 20 20 20 20 20 20 19 rin 60 16 0.001 - 0.086 Cadmium 3 17 20 20 19 14 19 18 5 18 14 3 ium 57 0 0.010 - 0.340 Lead 0 5 12 5 2 17 8 14 11 6 3 2 3DE2 52 16 0.001 - 0.048 Dieldrin 15 19 1 4 2 0 1 13 2 0 0 C 46 31 0.0003- 0.007 Selenium 4 20 20 3 1 5 2 0 0 0 0 lie 31 0 0.030 - 0.460 P.p'-DDE 14 20 0 3 8 1 3 2 0 0 0 ichlor epoxide 30 19 0.001 - 0.003 a-BHC 17 19 0 0 0 0 0 3 1 5 0 Ihion 29 3 0.004 - 0.096 Arsenic 1 17 8 0 0 1 1 1 0 0 1 Liry 24 0 0.006 - 0.080 Heptachlor epoxide 13 15 0 2 0 0 0 0 0 0 0 ine 24 11 0.0006- 0.004 Malathion 0 0 19 0 0 0 0 0 0 3 0 19 12 0.0002- 0.0060 Mercury 0 18 1 0 0 0 0 0 1 1 2 tilor epoxide 17 15 0.0020 Lindane 2 7 1 0 1 0 0 5 0 7 0 )DT 16 9 0.0030- 0.010 HCB 5 11 0 0 0 0 0 0 0 3 0 0 iulfan sulfate 13 5 0.003 - 0.030 Octachlor e poxide 5 12 0 0 0 0 0 0 0 0 0 0 sulfan 1 12 1 0.0010- 0.0110 P.p'-DDT 0 15 0 0 1 0 0 0 0 0 0 0 sulfan 11 11 5 0.002 - 0.0120 Endosulfan sulfate 0 0 0 2 6 0 0 3 2 0 0 0 oran 10 1 0.002 - 0.163 Endosulfan I 0 0 0 0 5 0 0 6 1 0 0 0 non 10 2 0.001 - 0.004 Endosulfan II 0 0 0 0 5 0 0 4 2 0 0 0 3 8 0 0.002 - 0.114 Dichloran 0 0 0 0 4 1 0 0 4 0 1 0 DE 7 6 0.004 Diazinon 0 0 5 0 2 0 0 2 1 0 0 0 n 6 2 0.005 - 0.050 TCNB 0 0 1 6 0 0 0 1 0 0 0 0 hion 5 0 0.002 - 0.006 P.p'-TDE 0 7 0 0 0 0 0 0 0 0 0 0 5 0 0.010 - 0.229 Ethion 0 1 0 0 0 0 1 1 3 0 0 0 lal® 5 1 0.002 - 0.014 Parathion 0 0 0 0 1 2 1 1 0 0 0 0 i 5 2 0.002 - 0.003 CI PC 0 0 0 5 0 0 0 0 0 0 0 0 iryl 5 4 0.050 DCPA 0 0 0 0 3 0 2 0 0 0 0 0 ol 4 0 0.007 - 0.028 PCNB 0 0 0 0 0 0 0 0 0 5 0 0 choloroaniline 4 1 0.007 - 0.018 Carbaryl 0 0 0 0 0 0 0 2 3 0 0 0 ane 3 0 0.014 - 0.044 Dicofol 0 0 0 0 0 0 0 0 4 0 0 0 jxychlor 3 2 0.013 Pentachloroaniline 0 0 0 0 0 0 0 0 0 4 0 0 3 3 T Perthane 0 0 0 0 2 0 0 0 1 0 0 0 n 2 0 0.026 - 0.040 Methoxychlor 3 0 0 0 0 0 0 0 0 0 0 0 2 0 0.026 - 0.060 PCS 1 2 0 0 0 0 0 0 0 0 0 0 chlorobenzene 2 0 0.004 - 0.005 Captan 0 0 0 0 0 0 0 0 2 0 0 0 2 0 0.002 - 0.005 PCP 0 0 0 0 0 0 0 0 0 0 1 1 :1 2 0 0.002 - 0.006 Pentachloro benzene 0 0 0 0 0 0 0 0 0 2 0 0 phos 2 1 0.009 PCTA 0 0 0 0 0 0 0 0 0 2 0 0 dane 2 2 T Ronnel 0 1 1 0 0 0 0 0 0 0 0 0 2 0 0.008 Leptophos 0 0 0 0 0 0 0 2 0 0 0 0 4ethyl ether 0 0.002 Chlordane 0 0 1 1 0 0 0 0 0 0 0 0 Nonachlor 0 0.002 P-BHC 0 0 0 0 1 0 0 0 0 0 0 0 iphenothion 0 0.195 PCP Methyl ether 0 0 0 0 0 0 0 0 0 1 0 0 lone 0 0.008 rra/is-Nonachlor 0 1 0 0 0 0 0 0 0 0 0 0 nylphenol 1 T Carbopheno thion 0 0 0 0 0 0 0 1 0 0 0 0 ihene 1 T Phosalone 0 0 0 0 0 0 0 0 1 0 0 0 o-Phenylphenol 0 0 0 0 0 0 0 0 0 0 1 0 Toxaphene 0 0 0 0 1 0 0 0 0 0 0 0 nicals capable of being detected by the specific analytical meth- gy may be confirmed qualitatively but are not quantifiable when are present at concentrations below the limit of quantitation, of quantitation varies with residue and food class. ' See Table 1 for key to food classes. based on the 20 composites examined; trace resi- , if present, were treated as zero in calculating the ages. For this reason, an average value reported as can be well below the detection limits of the lods for that compound. ;an et al. reported the human dietary intake of :ides and industrial chemicals detected in mg/kg weight/ day, for the period July 1969 through 1976 (6). Comparative values for fiscal years -75 are also given (6). Because Duggan et al. do eport dietary intakes for metals determined in the I Diet studies, they are shown here in Table 5 for '6. The daily intakes in /xg/day (mg/day for zinc) are listed in Table 5 by food group, together with the percentage of the total daily intake contributed by each. The most common residues and their maximum levels for each of the 12 food classes are discussed below. No findings have been corrected for recovery. DAIRY PRODUCTS Metal residues were found most frequently and at the highest levels in dairy products. Averages were 4.92 ppm zinc, 0.004 ppm selenium, 0.004 ppm arsenic, and 0.002 ppm cadmium. Of the organochlorine residues, p,p'- DDE levels, ranging from 0.001 to 0.010 ppm and aver- aging 0.002 ppm for the series, were the highest. Other 15, No. 1, June 1981 55 TABLE 4. Levels of chemical and metal residues, by food class, in adult food composites from 20 United States ci August 1975~July 1976 Chemical Residues, ppm Chemical I. DAIRY PRODUCTS ZINC Average Positive composites Total number Number reported as trace Range P,P'-DDE Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range HEPTACHLOR EPOXIDE Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites Total number Number reported as trace Range OCTACHLOR EPOXIDE Average Positive composites 4.92 20 0 3.50-5.90 0.002 14 6 0.0010-0.0100 15 7 0.001-0.003 13 10 0.001 0.004 4 0 0.02-0.03 a-BHC Average Positive composites Total number Number reported as trace Range METHOXYCHLOR Average Positive composites Total number Number reported as trace Range HCB Average Positive composites Total number Number reported as trace Range LINDANE Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range ARSENIC Average Positive composites Total number 5 Total number J Number reported as trace S Number reported as trace ( Range T Range ( PCB Average T Positive composites Total number 1 Number reported as trace 1 Range T II. MEAT. FISH, AND POULTRY ZINC Average Positive composites Total number Number reported as trace Range MERCURY Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported a^ trace Range P,P'-DDE Average Positive composites Total number Number reported as trace Range SELENIUM 32.2 Average Positive composites 20 Total number 0 Number reported as trace 25.3-76.0 Range LEAD 0.02 Average Positive composites 18 Total number 0 Number reported as trace 0.007-0.08 Range ARSENIC 0.01 Average Positive composites 17 Total number 0 Number reported as trace 0.01-0.03 Range p,p'-TDE 0.010 Average Positive composites 20 Total number 1 Number reported as trace 0.002-0.048 Range 56 Pesticides Monitoring Joi* ,E 4. (cont'd.). Levels of chemical and metal residues, by food class, in adult food composites from 20 United Slates cities — August 1975-July 1976 Residues, ppm Chemical Residues, ppm DT age ive composites tal number imber reported as trace inge age ive composites tal number imber reported as trace nge CHLOR EPOXIDE age ive composites tal number imber reported as trace nge DIELDRTN 0.002 Average Positive composites 15 Total number 9 Number reported as trace 0.003-0.01 Range HCB T Average Positive composites 19 Total number 17 Number reported as trace 0.001 Range HEPTACHLOR EPOXIDE T Average Positive composites 12 Total number 10 Number reported as trace 0.002 Range 0.007 19 1 0.001-0.086 11 8 0.0002-0.002 15 9 0.001-O.0O2 EL age ive composites tal number imber reported as trace nge PCB T Average Positive composites 1 Total number 0 Number reported as trace 0.006 Range 2 2 T ^NE age ive composites tal number mber reported as trace nge 7 3 0.0006-0.003 (rans-NONACHLOR Average Positive composites Total number Number reported as trace Range 1 0 0.002 iN age ive composites tal number mber reported as trace nge 1 1 T III. GRAIN AND CEREAL PRODUCTS ige ive composites lal number mber reported as trace nge SELENIUM 9.0 Average Positive composites 20 Total number 0 Number reported as trace 5,5-15.5 Range 0.19 20 0 0.04-0.34 Ige ive composites :al number mber reported as trace nge CADMIUM 0.05 Average Positive composites 12 Total number 0 Number reported as trace 0.04-0.14 Range 0.03 20 0 0.02-0.05 FHION Ige ive composites al number mber reported as trace Ige DIELDRIN 0.02 Average Positive composites 19 Total number 0 Number reported as trace 0.004-0.096 Range 1 0 0.003 ;dane ge ve composites al number Tiber reported as trace Ige 1 1 T ARSENIC Average Positive composites Total number Number reported as trace Range 0.02 0.0303-0.10 JRY ■ge ve composites al number nber reported as trace Ige 15, No. 1, June 1981 DIAZINON T Average Positive composites 1 Total number 0 Number reported as trace 0.01 Range 5 0 0.001-0.004 57 TABLE 4. (cont'd.). Levels of chemical and metal residues, by food class, in adult food composites from 20 United S cities — August 1975-July 1976 Chemical Residues, ppm Chemical Residues TCNB Average Positive composites Total number Number reported as trace Range RONNEL Average Positive composites Total number Number reported as trace Range LINDANE T Average Positive composites 1 Total number 0 Number reported as trace 0.002 Range 1 0 0.002 IV. POTATOES ZINC Average Positive composites Total number Number reported as trace Range TCNB Average Positive composites Total number Number reported as trace Range HEPTACHLOR EPOXIDE Average Positive composites Total number Number reported as trace Range ENDOSULFAN SULFATE Average Positive composites 5.18 20 0 2.6-14.5 0.007 6 0 0.002-0.114 2 0 0.001-O.002 CADMIUM Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites 0 20 0 0.02- C 5 0 0.06- 1 4 0.001- Total number 2 Total number Number reported as trace 0 Number reported as trace ( Range 0.003-0.012 Range O.ISU CIPC CHLORDANE Average 0.04 Average 1 Positive composites Positive composites Total number 5 Total number Number reported as trace 0 Number reported as trace Range 0.01-O.23 Range 1 p,p-DDE Average T Positive composites Total number 3 Number reported as trace 2 Range 0.003 V. LEAFY VEGETABLES ZINC CADMIUM Average 2.67 Average Positive composites Positive composites Total number 20 Total number 1 Number reported as trace 0 Number reported as trace Range 1.7-7.0 Range 0.02 ENDOSULFAN I ENDOSULFAN II 1 Average O.OOI Average Positive composites Positive composites Total number 5 Total number Number reported as trace 0 Number reported as trace Range 0.001-0.011 Range o.oow ENDOSULFAN SULFATE LINDANE Average 0.004 Average Positive composites Positive composites Total number 6 Total number Positive composites 2 Number reported as trace Range 0.008-0.030 Range r 58 Pesticides Monitoring Joi|i E 4. (cont'd.)- Levels of chemical and metal residues, by food class, in adiill food composites from 20 United States cities — August 1975-July 1976 Residues, ppm Chemical Residues, ppm HION ige ve Composites al number mber reporled as trace ige 'HENE ige ve composites :al number mber reported as trace Ige Ige ve composites al number mber reported as trace Ige ORAN Ige ve composites al number nber reported as trace Ige ANE Ige ve composites al number mber reported as trace Ige Ige ve composites al number ;nber reported as trace Ige 1 0 0.004 1 1 T 0.007 2 0 0.06-0.09 0.002 4 1 0.002-0.025 0.003 0.024-0.044 0.001 3 0 0.002-0.014 DIAZINON Average Positive composites Total number Number reported as trace Range P,P'-DDE Average Positive composites Total number Number reported as trace Range P.P'-DDT Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites Total number Number reported as trace Range P-BHC Average Positive composites Total number Number reported as trace Range 2 1 0.003 0.003 8 3 0.001-0.023 1 0 0.005 2 1 0.002 1 0 0.010 1 0 0.008 VI. LEGUME VEGETABLES Ige ve composites al nun'iber mber reported as trace Ige [UM Ige ve composites al number mber reported as trace Ige lUM Ige ve composites al number Tiber reported as trace Ige IE ge ve composites al number nber reported as trace ge 7.62 20 0 5.30-12.0 0.01 14 0 0.01-0.07 0.008 5 0 0.02-0.05 1 0 0.001 LEAD Average Positive composites Total number Number reported as trace Range ARSENIC Average Positive composites Total number Number reported as trace Range PARATHION Average Positive composites Total number Number reported as trace Range DICHLORAN Average Positive composites Total number Number reported as trace Range 0.26 17 0 0.08-0.82 0.004 1 0 0.07 0.002-0.003 0.001 1 0 0.027 VII. ROOT VEGETABLES ge •"e composites al number nber reported as ge LEAD 2.32 Average Positive composites 20 Total number 0 Number reported as trace 1.30-^.60 Range 0.036 8 0 0.06-0.14 15, No. 1, June 1981 59 TABLE 4. (cont'd.). Levels of chemical and metal residues, by food class, in adult food composites from 20 United S cities — August 1975-July 1976 Chemical Residues, ppm Chemical CADMIUM Average Positive composites Total number Number reported as trace Range SELENIUM Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range DCPA Average Positive composites Total number Number reported as trace Range ARSENIC 0.027 Average Positive composites 19 Total number 0 Number reported as trace 0.01-0.08 Range PARATHION 0.002 Average Positive composites 2 Total number 0 Number reported as trace 0.020 Range P.P'-DDE T Average Positive composites 1 Total number 1 Number reported as trace T Range ETHION T Average Positive composites 2 Total number 1 Number reported as trace 0.004 Range VIII. GARDEN FRUITS ZINC Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range ENDOSULFAN I Average Positive composites Total number Number reported as trace Range ENDOSULFAN SULFATE Average Positive composites Total number Number reported as trace Range DIAZINON Average Positive composites Total number Number reported as trace Range p,p'-DDE Average Positive composites Total number Number reported as trace Range a-BHC Average Positive composites Total number Number reported as trace Range LEAD 2.08 Average Positive composites 20 Total number 0 Number reported as trace 1.20-3.50 Range ARSENIC 0.02 Average Positive composites 18 Total number 0 Number reported as trace 0.01-0.04 Range LEPTOPHOS 0.002 Average Positive composites 13 Total number 2 Number reported as trace 0.002-0.009 Range ENDOSULFAN II T Average Positive composites 6 Total number 1 Number reported as trace 0.002-0.004 Range CARBARYL T Average Positive composites 3 Total number 2 Number reported as trace 0.005 Range LINDANE T Average Positive composites 2 Total number 1 Number reported as trace 0.002 Range PARATHION T Average Positive composites 2 Total number 2 Number reported as trace T Range ETHION T Average Positive composites 3 Total number 0 Number reported as trace 0.004-0.007 Range 60 Pesticides Monitoring Joib ,E 4. (cont'd.). Levels of chemical and metal residues, hy food class, in adult food composites from 20 United States cities — August 1975-July 1976 Residues, ppm Chemical Residues, ppm 3FENOTHION age ive composites tal number mber reported as trace nge TCNB 0.010 Average Positive composites 1 Total number 0 Number reported as trace 0.195 Range 1 0 0.002 IX. FRUITS age ive composites lal number mber reported as trace nge ,ORAN age ive composites tal number mber reported as trace age [ANE age ive composites ;al number mber reported as trace age iULFAN I ige ve composites :al number mber reported as trace ige iULFAN SULFATE Ige ve composites al number muber reported as trace age XONE ige ve composites ;al number mber reported as trace iige RIN Ige ve composites al number mber reported as trace age Ige ve composites al number mber reported as trace age JRY Ige ve composites al number aaber reported as trace Ige 2.44 20 0 0.10-19.0 LEAD Average Positive composites Total number Number reported as trace Range 0.009 4 0 0.006-0.163 CARBARYL Average Positive composites Total number Number reported as trace Range T 1 0 0.014 DICOFOL Average Positive composites Number reported as trace Range T 1 0 0.007 ENDOSULFAN II Average Positive composites Total number Number reported as trace Range T 2 1 0.005 CADMIUM Average Positive composites Total number Number reported as trace Range T 1 0 0,008 ETHION Average Positive composites Total number Number reported as trace Range T 2 0 0.001 DIAZINON Average Positive composites Total number Number reported as trace Range T 1 0 0.001 CAPTAN Average Positive composites Total number Number reported as trace Range 0.041 11 0 0.05-0.11 3 3 T 0.003 4 0 0.007-0.028 2 1 0.012 0.003 5 0 0.01-0.02 3 0 0.005-0.006 1 0 0.004 0.003 2 0 0.026-0.040 1 0 0.015 X. OILS, FATS, AND SHORTENING ge ve composites al number Tiber reported as trace >ge CADMIUM 4.14 Average Positive composites 20 Total number 0 Number reported as trace 0.20-6.20 Range 0.016 18 0 0.01-0.03 15, No. 1, June 1981 61 TABLE 4. (cont'd.). Levels of chemical and metal residues, by food class, in adult food composites from 20 United I cities — August 1975-July 1976 Chemical Residues, ppm Chemical 0.003 7 2 0.005-0.03 P,P'-DDE Average Positive composites Total number Number reported as trace Range T 3 2 0.002 MERCURY Average Positive composites Total number Number reported as trace Range 0.002 1 0 0.04 HCB Average Positive composites Total number Number reported as trace Range T 5 2 0.002-0.003 PENTACHLOROANILINE Average Positive composites Total number Number reported as trace Range T 1 1 T LINDANE Average Positive composites Total number Number reported as trace Range 0.028 6 0 0.05-0.14 SELENIUM Average Positive composites Total number Number reported as trace Range T 2 0 0.004-0.005 PCTA Average Positive composites Total numuber Number reported as trace Range MALATHION Average Positive composites Total number Number reported as trace Range DIELDRIN Average Positive composites Total number Number reported as trace Range ARSENIC Average Positive composites Total number Number reported as trace Range PCNB Average Positive composites Total number Number reported as trace Range a-BHC Average Positive composites Total number Number reported as trace Range LEAD Average Positive composites Total number Number reported as trace Range PENTACHLOROBENZENE Average Positive composites Total number Number reported as trace Range PCP METHYL ETHER Average Positive composites Total number Number reported as trace Range 1 0 0.002 XL SUGAR AND ADJUNCTS ZINC Average Positive composites Total number Number reported as trace Range CADMIUM Average Positive composites Total number Number reported a . trace Range LINDANE Average Positive composites Total number Number reported as trace Range 2.95 20 0 0.10-16.0 PCP Average Positive composites Total number Number reported as trace Range 0.011 14 0 0.01-0.03 o-PHENYLPHENOL Average Positive composites Total number Number reported as trace Range T 7 3 0.001-0.003 a-BHC Average Positive composites Total number Number reported as trace Range 62 Pesticides Monitoring Jo J E 4. (cont'd.). Levels of chemical and metal residues, by food class, in adult food composites from 20 United States cities — August 1975-July 1976 Residues, ppm Chemical Residues, ppm PHION ige ve composites al number mber reported as trace ige ORAN Ige ve composites al number mber reported as trace Ige LEAD T Average Positive composites 3 Total number 1 Number reported as trace 0.005-0.008 Range MERCURY T Average Positive composites 1 Total number 0 Number reported as trace 0.005 Range 0.015 3 0 0.06-O.14 1 0 0.012 XII. BEVERAGES Ige ve composites al number mber reported as trace Ige IC ge ve composites al number mber reported as trace Ige Ige ve composites al number mber reported as trace Ige LEAD 0.46 Average Positive composites 19 Total number 0 Number reported as trace 0.20-1.90 Range CADMIUM 0.008 Average Positive composites 1 Total number 0 Number reported as trace 0.15 Range MERCURY 0.001 Average Positive composites 1 Total number 0 Number reported as trace 0.026 Range 0.004 2 0 0.04-0.05 0.002 3 0 0.01 0.001 2 0 0.006-0.018 Average values are based on 20 composites examined; trace residues, if present, were treated as zero in calculating averages. Thus, an value of "T" can be well below detection limits of the methods for that compound. TABLE 5. FY 76 daily intakes, by food group , of metals in the diet of United States adults Lead Cadi muM Zinc Arsenic i Selenium Mercury % Total % Total % Total % Total % Total % Total Food Group HG/day Intake tJG/DAY Intake mo/day Intake |aG/DAY Intake HG/day Intake ^ig/day Intake )airy products 0.00 0.0 1.63 5.0 3.72 19.4 3.17 4.8 3.26 2.4 0.00 0.0 'leat. fish, and poultry 3.67 5.2 2.63 8.0 8.44 44.1 49.46 74.4 52.52 38.7 5.29 81.3 Jrains and cereal products 19.90 28.0 11.97 36.4 3.81 19.9 7.56 11.4 78.41 57.8 0.21 3.2 'otatoes 5.15 7.2 7.46 22.7 0.82 4.3 0.00 0.0 0.59 0.4 0.00 0.0 .eafy vegetables 0.38 0.5 2.43 7.4 0.15 0.8 0.00 0.0 0.03 0.02 0.00 0.0 -egume vegetables 18.98 26.7 0.82 2.5 0.56 2.9 0.28 0.4 0.61 0.4 0.00 0.0 loot vegetables 1.27 1.8 0.87 2.6 0.08 0.4 0.10 0.1 0.06 0.04 0.00 0.0 jarden fruits 6.07 8.5 1.42 4.3 0.15 0.8 0.36 0.5 0.00 0.0 0.00 0.0 •ruits 9.07 12.8 0.66 2.0 0.54 2.8 0.00 0.0 0.00 0.0 0.10 1.5 )ils, fats, and shortening 2.04 2.9 1.11 3.4 0.30 1.6 0.00 0.0 0.16 0.1 0.02 0.3 ugar and adjuncts 1.24 1.7 0.87 2.6 0.24 1.3 0.00 0.0 0.00 0.0 0.04 0.6 leverages (including 3.31 4.7 1.02 3.1 0.32 1.7 5.57 8.4 0.00 0.0 0.85 13.1 drinking water) Total intake 71.08 100.0 32.89 100.0 19.13 100.0 66.50 100.0 135.64 99.9-' 6.51 100.0 calculated as arsenic trioxide (AsuOs). ot total 100 because of rounding error. ichlorine compounds present at low levels included ' (hexachlorocyclohexane), dieldrin, heptachlor e, octachlor epoxide, methoxychlor, HCB (hexa- benzene), and lindane. A trace of an industrial :al, a PCB (polychlorinated biphenyl), was found of the composites. No organophosphorus com- i were found. MEAT, FISH. AND POULTRY Metal residues dominated this food class, with the fol- lowing series averages: 32.2 ppm zinc (range 25.3-76.0 ppm), 0.20 ppm selenium, 0.19 ppm arsenic, 0.02 ppm mercury, 0.014 ppm lead, and 0.01 ppm cadmium. Of the organochlorine residues, p,p'-DDE, ranging from 0.002 to 0.048 ppm and averaging 0.010 ppm for the 15, No. 1, June 1981 63 series, was found in all 20 composites; dieldrin, averag- ing 0.007 ppm. was reported in 19 composites; and p,p'- DDT averaged 0.002 ppm with positive findings in 15 composites. Trace averages were reported for p.p'-TDE, a-BHC, HCB, octachlor epoxide, heptachlor epoxide, ronnel, lindane, and rran^-nonachlor. Traces of ethion, an organophosphorus pesticide, and a PCB also were found in one and two composites, respectively. GRAIN AND CEREAL PRODUCTS All 20 composites contained zinc, selenium, and cad- mium residues, averaging 9.0, 0.19, and 0.03 ppm, re- spectively. Twelve composites had lead residues, averag- ing 0.05 ppm for the series, and eight composites had arsenic residues, for a series average of 0.02 ppm. Mala- thion, one of two organophosphorus pesticides, was reported in 19 composites and averaged 0.02 ppm for the series; the other, ronnel, occurred as a trace amount in one composite. Also reported were traces of dieldrin. chlordane, TCNB, lindane, diazinon. and mercury. POTATOES Zinc, ranging from 2.6 to 14.5 ppm, and cadmium, ranging from 0.02 to 0.09 ppm, were reported for all 20 composites, with averages of 5.18 and 0.05 ppm, respec- tively. Lead, averaging 0.03 ppm for the series, was found in five composites, and selenium, ranging from 0.02 to 0.05 ppm in three composites, averaged 0.006 ppm for the 20-composite series. CIPC, ranging from 0.01 to 0.23 ppm in five composites, averaged 0.04 ppm for the series. TCNB averaged 0.007 ppm for the series with a range of 0.002-0.114 ppm in six composites. Traces of heptachlor epoxide, dieldrin, endosulfan sul- fate, p.p'-DDE, and chlordane were also found. LEAFY VEGETABLES Only zinc, ranging from 1.7 to 7.0 ppm and averaging 2.67 ppm, was reported for all 20 composites. Cadmium ranged from 0.02 to 0.10 ppm in 19 composites and averaged 0.04 ppm for the series. The most frequently reported pesticide was p.p'-DDE, averaging 0.003 ppm for the series, with eight reported findings. Endosulfan I, ranging from 0.001 to 0.011 ppm, and endosulfan II, ranging from 0.002 to 0.004 ppm, were each reported for five composites; endosulfan sulfate, ranging from 0.008 to 0.030 ppm, was reported for six composites. Other reportable residues and their averages included dichloran, 0.002 ppm; DCPA, 0.001 ppm; Perthane®. 0.003 ppm; and lead, 0.007 ppm. Traces of lindane, diazinon, parathion. toxaphene. dieldrin, p,p'-DDT, selenium, and /J-BHC were also found. LEGUME VEGETABLES Legume vegetables exhibited high metal residues. Zinc, reported in all 20 composites, ranged from 5.30 to 12.0 ppm and averaged 7.62 ppm. Lead ranged from 0.08 to 0.82 ppm and averaged 0.26 ppm for the series. Cad- mium, ranging from O.OI to 0.07 ppm, averaged ppm for the series. Arsenic and selenium occurre( frequently. The pesticides parathion. p,p'-DDE, dichloran were found at low levels. ROOT VEGETABLES Zinc ranged from 1.30 to 4.60 ppm and averaged ppm for the 20 composites. Cadmium, ranging 0.01 to 0.08 ppm in 19 composites, averaged 0.027 overall. Lesser amounts of lead, arsenic, and selei averaging 0.036, 0.004, and 0.002 ppm, respect were also reported. Only traces of parathion, die p,p'-DDE, DCPA, and ethion were found. GARDEN FRUITS Four metals were reported in this food class: ranging from 1.20 to 3.50 ppm in 20 composite; averaging 2.08 ppm; cadmium, ranging from 0.( 0.04 ppm in 18 composites and averaging 0.02 ppi the 20-composite series; lead, ranging from 0.06 to ppm in 14 composites and averaging 0.081 ppm ft series; and arsenic, reported in one composite at ppm. The most significant pesticide residue, die ranged from 0.002 to 0.009 ppm in 13 composite averaged 0.002 ppm for the series. Carbophenothio found in one composite at 0.195 ppm. with a average of 0.01 ppm. The following trace average:! were reported: leptophos; endosulfan I, II, and si carbaryl; diazinon; lindane; p,p'-DDE; para a-BHC; ethion; and TCNB. FRUITS The two most prevalent residues in this food classi zinc, reported for all 20 composites, ranging from to 19.0 ppm and averaging 2.44 ppm, and lead, ra from 0.05 to 0.11 ppm in 11 composites and avei! 0.041 ppm for the series. Cadmium, ranging frorr to 0.02 ppm in five composites, averaged 0.003 pp i the series. Both dichloran and dicofol were fou i four composites and averaged 0.009 ppm and 1 ppm. respectively, for the series. Ethion ranged 1 0.005 to 0.006 ppm for three composites but ave' trace for the series. Less frequently occurring re i were carbaryl, averaging a trace for the series; c: [ endosulfan I, II, and sulfate; Perthane; phosalone; J non; dieldrin; and o-BHC. Mercury, 0.015 ppmi reported for one composite. OILS, FATS. AND SHORTENING High zinc levels, ranging from 0.20 to 6.20 ppi averaging 4.14 ppm, were reported for 20 com Cadmium, ranging from 0.01 to 0.03 ppm in 18(c posites, averaged 0.016 ppm for the series. Sevemji posites contained malathion residues, ranging from to 0.03 ppm; series average was 0.003. Lead, ave- 0.028 ppm for the series, ranged from 0.05 to 0.1 64 Pesticides Monitoring JohIi .E 6. Pesticide residues in individual commodities of dairy composite oj four market basket samples — August 1975- July 1976 IE Found Commodity' Whole Milk (4) Evaporated Ice Cottage Processed Natural Milk (4) Cream (4) Cheese (4) Cheese (4) Cheese (4) Butter (4) Skim Milk (4) Ice Milk (2) :s found ge, ppm 1 T 4 T-0.002 4 T-0.002 3 T 4 0.002-0.005 4 0.001-O.008 4 0.008-O.011 2 T-O.OOl DE ;s found ;e, ppm 2 0.002-0.003 4 T-0.020 3 0.002-O.010 2 0.003-0.009 4 0.002-0.016 3 T-0.004 4 0.004-0.132 2 0.002-0.006 ;s found le, ppm 1 T 2 T 3 T 1 0.001 3 T-O.OOl 3 T-0.002 4 1 T-0.004 T 1 T •h\oT epoxide ;s found •e, ppm 2 T 2 T 1 T 3 0.002-0.005 4 T-0.004 4 0.004-0O19 ,n ;s found se, ppm 4 T-0.002 4 T-0.002 2 T 4 0.005-0.010 4 0.003-0.010 4 0.017-0.053 sychlor ;s found se, ppm 1 0.016 1 T 1 T 1 T 1 0.141 ,e :s found se, ppm 2 T 1 0.001 2 T-0.002 lor epoxide s found !e, ppm 1 T 3 T-0.002 3 T 3 0.004-0.008 5T s found le, ppm 2 T 1 T )E s found ;e, ppm 1 T T = trace, ■milk and nonfat dry milk not included because no residues were found «rs in parentheses indicate number of times that commodity was analyzed. composites. Pentachloroaniline, averaging 0.002 for the series, was found in four composites. The ning residues included HCB, selenium, PCNB, i, pentachlorobenzene, dieldrin, a-BHC, arsenic, )DE, and lindane. One composite contained 0.008 nercury. I AND ADJUNCTS tietal residues were among the highest in this food Zinc, ranging from 0.10 to 16.0 ppm, was reported 20 composites and averaged 2.95 ppm. Cadmium, in 14 composites, averaged 0.011 ppm for the Lead, ranging from 0.06 to 0.14 ppm in three asites, averaged 0.015 ppm for the series. Mercury 12 ppm was reported for one composite. Other resi- tvere a-BHC, PCP, lindane, malathion, o-phenyl- 1, and dichloran. tAGES found in 19 composites at levels ranging from 0.20 0 ppm, averaged 0.46 ppm for the series. The ning residues, each found in three or fewer com- s, had the following series averages: cadmium. 0.002 ppm; lead, 0.004 ppm; mercury, 0.001 ppm; ar- senic. 0.008 ppm; and PCP, 0.001 ppm. Discussion Of the 240 composites analyzed, 125, or 52 percent, contained organochlorine pesticide residues, compared with 49, 48, 52, and 54 percent reported for fiscal years 1975, 1974, 1973, and 1972, respectively. Organophos- phorus residues in the current reporting period were found in 45, or 18.7 percent, of the composites. Corre- sponding findings for fiscal years 1975, 1974, 1973, and 1972 were 25, 28, 31, and 28 percent, respectively. The present report and that for FY 75 were based on 20 market baskets, whereas all earlier reports were based on 30 market baskets. Sixty percent of the 346 organochlorine residues in the current reporting period were found in two food classes: dairy products and meat-fish-poultry. The remaining organochlorine residues were distributed among the other food classes with the garden fruits and leafy vege- tables containing half of them. No organochlorine resi- 15, No. 1, June 1981 65 TABLE 7. Pesticide residues in individual commodities of meal and fish composites of four market baskets, July 1976 Residue Found Roast Beef (4) COMMODirV 1 Ground Beef (4) Pork Chops (4) Bacon (4) Chicken (4) Fish Fillet (4) Dieldrin Times found Range, ppm 4 T-0.003 0.006-0.007 0.002-0.006 2 T-2.25 0.002-0.007 1 T p,p'-TDE Times found Range, ppm 1 0.008 1 0.016 0.007 2 T-0.081 HCB Times found Range, ppm 3 T-0.002 2 0.002 0.002 0.030 0.002-0.008 2 T-0.003 1 T a-BHC Times found Range, ppm 2 T-O.OOl 2 0.001 1 T 2 0.002 1 T p.p '-DDE Times found Range, ppm 3 T-0.048 1 0.031 0.002-0.152 0.002-0.028 0.010-0.875 Heptachlor epoxide Times found Range, ppm 2 2 0.001-0.009 0.002 2 T-0.005 2 T Ethion Times found Range, ppm Octachlor epoxide Times found Range, ppm 1 0.002 1 0.05 1 0.002 3 T-O.OU 1 0.003 rran^-Nonachlor Times found Range, ppm 1 0.034 1 0.003 p,p'-DDT Times found Range, ppm 1 0.034 2 T-0.141 3 0.023-0.130 Endrin Times found Range, ppm 1 0.001 PCB (Aroclor 1254) Times found Range, ppm 1 T 1 T T 1 Chlordane Times found Range, ppm 1 T 1 T Lindane Times found Range, ppm TCNB Times found Range, ppm NOTE: T = trace. 1 Numbers in parentheses indicate the number of times the item was analyzed. 66 Pesticides Monitoring Joii" Frank- furters (4) Beef Liver (4) Eggs (4) Commodity! Ham (4) Round Steak (4) Veal (1) Lamb (2) Shrimp (2) 4 1 0.004-0.054 0.014 T-0.018 2 T-0,002 2 1 O.002-O.O04 T 1 T 0,001-0.002 T 2 T 2 T 2 0.002 1-0.003 T-0.004 T-0.004 3 T 2 T-0.003 4 2 4-0.030 T-0.029 T-0.003 3 1 0.002-0.026 0.002 0.006-0.026 0.011-0.037 3 1 1-0.002 T-0.002 0.005 0.002 2 1 T-0.002 T 1 0.002 1 0.003 1 T 15, No. 1, June 1981 67 TABLE 8 . Recovery data on residues found in adult total diet samples, August 1975-July 1976 Range of Range of Type OF Unforti- Range of No. of Type of Unforti- Range op Nc Food Spike fied Com- Total Resi- Recov- Food Spike fied Com- Total Resi- Ri Com- Level, POSITE, due Found, ery At- Com- Level posite, DUE Found, eri Residue posite PPM PPM PPM 1-2 tempts RESIDtm posite PPM PPM PPM 1.= IE Heptachlor fatty 0.003 0-0.001 0.0023-0.0035 4 Picloran fatty 0.10 0.00 0.00-0.043 epoxide (0.0031) (-) nonfalty 0.003 0-0.001 0.0027-O.0039 (0.0032) 6 nonfatty 0.10 0.00 0.033-O.075 (0.046) Oxychlordane fatty 0.003 0-0.0007 0.0022-0.0031 (0.0027) 4 Silvex fatty 0.04 0.00 0.00-O.032 (0.015) nonfatty 0.003 0-0.0006 0.0024-O.0035 (0.0027) 6 nonfatty 0.04 0.00 0.020-O.053 (0.033) Ethion fatty 0.01 0.00 0-0.0056 (-) 0.0066-0.012 4 2,4-DB fatty 0.02 0.00 T-O.005 (-) 0.0O-O.033 nonfatty 0.01 0.00 6 0.04 0.00 (0.0086) (0.014) DCPA tatty 0.005 0.00 0.0027-0.0047 (0.0037) 6 nonfatty 0.02 0.00 O.002-O.015 (0.008) nonfatty 0.005 0-0.0084 0.0029-0.0059 (0.0050) 12 0.04 0.00 0.00-O.038 (0.025) Perthane fatty 0.01 0.00 T-0.0104 (0.0069) 6 2,4,5-T fatty 0.02 0.00-0.001 0.0058-0.021 (-) nonfatty 0.01 0.00 0.0035-0.014 (0.0091) 12 0.08 0.00 0.026-0.059 (-) Methyl tatty 0.005 0.00 0.0022-0.0030 3 nonfatty 0.02 0.00 0.003-0.0198 (0.014) 0.032-0.069 (0.048) parathion nonfatty 0.005 0.00 (0.0026) 0.0031-0.0045 (0.0037) 5 0.08 0.00 Endosulfan tatty O.OI 0.00 0.002-0.0076 2 MCP fatty 0.02 0.00 0.009-0.013 sulfate (0.0048) 2-methyl-4- (0.011) nonfatty 0.01 0.00-O.004 0.0035-0.0143 (0.0095) 6 chlorophenoxy- acetic acid nonfatty 0.02 0.00 0.0055-0.026 (0.014) Tetradifon fatty 0.02 0.00 T-0.027 (0.015) 4 Carbaryl nonfatty 0.20 0.00 0.00-0.20 (0.157) 0.10 0.00 0.088-0.089 (-) 2 o-Phenylphenol nonfatty 0.40 0.00 0.00-0.40 (0.24) nonfatty 0.02 0.00 0.0104-0.022 8 (0.0160) Arsenic fatty 0.30 0.00-0.35 0.26-0.81 0.10 0.00 0.054-0.188 (0.109) 6 0.40 0.00-0.28 (0.376) 0.37-0.86 Malathion fatty 0.005 0.00 0.0037-0.0038 2 nonfatty 0.30 0.00-0.03 (0.44) 0.19-0.46 nonfatty 0.005 0.00 ( — ) 0.0022-0.0064 (0.0041) 6 0.40 0.00-0.03 (0.30) 0.13-0.57 (0.44) Phnsalone fatty 0.02 0.00 0.0-0.017 3 X iii^aaivi^' (-) Cadmium fatty 0.10 0.00-0.027 0.094-0.199 nonfatty 0.02 0.00-0.002 0.007-O.026 (0.0166) 6 nonfatty 0.10 0.00-0.058 (0.113) 0.058-O.156 Leptophos fatty 0.05 0.00 0.016-0.040 3 (0.116) (0.027) Lead fatty 0.20 0.0O-0.14 0.020-0.340 nonfatty 0.05 0.00 0.030-0.053 (0.043) 6 nonfatty 0.20 0.00-0.310 (0.133) 0.058-0.480 Fonofos fatty 0.01 0.00 0.002 1 (0.211) nonfatty 0.01 0.00 0.0067-O.0095 (0.0083) 6 Mercury fatty 0.06 0.00-0.049 0.018-0.110 (0.073) 0.062-0.088 Toxaphene fatty 0.20 0.00 0.148 1 nonfatty 0.06 O.OO-O.Oll nonfatty 0.20 0.00 0.147-0.226 6 (0.075) (0.187) Selenium fatty 0.20 0.00-0.23 0.00-0.39 2,4-D fatty 0.04 0.00-0.009 0.00-0.050 (0.021) 7 ..JklWIIlUlll nonfatty 0.20 0.00-O.24 (0.227) 0.11-0.48 nonfatty 0.04 0.00 0.008-0.046 (0.028) 14 (0.216) PC? fatty 0.02 0.04 0.00-0.003 0.00-0.001 0.0012-0.009 (0.007) 0.00-0.030 4 7 Zinc fatty 5.0 25.0 1.23-6.20 4.00-76.00 5.74-11.00 (9.54) 29.00-99.00 nonfatty 0.02 0.0-0.0004 (0.015) 0.003-0.018 (0.0084) 1 nonfatty 5.0 0.10-12.00 (54.2) 4.68-15.0 (8.09) 0.04 0.00-0.0062 0.003-0.039 (0.022) 1 25.0 0.38-15.50 24.38-38.0 (29.8) NOTE: T = trace. 1 Numbers in parentheses represent average residue levels. ' These values are uncorrected for background. 68 Pesticides Monitoring Joi R > were found in beverage composites and only two ; found in the legume vegetable composite. 56 organophosphorus residues constitute about 14 :ent of the total pesticide residues reported, with ithion representing 29 of them. Nineteen were found rain and cereal products, seven in fats and oils, and e in the sugar composites. No organophosphorus lues were four»d in the dairy products, potatoes, or :rage composites. carbamate pesticide carbaryl occurred in five com- tes, once at the 0.05 ppm level and four times at the i level. The method for determination of carbaryl also detect the fungicide o-phenylphenol, which was Tted in one sugar composite at the trace level. I industrial chemicals were detected. Trace amounts PCB, Aroclor 1254, were found in one dairy com- te and in two meat-fish-poultry composites. Low s of pentachlorobenzene were found in two fat posites. ill the residues reported, 606, or 58 percent, were lis. Zinc was reported in almost every composite, the highest levels being found in the meat com- es. Cadmium was found in 170 composites and lead 5 composites; both were found throughout the vari- ;lasses of foods with fewest findings in the dairy and leverage composites. The 57 selenium residues, 31 lie residues, and 24 mercury residues were found ominantly in the meat-fish-poultry composites and i-cereal composites. idition to the analysis of the various food class com- es, four market baskets, one from each region, were ted for individual item analysis of two food groups, item-by-item analysis often provides a more ex- ; picture as to the source of residues within a Josite. The dairy and meat classes were chosen use those composites have consistently contained tiighest levels of organochlorine and organophos- us residues. Tables 6 and 7 present these findings. ivery studies were conducted with each market bas- Composites were fortified with known compounds ^senting each type of residue (metal, pesticide, etc.), :orrections were made for the unfortified composite ibution. The total amount recovered through the od was determined. These results are presented in A cknowledgments authors acknowledge the contributions of all staff bers assigned to the Total Diet Section, Food and Administration, Kansas City District Laboratory. LITERATURE CITED (/) Corneliussen, P. E. 1969. Pesticide residues in total diet samples (IV). Pestic. Monit. J. 2(4) : 140-152. (.2) Corneliussen, P. E. 1970. Pesticide residues in total diet samples (V). Pestic. Monit. J. 4(3):89-I05. (3) Corneliussen, P. E. 1972. Pesticide residues in total diet samples (VI). Pestic. Monit. J. 5(4) :313-330. (4) Duggan, R. £., H. C. Barry, and L. Y. Johnson. 1966. Pesticide residues in total diet samples. Science 151 (3706): 101-104. (5) Duggan, R. E., H. C. Barry, and L. Y. Johnson. 1967. Pesticide residues in total diet samples (II). Pestic. Monit. J. 1(2):2-12. (6) Duggan, R. E., P. E. Corneliussen, M. B. Duggan, B. M. McMahon, and R. J. Martin. 1981. Pesticide residue levels in foods in the United States from July 1, 1969, to June 30, 1976. Pestic. Monit. J. (sub- mitted). (7) Duggan. R. E., and F. J. McFarland. 1967. Residues in food and feed. Assessments include raw food and feed commodities, market basket items prepared for consumption, meat samples taken at slaughter. Pestic. Monit. J. 1(1): 1-5. (S) Finocchiaro, J. M., and W. R. Benson. 1965. Thin- layer chromatographic determination of carbaryl (Sevin) in some foods. J. Assoc. Off. Anal. Chem 48(4):736-738. (9) Food and Drug Administration. 1971. Pesticide Ana- lytical Manual. Vols. 1 and II. U.S. Department of Health and Human Services, Washington, D.C. (10) Hundley, H. K., and J. C. Underwood. 1970. Determi- nation of total arsenic in total diet samples. J. Assoc. Off. Anal. Chem. 53(6) :1 176-1178. (//) Johnson, R. D., and D. D. Manske. 1975. Pesticide residues in total diet samples (IX). Pestic. Monit J 9(4):157-169. (/2) Johnson, R. D.. and D. D. Manske. 1977. Pesticide and other chemical residues in total diet samples (XI) Pestic. Monit. J. 11 ( 3 ) : 1 1 6-1 3 1 . (13) Johnson, R. D., D. D. Manske, D. H. New, and D. S. Podrebarac. 1979. Pesticide and other chemical resi- dues in infant and toddler total diet samples — (I) August 1974-July 1975. Pestic. Monit. J. 13(3):87-98. (14) Manske. D. D., and P. E. Corneliussen. 1974. Pesti- cide residues in total diet samples (VII). Pestic Monit J. 8(2):110-124. {15) Manske, D. D., and R. D. Johnson. 1975. Pesticide residues in total diet samples (VIII). Pestic. Monit J 9(2):94-105. (16) Manske, D. D., and R. D. Johnson. 1977. Pesticide and other chemical residues in total diet samples (X) Pestic. Monit. J. 10(4) : 1 34-148. (17) Martin. R. J., and R. E. Duggan. 1968. Pesticide resi- dues in total diet samples (III). Pestic Monit J 1(4): 11-20. (18) Official Methods of Analysis. 1975. AOAC, Arling- ton, VA, 12th ed., sections 25.026-25.030,' 25.065- 25.070, 25.103-25.105, 25.117-25.120, 25.143-25.147. (19) Porter, M. L., R. J. Gajan, and J. A. Burke. 1969. Acetonitrile extraction and determination of carbaryl in fruits and vegetables. J. Assoc. Off. Anal. Chem 52(1):177-181. 15, No. 1, June 1981 69 APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN AROCLOR 1016 or 1242 AROCLOR 1242 AROCLOR 1254 BHC (Benzene Hexachloride) CAPTAN CARBARYL CARBOPHENOTHION CHLORDANE CIPC 2,4-D DACTHAL 2,4-DB DDE DDMU DDT DIAZINON DICHLORAN DICOFOL DIELDRIN ENDOSULFAN ENDOSULFAN SULFATE ENDRIN ETHION FONOFOS HCB HEPTACHLOR HEPTACHLOR EPOXIDE LEPTOPHOS LINDANE MALATHION MCP Hexachlorohexahydro-enrfo^exo-dimelhanonaphthalene 95% and related compounds 5% PCB, approximately 42% chlorine PCB, approximately 42% chlorine PCB, approximately 54% chlorine 1,2,3,4,5,6-Hexachlorocyclohexane (mixture of isomers) N-Trichloromethylthio-4-cyclohexene-l,2-dicarboximide 1-Naphthyl methylcarbamate ■y-[[(p-ChlorophenyI)thio]methyl] 0,0-diethyl phosphorodithioate Technical: 60% octachloro-4,7-methanotetrahydroindane and 40% related compounds Isopropyl N-(3-chlorophenyl) carbamate 2,4-Dichlorophenoxyacetic acid Dimethyl tetrachloroterephthalate 4- (2,4-Dichlorophenoxy) butyric acid Dichlorodiphenyldichloroethylene (degradation product of DDT) l-Chloro-2,2-bis (p-chlorophenyl ) ethylene Dichloro diphenyl trichloroethane. Principal isomer present (p,p'-DDT; not less than 70%: 1,1.1-trichlo^ bis (p-chlorophenyl ) ethane 0,0-Diethyl 0-(2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate 2,6-Dichloro-4-nitroaniline l,l-Bis(chlorophenyl)-2.2,2-trichloroethanol Hexachloroepoxyoctahydro-endo,ej:o-dimethanonaphthalene 85% and related compounds 15% Hexachlorohexahydromethano-2,4,3-benzodioxathiepin 3-oxide l,4,5,6.7,7-Hexachloro-5-norbornene-2,3-dimethano! cyclic sulfate Hexachloroepoxyoctahydro-endo.e/irfo-dimethanonaphthalene 0,0, 0'.O'-Tetraethyl 5,S'-methylene bisphosphorodithioate O-Ethyl S-phenyl ethylphosphonodithioate Hexachlorobenzene Heptachlorotetrahydro-4,7-methanoindene l,4,5,6.7.8,8-Heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 0-(4-Bromo-2,5-dichlorophenyl) 0-methyl phenylphosphonothioate Gamma isomer of benzene hexachloride (BHC) 0,0-Dimethyl dithiophosphate of diethyl mercaptosuccinate See MCPA (Continued next page) 70 Pesticides Monitoring Joi'lt APPENDIX (continued) rHOXYCHLOR [■HYL PARATHION EX 4ACHLOR ACHLOR EPOXIDE 'CHLORDANE ATHION s (Polychlorinated Biphenyls) B s (Polychlorinated Terphenyls) THANE ISALONE iTOMIREX -ORAM INEL ■T B A RADIFON APHENE TP 2-Methyl-4-chlorophenoxyacetic acid 2,2-Bis(p-methoxyphenyl),l,l,l-trichloroethane 88% and related compounds 12% 0,0-Dimethyl O-p-nitrophenyl phosphorothioate Dodecachlorooctahydro-l,3,4-metheno-l//-cyclobuta[cd]pentalene l,2,3,4,5,6,7,8,8-Nonachloro-3a,4,7,7a-tetrahydro-4.7-methanoindan l-e.xo-2-fn(/o-4,5,6,7,8,8a-Oclachloro-2,3-e-xo-epoxy-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene l-*>.vo-2-6'ntio-4.5,6,7,8,8a-Octachloro-2,3-f-xo-epoxy-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene 0,0-Diethyl O-p-nitrophenyl phosphorothioate Pentachloroaniline Mixtures of chlorinated biphenyl compounds having various percentages of chlorine Pentachloronitrobenzene Penlachlorophenol Pentachlorothioanisole Mixtures of chlorinated terphenyl compounds having various percentages of chlorine 1, 1-Bis (ethylphenyl) -2,2-dichloroethane S-[6-Chloro-3-(mercaptomethyl)-2-benzoxazolinone) 0,0-diethyl phosphorodithioate l,2,3,4,5,5,6,7,9,10,10-Undecachloropentacyclo[5.3.0.0=».03.''.0«.«]decane 4-Amino-3,5,6-trichloropicoUnic acid 0,0-Dimethyl 0-(2,4,5-trichlorophenyl) phosphorothioate 2,4,5-Trichlorophenoxyacetic acid l,2,4,5-Tetrachloro-3-nitrobenzene Tetrachlorothioanisole Dichloro diphenyl dichloroethane (l,l-dichloro-2,2-bis(p-chlorophenyl)ethane, principal component) 4-Chlorophenyl 2,4,5-trichlorophenyI sulfone Technical chlorinated camphene (67-69% chlorine) 2- (2,4,5-Trichlorophenoxy) propionic acid 15, No. 1, June 1981 71 ERRATUM Pesticides Monitoring Journal, Volume 14, Number 4, page 136. The abstract of the article "Organochlorine Residues in Fish: National Pesti- cide Monitoring Program, 1970-74" should be corrected to read as follows: Highest PCB residues were found in the industrial- ized areas of the Northeast and Midwest. . . . 72 Pesticides Monitoring Joi|i PLANT GROWTH REGULATOR WORKING GROUP EIGHTH ANNUAL MEETING August 3-6, 1981 The Plant Growth Regulator Working Group (PGRWG) is announcing its eighth annual meeting, to be held at the Don Cesar Hotel, St. Petersburg, Florida, August 3-6, 1981. The meeting will feature two symposia: • Natural Products as Plant Growth Regulators • Plant Growth Regulators in Biological Systems Fifty-two technical papers will be presented by industry and university scientists, covering a range of chemicals being tested or having potential for future food production and crop management. The best basic and the best applied paper presented by a student will receive a $100 award. For further information contact Dr. L. H. Aung Virginia Polytechnic Institute and State University Blacksburg, VA 24061 (703-961-6511) 5, No. 1, June 1981 73 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 jjesticide 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 Estuaries. The sixth is a general heading; the seventh encompasses briefs. 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Krishna Murti, and D. Kutty FISH, WILDLIFE, AND ESTUARIES Organochlorine Insecticide Residues in Soil and Earthworms in the Delhi Area, India. August-October, 1974 80 Dharam Vir Yadav, Pradeep K. Mittal, Hari C. Agarwal, and M.K. Krishna Pillai Organochlorine Insecticide Concentrations in Fish of the Des Moines River. Iowa, 1977-78 ^ 86 Ross V. Bulkley. Siu-Yin Theresa Leung, and John J. Richard Organochlorine and Metal Residues in Eggs of Waterfowl Nesting on Islands in Lake Michigan off Door County, Wisconsin. 1977-78 90 Susan D. Haseltine, Gary H. Heinz. William L. Reichel, and John F. Moore Persistence of Dieldrin in Water and Channel Catfish from the Des Moines River, Iowa, 1971-73 and 1978 98 Siu-Yin Theresa Leung, Ross V. Bulkley, and John J. Richard DDT and BHC Residues in Some Body Tissues of Goals, Buffalo, and Chickens, Lucknow, India 103 Bhupendra S. Kaphalia and Tejeshwar D. Seth APPENDIX 107 ANNOUNCEMENTS 108 Information for Contributors 109 HUMANS Chlorinated Hydrocarbon Pesticides in Blood of Newborn Babies in India Mohammed K.J. Siddiqui,' Mukesh C. Saxena,' Ajeet K. Bhargava,- Coimbatore R. Krishna MurtI,- and D. Kutty- ABSTRACT Jmbilical cord blood collected during labor of 100 Indian vomen was analyzed for organochlorine pesticides by ',as-liquid chromatography with electron-capture detection, iignificant levels of p,p' -DDT and its metabolites. p.p'-TDE md p.p' -DDE. as well as a-. (J-, and y-isomers of BHC were 'stimated. Residues in the neonatal blood were related to age, iietelic habits, and area of residence of the mothers. The lud\ highlights the extent of placental transfer of the body nirden of toxic chemicals from the mother to the fetus. Introduction In recent years, man has become more conscious of the A/ay in which the environment is polluted by chemicals hat harm plants, animals, and humans. Organochlorine pesticides have been a major cause of concern to :cologists, not only because they persist so long in the environment (77. 14) but also because of the readiness with which they accumulate in the human body. Their ;endency to accumulate in fatty tissues (i), because of their lipophilic nature and resistance to biodegradation (2), has caused significant residue burdens in adipose tissues (8), blood (7, 4), and even human milk (7, 10, 13. 18). These toxic agrichemicals have access to the growing fetus through placental tissue (5, 12, 15). Stillborn infants have been determined to be contaminated with such compounds (6). Earlier studies have also drawn attention to the presence of organochlorine pesticides in the cord blood of the fetus (16, 17). Persistent organochlorine pesticides like DDT, which have been banned in other countries, are still commonly used in India in agriculture and malaria eradication Industrial Toxicology Research Centre. Post Box 80. Lucknow-226001 , India Obstetrics and Gynaecology Department. King George's Medical College. Lucknow-226001. India programs. Therefore, it was considered worthwhile to assess organochlorine residues in neonatal blood in India. The present report also relates the extent of placental transfer of these compounds from mother to child according to age, dietetic habits (vegetarian/ nonvegetarian), and area of residence (rural/urban). Materials and Methods A total of 100 pregnant women were studied. The women were admitted to Queen Mary's Hospital, associated with the Department of Obstetrics and Gynaecology, King George's Medical College, Luck- now, capital of the most populous state in India. None of the women, on inquiry, reported any accidental or occupational exposure to any of the pesticides studied. None of the women suffered from any serious diseases except mild hypertension. Umbilical cord blood of these subjects was collected in heparinized vials during labor and stored at 10°C until the analysis was carried out, generally within 48 hours. A 1-ml aliquot of blood was mixed with 5 ml formic acid and 2 ml «-hexane in a 25-ml conical flask. Contents were shaken 1 hour at 37°C in a mechanical shaker, and centrifuged 10 minutes at 2,000 rpm in a refrigerated centrifuge. Losses due to evaporation were made up by weighing the container before and after shaking. The upper layer (hexane) was recovered by disposable suction pipet. The extracted samples were further cleaned up according to the method of Dale et al. (9) as follows: The hexane extract plus 1 ml distilled water in a clean test tube were kept in a liquid air-methanol bath to remove traces of formic acid. The unfrozen hexane phase was further treated with 1 ml fuming H2SO4 (three times) to remove the fat. Recoveries through this cleanup procedure were greater than 84% for all pesticides in the fortified samples, except lindane. Vol. 15, No. 2, September 1981 77 which was recovered at about 79%. The cleaned samples in hexane were analyzed for organochlorine pesticides on a Varian Aerograph Series 2400 gas-liquid chromatograph, equipped with an electron-capture detector CH). The operating conditions of the instru- ment were as follows: Camer gas: purified nitrogen (99.9%) passed through sUica gel and molecular sieve to remove inoisture and oxygen, respectively Gas pressure: Row rate: 65 psi 45 ml/min Temperatures, °C injector 190 colmun 180 detector 200 Attenuation: 4x10-' Current: Column: 10-' (lamp glass spiral column, 6 ftxi/s-in- ID. packed with l.S^c OV-17 + 1.95% OV-210 on 80-100-mesh Gas- Chrom Q Sample size: 4-8 [i.\ Pesticide standards were obtained from PolyScience Corp., Niles, Illinois. Compounds were quantitated by comparing the peak area of detected pesticides in the samples with those of known pesticide standards. The presence of detected residues was further confirmed by thin-layer chromatography. Results and Discussion Levels of organochlorine pesticides estimated neonatal blood are summarized in Tables 1-3. the The results of random sampling grouped on the basis of age (Table 1), dietetic habits (Table 2), and area of residence (Table 3) of the mother have been computed. Residues of total BHC (45.79 ppb) were highest in the neonatal blood from mothers 26-34 years old compared with 32.97 ppb observed in 18-25-year old mothers, i.e., residues were about 39% higher for the upper age group. Likewise, significant difference was observed in the levels of lindane between the two age groups (P<0.05). There was no variation in the concentration of total DDT (SDDT) residues in the two age groups. However, concentrations of p.p'-DDT, the parent compound, were about three times greater in the 26-34-year old group compared with those in the 18-25-year old mothers (/'<0.005). Relatively higher concentrations of DDT metabolites (DDE, 23.1 ppb; TDE, 8.01 ppb) were detected in the neonates associated with the older women compared with the younger age group (DDE, 12.33 ppb; TDE, 5.84 ppb). Differences in the levels of total BHC and its isomers in neonatal blood on the basis of vegetarian vs. nonvegeta- rian diets of the mother were not significant: Cord blood associated with vegetarian mothers contained 38.3 ppb BHC compared with 35.64 ppb BHC for nonvegetarian 78 mothers. Cord blood associated with vegetarian mother contained 62.22 ppb total DDT compared with 50.0' ppb total DDT in cord blood associated with nonvegeta rian mothers. BHC (47.38 ppb) was detected in th blood of newborns of mothers residing in urban area compared with 27.06 ppb in that of neonates of rura mothers (P<0.05). A statistically significant differenc (P<0.05) was also observed in the levels of lindan (-y-BHC) between the two residential groups. There wa no significant difference in total DDT residues by arej of residence, but a slightly higher concentration of DDlj was estimated in urban subjects, i.e., 22.81 ppb vs 15.48 ppb in rural subjects. The relatively higher level TABLE I . Organochlorine pesticides delected (ppb) in cor* blood collected at term from 100 pregnant women, by age group Women 18-25 Years Old (58 Cases) Women 26-34 Years Old (42 Cases) Pesticides Arithmetic Arithmetic Detectted Range Mean SE Range Mean S Total BHC 6,9-278.3 32,97 16,89 4,20-104,92 45,79 5, Lindane* 1,60-78,69 10,27 2,18 3,10-27,98 14,99 1, p.p'DDE 2.16-144,37 12.33 1,98 2,05-78,14 23,10 4, p.p'-TDE NI>48.21 5.84 1,25 ND-48,21 8,01 2, p.p'-DDT* 1,43^9,21 7,30 2,32 ND-57,52 22,13 2, SDDT' 7 79-1029 85 49,55 23,23 4,59-149,62 51 18 8, • Statistically significant {P<0.05 and 0,005. respectively). ' XDDT = total DDT equivalent. TABLE 2. Organochlorine pesticides detected (ppb) in coi blood collected at term from 100 pregnant women, by dietetic habit Vegetarian Diet (36 Cases) Nonvegetarian Diet (64 Cas Pesticides Detected Range Arithmetic Mean SE Range Arithmetic Mean Total BHC Lindane p.p'DDE p.p'-TDE pp-DDT SDDT 6,9-278,43 2,1-78,68 1,8-850 00 NI>48 21 ND-55,56 403-1029,85 38,3 12,47 35,33 6,55 14,89 62.22 7 29 0.34 23.26 1 85 3,05 8,50 4,18-104,92 1,8-29,81 1,9 + 150,00 0,89-32,09 1,78-140.00 2.73-240,41 35.64 11.41 20,53 8,49 17,08 50,07 TABLE 3. Organochlorine pesticides detected ippb) in co: blood collected at term from 100 pregnant women, by are of residence Urban Population (48 Cases) Rlral Popllation (52 Cas Pesticides Detected Range Arithmetic Mean SE Range Arithmetic Mean Total BHC* 2,0-507,84 Lindane* p.p -DDE PP' PP' -TDE -DDT ZDDT 1 28-175,73 1 02-257,50 ND-48,21 0 5-50 23 2,73-338,43 47,38 16,94 22,81 7,33 13,71 41,60 13 87 0,72 7,05 3,88 2,19 10,88 3,0-76,97 1.8-33,43 2.2-144.37 ND-32,09 ND-140,00 7,14-222,11 27 06 8,88 15,48 6,25 17,08 40,65 ' Statistically significant (/'<0,05 and 0,05. respectively). Pesticides Monitoring Journ f DDE compared with DDT suggest that mothers were xposed either to DDE or to long-term low levels of )DT, presumably the latter. lecause histories revealed no accidental or occupational xposure to any of the detected pesticides, subjects /ere exposed through the food chain and the environ- lent. Placental transfer is undoubtedly responsible for le presence of these toxicants in newborn babies. A ossible route of entry has been traced in Figure 1 . SPRAY (vector control and agricultural use) air pollution ''' INHALATION LUNG ABSORPTION i MATERNAL CIRCULATION PLACENTA CORD BLOOD FOOD CHAIN CONTAMINATION FIGURE 1 . Possible route of entry for pesticides into developing embryo. Relatively higher concentrations of BHC in neonatal lood associated with mothers in the older age group lay be the result of comparatively longer periods of xposure to this food and environmental contaminant. It /ould be advisable for pregnant women to avoid areas /here pesticides are sprayed and to decrease consump- lOn of fatty foodstuffs. Acknowledgment authors express their gratitude to H.O. Mishra for istrumental facilities and to Swaran Lata and B.K. iingh for technical assistance. LITERATURE CITED /) Agar^\^al, H. C. et al. 1976. Residues of DDT, its metabolites in human blood samples in Delhi. Bull. W.H.O. 54(3):394. 2) Anonymous. 1979. Chemicals and the environment. Pestic. Abstr. 12(5);253. 3) Bindra. O. S., and R. L. Kalra. 1973. A review of work done in India on pesticide residues. In Progress and Problems in Pesticide Residues Analysis. O. S. Bindra and R. L. Kalra, eds. Joint Publ. of PAU, Ludhiana, and ICAR, New Delhi, p. 9. (4) Brown, J. R., and L. Y. Chow. 1975. Comparative study of DDT and its derivatives in human blood samples in Norfolk County and Holland Marsh, Ontario. Bull. Environ. Contam. Toxicol. 13(4):483^88. (5) Casarett, L. J., G. C. Fryer, W. L. Yauger, and H. W. Klemmer. 1968. Organochlorine pesticide residues in human tissues — Hawaii. Arch. Environ. Health 17(3):306-311. (6) Curley, A., M. F. Copeland, and R. D. Kimbrough. 1969. Chlorinated hydrocarbon insecticides in organs of still-bom and blood of new-bora babies. Arch. Environ. Health 19(5);628-632. (7) Curley, A., and R. Kimbrough, 1969. Chlorinated hydrocarbon insecticides in plasma and milk of pregnant and lactating women. Arch. Environ. Health 1 8(2): 156- 164. (8) Dale, W. E.. M. F. Copeland. and W. J. Hayes. 1965. Chlorinated insecticides in the body fat of people in India. Bull. W.H.O. 33:471^77. (9) Dale, W. £., J. W. Miles, and T. B. Gaines. 1970. Quantitative method for DDT and DDT metabolites in blood serum. J, Assoc. Off. Anal. Chem. 53(6); 1287- 1292. (10) Gladden, B., and W. Rogan. 1977. Environmental contamination of foods for infants. Environ. Health Perspect. 20:248. (11) Gowda, T. K. S.. andN. Sethunathan. 1976. Persistence of endrin in Indian rice soils under flooded conditions. J. Agric. Food Chem. 24(4):750-752. (12) Grasso, C. 1975. Transplacental passage of organoch- lorine insecticides. In Proc. Int. Symp, on Recent Advances in Assessment of Health. Effects of Environ- mental Pollution. Commission of the European Com- munities, Luxembourg, pp. 861-875. (13) Hashemy-Tonkabony, S. E., and F. Fateminassab. 1977. Chlorinated pesticide residues in milk of Iranian nursing mothers. J. Dairy Sci. 60(1 2); 1858-1 860. (14) Mathews. H. B.. P. R. Chen, H. M. Mahendale, and M. W. Anderson. 1974. The metabolism, storage and excretion of highly chlorinated compounds by mammals. In Mechanism of Pesticide Action, G. K. Kohn, ed., p. 55. (15) O'Leary, J. A., J . E. Davies, W. F. Edmudson, and G. A. Reich. 1970. Transplacental passage of insecticides. Am. J. Obstet. Gynecol. 107(1 ):65-68. (16) Polishuk. Z. W., M. Wassermann, D. Wassermann, Y. Groner, S. Lazarovici, and L. Tomatis. 1970. Effects of pregnancy on the storage of organochlorine insecticides. Arch. Environ. Health 20(2):215-217. (17) Rappolt. R. T.. and W. E. Hall. 1968. p,p'-DDE and p.p'-DDT residues in human placentas, cords and adipose tissues. Clin. Toxicol. l(l):57-62. (18) Thacher, P. S. 1979. Toxic human milk may become a serious global problem. World Environ. Rept. 5(I8):Aug. 16. 'OL. 15, No. 2, September 1981 79 FISH, WILDLIFE, AND ESTUARIES Organochlorine Insecticide Residues in Soil and Earthworms in the Delhi Area, India, August-October, 1974 Dharam Vir Yadav.' Pradeep K Miltal. Han C. Agarwal." and M K Krishna Pillai ABSTRACT DDT residues in soil ami earlhworms from 50 sites in Delhi were monitored. DDT was detected in all but nvo samples each of soil and earthworms. Among DDT residues. p,p'-DDE was most common and was found in 48 samples each of soil and earthworms; p.p'-DDT was detected in only 43 soil samples and 46 earthworm samples. p.p'-TDE and o.p'-DDT were also present in smaller concentrations in 29 and 15 soil samples and in 43 and 25 earthworm scmiples. respectively. Maximum total DDT concentration of 2 .6 ppm was detected in the sod from Durga Nagar in the vicinity of a DDT factory. The highest concentration of 37.7 ppm total DDT in earthworms was also obtained from the same .site. The maximum concentration factor found in the earthworms was 551. The total DDT concentration in the earthworms and soil showed significant correlation. Introduction Large-scale use of organochlorine insecticides, espe- cially DDT. by agricultural and health agencies has resulted in global contamination of the ecosystem (10. 24). Because of its lipophilic tendency, coupled with its stability and persistence, DDT in the environment accumulates in nontarget organisms (10). DDT residues in soil are known to be concentrated by earthworms. Levels of DDT residues in soil and earthworms in a given area indicate the extent of environmental con- tamination over a period of time. DDT has been used extensively in the Delhi area for agricultural and mosquito control, and so this study was undertaken to assess the extent of DDT pollution. In addition, a DDT factory in Delhi might be contributing ' R.M College. Depanmem of Zoology. Delhi-1 10007. India - Universilv of Delhi. Depanmem of Zoology. Delhi-1 10007. India to the. environmental contamination of the surroundini areas. Materials and Methods Soil samples and earthworms were collected from 5 different sites in Delhi (Figure 1) from August t October 1974. The earthworms were of the one specie available in the area, Pheretima posthiima (L. Vaill Samples were dug from the upper 15 cm of soil, place in polyethylene bags, and transported to the laboraton within 6 hours. In the laboratory, the living earthworn( were removed from the soil, washed with water, an stored in a freezer. The soil was air-dried and mixe thoroughly, and at least three samples of 10 g each wei stored in a freezer. Physical and chemical properties ( the soil were not studied. Earthworms from each site were pooled to obtain sample weight of about 10 g. Pooled samples we< accurately weighed, and insecticide residues wej extracted by homogenizing the pooled samples wi| four times their weight of anhydrous sodium sulfate j acetone-hexane (1 -I- 1). The mixture was stirred forj hour and filtered. The residue was extracted three timij more with acetone-hexane (1 -I- 1). The total volunj of solvents used was 100 ml. The soil samples we| moistened, mixed with equal weights of anhydro sodium sulfate, and ground with a mortar and pestl Samples were mixed with acetone-hexane (59 -I- 4f shaken for 1'/: hours, and filtered. The residue w extracted three times more. The total volume solvents used was 100 ml. The extract (earthworms soil) was washed with 100 ml of 2% sodium sulfaij and the hexane layer was filtered through anhydro | sodium sulfate. The extract was then concentrated j flash evaporation and cleaned on an alumina column i| described by Holden and Marsden (14). The clean | sample was analyzed by gas-liquid chromatograp i 80 Pesticides Monitoring Journ KALKAJI TCHnf ® FIGURE 1. Areas sampled for DDT residues in soil and earthworms in Delhi. LC). Instrument parameters and operating conditions ;re as follows: jas-liquid chromatograph: Hewlett Packard Model 7300 series Jetector: electron-capture rolumn: coiled glass, 2 m x 4 mm ID packed with 1.5% SP 2250/1.95% SP 2401 on 100-120-mesh Supel- con AW-DMCS remperatures, °C: detector 200 injector 200 column 190 _amer gas; nitrogen flowing at 70 ml/min :aks were identified by comparing relative retention nes with those of standards. Identifications were ■nfirmed by GLC on another column packed with 6% icone DC- 11 on 80-100-mesh Chromosorb W-AW d 5% DEGS on 100-120-mesh Gas-Chrom Q. p'-DDT, p,p'-TDE, and o,p'-DUY were confirmed by dehydrochlorination (9). Peaks for p,/?'-DDE and DDMU were confirmed if they coincided with the dehydrochlorinated products from p,p'-DDT and p.p'- TDE. Further confirmation was performed by thin-layer chromatography of the pooled extract. Solvent systems used were heptane-acetone (98 -I- 2) and hexane- chloroform (90 -I- 10). The spots corresponding to the position of standards were scraped, extracted, and analyzed by GLC. Recovery of DDE, TDE, p.p'-DDT, and o.p'-DDl from spiked soil samples was 89.7%, 88.5%, 96.1%, and 91.8%; recovery was 93.6%, 93.9%, 97.8%, and 83.7% from spiked earthworms. However, data pre- sented have not been corrected for recoveries. The detection limit of the method under the conditions used u. 15, No. 2, September 1981 was about 0.1 ng for DDE, TDE, p.p'-DDT. and o.p'-DDT. Results and Discussion The areas from which samples were collected and the range of DDT and its metabolites found are given in Figure 1 . The levels of organochlorine residues in soil and earthworms, and the locations where they were found, are presented in Tables 1 and 2. Organochlorine insecticide residues detected in soil and earthworms were predominantly DDT and its metabolites. Tipathi {19} reported DDT in 120 of 138 samples analyzed from Tarai area in Uttar Pradesh, India. In the present study, residues in soil ranged from about 0.01 to 2.61 ppm; the highest concentration was found at Durga Nagar (Area 17). where the DDT factory is located. Other areas, such as Inderlok (Area 31), I. A. R.I. (Area 48b), and R.K. Puram (Area 36). also had appreciably higher concentrations of total DDT residues. Concentra- tions of DDT residues were below detection limits at two sites, Wazirabad pumping station (Area 47) and Vivek Vihar (Area 24). Total DDT concentration as high as 29.45 ppm in agricultural soils (7) and 388.16 ppm in urban soils (5) has been reported in the United States. Lang et al. (75) found a maximum of 13.93 ppm total DDT from a survey of six U.S. Air Force Bases. The occurrence of DDT residues in Delhi soils might be predominantly attributed to volatilization and subse- quent dispersal of DDT in the vicinity of the factory; DDT has been shown to volatilize into the atmosphere (21), from which it ultimately reaches the surface soils. In addition to the dispersal from the DDT factory, large-scale use of DDT in the control of malaria might have resulted in widespread contamination of Delhi soils. DDT residues in soils are highly stable and persist for a long time (22). However, Agnihotri et al. (2) reported up to 959c loss of DDT in 6 months from agricultural soils under tropical conditions. Therefore, the comparatively lesser concentration of DDT in Delhi soils might be due to their loss under the tropical environment. In earthworms, the concentration of total DDT residues varied from 0.1 ppm to 37.74 ppm, with a maximum concentration factor of 551 (Tables 1 and 2). The highest concentration of DDT was detected in samples from Durga Nagar, where DDT concentration in the soil was also highest. However, the concentration factor, which was obtained by dividing the concentration of DDT in the earthworms by the concentration in the soil, was only 14.5 at Durga Nagar. compared with 551 at one site l.A.R.I. (Area 48a). Barker (3) reported total DDT as high as 680 ppm in Lumbricus rubellus and 492 ppm in Helodriliis zeteki. compared with 37.7 ppm DDT in P . posthuma in the present investigation. There TABLE 1. Concentration (range in ppm) of DDT and its metabolites in soil and earthworms collected from different areas in Delhi during 1974 SAMPL.bTYPt ;).p'-DDE o.p'-DDT p.p'-lDE /j.p'-DDT Total DD Soil 001-0.81 0.01-0.27 0,01-0,60 001-1,20 0 01-2,6 (48) (15) (29) (43) (48) Eanhwi.rms 0,02-9 78 0 02-3,89 0,01-8,69 0,03-20 60 0,10-37,7 (48) (25) (43) (46) (48) NOTE: Fitly samples each ol soil and earthworms were analyzed. Numbers parentheses indicate number of samples with positive detection. are several other reports showing the concentration ( DDT residues in earthworms (12, 13, 23). Total DD concentration in earthworms and soil from the san area showed significant correlation (r = 0.792; P<0.01). Similarly, Gish (13) observed a line: relationship between pesticide residues in earthworn and soil. Edwards and Thompson (12) obtaine significant correlation between residues in earthworn and soil from data collected by different worker However, Wheatley and Hardman (23) found that DD residues in earthworms and soil were not relate linearly. DDT in soil and earthworms was comprised mainly i p.p'-DDT and its metabolites /J.p'-DDE and p,/?'-TDl In certain samples, o,/j'-DDT was also detected, addition to p,p' -DDJ and its metabolites (Tables 1 ar 2). These are commonly reported DDT components soils (4, 17, 18). Carey et al. (6-8) reported o.p'-DC and o.p'-TDE residues in addition to these common occurring metabolites. DDT in soils undergoes tran formation in the presence of various physical, chemici and biological factors and degrades to DDE, tl terminal residue of DDT (76). TDE is also formed the soil, mainly a result of microbial degradation (20 The occurrence of DDT metabolites in earthworms m. be due either to their direct uptake from soil or metabolism of DDT by the earthworms (7, 77, 25). T proportions of DDT metabolites (DDE and TDE) relation to unchanged DDT showed large variations different soil and earthworm samples. However, majority of these samples contained higher concenti tions of p,p'-DDT than its metabolites, suggesting tl p.p'-DDT was being transferred quite frequently these soils. The higher proportions of DDE and TDE certain samples may be due to the faster degradation p,p'-DDT in soil in those particular areas; DI degradation depends on various environmental facto i Ware et al. (27) showed a shift in DDE: DDT ratio frci 56:44 to 62:38 after 3 years in Arizona soils. T variable proportions of DDT metabolites in relation I unchanged DDT in the earthworms might have bzi due to variations in the duration of exposure to r insecticide and its concentration in the soils. 82 Pesticides Monitoring JouR^i' TABLE 2. Concentration (in ppm) of DDT and its metabolites in soil(S) and earthworms(E) from different areas in Delhi during 1974 AREAS p.p'DDE o.p -DDT p.p'JDE p.p'-DDl Total DDT CoNCN Factor 1. Old Jamuna Bridge s 008 0.01 0,21 0.30 Kashmere Gale E 0,32 — 0.01 1.02 1.35 4.5 2. Raj Ghat s 0,07 — 0.01 0.08 E 0,18 — 0.15 0.81 1.14 14.3 3. Lajpat Nagar S 0.01 — 0.08 0.09 E 0,23 — 0.24 0.76 1.23 13.7 4. Wazirpur S 005 — — 0.02 0.07 E 069 0.09 0.98 2.41 4.17 59.6 5. Azadpur S 008 — , — 0.02 0.10 E 003 — — 0.07 0.10 1.0 5. South Extn Pt -II S 0.10 — 0.04 0.05 0.19 E 0.03 — 0.10 0.14 0.27 1.4 7. Kalindi Colony S 0.05 0.01 0.06 E 0.03 — 0.01 0.14 0.18 3.0 S. Safdaijang Enclave S 006 — — 0.04 O.IO E 0.92 005 0.04 0.65 1.66 16.6 ?. Timarpur S 0.19 — 0.04 0.23 E 005 — — 0.06 0.11 0.48 ). Naraina S 0.05 — 0.50 0.55 E 0.05 0.02 0.83 — 0.90 1.6 1. Delhi Airport S 0.14 — 0.04 0.20 0.38 E 0.89 0.19 0.24 1.13 2.45 6.4 I. Kataria Nursury S 0.11 — — 0.04 0.15 Nizamuddin E 1 65 0.37 0.02 1.80 3.84 25.6 i. Palam Road S 0.06 — 0.02 0.08 E 0.75 — — 1.54 2.29 28.6 t. Roshanara Garden S 0,10 0.02 0.06 0.08 0.26 E 0 18 — 0.02 0.27 0.47 1.8 j. Delhi Zoo S 0,03 — 0.02 0.01 0.06 E 0,14 — 0.03 0.20 0.37 6.2 5. Punjabi Bagh S 0,06 — 0.01 0.02 0.09 E 0.40 — 0.68 0.77 1.85 20.6 ^ Durga Nagar S 0.76 0.08 0.57 1.20 2.61 E 5.24 3.21 8.69 20.60 37.74 14.5 !. Kalkaji S 0.02 — — 0.02 E 0 19 — — 0.16 0.35 17.5 *. Greater Kailash S 0.02 — 0.02 E 0.58 0,10 0.08 0.43 1.19 59.5 ). Govind-Puri S 005 — 0.04 0.04 0.13 E 0.02 — 0.97 0.97 1.96 15,1 1. Jamia Nagar S 0.15 — 0.03 0.04 0.22 E 0.59 — 0.01 0.03 0.63 2.9 !. Okhla S 0.02 — 001 0.02 0.05 E 0.12 — 0.07 0.14 0.33 6.6 1. Navin Shahdara S 0.10 0.02 0.05 0.27 0.44 E 0.26 — 0.03 0.30 0.59 1.3 1. V.vek Vihar S E — — — — — ). Central S 0.04 0.05 0.05 0.14 Secretariat E 0.13 — 0.49 0.27 0.89 6,4 i. Geeta Colony S 0.06 0.01 0.02 0.05 0.14 E 0.92 — 0.62 1.56 3.10 22.1 '. Jheel S 0.03 — 0.01 0.02 0.06 E 1.72 — — — 1.72 28.7 i. Tilak Nagar S 0.09 — 0.01 — 0.1 E 0.54 — 0.44 0.2 1.18 11.8 h Moti Nagar S 0.03 — — 0.03 0.06 E 6.10 1,50 1 90 8.60 18.10 302 ). Shanti Nagar S 0.01 — 0.01 E 1.20 — 0,05 0.03 1.28 128 continued OL. 15, No. 2, September 1981 83 TABLE 2. (cont'd). 31 Inderlok S E 0,19 9.78 0,27 2,30 0.60 5.63 0.91 9.30 1.97 27.01 13.7 32, Budha Memorial Park S E 0.02 0.83 0,01 0.02 0.01 0.22 0.02 0.62 0.06 1.69 28.2 33, Pusa Chowk Karol Bagh S E 0.04 0.38 0.02 0.03 0.17 0.20 1.29 0.27 1.86 6.9 34 Pahar Ganj S E 0,04 0,05 0.04 0.01 0.05 0.27 0.78 0.32 0.92 2.9 35, Ajmal Khan Park S E 0,01 0,02 — 0.10 0.10 0.01 0.07 0.12 0.19 1.6 35 R K, Puram S E 0.19 0.87 0.03 0.04 0.01 0.08 0.57 2.55 0.80 3.54 4.4 37. Dhaula Kuan S E 0.04 0.22 0.04 0.03 O.U 1.03 0.15 1.32 8.8 38- Wazirabad S E 0.19 0.26 0.01 O.OI 0.11 0.38 0.48 0.59 0.85 1.4 39, Nirankarl Colony S E 0.02 0.31 0.01 0.03 0.01 0.14 0.09 0.63 0.13 1.11 8.5 40. Radio Colony S E 0.81 3.16 0.02 0.04 0.33 0.16 0.42 1.01 3.93 3.9 41, Subhadra Colony S E 0.34 1,55 0.05 0.06 0.50 0.89 1.54 0.69 3.64 5.3 42. Karam Pura S E 0.11 0.26 0.01 0.09 0.09 0.20 0.29 2.13 0.50 2.68 5.4 43. Bharat Nagar S E 0.03 0.03 0.02 0.02 0.02 0.43 0.17 0.23 0.24 0.71 3.0 44. Raja Garden S E 0.09 0.14 0.02 0.02 0.32 0.22 0.24 0.34 0.67 0.72 1.1 45. Daya Basti S E 0.12 0.18 0.03 0.05 0.06 0.17 0.32 0.72 0.53 1.12 2.11 46. Delhi University S E 0.02 0.31 0.26 0.22 0.03 0.73 0.05 1.52 30.4 47. Wazirabad Pumping Station S E — — — — — 48. Indian Agnc. Research Inst. S E 0.02 0.57 3.89 2.32 0.01 9.74 0.03 16.52 551 48(a) Indian Agric Research Inst. S E 0.05 0.12 0.20 0.08 0.08 0.51 0.13 091 7 48(b) Indian Agric. Research Inst. S E 0.75 0.36 0.10 1.77 1.12 0.27 6.00 1.12 9.25 8.3 Acknowledgments This work was partly supported by a grant from the Department of Science and Technology under the Man and Biosphere Programme. One of the authors, D.V. Yadav, was a recipient of an All India University Grants Commission Junior Research Fellowship. LITERATURE CITED (/) Agarwal, H.C.. D.V. Yadav. and M.K.K. Pillai. 1978. Metabolism of '"C-DDT in Pheretima posthuma and effect of pretreatment with DDT, lindane, and dieldrin. Bull. Environ. Contam. Toxicol. 19:295-299. (2) Agnihotri. N.P.. S.Y. Pandey. H.K. Jain, and DP. Srivastava. 1977. Persistence of aldrin, dieldrin, lin- dane, heptachlor, and p.p'-DDT in soil. J. Enlomol. Res. 1:89-91. (i) Barker. R.J. 1958. Notes on some ecological effects of DDT sprayed on elms. J. Wildl. Manage. 22:269-274. (4) Brown. JR.. L.Y. Chow, and F.C. Chai. 1975. Distribution of organochlorine pesticides in an agricultu- ral environment, Holland Marsh, Ontario — 1970-72. Pestic. Monit J. 9(l):30-33. (5) Carey. A.E.. 1979. Monitoring pesticides in agricultural and urban soils of the United States. Pestic. Monit. J. 13(0:23-27. (6) Carey. A.E.. P. Douglas. H. Tai. W.G. Mitchell, and G.B. Wiersma. 1979. Pesticide residue concentrations in soils of five United States cities, 1971 — Urban Soils Monitoring Program. Pestic. Monit. J. 13(l):17-22. (7) Carey. A.E.. J.A. Gowen. H. Tai. W.G. Mitchell, and G.B. Wiersma. 1979. Pesticide residue levels in soils and crops from 37 states, 1972 — National Soils Monitor- ing Program (IV). Pestic. Monit. J. 12(4):209-229. (8) Carey. A.E.. G.B. Wiersma. and H. Tai. 1976. Pesticide residues in urban soils from 14 United States cities, 1970. Pestic. Monit. J. 10(2):54-60. (9) Chau. A.S.Y. 1972. Analysis of chlorinated hydrocarbon pesticides in water and waste waters. Inland Waters Branch, Environment Canada, Ottawa, Ontario, Canada, pp. 1-56. 84 Pesticides Monitoring Journa 70) Edwards. C.A. 1970. Pesticides in the Environment. Chemical Rubber Co., Cleveland, Ohio. ;/) Edwards. C.A.. and K.A. Jeffs. 1974. Rate of uptake of DDT from soil by earthworm. Nature (London) 47:157- 158. 12) Edwards. C.A., and A.R. Thompson. 1973. Pesticides and the soil fauna. Residue Rev. 45:1-81. 13) Gish, CD. 1970. Organochlorine insecticide residues in soils and soil invertebrates from agricultural lands. Pestic. Monit. J. 3(4):241. 14) Holden. A.V.. and K. Marsden. 1969. Single stage clean up of animal tissue extracts for organochlorine residue analysis. J. Chromatogr. 44:481^92. 75) Lang. J.T.. L.L. Rodriguez, and J.M. Livingston. 1979. Organochlorine pesticide residues in soils from six U.S. Air Force Bases, 1975-76. Pestic. Monit. J. 12(4):230- 233. 16) Maisumura. F. 1973. Degradation of pesticide residues in the environment. In Environmental Pollution by Pesticides, Vol. 3, C.A. Edwards (ed.). Plenum Press, London, U.K. pp. 494-513. 17) Miles. J.R.W.. C.R. Harris, and P. Moy. 1978. Insecticide residues in organic soil of the Holland Marsh, Ontario, Canada, 1972-75. J. Econ. Entomol. 71:91- 10!. 18) Suzuki. M.. Y. Yamato. and T. Walanobe. 1977. Organochlorine insecticide residues in field soils of the Kitakyushu District — Japan, 1970-74. Pestic. Monit. J. ll(2):88-93. (79) Tripathi. H.C. 1966. Organochlorine insecticide re- sidues in agricultural and animal products in Tarai area. M.Sc. thesis, U.P. Agric. Univ., Pant Nagar, India. (20) Tu, CM., and J.R.W. Miles. 1976. Interaction between insecticides and soil microbes. Residue Rev. 64:17-65. (27) Ware. G.W.. W.P. Cahill. and B.J. Esteson. 1975. Volatilization of DDT and related materials from dry and irrigated soils. Bull. Environ. Contam. Toxicol. 14:88- 97. (.22) Ware. G.W., B.J. Estesen. N.A. Buck, and W.P. Cahill. 1978. DDT moratorium in Arizona — agricultural re- sidues after seven years. Pestic. Monit. J. 12(1): 1-3. (23) Whealley. G.A.. andJ.A. Hardman. 1968. Organochlor- ine insecticide residues in earthworms from arable soils. J. Sci. Food Agric. 19:219-225. (24) Woodwell. G.M.. P.P. Craig, and H.A. Johnson. 1971. DDT in the biosphere: Where does it go? Science 1974:1101-1107. (25) Yadav, D.V.. M.K.K. Pillai. and H C. Agarwal. 1976. Uptake and metabolism of DDT and lindane by earthworm Pheretima posthuma. Bull. Environ. Con- tam. Toxicol. 16:541-545. OL. 15, No. 2, September 1981 85 Organochlorine Insecticide Concentrations in Fish of the Des Moines River, Iowa, 1977-78' Ross V. Bulkley,- Siu-Yin Theresa Leung." and John J- Richard ' ABSTRACT Organochlorine insecticides were measured in fish of the Des Moines River. Iowa, in 1977 and 1978 to determine whether concentrations exceeded allowable levels and to compare differences among species. Significant differences in mean concentrations of dieldrin. "LDDT. and hcplachlor epo.\ide in whole-body samples of seven species of fish, Dorosoma cepedianum, Carpiodes carpio, Cyprinus carpio, Ictalurus punctatus, Pomoxis annularis, Micropterus salmoides, Sti- zostedion vitreum. could not be adequately explained by body size, position of species in the food chain, or percent body fat. of southwestern Minnesota and flows southeasterly across Iowa to the Mississippi. It is the largest river ir Iowa. About 79% of the watershed upstream from De; Moines is cropland (primarily com and soybeans), 6^ is permanent pasture, 57c is forest, and 7% is urban (7) Normal annual precipitation over the drainage are: ranges from 62.5 to 77.5 cm from north to south am averages 70.7 cm (19). The major source of pollution ii the river is nonpoint agricultural runoff (8). Sampling and Analysis Introduction The use of organochlorine insecticides on midwestern farmland to control agricultural insects has caused widespread contamination of fish in streams and rivers. Dieldrin residues in catfish (Ictalurus) and buffalo fish (Ictiobus) caused closure of certain commercial fisheries in Iowa during the 1970's and generated considerable public concern (2, 3. 4, 9, 10, 14). Several years after DDT, aldrin, dieldrin, and other insecticides were removed from the market, these chemicals or their breakdown products were still present in water, sediment, and fish of the Des Moines River and at least dieldrin was evidently still being washed into the river from farmland (11). Leung (//) examined pesticide concentrations in water, sediment, and seven species of fish collected from 1977 to 1978 in conjunction with the impoundment of water behind the newly constructed Saylorville Dam in central Iowa. She detected no noteworthy seasonal or spatial differences in concentra- tion of dieldrin, SDDT, or heptachlor expoxide in whole-body analyses of Des Moines River fish. The portion of the study reported here concerns variation in insecticide residues in different species of fish. The Des Moines River rises in the glacial moraine area ' This study was conducted as part of Project 2225 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa, in cooperation with the Iowa Cooperative Fishery Research Unit, which is sponsored by the Iowa State Conservation Commission, Iowa State University, and the Fish and Wildlife Service, US, Department of the Interior. ^ Utah Cooperative Fishery Research Unit, Logan, UT 84322 ' Minnesota Pollution Control Agency, Roseville, MN 551 13 ■' Iowa State University, Ames, lA 5001 1 SAMPLE COLLECTION AND PREPARATION Three collection sites were established on the De Moines River in central Iowa. The drainage area total about 14,530 km- above Station I at Boone, 15.081 km above Station 2, and 15,128 km- above Station 3 a Saylorville. Stream distance from Station I to Station '. is about 76 km. Fish samples were collected quarterly from Octobe 1977 to October 1978 with gill nets, hoop nets, am electrofishing gear. Species analyzed for pesticid residues were three forage fish, including gizzard shai (Dorosoma cepedianum), river carpsucker (Carpiode carpio), and carp (Cyprinus carpio); and four piscivor ous fish, including channel catfish (Ictalurus pitnc tatus), white crappie (Pomoxis annularis), largemout bass (Micropterus salmoides), and walleye (Stizostedio, vitreum). Each species was not always collected z every station during each quarter, but all species wer collected at one or more stations each quarter Specimens were grouped by collection data, location species, and length. Authors attempted to collect sma juveniles within a limited length range and to avoi large, old fish of each species. Individuals in the sam group were ground together in a hand grinder and the mixed manually in an effort to obtain a homogenou mixture. Subsamples were then taken, wrapped i aluminum foil, and frozen until analysis. ANALYSIS The method of tissue analysis described in the Pesticid Analytical Manual of the U.S. Department of Healt 86 Pesticides Monitoring Journa and Human Services (18) was used, with slight modification. After samples were thawed, a 25-30 g subsample was extracted with 200 ml of 65% acetonit- rile-water for 5 minutes in a 1 -liter stainless steel blender. The samples were filtered and transferred to a 1-liter separatory funnel; 100, ml petroleum ether, 600 ml water, and 10 ml saturated aqueous sodium chloride were added. The pesticides were partitioned into the organic layer by vigorously shaking for 30-60 seconds. The aqueous layer was discarded. The petroleum ether layer was washed with two 100-ml portions of water to remove the remaining acetonitrile, and then transferred to a 100-ml graduated cylinder, and the recovered volume was recorded. The wet weights of tissue samples were corrected for the losses of acetonitrile- water mixture and petroleum ether. The extracts were subjected to Florisil column cleanup. The eluate was concentrated to 10 ml for quantification. Results were expressed in nanograms of pesticide per gram of fish tissue (ppb wet weight). Dieldrin, p,p'-DDE, p.p'-TDE, p,p'-DDT, and hep- tachlor epoxide were quantified by gas chromatography. Instrument parameters and operating conditions were as follows: TABLE I . Number and length of fish collected from Des Moines River, Iowa. J977-78 Gas chromatograph: Detector: Columns: Temperatures, "C Carrier gas: Tracer 550 ^^Ni electron-capture packed with 10% DC-200 packed with 4% SE-30/6% OV-210 detector 340 columns 210 flowing at 90-100 ml/min Values were not corrected for the ca 80% recovery obtained in extraction. Preliminary tests revealed little interference from polychlorinated biphenyls (PCBs) and chlordane. The majority of the PCBs were present as Aroclor 1242 or 1246 which did not interfere in the other pesticide analyses. No chlordane was observed in water or fish samples. Pesticide detection limits were about 10 ppb. One of the authors, John J. Richard, supervised all analyses. Authors transformed data on pesticide concentrations to log 10 values before conducting analysis of variance or r-tests or computing correlation coefficients. Results Carp were most abundant and walleyes were least abundant in the collections (Table 1). Because large older fish were not included in the composited samples, mean length of samples for the seven species was ivithin a 120-mm range. Average length of forage fish ivas 56 mm less than that of piscivorous fish. Dieldrin and SDDT were detected in all 173 samples inalyzed. Heptachlor epoxide was present in quanti- No Total Length, mm Species Gizzard shad River carpsucker Carp Channel catfish White crappie Walleye Largemouth bass Fish Mean Range 377 137 56-212 302 178 76-400 536 151 83-402 86 253 98-487 217 134 75-332 40 232 144_430 132 225 95-387 fiable amounts in most samples but was not detected in at least 15% of the samples from a given species; it was not found in 33% of river carpsucker samples, 27% of carp samples, and 15%-23% of the samples of other species. Most of the samples with undetectable heptach- lor epoxide were collected at Station 2 in October 1977. Average concentrations of dieldrin and SDDT were somewhat similar; concentrations of heptachlor epox- ide, when present, were considerably lower. Comparison of concentrations of the three insecticides indicated significant differences among fish species for all three chemicals (Table 2). Differences were greatest in dieldrin concentrations (P <0.01). Levels of dieldrin were highest in gizzard shad and channel catfish (114 ppb), and lowest in walleyes (28 ppb). Patterns of heptachlor epoxide concentrations were similar to those for dieldrin (P <0.01). Concentrations of SDDT were more similar among species, but still significantly different (P <0.05). TABLE 2. Mean insecticide concentrations in whole-body samples of fish from Des Moines River. Iowa, 1977-78 No Concentration. PPB Species Dieldrin ZDDT Heptachlor Samples Epoxide Gizzard shad 20 114(14-191) 57 (8-188) 14 (0-68) River carpsucker 39 63 (7-197) 64(10-329) 7 (0-42) Carp 39 35 (13-62) 42 (12-125) 5 (0-23) Channel catfish 17 114(31-240) 67 (16-136) 16(0-42) White crappie 23 60(15-301) 44 (6-72) 6(0-19) Walleye 11 28 (7-62) 76(7-138) 2(0-6) Largemouth bass 24 58(15-182) 65 (7-109) 7 (0-23) NOTE: Range is given in parentheses. Levels of insecticides in the three forage species were compared with those found in the four piscivorous species to determine if bioaccumulation through the food chain was evident. Differences between concentra- tions found in the forage fish and the fish-eating species were not statistically significant for any of the three ^OL. 15, No. 2, September 1981 87 chemicals. Average whole-body concentrations (ppb) were as follows; TABLE 4. Correlation coefficient (r) between percent body fat and insecticide concentrations for combined composite samples offish collected during July and October 1978 Forage fish Piscivorous fish Dieldrin 71 65 IDDT 54 65 Heptachlor epoxide 9 Inasmuch as whole-body concentrations of the three insecticides failed to correlate significantly with posi- tion of species in the food chain, authors compared pesticide concentration to percent body fat. Only fish sampled during the last two quarters, July and October 1978, were available for fat analysis (Table 3). Average percent body fat was highest in gizzard shad (17) and lowest (2) in walleyes. Fat concentrations were similar in July and October samples of each species except gizzard shad. Concentrations of fat in shad samples were 7% in July and 29% in October. TABLE 3. Average percent fat content and mean whole-body insecticide levels in seven species of fish collected in Julv and October 1978 No Fat, Concentration, PPMi Heptachlor Fish Species Fish % Dieldrin SDDT EPO.XIDE Gizzard shad 104 17.0 81 (0.48) 55 (0 32) 14 (0,08) River carpsucker 72 5,4 45 (0,83) 39(0,72) 3 (0,06) Carp 91 4,5 35 (0,78) 45 (1,00) 6(0 13) Channel catfish 3 8,5 101 (1,19) 101 (1 19) 10(0,12) White crappie 79 2,7 56 (2,07) 46 (1,70) 8 (0,30) Walleye 26 2,0 26(1,30) 106 (5,30) 2 (0,10) Largemouth bass 52 4,0 61 (1,52) 75(1,87) 8 (0,20) 'Based on ppm fat shown in parentheses. The correlation between percentage fat and insecticide concentrations within each species was first examined. In July samples, correlation was significant at the 0.01 level between percent fat and dieldrin and heptachlor epoxide levels for white crappies and between percent fat and SDDT for gizzard shad. In October samples, correlation was significant at the 0.05 level between percent fat and dieldrin and heptachlor epoxide in largemouth bass. Percent fat was not significantly correlated with insecticide concentrations in the other species. In combined July and October samples (Table 3), the relation between percent fat and dieldrin was significant at the 0.05 level or higher in river carpsucker, carp, white crappies, and largemouth bass (Table 4). Correla- tion coefficients for gizzard shad and walleyes, although not statistically significant, suggested a similar relation. Body fat was significantly correlated with SDDT only in gizzard shad, whereas correlation between fat and heptachlor epoxide was significant in both white crappies and largemouth bass. No Heptachlor Species Samples Dieldrin SDDT Epoxide Gizzard shad 5 0.70 0,93* 0.45 River carpsucker 9 0,73* 0,25 0.69 Carp 8 0,83** 0,32 0.26 Channel catfish 1 — — — White crappie 10 0,90" 0,41 0.82** Walleye 6 070 0,47 0.46 Largemouth bass 13 0,84»» 0,36 0.85»* *Significant at 0.05 probability level. •♦Significant at 0.01 probability level. But even though fish species varied widely in mean percent body fat, differences in concentrations of each of the three insecticides were evidently not caused by differences in body fat. When the seven species were compared, correlation coefficients were 0.65 for fat vs. whole-body dieldrin concentrations, —0.12 for fat vs. whole-body SDDT concentrations, and 0.80 for fat vs. whole-body heptachlor epoxide concentrations. These coefficients were not statistically significant. Expression of insecticide concentrations on the basis of fat content also failed to reduce species differences (Table 3). White crappies contained over 2 ppm dieldrin on a fat basis and gizzard shad only 0.48 ppm. Walleyes contained the highest SDDT concentrations on the basis of fat (5.30 ppm) and gizzard shad the lowest (0.32 ppm), whereas concentrations of heptach- lor epoxide in terms of fat were very low in all species. These relatively high levels of pesticide per unit of body fat in white crappies, walleyes, and other species (Table 3) suggested one additional comparison — concentration of pesticide in forage fish vs. piscivorous fish on a fat basis, for evidence of biological magnification. Mean concentrations of insecticide on a fat basis in gizzard shad, river carpsucker, and carp (forage fish) were lower than those in catfish, crappies, walleyes, and bass (piscivorous fish) as follows: dieldrin, 0.70 ppm vs. 1.52 ppm; SDDT, 0.68 ppm vs. 2.51 ppm; andi heptachlor epoxide, 0.09 ppm vs. 0.18 ppm. Thesei differences suggested that biological magnification ir the food chain was occurring. However, even though concentrations were seemingly higher on the basis of fai in all piscivorous fish than in forage fish (except foi heptachlor epoxide in carp), only those for dieldrin were significantly higher (P = 0.05, t = 3.50). Discussion Body concentrations of an insecticide frequently diffe'i from one species of fish to another from the same bod; of water. Many factors, including length and weight Pesticides Monitoring Journai age, food, fat content, enzyme systems, and trophic levels, have been considered by researchers to explain species variation in insecticide concentrations (5, 8). Lyman et al. (/2) and Matsumura (13) observed that fish species also vary greatly in their ability to metabolize and eliminate insecticides. Additional varia- tion may arise from uneven exposure due to differences in location of capture or time of year. In our study, five samples were collected over a I -year period at three locations on the river. Seasonal and spatial differences in pesticide concentrations were not statistically signi- ficant within species, with minor exceptions (//). However, fish may be captured at the same location and still have been exposed to different levels of pesticide. Bottom-dwelling species are in contact with greater concentrations of pesticide adsorbed on bottom and suspended sediment than are species occupying strata near the water surface where suspended sediment levels are lower. Whether fish can absorb pesticides directly from sediment in significant amounts is still uncertain. Percent body fat tended to explain levels of insecticides within certain species, as has been noted by many researchers (7, 6, 16, 17). but did not explain differences in concentrations among the seven species in the present study. Gizzard shad and channel catfish had higher percent fat in their bodies than did other species tested and also accumulated greater concentra- tions of dieldrin and heptachlor epoxide on a wet- weight basis. Even expression of concentrations in the seven species of fish on the basis of fat or oil content did not reduce differences in insecticide level among species. Reinert (16) found less difference in DDT and dieldrin concentrations in fish species when concentra- tions were expressed in terms of oil content of the fish. Position of a species in the food chain was related to insecticide concentration — especially dieldrin — in the present study when concentrations were expressed on the basis of fat content. Most striking was a 5.30-ppm SDDT level in the highly piscivorous walleye vs. 0.32, 0.72, and 1.00 ppm in the three forage species. This relation between position in the food chain and insecticide level was not evident when the comparisons were based on whole-body concentrations instead of on fat content alone. Authors' data illustrate once again the many factors influencing insecticide dynamics in fresh- water fish and the difficulty in attributing differences to a single factor. LITERATURE CITED (/) Anderson. R. B.. and W. H. Everhart. 1966. Concentra- tions of DDT in landlocked salmon (Salmo salar) at Sebago Lake, Maine. Trans. Am. Fish. Soc. 95:160- 164. (2) Anonvmous. 1970. Crisis in Iowa water. Iowa Waltonian 12(4)': 1-3. (3) Bulkley, R. V. (ed.) 1977. Pesticides in Iowa surface waters: summary of a workshop held March 1977. Iowa State Water Resources Research Institute, ISWRRI-83. Iowa State University, Ames, Iowa. 117 pp. (4) Bulkley. R. V.. L. R. Shannon. andR. L. Kellogg. 1974. Contamination of channel catfish from agricultural runoff. Iowa State Water Resources Research Institute Completion Rept. 62. Project No. A-042-IA. 144 pp. (5) Bulkley. R. V., R. L. Kellogg, and L. R. Shannon. 1976. Size-related factors associated with dieldrin concentra- tions in muscle tissue of channel catfish Ictalurus punctatus. Trans. Am. Fish. Soc. 105:301-307. (6) Earnest. R. D.. and P. E. Benville. Jr. 1971. Correlation of DDT and lipid levels for certain San Francisco Bay fish. Pestic. Monit. J. 5(3):235-241 . (7) Iowa Department of Environmental Quality. 1976. Water quality management plan, Des Moines River basin, Des Moines, Iowa. (8) Johnson, D. W. 1973. Pesticide residues in fish. In C. A. Edwards (ed.). Environmental Pollution by Pesti- cides. Plenum Press, London, U.K., pp. 181-212. (9) Johnson. L. G.. and R. L. Morris. 1971. Chlorinated hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J. 4(4):216-219. (10) Kellogg. R. L., and R. V. Bulkley. 1976. Seasonal concentrations of dieldrin in water, channel catfish, and catfish-food organisms, Des Moines River, Iowa — 1971-73. Pestic. Monit. J. 9(4): 186-194. Ul) Leung, S. T. 1979. The effect of impounding a river on the pesticide concentration in warmwater fish. Ph.D. thesis, Iowa State University Library, Ames, Iowa. 155 pp. Univ. Microfilm No. 8010239. (/2) Lyman. L. D.. W. A. Tompkins, and J. A. McCann. 1968. Massachusetts pesticide monitoring study. Pestic. Monit. J. 2(3):109-122. (13) Matsumura. F. 1977. Absorption, accumulation and elimination of pesticides by aquatic organisms. In M. A. Q. Khan (ed.). Pesticides in Aquatic Environment. Plenum Press, New York, N.Y., pp. 77-105. (14) Morris. R. L., and L. G. Johnson. 1971. Dieldrin levels in fish from Iowa streams. Pestic. Monit. J. 5(1):12-16. (15) Ostle, B. 1954. Statistics in Research. Iowa State College Press, Ames, Iowa. 487 pp. (16) Reinert, R. E. 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4):233-240. (17) Reinert, R. E.. and H. L. Bergman. 1974. Residues of DDT in lake trout (Salvelinus namavcush) and coho salmon (Oncorhynchus kisutch) from the Great Lakes. J. Fish. Res. Board Can. 31:191-199. (18) U.S. Dept. of Health and Human Services. Food and Drug Administration. 1970. Pesticide Analytical Manu- al, Vol. 1, sec. 212.1. U.S. Government Printing Office, Washington, D.C. (19) U.S. Dept. of Interior. Geological Survey. 1970. Floods in the Upper Des Moines River basin, Iowa. H. H. Schwob, Iowa City, Iowa. 49 pp. Vol. 15, No. 2, September 1981 89 Organochlorine and Metal Residues in Eggs of Waterfowl Nesting on Islands in Lake Michigan off Door County, Wisconsin, 1977-78 Susan D. Haseltine, Gary H. Heinz, William L. Reichel, and John F. Moore' ABSTRACT One egg from each of 114 red-breasted merganser fMergus serratorj nests in 1977 and 92 nests in 1978 was collected and later analyzed for organochlorines, polybrominated biphenyls (PBBs), polychlorinated styrenes (PCSsj, and metals. One egg was also collected from each of the dabbling duck nests located. Twenty-nine of these eggs were analyzed for organochlorines and metals in 1977: 10 eggs were analyzed in 1978. All merganser eggs contained DDE, polychlorinated biphenyls (PCBs), and dieldrin: all but one egg collected in 1978 contained DDT. DDE and PCS levels had declined since 1975 to a geometric mean of 7.4 ppm DDE and 20 ppm PCBs in 1977 and 7.6 ppm DDE and 19 ppm PCBs in 1978. Dieldrin residues in eggs had not declined from 1975 levels: the geometric mean was 0.78 ppm in 1977 and 0.76 ppm in 1978. Other organochlorines were present at low levels. Mercury residues averaged >0.50 ppm in merganser eggs and had not declined since 1975 . Other metals were present at low levels. Dabbling ducks generally had much lower organochlorine and Hg residues than mergansers: DDE and PCBs were the only organochlorines present in the majority of eggs. Geometric means of PCBs and DDT in dabbling duck eggs did not exceed 2.0 ppm and 1 .0 ppm. respectively. PBBs and PCSs were detected only in a few merganser eggs, at low levels. Eggshell thickness for red-breasted merganser eggs averaged 0.359 mm in 1977 and 0.355 mm in 1978, which is only 2%-3% below pre-1946 thicknesses. Mallard fAnas platyrhynchos) eggshell thicknesses averaged 0.331 mm in 1977 and 0.337 mm in 1978. Introduction Organochlorine residues, especially polychlorinated biphenyls (PCBs) (18), have been a contaminant problem in Lake Michigan biota for years, and fish have accumulated high concentrations of these lipid-soluble compounds (26). The build-up is especially persistent in the Green Bay watershed (2). Fish-eating birds nesting in this watershed accumulate high organochlorine residues (10) and exhibit significant eggshell thinning (6). In 1975, red-breasted merganser (Mergus serrator) and common merganser (Mergus merganser) eggs collected on islands off Door County, Wisconsin, contained up to 29 ppm DDE and 113 ppm PCBs; shells were 17.7% thinner than eggshells collected before the use of DDT (27). In 1977 and 1978, authors studied the reproduc- tive success of mergansers on several islands in the same area (Figure 1). The present paper reports the levels of organochlorines and metals in eggs randomly collected from the nests of mergansers and other waterfowl on the islands. Sample Collection and Preparation All but two of the eggs in the present study were obtained from Spider, Hog, and Pilot islands (Figure !). OO IllAND LONGITUDE ' Fish and Wildlife Service, U.S. Department of the Interior, Patuxent Wildhfe Research Center. Laurel, MD 20811 FIGURE 1. Location of islands where waterfowl eggs were collected for residue analyses. Lake michigan. 1977 and 1978. 90 Pesticides Monitoring Journal One red-breasted merganser nest each was found on Gravel and Plum islands. The main three islands were divided into 5-6-m transects and each transect was searched by at least two people. Eggs were randomly selected, one egg per clutch, from all merganser and many dabbling duck nests that contained three or more eggs. Nests containing fewer than three eggs were revisited several times and, if more eggs were added, then they too were sampled. Waterfowl nesting on the three islands during the 2-year study included red-breasted mergansers, common mer- gansers, mallards {Anas plan rhynchos). gadwalls (Anas strepera), and black ducks (Anas ntbripes). Red- breasted mergansers were by far the most prevalent species; eggs were taken from 1 14 nests in 1977 and 92 nests in 1978. Common merganser nests (two) were found only in 1978. In 1977, 22 mallard, 4 gadwall, and 3 black duck nests were sampled. In 1978, eggs from five mallard and five gadwall nests were collected and analyzed for organochlorines and a few metals. Eggs were labeled and carried in egg cartons to the laboratory. Eggs were cleaned and the length, breadth, and weight of each was measured. Volume was measured by water displacement if whole and if cracked was considered comparable to another egg of the same species with the same length and breadth measure- ments. Because dehydration and/or loss of lipid may occur in embryonated eggs, a specific gravity of 1.0 was assumed for all eggs; residue values (ppm) were based on egg volume (25). All eggs were opened at the equator and the contents were stored frozen in a glass jar until chemical analysis. Stage of embryonic development based on the mallard was noted. Eggshells were rinsed with membranes intact and air-dried for at least 2 weeks before being measured and weighed. Thickness was measured three times at the equator of each egg with a Starrett lOlOM micrometer having 0.01-mm graduations. A mean of these three values was considered the shell thickness for each egg. Statistical Analysis Comparisons of organochlorine and metal levels in eggs randomly collected during 1977 and 1978 were made by using a Mann-Whitney U-test. Geometric means and ranges and nonparametric correlations are presented because some organochlorines did not show a normal distribution. Pre- 1946 eggshell thicknesses in red- breasted and common mergansers, as reported by White and Cromartie (27), were compared with 1977 and 1978 values by means of Student's r-test. Intercorrelations of residues were tested with Spearman correlation coef- ficients. Analytical Procedures ORGANOCHLORINES, POLYCHLORINATED STYRENES. AND POLYBROMINATED BIPHENYLS Eggs were analyzed for p,p'-DDE, p.p'-lDE, p,p'- DDT, dieldrin, heptachlor epoxide, oxychlordane, c/i-chlordane, /ra«.y-nonachlor, tw-nonachlor, endrin, hexachlorobenzene (HCB), mirex, toxaphene, PCB, PBB, and PCS residues. Samples were ground with anhydrous sodium sulfate and extracted in a Soxhlet apparatus. Extracts were cleaned on a Florisil column, and pesticides and PCBs were separated into three fractions on a SilicAR® column, as described by Cromartie et al. (4). The SilicAR procedure was modified for the 1978 samples: The cleaned extracts were separated into four fractions, which produces a discrete fraction for endrin and dieldrin (16). Instrument parameters and operating conditions for quantitation of PCB, PCS, PBB, and pesticide residues were as follows: Gas-liquid chromatograph; Detector: Columns: Hewlett-Packard Model 5713 or 5840A equip- ped with automatic sampler and digital pro- cessor "Ni PCBs, PCSs, pesticides: glass. 183x0.4 cm ID, packed with 15% OV-17/1 95% QF-I on 100-120-mesh Supelcoport at I96-I98°C and with 5% methane in argon flowing at 60 ml/min PBBs: glass. 183x0 4 cm ID. packed with 3% OV-I on 80-IOO-mesh Supelcoport at 245°C and with 5% methane in argon flowing at 100 ml/min Pesticides were measured by digital integration of peak areas; PCBs were estimated by comparing total area with that of Aroclor 1260; PCS values were estimated on the octachlorostyrene peak (24), and PBB values were based on hexabromobiphenyl. Toxaphene esti- mates were based on the area of two peaks eluting after DDT (23). Average percentage recoveries from spiked chicken eggs were DDE, 91; TDE, 97; DDT, 93; dieldrin, 99; heptachlor epoxide, 78; oxychlordane, 97; cis- chlordane, 102; fra«.y-nonachlor, 99; endrin, 90; HCB, 75; mirex, 92; and Aroclor 1260, 101. Residue levels were not corrected for recovery. The lower limits of reportable residues were 0.10 ppm for pesticides, 0.50 ppm for PCBs, 0.02 ppm for PBBs, and 0.05 ppm for PCSs. Endrin was quantified as low as 0.05 ppm in the 1977 samples and as low as 0.02 ppm in the 1978 samples. Residues in 63 specimens were confirmed on an LKB 9000 or a Finnigan 4000 Series gas chromato- graph-mass spectrometer (76). Vol. 15, No. 2, September 1981 91 METALS Analyses for chromium (Cr), lead (Pb), copper (Cu), zinc (Zn), cadmium (Cd), arsenic (As), and selenium (Se) in 1978 were performed at Patuxent Wildlife Research Center, Laurel. Maryland. Eggs were homo- genized in a Virtis blender. A 5-g portion was placed in a Vycor crucible for Pb, Cu, Zn, Cd, and Cr analyses, and a 2-g portion was placed in a 125-ml Erienmeyer flask for As and Se analyses. Pb. Cu. Zn. Cd. Cr— After drying for 2 hours at 1 10°C, the Vycor crucible was covered and placed in a muffle furnace at 200°C for 2 hours. The temperature was then increased to 550°C at a rate of 100°C/hr and the sample was left to ash overnight. The ash was cooled, dissolved in approximately 4 ml nitric and hydrochloric acids over a hot plate, transferred to a 12-ml polypropylene tube, and diluted to 10 ml with distilled. deionized water. Residues were determined by compari- son with aqueous standards on a Perkin-Elmer Model 703 atomic absorption spectrophotometer. Except for the Pb line of 217.0 nm, the standard conditions as published by the manufacturer were used. As. Se — The 2-g sample was dissolved in 40 ml concentrated nitric acid over a hot plate and heated slowly to boil away all but 1 ml of acid, which was then transferred to a 50-ml polypropylene tube and diluted to 50 ml with distilled, deionized water. Arsenic and selenium were determined by the method of additions on a Perkin-Elmer Model 403 atomic absorption spectrophotometer equipped with a Perkin-Elmer MHS- 1 hydride generator. Authors performed the As analyses at 193.7 nm with a 59c NaBH4 reducing solution at 1,000°C, and the Se analyses at 196.0 nm with a 10% NaBHa reducing solution at 900°C. Recoveries from spiked chicken livers ranged from 83% to 110%; residues were not corrected on the basis of these data. The lower limits of reportable residues, on a wet-weight basis, were 0.10 ppm for Pb, Cu, Zn, Cd, and Se, and 0.05 ppm for Cr and As. All mercury (Hg) analyses and As and Se analyses in 1977 were made by Environmental Trace Substances Research Center, Columbia, Missouri. Mercury sam- ples were first wet-digested in nitric acid. Stannous chloride was added to reduce ionic Hg to elemental Hg, which was measured photometrically in the vapor phase by atomic absorption. The lower limit of quantification was 0.001 ppm Hg, wet weight. Arsenic samples of 0.25 g were added to 15 ml concentrated nitric acid and 1 ml perchloric acid and heated to fumes. The samples were cooled and diluted to 25 ml with distilled, deionized water. A lO-ml aliquot of each sample was run in duplicate on a Perkin-Elmer MHS-1 hydride system with a NaBH4 pellet at 1,000°C. The lower limit of quantification was 0.005 ppm As, dry weight. Selenium was determined with the Se 77' method outlined by McKown and Morris {21). The lower limit of quantification was 0.01 ppm Se, dry weight. Results and Discussion MERGANSERS Organochlorines — In 1977. all 114 red-breasted mer- ganser eggs contained PCBs, DDE, dieldrin, and DDT. Geometric means for these four organochlorines were 20, 7.4, 0.78, and 0.36 ppm, wet weight, respectively. In 1978, all 92 of the red-breasted merganser eggs contained PCBs, DDE, and dieldrin; 91 of the 92 eggs contained DDT. Geometric means for the four residues were 19, 7.6, 0.76, and 0.31 ppm, respectively (Table 1). The means of these four organochlorines did not change significantly (P>0.05) between 1977 and 1978, but the range of PCBs (up to 229 ppm in 1977, but only 36 ppm in 1978) and of DDE (up to 28 ppm in 1977, but only 16 ppm in 1978) decreased. The range of dieldrin and DDT did not change dramatically between 1977 and 1978. Although PCB values from the present study are not easily compared quantitatively with previous findings, there is a general downward trend. In 1969, Faber and Hickey (6) reported an arithmetic mean of 84 ppm PCBs, wet weight, in red-breasted merganser eggs from the Green Bay area. In 1975, the mean had decreased to 45 ppm PCBs (27). Our arithmetic means were 25 ppm and 20 ppm, respectively. The same trend was apparent in DDE residues for these 4 years: 44 ppm in 1969 (6), 16 ppm in 1975 {27). 8.3 ppm in 1977, and 8.1 ppm in 1978. Dieldrin residues showed no such decrease; arithmetic means for the 4 years were 0.77 ppm in 1969, 1.0 ppm in 1975, 0.86 ppm in 1977. and 0.81 ppm in 1978. DDT was not reported singly in 1969. but in 1975 the mean (0.62 ppm) was slightly higher than in 1977 and 1978. This is also true for TDE values. The mean value of 0.40 ppm reported in 1975, with 17 of 18 eggs containing TDE, was higher than the 0.16 ppm and 0.07 ppm means found in 1977 and 1978, respectively. The incidence of TDE had also dropped dramatically in 1978 (Table I). A slight decrease was also apparent in the 1978 common merganser eggs with regard to DDE, PCBs, DDT, and TDE when compared to 1975 values {27). The 1978 dieldrin values j.v= 1.7 ppm) were higher than those found in 1975 (.v = 0.64 ppm). Other organochlorine residues were found at low levels in merganser eggs collected during 1977 and 1978. Mirex and endrin residues decreased from 1975 values 92 Pesticides Monitoring Journal TABLE 1. Organochlohne. PBB, and PCS residues in the eggs of waterfowl nesting on three Lake Michigan islands off the tip, of Door County, Wisconsin, J 977-78 Hepta- chlor toxa. PCB' DDE DDT TDE DiELDRiN Epoxide phene HCB MlREX Endrin OXY CIS NON- TRANS- CIS- CHLOR- ACHLUR NONA- Chlor- DANE CHLOR DANE PCS PBB RED-BREASTED MERGANSER, 1977 (114)- 20,0' 4,9-229' 114' 7.4 2.4-28 114 0.36 0.09-1.7 114 0.14 ND-0.71 97 0.78 0.25-2.3 114 0.20 0.14 0.06 0.05 0.05 ND-0.88 ND-0.89 ND-0-3 NE>-0.25 ND-0.05 109 57 24 12 3 0,30 ND-0.84 III 0.11 ND-0.41 79 0.22 ND-0.73 103 0.08 ND-0.28 46 NA 0.06 ND-0.13 109 RED-BREASTED MERGANSER. 1978 {<, 12) 19.0 6.6-36 92 7.6 2.3-16 92 0.31 ND-0.61 91 0.06' ND-0,33 19 0.76 0.20-1.9 92 0.22 0.27' 0.05 0.05 0.03 ND-0.55 ND-0.64 ND-0.2 ND-0.4 ND-0.08 91 88 11 7 28 0.41" ND-0.9 91 0.14 ND-0.31 86 0.33» 0.15' 0.04 ND-0.67 ND-0.28 ND-0.80 90 87 29 NA COMMON MERGANSER. 1978 (2) 40.0 33^8 2 190 19-20 2 0.18 0,1-0,34 0.07 ND-0.11 1 1.7 1.5-1.9 2 0.44 2 0.24 0.14 ND 0.20-0,28 ND-0.37 2 1 ND 0.76 0.73-0 80 2 0.44 1 1 2 0.96-1.5 2 0.22 2 0.08 ND-0.25 1 NA MALLARD. 1977 (22) 2.0 ND-10 18 0.89 ND-3.6 21 0.06 ND-0.27 4 ND 0.06 ND-0.18 2 ND 0,05 ND ND ND-0,12 2 ND 0.05 ND-0.09 1 ND 0.05 ND-0.13 3 ND NA ND MALLARD. 1978 (5) 1.1 0.25^.9 5 1.0 0.28-4.2 5 ND ND 0.13 ND-0 53 3 ND ND ND ND ND ND ND 0.06 ND-0.13 1 ND ND NA GADWALL. 1977 |4> 1.1 0.35 0,78-2.2 0.13-0.55 4 5 ND ND ND ND ND ND ND ND ND ND ND ND NA ND GADWALL. 1978 |5) 1.3 0,73-2.5 5 0.80 0.45-1.4 5 ND ND 0.24 ND-0.56 4 ND 0.06 ND ND ND-0.10 1 ND ND ND 0.06 ND-0.09 1 ND ND NA BLACK DUCK. 1977 (3) 2.2 0.71-6.7 3 0.77 0.21-2.5 3 ND ND ND ND ND ND ND ND ND ND ND ND NA ND NOTE; NA = no analyses performed for that substance; ND = No residue of quantifiable leveL Levels over which quantification was possible were 0 1 ppm for all chemicals e.xceptendnn.O 05 ppm( 1977). 0 02 ppm ( 1978). PCB = 0,50 ppm; PCS = 0 05 ppm. PBB = 0,02 ppm Samples with no detectable residues were calculated in the means as one-half the quantification level, ' PCB as Aroclor 1260. ^ Number in parentheses = total number of eggs analyzed. ' Geometric mean, ppm wet weight. ■* Range. ' Number of total samples analyzed which contained residues of reportable level. ' Significantly different from residues in the eggs of the same species. 1977. Mann-Whitney U-test, P < 0.01. ' Significantly different from residues in the eggs of the same species. 1977, Mann-Whitney U-test, P < 0.025. " Significantly different from residues in the eggs of the same species, 1977, Mann-Whitney U-test, P < 0.005. (27, Table 1). In fact, mirex was detected in only 12 and 7 eggs collected from red-breasted merganser nests in 1977 and 1978, respectively, and endrin in only 3 and 28 eggs, respectively. Levels of toxaphene, oxychlordane, trans-nonacMor , and c/i-chlordane in- creased slightly, but significantly, from 1977 to 1978. PBBs were detected in 109 of the 114 red-breasted merganser eggs analyzed in 1977. and PCSs were detected in 29 of the 92 red-breasted merganser eggs analyzed in 1978 and in one of the two common merganser eggs. (Table 1). The residues were extremely low Metals — Mercury was detected in all merganser eggs in 1977 and 1978 (Table 2). The arithmetic mean in both years for red-breasted merganser eggs was 0.55 ppm Hg, which is similar to the 0.56-ppm Hg levels found during 1975. The mean value of Hg in common merganser eggs did not differ significantly in 1975 (0.56 ppm Hg) and 1978 (0.58 ppm). Arsenic and Vol. 15, No. 2, September 1981 93 TABLE 2. Metol residues in the eggs of waterfowl nesting on three Lake Michigan islands off Door County, Wisconsin, 1977-78 Species AND Year RESIDIj'ES. PPM Wet Weight Hg As Se Cr Pb Cu Zn CD Red-breasted merganser 1977 052' 0.24-1 3- (113113)' 0.060 0040-0.083 (5/5) 0.74 060-0.82 (5/5) NA NA NA NA NA Red-breasted merganser 1978 0.51 0.26-1.3 (92/92) 0.060 ND-O.U (1/7) 0.61 0.47-1.0 (7/7) 0.12 ND-0.24 (6/7) 0,93 0.53-1.4 (7/7) 0.75 0.54-1.0 (7/7) 15 12-20 (7/7) ND Common merganser 1978 0.58 0.46-0.73 (2/2) NA NA NA NA NA NA NA Mallard 1977 0.08 0.07-0.39 (22/22) 0.013 ND-0.022 (3/5) 0.54 0 28-0.81 (5/5) NA NA NA NA NA Mallard 1978 0.08 0.05-0.17 (5/5) NA NA NA NA NA NA NA Gadwall 1977 0.07 0.04-0.13 (4/4) NA NA NA NA NA NA NA Gadwall 1978 0.04 0.03-0.12 (5/5) NA NA NA NA NA NA NA Black duck 1977 0.12 0 06-0.19 (3/3) NA NA NA NA NA NA NA NOTE: NA = not analyzed; ND = None detected above the level of quantification. Any egg containing less than this level of residue was averaged into the mean using one-half the lower limit of detection. ' Geometric mean ■ Range ' (Number of samples that contained quantifiable levels of residue/number of eggs analyzed). selenium residues in merganser eggs were generally low (Table 2) and did not change from 1977 to 1978. Chromium, lead, copper, and zinc were detected in 1978 in the seven eggs analyzed; geometric means were 0.12, 0.93, 0.75, and 15 ppm, respectively. Cadmium was not detected at quantifiable levels. Banded Hens — Six red-breasted merganser hens, cap- tured and banded on their nests in 1977, were recaptured on their nests in 1978. The residues of six of the major contaminants in the eggs collected from these nests are listed in Table 3. As was the case with other nests checked, the only significant change between 1977 and 1978 was the TDE residues; both the amount and incidence of TDE had decreased. Levels of Hg were slightly, but not significantly, higher in the eggs from the nests of banded hens; otherwise, residues were comparable. DABBLING DUCKS Organochlorines — Generally, organochlorine residues were much lower in dabbling duck than in merganser eggs (Table 1). DDE and PCBs were the only organochlorines found in the majority of dabbling duck eggs. Geometric means of DDE for the 2 years ranged from 0.35 ppm in 1977 gadwall eggs to 1.0 ppm in 1978 mallard eggs. Geometric means for PCBs in dabbling duck eggs ranged from 1.1 ppm in 1977 gadwall and 1978 mallard eggs to 2.2 ppm PCBs in 1977 black duck eggs. Other organochlorines — DDT, dieldrin, toxaphene, oxychlordane, rrawi-nonachlor — were detected at very low levels in a few eggs. PCSs and PBBs were not present in any of the eggs analyzed. Metals — Mercury residues were also lower in dabbling duck eggs than in merganser eggs (Table 2). Geometric means ranged from 0.04 ppm Hg in 1978 gadwall eggs to 0.12 ppm Hg in 1977 black duck eggs. Arsenic and. selenium were measured in 1977 mallard eggs, and thei geometric means were 0.013 ppm As and 0.54 ppm Se, wet weight. Three of five eggs contained As; all five eggs contained Se. EGGSHELL THICKNESS Mean eggshell thickness for 92 randomly collected! red-breasted merganser eggs of less than 9 days incubation was 0.359 mm in 1977. In 1978, the mean thickness for 87 eggshells was 0.355 mm. This is a 2.2% and 3.3% decrease from pre- 1946 values, respectively (Table 4). but a 14%-15% increase in thei shell thickness over those measured in 1969 (6) and 1975 {27). The same pattern is reflected in common 94 Pesticides Monitoring Journal., TABLE 3. Organochlorine and mercury residues in randomly sampled eggs from clutches of ihe same six red-breasted mergansers in Door County. Wisconsin. 1977-78' Residues ppMWtT Weight Year DDE PCB TDE DDT DlELDRlN Hg 1977 1978 7 5 ± 1.92' 6' 7.9 + 1.14 6 19 ± 4.3 6 20 ± 1.0 6 0 10 ± 0 012 5 0.06 ± 0.008 1 0,28 ± 0.048 6 0.32 i 0.066 6 0.67 ± 0 113 6 0.85 ± 0.145 6 0.62 ± 0.080 6 0.70 ± 0.130 6 ' The same six nests were sampled both years. ■ Mean ± standard error. ' Number of samples that contained quantifiable levels of a residue. Those under that level were assigned a value of one-half the detection limit. merganser eggshells. The 0.414-mm mean found in 1978 eggs was only 3.2% lower than the pre-DDT reports, whereas the 1975 values were 23.5% thinner. Mallard eggshell thickness from the study averaged 0.331 mm in 1977 and 0.337 mm in 1978. Although authors could locate no measurements of mallard eggshell thickness from the pre-DDT era for compari- son with these values, they are comparable to those of black duck eggs from the Atlantic Flyway collected before the use of DDT and in 1978 (12). The decrease in DDE over the sampling years, rather than any change in residue levels of other organochlor- ines or metals, is most likely responsible for the improvement in eggshell thickness in both species of mergansers. DDE has been implicated in both field (3, 6. 10) and laboratory studies (11, 20) as the primary cause of avian eggshell thinning. And again in this study, DDE was correlated with eggshell thickness in the red-breasted mergansers (Figure 2, r = 0.029). The slope of the relation was significantly different from zero (P<0.02). The correlation was weak, but signi- ficant, as was the correlation of several other organoch- lorines (oxychlordane, trans-nonacMor. hexachloroben- zene) to eggshell thickness. Because of the additional significant correlations, authors cannot show statistical- ly that decreasing residues of DDE were alone responsible for improved eggshell thickness in 1977 and 1978. We do, however, feel that the evidence points to DDE, and that other organochlorines are correlated with eggshell thickness because all the major chlorinated hydrocarbons react similarly in biological systems and their residues are therefore correlated with each other (Table 5). The only major residue which is not correlated to the others is Hg. DDE residues were correlated to this metal in the 1978 sample. Other organochlorines show no such correlation. POTENTIAL BIOLOGICAL EFFECTS The relationship of contaminants and reproductive success of red-breasted mergansers will be thoroughly discussed in a manuscript now in preparation, but some general observations on the effects of contaminants on waterfowl are discussed below. PCBs were the most abundant contaminant found in red-breasted merganser eggs. The levels detected were below levels found to have no effect on hatchability and survival of young in pen studies with mallards. This is true of studies where both natural (5) and artificial (13) incubation were used. Comparable levels in the egg were associated with embryo mortality in ring doves (Streptopelia risoria) (22) and decreased growth in young chickens (Callus domesticus) (15). 0 40 _ 0 39 I 0 38 S 0 37 i 0 36 ^ 0 35 ^ 0 34 ^0 33 1.0 O 0 32 O uj 0 31 0 30 \ • . • J •:• • •• 1.09(101 D°E (PP"!) FIGURE 2. Correlation of DDE residues (log. ppm wet weight) with eggshell thickness of red-breasted merganser eggs collected in 1977 and 1978 on islands in northern Lake Michigan. TABLE 4. Shell thickness in eggs of waterfowl nesting on islands in northern Lake Michigan' Shell Thickness, mm Year Red-breasted Merganser Common Merganser Mallard Pre-1946 0.367 ± 0.001=' (8/105)" 1975 0.302 ± 0.004='' (18/178) 1977 0.359 ± 0.002' (92/92) 1978 0.355 ± 0.002' (87/87) 0.426 ± 0.011=' — ' (3/33) 0.314 ± 0.006* — (2/16) — 0.331 ± 0.008 (6/6) 0.414 ± 0.003' 0 337 ± 0.025 (2/2) (4/4) Mean ± standard error of the mean of all eggs measured; means with different letters are statistically different, Student's Mest. P < 0.01. •' Data are from White and Cromanie (1977). ^ No data are available. ' (Number of clutches represented/number of eggs measured). Vol. 15, No. 2, September 1981 95 TABLE 5. Correlation of five organochlorines and mercury in the eggs of red-breasted mergansers. Door Coi ' x-m ID. packed v.ilh 80-100-mesh Gas-Chroni Q coated with a nii.xture ol 1 .S% OV-17 and 1,95<7, OV-210 by weight Temperatures. ^C: injector 200 detector 200 column 180 Carrier gas: lOLAR-I grade nitrogen purified by bemg passed through silica gel and a molecular sieve to remove moisture and oxygen, respectively: pressure, 65 psi; flowing at 40 ml/min Residue peaks were confirmed by thin-layer chroma- tography (TLC), using reference standards obtained from PolyScience Corp., Niles, Illinois. Recoveries of isomers and metabolites of DDT and BHC ranged from 70% to 89% from the fortified samples of liver, brain, muscles, and body fat. Sensitivity of the method was 0.001 ppm for isomers of BHC, aldrin. and p.p'-DDE. and 0.002 ppm for p.p'-TDE and p.p'-DDT. Results and Discussion Widespread application of pesticides and spillage during their transportation or storage are the main sources of environmental contamination. Domestic animals and poultry have little chance for contact with industrial chemicals. However, their feed has been found to be a major source of DDT and BHC (14). and domestic food animals and poultry are a major source of pesticide contamination of the human body. DDT and BHC residues found in goats, buffalo, and chickens are presented in Tables 1, 2, and 3, respectively. Table 4 shows the relative accumulation of pesticide residues in chicken leg and breast muscles. 2BHC. lindane (7-BHC), p.p'-DDE. p.p'-TDE. o.p'- DDT, and p.p'-DDT were determined in the present study. Results are expressed on a whole-tissue, wet- weight basis and are not corrected for recovery. GOATS All goat tissues contained DDT residues except o.p'-DDJ which was not detected in bone marrow, body fat. or liver tissues. Average levels of XDDT in specific tissues were 0.577 ppm in bone marrow, 0. 193 ppm in body fat, 0.053 ppm in liver, 0.019 ppm in brain, and 0.020 ppm in muscle. Generally, among DDT residues, p.p'-DDE was found in the greatest quantity. Average BHC and lindane levels were 0.536 ppm and 0.134 ppm in body fat and 0.203 ppm and 0.063 ppm in bone marrow samples, respectively. BHC residue levels were lowest in muscle tissue, but higher in brain than in liver tissues. BUFFALO DDT residues were detected generally in all buffalo tissues. o.p'-DDJ was detected only in muscle tissues. Of the DDT residues. p.p'-TDE residues were highest and were detected in all body tissues. The average levels of SDDT in specific tissues were: 3.009 ppm in bone marrow. 1.043 ppm in body fat. TABLE 1 . Residue levels of BHC and DDT in some body tissues of goals. Lucknow. India TlSSLE Residues, ppm Wet Weight Lindane BHC fP-DDE F p -TDE 0 f DDT pp-DDT iDDT 0,003-0 007 0 010-0 034 0 001-0 003 0 002-0 005 ND-0 011 0,002-fl 039 0 OOS-0 (H5 0,005 1 0 001 0 01810 002 0002±0001 0 002 ±0 001 0006±000l 0 008±0 00l 0020±0003 (24) (24) (24) 124) (22) 124) (241 0,008-0,018 0,033-0 115 0 002-0 008 0 00,1-0 013 ND-0,a03 ND-0015 0,013-0,027 0,010±0,001 0 068 ±0 007 0 004±0 001 0 005 ±0 001 0 001 ±0,001 0 007 ±0,001 0019±0,001 (14) 114) (141 (14) (3) (13) 114) 0,006-0,014 0 020-0 067 0,002-0 115 0,004-0,039 0 003 ND-0 015 0,009-0 190 0.009±OOOI 0 032 ± 0 002 0 028±0 0Ol 0 01,1 ±0,002 _ 0 007±0 00l 0 053 ±0011 (18) 118) (181 tl8l (11 (17) (18) 0,054-0 347 0 146-1 522 0 017-0 467 0 006-0 420 ND 0 006-0 097 0039-1 014 0,1 34 ±0,024 0,536±0 100 0 093 ±0,029 0 056 ±0 026 ND 0 027 ±0 006 0 193±006l (16) (16) (16) 1I6) (16) (161 0.036-0.123 0,114-0 470 0,093-1,806 0,025-0 294 ND 0 023-0,476 0 169-2 816 0.063*0.013 0 203 ±0 044 0 358 ±0 207 0 065 ±0 032 0 106 ±0 055 0 577 ±0 320 (81 18) (8) (8) 181 18) Muscle (24) Range Meani SE Tissue^ with residues Brain ( 14) Range Mean±SE Tissues wilh residues Liver ( 18) Range Mean ± SE Tissues with residues Body fat (16) Range Mean ± SE Tissues with residues Bone marrow (81 Range Mean :t SE Tissues with residues NOTE Number in tirsi column indicates number of samples analyzed. SE = standard error. ND = noi detected 104 Pesticides Monitoring Journal TABLE 2. Residue levels of BHC and DDT in some body tissues of buffalo. Lucknow, India Residues, ppm Wet Weight Tissue Lindane BHC f p-DDE CP-TDE OP DDT pp. DDT SDDT 0.00 m), 015 0,004±0.001 (22) 0.006-0,029 0.012±0.002 (22) 0 001-0.011 0.005*0.001 (22) 0,002-0 (MS 0 011 ±0 001 (22j 0,002-0.008 0 003 ±0001 (22) 0.002-0.023 0.006 ±0.002 (22) 0.011-0.081 0.028 ±0.006 (22) 00O7-O0I6 0,012»0,001 (16) 0.024-0.117 0.076 ±0.006 (161 0.009-0.071 0 047 ±0.004 (16) 0,009-0,054 0.038 ±0,003 (16) NO 0.007-0.078 0.044 ±0.004 (16) 0.027-0.211 0.1 38 ±0.01 2 (161 0 005-0 022 o.oi2±aooi (17) 0020-0 090 0.038 ±0.004 (17) 0 011-0 478 0.074 ±0.027 (17) 0,024-0 285 0094±0,019 (171 ND 0.002-0.107 0.018±O.0O7 (17) 0.043-0 635 0.205 ±0.045 (17) 0.011-0.209 0.058±0.011 (17) 0.039-0,485 0.165 ±0.027 (17) 0.036-0.587 0.284±0.O41 (17) 0,049-1,414 0,490 ±0.086 (17) ND 0.021-0.920 0.1 83 ±0.055 (17) 0.116-3.143 1.043+0.181 (17) 0 041-0,198 0 121 ±0033 (51 0.123-0.366 0.252±0.52 (5) 0.135-1.544 0.773 ±0.246 (5) 0,165-2,605 1,289±0,446 (5) ND 0.019-1.718 0.720±0.351 (5) 0.337-5.038 3.009 ±0.985 (5) Muscle (22) Range Mean ± SE Tissues with residues Brain (16) Range MeaniSE Tissues with residues Liver (17) Range Mean ± SE Tissues with residues Body fat (17) Range Mean ± SE Tissues with residues Bone marrow (5) Range Mean ± SE Tissues with residues NOTE: See note. Table I TABLE 3. Residue levels of BHC and DDT in some body tissues of chickens, Lucknow . India Residues, ppm Wet Weight Tissue Lindane BHC p,p-DDE P.P-TDE o.pDDT p.p-DDT IDDT 0.002-0 037 0.014-0.243 0007-0,251 0.002-0 021 0.002-0. 107 0.010-0 .166 0.017 ±0.003 0.109 ±0.024 0 090 ±0,024 0 007 ±0 002 ND 0.030 ±0.0 10 0 138 ±0.030 (10) (10) (10) (10) (10) (101 0.012-0.051 0,108-0,230 0 009-0,052 0,002-0.505 ND-0.024 ND-0.022 0.022-0.121 0.027 ±0 002 0 162 ±0,007 0 022 ±0,003 0 038 ±0.002 0.005 ±0 001 0.011 ±0 002 0.082 ±0.006 (19) (19) (19) (19) (10) (16) (19) 0004-0.091 0,040-0,445 0039-0,537 0.047-0.447 ND-0.130 ND-0 130 0,134-1 447 0.049 ±0 004 0 195±0018 0,253 ±0,025 0 170 ±0.023 0.040±0.013 0.025±0006 0,535 ±0 068 (20) (20) (20) (201 (18) (18) (20) 0.284-^ 150 0,819-14,104 0095-10,939 0.043-6 372 ND ND-3.200 0,480-20,832 1.217±0 188 3 879 ±0 580 2 377±0,586 0.778±0306 0.644±0301 4,157±1 027 (221 (22) (22) (22) (20) (22) Muscle (lOi Range Mean i SE Tissues with residues Brain (19) Range Mean ± SE Tissues with residues Liver (20) Range Mean ± SE Tissues with residues Body fat (22) Range Mean±SE Tissues with residues NOTE: See note. Table I TABLE 4. Relative accumulation of BHC and DDT residues in chicken leg and breast muscle, Lucknow, India Residues, ppm Wet Weight Lindane BHC p p -DDE p.p TDE ppDDT I DDT 0.036 0.243 0.251 0.016 0068 0,366 0.018 0.132 0 117 0 005 0.019 0,154 0.037 0.216 0.170 0.021 0,107 0.326 0.019 0 177 0 062 0004 0,011 0.084 0.007 0.034 0.063 0.008 0031 0 110 0002 0 014 0018 0003 0,008 0031 Chicken A Leg Breast Chicken B Leg Breast Chicken C Leg Breast 0.205 ppm in liver, 0. 138 ppm in brain, and 0.028 ppm in muscle. BHC levels were 0.252, 0.165. 0.038, 0.076, and 0.012 ppm in the respective tissues. Relatively high levels of lindane which accounted for about half of the total BHC residues were detected in bone marrow samples. Mean values of lindane were comparable in liver and brain samples. CHICKENS DDT residues as high as 20.832 ppm DDT, 10.939 ppm p.p'-UDE, 6.372 ppm p.p'-TDE, and 3.2 ppm /7,p'-DDT were detected in chicken body fat. SDDT averages in specific tissues were 4. 157 ppm in body fat, 0.535 ppm in liver, 0.138 ppm in muscle, and 0.082 ppm in brain. All chicken body tissues contained p.p'-DDE and p.p'-TD¥. residues, p.p' -DDE accounted for most of the DDT residues except in brain samples, where p,p'-TDE was highest. cp'-DDJ was not detected in muscle and body fat samples. BHC residues were also detected in all chicken tissues. Average levels were comparable to S^DDT levels in the Vol. 15, No. 2, September 1981 105 body fat, brain, and muscles. In chicken body fat samples, total BHC varied from 0.819 to 14.104 ppm and lindane varied from 0.284 to 4.15 ppm. The accumulation of organochlorine pesticide residues (Table 4) was always higher in leg muscle than in breast muscle. Conclusion Accumulation of persistent organochlorine pesticide residues in the body and their //; vitro biotransformation varies from species to species. Various environmental factors and dietary habits of individual species are also involved in bioaccumulation and biodegradation of the residues. Buffalo brain contained highest DDT residues in brain, although overall DDT contamination was highest in chickens. DDT concentration was always higher in goat and buffalo bone marrow than in body fat. In general, p.p'-DDE was the major metabolite found in biological tissues, hut p.p'-TDE was the major metabolite in buffalo body tissues and accounted for nearly 40%^50% of SDDT. The levels of p.p'-TDE were also higher than p.p'-DDE levels in chicken brain tissue. The accumulation of residues was always higher in leg muscle than in the breast muscle of chickens. DDT levels were found in the following order of increasing concentration: goat'7f and related compounds 5% PCB, approximately 42^ chlorine PCS. approximately 46% chlorine PCB. approximately 60% chlorine 1 ,2.3.4,5,6-HexachlorocycIohexane (mixture o\ isomers) Technical: 60% octachloro-4.7-methanotetrahydroindane and 40% related compounds Dichiorodiphenyldichloroethylene (degradation product ot DDT) l-ChIoro-2.2-bis(/7-chlorophenyl) ethylene Dichloro diphenyl tnchloroethane. Pnncipal isomer present ip.p'-DDT. not less than 70%^); 1 .1.I-trichloro-2.2-bis(;J- ch!o^ophenyl )ethane I.l-Bis(chlorophenyl)-2.2.2-trichloroethanol Hexachloroepoxyoctahydro-eHf/p.t'AY'-dimeihanonaphihalene 85% and related compounds 15% Hexachloroepoxyoctahydro-ffft/^'.cnt/o-dimethantinaphthalene Hexachlorobenzene 1 .4.5,6.7.8,8-Heptachloro-2.3-epoxy-3a.4.7.7a-tetrahydro-4.7-methanoindan Gamma isomer of benzene hexachloride (BHC) Dodecachlorooctahydro-1 ,3,4-metheno-IW-cyclobuta[cd|pentatene l.2.3.4.5.6,7.8.8-Nonachloro-3a.4.7.7a-telrahydro-4.7-methanomdan l-e.vo-2-eWo-4.5.6.7.8.8a-Octachloro2.3-('A('-epoxy-2.3.3a.4.7,7a-hexahydro-4.7-methanomdene Mixtures of brominaled bipheny! compounds having various percentages of bromine Mixtures ot chlormated biphenyi compounds having various percentages of chlorme Mixtures of chlormated styrenes havmg various percentages ot chlorme Dichloro diphenyl dichloroethane ( 1 .l-dichloro-2.2-bis(/j-chlorophenyl)ethane. principal component) Technical chlorinated camphene (67-69% chlorine) Vol. 15, No. 2, September 1981 107 The 34th International Symposium on Crop Protection will take place on May 4, 1982, at the Faculty of Agricultural Sciences. State University, Gent, Belgium. The proceedings of the symposium will be published in Meded. Fac. Landhuuwwet . Ryksuniv. Summaries of the papers will be made available in English to participants. All correspondence should be sent to: Secretary, Faculteit Van de Landbouwwetenschappen Coupure Links 533 B-9000, Gent, Belgie The Rocky Mountain Center for Occupational and Environmental Health at the University of Utah announces the availability of "Industrial Hygiene Chemistry (NIOSH 590)," at the University of Utah. Salt Lake City, on November 16-20, 1981. The tuition is $500. For further information: RMCOEH Ms. K. Blosch University of Utah, Bldg. 1 12 Salt Lake City, UT 84112 (801) 581-5710 108 Pesticides Monitoring Journai The Administrator of the U.S. Environmental Protection Agency has determined that the publication of this periodical is necessary in the transaction of public business required by law of this Agency. 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United States Postage and Environmental Protection Fees paid Agency Environmental Wastilngton DC 20460 Protection TS-793 Agency EPA 335 Official Business Third-Class Penalty for Private Use $300 Bulk Rate If you do not desire to continue receiving this publication, please CHECK here □; cut ofT this label and return it to the above address Your name will be removed from Ihe mailing list. 1 747a FREE UBRART ofPhnadelphUi NOV 9 198^ PESTICIDES MONITORING JOURNAL ¥ DECEMBER 1981 VOLUME 15 NUMBER 3 PEMJAA (15) 111-146 (1981) .i ■rK/49./.^/^ CONTENTS Volume 15 December 1981 Number 3 FISH, WILDLIFE, AND ESTUARIES Page Factors Influencing Dieldrin and DDT Residues in Carp from the Des Moines River, Iowa, 1977-80 ^ 111 Wayne H. Hubert and Edward D. Ricci Influence of a New Impoundment on Pesticide Concentrations in Warmwater Fish, Saylorville Reservoir, Des Moines River, Iowa, 1977-78 117 Siu-Yin Theresa Leung, Ross V. Bulkley, and John J. Richard Polychlorinated Bipheiiyls in Clams and Oysters from New Bedford Harbor, Massa- chusetts. March 1978 123 Walter I. Hatch, Donald W. Allen, Phillips D. Brady, Alan C. Davis, and John W. Farrington Nationwide Residues of Organochtorine Compounds in Wings of Adult Mallards aiui Black Ducks. 1979-80 128 Brian W. Cain HUMANS Organochlorine Pesticide Residues in Human Milk Samples from Comarca Lagunera, Mexico, 1976 135 L. Albert, P. Vega, and A. Portales WATER I.2-Dihromo-3-chloropropane Residues in Water in South Carolina, 1979-80 139 George E. Carter, Jr., and Melissa B. Riley APPENDIX 143 ERRATUM 144 Information for Contributors 145 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. The Pesticides Monitoring Journal is published by the Management Support Division in the Office of Toxic Substances, 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 mtended 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 Allan R. Isensee, Science and Education Administration — Agricultural Research Herman R. Feltz, Geological Survey Address correspondence to; PaulFuschini (TS-793) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, DC. 20460 Editor Roberta B. Maltese FISH, WILDLIFE, AND ESTUARIES Factors Influencing Dieldiin and DDT Residues in Carp from the Des Moines River, Iowa, 1977-80^ Wayne H. Hubert and Edward D. Ricci" ABSTRACT Concentrations of dieldrin and DDT in muscle tissue and fat of carp, Cyprinus carpio, from the Des Moines River, Iowa, differed significantly with month of collection, fish age, and sampling location. Pesticide levels expressed on the basis of wet weight of flesh often differed from those ex- pressed on a fat basis. Fish from reservoirs tended to have higher levels of dieldrin, but not of DDT, than did fish from riverine locations. Introduction Interpretation of data from organochlorine pesticide residue monitoring programs for freshwater fish is diffi- cult because numerous factors influence sample vari- ability. Identification of the factors that contribute to sample variability would improve the reliability of mon- itoring programs. Authors assessed the influence of selected variables in concentrations of aldrin and DDT in carp (Cyprinus carpio) from a midwest river, the Des Moines. Aldrin and DDT were extensively used to control in- sects on midwestern cropland for many years. About 3 million kg of aldrin was applied to Iowa cropland in the mid-1960"s to control corn rootworm and cutworm (16), The U.S. Environmental Protection Agency can- celed registration of aldrin in 1975, and its use was discontinued in 1978. The pesticide DDT was used pri- marily to control European cornborer, Dutch elm dis- • Journal Paper No. J-10204 of the Iowa Agriculture and Home Eco- nomics Experiment Station, Ames, lA. Project No. 2465. Financed by a grant from the U.S. Department of Defense, Army Corps of Engi- neers, and made available through the Engineering Research Institute, Iowa State University, to the Iowa Cooperative Fishery Research Unit. 2 Iowa Cooperative Fishery Research Unit, Iowa State University, Ames, lA 50011. The Unit is jointly supported by Iowa State Univer- sity, the Iowa State Conservation Commission, and the Fish and Wildlife Service, U.S. Department of the Interior. ease, and mosquitoes during the I950's and 1960's; it use was banned in 1970. Both aldrin and DDT convert to persistent forms in nature, dieldrin and DDE or TDE, respectively. These compounds have long half-lives under field conditions — 8-10 years for dieldrin and 10-20 years for DDE (13, 15) — and tend to be strongly adsorbed to soil particles (7, 14). Because of these factors and the widespread use of these compounds on cropland, mid- western waters continue to be contaminated through soil erosion. Chlorinated hydrocarbons, being hydro- phobic, lipophilic chemicals, are absorbed from water into the fat of fish. The Des Moines River is the largest stream within Iowa. More than 80% of its drainage is cultivated, and the major source of contamination of the river is non- point agricultural runoff (9). Two reservoirs have been constructed on the river for flood control, water quality control, and recreational purposes. Red Rock Dam, completed in 1969, impounds 4,200 ha of water at nor- mal pool level. Saylorville Dam, completed in 1977, impounds 2,200 ha at normal pool level. A pesticide monitoring program was established on the Des Moines River in 1977, and several fish species were assessed for organochlorine pesticide residues from 1977 to 1979 (2, 3, 12). The cost of monitoring several species led to consideration of limiting analysis to a single sentinel species. Carp were selected because they are abundant and easy to collect in both the river and reservoirs. The objectives of the present paper are to compare wet weight of flesh- and fat-based units of measure for dieldrin and 2DDT residues in carp; to assess the influence of sampling month, fish age, and sampling location in the river on residue concentrations; and to evaluate trends in dieldrin and 5DDT residue concen- trations in Des Moines River carp from 1977 to 1980. Vol. 15, No. 3, December 1981 111 Methods Sampling stations were established at two impounded and two riverine locations on the Des Moines River (Figure I): Red Rock Reservoir; the river 80 km up- Vlcinity Map Sampling locations marked with X FIGURE 1, Sampling stations for carp on the Dcs Moines Rivi'r, Iowa. stream from Red Rock Reservoir at Des Moines; Saylorville Reservoir; and the river 80 km upstream from Saylorville Dam at Boone. Carp were collected from each location by electrofishing and hoop netting. Five samples were made up from each sampling loca- tion in June and in September. Each sample consisted of equal weights of lateral muscle from 10 fish of the same age. Fish ages were determined by standard scale- reading techniques (11 ); only 2- to 4-year-old fish were used. Fat content of individual samples was deter- mined by the modified Babcock method (7). Lateral muscle tissue samples were analyzed for di- eldrin, p.p'-DDT. /J.p'-TDE, and p,p'-DDE by the meth- ods described in the Pesticide Analytical Manual [8). Tissue samples were ground in a 35% water-acetoni- trile solution with a high-speed blender for 10 minutes. The sample was filtered, the filtrate was transferred to a 1-liter separatory funnel, 100 ml petroleum ether was added, and the mixture was shaken briefly. Then, 600 ml distilled water and 10 ml saturated saline solution were added and mixed by tumbling for 1 minute. After the layers had separated, the aqueous fraction was dis- carded. The solvent layer was washed with distilled water and filtered through a 50-cm anhydrous sodium sulfate column. The sample volume was recorded, and the extract was subjected to the standard Florisil clean- up procedure (8). A Tracor 550 gas chromatograph equipped with a "^Ni electron-capture detector was used for gas chromato- graphic analysis. A 4% SE-30/6% SP-2401 column was used for separating and quantifying the pesticides. Detected values were corrected for 80% extraction efficiency. Statistical procedures included the Student's /-test and the Pearson Product Movement Correlation Coefficient. All decisions to reject null hypotheses were at P < 0.10, because sources of variability were being sought. Results FAT IN CARP MUSCLE Fat content of carp muscle ranged from 0.8% to 3.3% (Table 1). Between June and September, fat content of TABLE 1. Fat content of carp muscle used for pesticide analysis from the Des Moines River, Iowa, 1980 Carp ACE. Years Percent Fat Month of Collection Red Rock Reservoir River at Des Moines Saylor- ville Reservoir River at Boone June 3 1.5 1.8 2.3 1.8 1.9 2.2 1.4 1.6 1.6 1.8 1.9 2.3 4 1.7 1.9 2.2 3.3 1.4 1.8 2.4 (Mean) (1.8) (2.3) (1.6) (2.0) Sept. 2 1.4 1.1 1.6 2.0 1.8 2.4 0.8 l.I 3 1.9 2.6 1.3 1.4 1.7 2.5 1.2 1.6 4 1.7 1.8 2.2 1.6 ( Mean) (1.7) (1.6) (2.1) (1.3) fish decreased significantly at the two riverine sites, Des Moines (0.10 > P > 0.05) and Boone (0.01 > P > 0.001), increased significantly in Saylorville Reservoir fish (0.3 > P > 0.01 ), and did not change significantly in Red Rock Reservoir fish. Fat content differed signifi- cantly between fish samples from Saylorville Reservoir and those from the river at Boone in both June and September. Fat levels were higher in river fish in June (0.02 > P > O.OI ) and in reservoir fish in September (0.01 > P > 0.001). These demonstrated variations in fat content indicated the need to consider this variable in the pesticide residue analyses. dieldrin In 1980. concentrations of dieldrin ranged from 10 to 128 ug/kg of flesh and from 630 to 5,790 |.tg/kg of fat (Table 2). Mean levels of dieldrin in flesh and in fat i declined between June and September at the four sam-j pling locations. The differences in mean levels were ' statistically significant at Red Rock Reservoir (0.10 > P > 0.05), the river at Des Moines (0.10 > P > 0.05), Pesticides Monitoring Journal TABLE 2. Dieldrin residues in muscle of carp from the Des Moines River, Iowa, 1980 Carp AOE, - Years Residues iug/kg Red Rock Reservoir River at Des Moines Saylorville Reservoir River AT Boone Collection Flesh ' Fat Flesh i Fat Flesh i Fat Flesh i Fat June 3 83 73 63 4,580 3,150 4,170 30 55 33 1,360 3,060 1,710 33 51 54 56 2,850 2,030 3,840 3,520 41 41 50 2,170 1,790 2,780 4 75 110 4,410 5,790 55 128 3,860 2,500 34 2,410 48 66 2,760 2,640 (Mean) (81) (4,420) (60) (2,500) (46) (2,930) (49) (2,430) Sept. 2 34 53 3,070 3,750 11 15 630 750 29 43 1,600 1,770 16 21 2,030 1,930 3 58 59 3,090 2,210 10 41 770 2,950 36 45 1,450 2,650 15 24 1,250 1,480 4 84 4,930 23 1,250 30 1,360 36 2,270 (Mean) (58) (3,410) (20) (1,270) (37) (1.770) (22) (1,790) 1 Wet-weight basis. and the river at Boone (0.01 > P > 0.001) when ex- pressed on a wet-weight flesh basis. On a fat basis, the differences were statistically significant in the river at Des Moines (0.10 > P > 0.05), the Saylorville Reser- voir (0.05 > P > 0.02), and the river at Boone (0.05 >P> 0.02). Statistically significant variation in mean dieldrin level related to fish age was noted in June (0.10 > P > 0.05) but not in September, when wet-weight flesh was used as the analytical basis. No statistically significant variation due to age was observed in either June or September on a fat basis. Trends in mean concentrations of dieldrin in carp muscle at the four sampling locations from 1977 to 1980 are illustrated in Figure 2. The 1977-79 samples were collected and analyzed in the same manner as described for 1980 samples. Size ranges of the fish indi- cate that the 1977-79 samples were predominantly com- posed of 2- and 3-year-old fish. Fish from the im- pounded sites tended to have higher levels of dieldrin than did those from the riverine sites (Figure 2). Sub- stantial variation in dieldrin levels between sampling periods occurred at all locations, but the magnitude of the fluctuations was greatest in the reservoirs. Differences in mean levels of dieldrin in carp samples occurred between some sampling locations. In June, no significant differences occurred between the reservoirs and their associated riverine stations when concentra- tions were expressed on a flesh basis, but a significantly higher level was observed in Red Rock Reservoir fish compared with fish from the river at Des Moines (0.02 > P > 0.01) on a fat basis. In September, di- eldrin concentrations in fish were significantly higher at both Red Rock and Saylorville reservoirs than at the upstream locations (0,01 > P > 0.001 and 0.05 > P > 0.02, respectively) on a flesh basis, but a signifi- cant difference was observed only between Red Rock Reservoir and the river at Des Moines on a fat basis. Levels of dieldrin were significantly higher in samples from Red Rock Reservoir than in those from Saylor- ville Reservoir in June (0.01 > P > 0.001 for flesh, 0.05 > P >> 0.02 for fat) and in September (0.05 > P > 0.02 for flesh, 0.02 > P > 0.01 for fat). No sig- nificant differences were observed between riverine locations. • — — • River a\ Boone owa •-- — • Saylorwille Reset voir a — — o River at Des Mo nes low a 0-- --C Red RocV Reser\ oir / J. I / 1 \ / . ' / / \ / \ s / ' \ \ If 1 \\ / ■ / \ 1 \\ / ^ 200 Q. Q. 13 175 t/l ™ 150 -- 125 c i 100 I 75 o c o 5 25 C 5 0 Oct Apr July Oct Apr July Oct June Sept 1977 1978 1978 1978 1979 1979 1979 1980 1980 FIGURE 2. Variation in dieldrin residues in flesh of carp from four sampling locations on the Des Moines River, Iowa, 1977-SO. Data for 1977-79 taken from Baumann et at. (2, 3). Vol. 15, No. 3, December 1981 113 TOTAL DDT The concentration of :iDDT (DDT, TDE, and DDE) in carp muscle ranged from 18 to 191 [^ig/kg of flesh and from 1,090 to 9,910 iig/kg of fat in 1980 samples (Table 3). In June, iDDT was composed of 54.8% DDE, 24.6% TDE, and 20.6% DDT in the average sample. Proportions were similar in September — 53.3% DDE, 27.9% TDE, and 18.8%- DDT. 2DDT levels in fish samples declined from June to September. The difference was statistically significant on a flesh basis at all sampling locations: Red Rock Reser- voir (0.02 > P > 0.01), the river at Des Moines (0.05 > P > 0.02), Saylorville Reservoir (0.10 > P > 0.05) and the river at Boone (0.01 > P > 0.001). The concentration of ^-DDT in the fat was significantly lower in September only in fish from the reservoirs: Red Rock (0.02 > F > 0.01) and Saylorville (0.05 > P > 0.02), The mean level of 5DDT was significantly higher in 4-year-old fish than in 3-year-old fish on both flesh (0.02 > P > 0.01) and fat (0.10 > P > 0.05) bases in June. No differences among samples of 2-, 3-, and 4-year-old fish were observed in September. Mean ^-DDT in carp varied significantly between some sampling locations. Concentrations were significantly higher in samples from Saylorville Reservoir than in samples from the upstream site near Boone in both June (0.10 > P > 0.05) and September (P > 0.001) on a flesh basis, but only in June on a fat basis (0.02 > P > 0.01 ). In September, mean level of 5DDT was significantly higher in fish from the river at Des Moines than in fish from Saylorville Reservoir on both flesh (0.10 > P > 0.05) and fat (0.01 > P > 0.001 ) bases. This was the only comparison made in which the mean level of pesticide residues was higher in samples from a riverine location than in samples from the associated downstream impoundment. Comparison of samples from the two reservoirs showed no significant differences in mean iDDT. However, statistically significant differences in mean iDDT oc- curred between fish from the two riverine sites in both June and September. Mean levels of 5DDT were sig- nificantly higher in both flesh (0.02 > P > 0.01 in June, 0.01 > P > 0.001 in September) and fat (0.01 > P > 0.001 in June, 0.01 > P > 0.001 in September) of fish sampled near Des Moines than in those collected at Boone. Mean 2DDT concentration in carp samples declined substantially between October 1977 and July 1978 at the two riverine locations (Figure 3). 5DDT levels in 250 a 225 a. i^ 200 s 2 175 m c 150 I 125 c S 100 75 50 25 Oct Apr July Oct Apr July Oct June Sept 1977 1978 1978 1978 1979 1979 1979 1980 1980 FIGURE 3. Vaiialion in total DDT residues in flesh of carp from four sampling locations on the Des Moines Ri^er, Iowa, 1977-SO. Data for 1977-79 taken from Baumann et al. (2, 3). TABLE 3. Total DDT (DDT, TDE, and DDE) residues in muscles of carp from the Des Moines River, Iowa, 1980 Carp Ace, Years Residues, ^g/kg Month of Collection Red Rock Reservoir River at Des Moines Saylorville Reservoir River at Boone Flesh Fat Flesh Fat Flesh Fat Flesh Fat June 3 55 125 76 4,240 5,490 2,670 83 88 88 3,980 4,860 4,340 96 74 46 85 4,720 2,820 5,270 6,020 35 50 55 2,890 2,170 1,560 4 149 130 7,650 7,830 191 159 4,810 8,690 185 9,910 28 55 1,830 1,290 (Mean) (107) (5,780) (122) (5,340) (97) (5,760) (45) (1,950) Sept. 2 31 20 2,230 1,820 51 79 3,200 3,940 40 53 2,920 1,670 28 21 2.500 2,660 3 41 44 2,170 1,680 43 50 3,270 3,570 53 54 2,150 3,090 23 18 1,880 1,090 4 56 3,310 91 5,070 43 1,930 29 1,800 (Mean) (38) (2,240) (63) (3,810) (49) (2,350) (24) (1,990) 114 Pesticides Monitoring Journal carp have fluctuated substantially at all locations since 1978, with no indication of significant differences in trends between impounded and riverine locations. Discussion The lipophilic nature of organochlorine pesticide resi- dues results in significant associations between fat con- tent and pesticide levels in fish (4. 5, 12). It has been suggested that the variance in organochlorine pesticide residue samples may be reduced by normalizing on a fat basis. Statistically significant variation in fat content of Des Moines River carp was observed between sam- pling months, ages of fish, and sampling location, indi- cating a need to consider the fat content in data analy- ses. However, normalization on a fat basis in Des Moines River carp samples did not reduce the vari- ability of the data. Comparisons of dieldrin and 2DDT concentrations between sampling months, fish ages, and sampling locations produced results that were different on fat and flesh bases in several instances. The mean levels of both dieldrin and SDDT in Des Moines River carp varied between sampling periods. A decline was observed between June and September 1980. Concentrations of dieldrin and 5DDT in carp from the Des Moines River fluctuated dramatically be- tween sampling periods from 1977 to 1979, but a spring-to-autumn decline did not consistently occur. During 1971-73, before the use of dieldrin was dis- continued, seasonal trends in dieldrin concentrations in Des Moines River channel catfish (Ictahinis punc'tatiis) were related to corn planting and aldrin application {10). Present patterns are more complicated and prob- ably relate to several factors, including water tempera- ture (and, consequently, metabolic rates of fish) before sampling (6), fat content of the fish (4, 5), extent of pesticide contamination in bottom sediments and on agricultural land within the watershed (17), tillage practices by farmers, and precipitation before sampling. The results indicate that evaluation of variations in organochlorine pesticide residues relative to sampling locations or time should be made on fish of the same age. The need to consider fish age was shown in June when levels of dieldrin and SDDT were significantly higher in 4-year-old than in 3 -year-old fish. Similar variation relative to age has been described in channel catfish from the Des Moines River {4, 5). The present study showed that impoundments within a river system may affect the data developed in a moni- toring project. Dieldrin in carp muscle tended to be higher in fish from reservoirs than from upstream riverine sites, but the same trend did not hold con- sistently for SDDT. Whole-body analyses of carp in 1977 and 1978 showed no difference in either dieldrin or 5DDT levels between Saylorville Reservoir and either upstream or downstream locations {12). Differ- ences in dieldrin and SDDT occurrence relative to the impoundments indicated that the dynamics of the two types of pesticide residues are different within reser- voirs. Differences also were noted between riverine and impounded locations. Concentrations of dieldrin and SDDT in 1980 carp samples from the Des Moines River were below Food and Drug Administration, U.S. Department of Health and Human Services, standards of 300 ppb dieldrin and 5 ppm DDT for food fish. Dieldrin in some samples of channel catfish fiesh from Des Moines River impound- ments in 1977 (6) and 1979 {3) exceeded those stan- dards, thereby indicating the need for monitoring as well as the need to define the relation between organo- chlorine pesticide residues in sentinel species, such as carp, and other fish species. Analysis of 1977-79 data (2, 3) from the Des Moines River showed a significant correlation {r = 0.51, 0.02 > P > 0.01) between mean levels of dieldrin in carp and channel catfish samples taken at the same time and location, but not between concentrations in carp and those in walleye (Stizostedion vitreum vitreum), or largemouth bass (Micropienis salmoides). From 1977 to 1979, the mean dieldrin level in channel catfish exceeded that of carp by 2.2 times in samples from Red Rock Reservoir and by 3.1 times in samples from Saylorville Reservoir; however, the factor varied sub- stantially between sampling dates. Leung (72) found a positive correlation (r = 0.56) between percentage fat of various species found in the Des Moines River and dieldrin levels in the flesh. She noted that channel catfish tended to have double the fat content and triple the dieldrin concentrations of carp, but observed no similar relations in SDDT concentrations. The extent of the relation between species and fat content pro- vides some basis for extrapolating dieldrin levels ob- served in carp to those in channel catfish, but not for SDDT or for other species. The relation between di- eldrin levels in carp and catfish would probably be strengthened if variables such as fish age, fat content, and capture location were controlled. A cknowledgments Authors thank John Richard, U.S. Department of En- ergy, for conducting the chemical analyses and review- ing the manuscript, and John Nickum, Jim Mayhew, and Gary Atchison for reviewing the manuscript. LITERATURE CITED (/) Association of Official Agricultural Chemists. 1965. Official Methods of Analysis, 10th Ed., Arlington, Va. p. 957. Vol. 15, No. 3, December 1981 115 (2) Baumann, E. R., C. A. Beckert, M. K. Butler, and D. M. Soballe. 1979. Water quality studies— EWQOS sampling Red Rock and Saylorville Reservoirs, Des Moines, Iowa. Engineering Research Institute, Iowa State University, Ames, Iowa. 364 pp. (i) Baumann, E. R., C. A. Beckert, M. K. Butler, and D. M. Soballe. 1980. Water quality studies— EWQOS sampling Red Rock and Saylorville Reservoirs, Des Moines River, Iowa. Engineering Research Institute, Iowa State University, Ames, Iowa. 484 pp. (4) Bulkley, R. V. 1978. Variations in DDT concentra- tion in muscle tissue of channel catfish, Ictalurus punctatus, from the Des Moines River, 1971. Pestic. Monit. J. Il(4):165-169. (5) Bulkley. R. V., R. L. Kellogg, and L. R. Shannon. 1976. Size-related factors associated with dieldrin con- centrations in muscle tissue of channel catfish, Ictalu- rus punctatus. Trans. Am. Fish. Soc. 105(2) ;301-307. (6) Bulkley, R. V., T. S. Leung, and J. Richard. 1978. Des Moines River pesticide monitoring. Proc. Seminar on the Water Quality in the Corps of Engineers' Reservoirs in Iowa. March 9, 1978. U.S. Army Corps of Engineers, Rock Island District, Rock Island, 111. 8 pp. (7) Eye, J. D. 1968. Aqueous transport of dieldrin resi- dues in soils. J. Water Pollut. Control Fed. 40 (8, Part 2) :3 16-332. (5) Food and Drug Administration. 1970. Pesticide Ana- lytical Manual, Vol. 1, Sec. 212.1. U.S. Department of Health and Human Services, Washington, D.C. (9) lon-a Department of Environmental Quality. 1976. Water quality management plan. Des Moines River basin. Des Moines, Iowa. (10) Kellogg, R. L., and R. V. Bulkley. 1976. Seasonal con- centrations of dieldrin in water, channel catfish, and catfish-food organisms, Des Moines River, Iowa — 1971-73. Pestic. Monit. J. 9(4) : 186-194. (//) Lagler, K. F. 1956. Freshwater Fishery Biology. Wm. C. Brown Co., Dubuque, Iowa. 421 pp. (12) Leung, S. T. 1979. The effect of impounding a river on the pesticide concentration in warmwater fish. Ph.D. dissertation, Iowa State University, Ames. 155 pp. (13) Mach, R. G., and E. A. Woolson. 1967. Persistence of chlorinated hydrocarbon insecticides in soils. Sci- ence 157(3791 ):924-927. (14) Pfisler, R. M., P. R. Dugan, and J. 1. Frea. 1969. Microparticulates: isolation from water and identifi- cation of associated chlorinated pesticides. Science 166(3907) :878-879. (15) Schnoor, J. L. 1979. Pesticide trends in Iowa rivers. Proc. Seminar on the Water Quality in the Corps of Engineers' Reservoirs in Iowa. March 21. 1979. U.S. Army Corps of Engineers, Rock Island District, Rock Island, 111. (16) Schnoor, J. L. 1980. Fate and transport of dieldrin in Iowa rivers: residues in fish and water following a pesticide ban. Proc. Seminar on the Water Quality in the Corps of Engineers' Reservoirs in Iowa. March 27, 1980. U.S. Army Corps of Engineers, Rock Island District, Rock Island, 111. (17) Weber, J. B. 1972. Interaction of organic pesticides with particu'ate matter in aquatic and soil systems. Pages 55-120 in R.F. Gould, Ed. Fate of Organic Pesticides in the Aquatic Environment. American Chemical Society, Washington, D.C. 116 Pesticides Monitoring Journai Influence of a New Impoundment on Pesticide Concentrations in Warmwater Fish, Saylorville Reservoir, Des Moines River, Iowa, 1977-78^ Siu-Yin Theresa Leung," Ross V. Bulkley,' and John J. Richard ' ABSTRACT Samples of seven species of warmwater fish were collected above, within, and below newly impounded Saylorville Res- ervoir, Des Moines River, Iowa, from October 1977 to October 1978. Whole-body analyses by gas chromatography were significantly higher in river carpsiicker (Carpiodes cyanazine and for the organochlorine insecticides dieldrin, p,p'-DDE, p,p'-TDE, p,p'-DDT, and heptachlor epoxide. Only the organochlorine insecticides were detected in fish tissue. Concentrations of dieldrin and heptachlor epoxide were significantly higher in river carpsucker (Carpiodes carpio) from the reservoir than in those from the river. Other species of fish showed no differences in pesticide concentration related to locality of collection. Introduction The construction of a reservoir on a river increases the complexity of pesticide dynamics in the aquatic system. Impoundments for flood control, water supplies, energy development, recreation, and other purposes are be- coming increasingly numerous in the United States. During 1977-78, a study was conducted on Saylorville Reservoir, a new impoundment on the Des Moines River up stream from Des Moines, Iowa, to determine the rate of pesticide deposition in the reservoir and the effect of impoundment on pesticide accumulation in different species of fish. The discussion here addresses pesticide accumulation in the fish. Elsewhere, Leung (6) reported on seasonal pesticide fluctuations and pesticide deposition in the reservoir. The Des Moines River rises in the glacial moraine area of southwestern Minnesota and flows southeasterly across Iowa to join the Mississippi (Figure 1). It is the largest river in Iowa. About 79% of the watershed up- stream from Des Moines is cropland, primarily corn ' This study was conducted as part of Project 2225 of the Iowa Agri- culture and Home Economics Experiment Station. Ames, Iowa, in ::ooperation with the Iowa Cooperative Fishery Research Unit, which is jointly sponsored by the Iowa State Conservation Commission, Iowa State LIniversity, and the Fish and Wildlife Service, U.S. Department jf the nterior. •Minnesota Pollution Control Agency, Roseville, MN 55113 ' Utah Cooperative Fishery Research Unit, Logan, UT 84322 Iowa Slate University, Ames, lA 50011 FIGURE 1. Upper Des Moines River watershed, showing sampling sites. and soybeans; 6% is permanent pasture, 5% is forest, and 7% is urban (4). Normal annual precipitation over the drainage area ranges from 62.5 to 77.5 cm from north to south and averages 70.7 cm (S). Precipitation is usually heaviest in June, but heavy rainfall and cloud- bursts occasionally cause high river flows in summer and early fall. The major source of contamination of the river is agricultural runoff. Three collection stations were set up for this study: Station 1 at Boone, Iowa, is about 73 km upstream from Saylorville Dam; Station 2 is located in Saylor- ville Reservoir; and Station 3 is located at the town of Saylorville, about 3 km downstream from Saylorville Dam. Drainage areas at the three points, upstream to downstream, are 14,530, 15,081, and 15,128 km-, re- spectively. Gates on the Saylorville Reservoir were closed in April 1977. During the study period, the reservoir remained Vol. 15, No. 3, December 1981 117 within 1.2 m of conservation pool level, and average water retention time was about 40 days (1). Volume at conservation pool level was about 90 million m-'. Materials and Methods Fish samples were collected quarterly at Stations 1, 2, and 3 from October 1977 to October 1978, with gill nets, hoop nets, and electroshockers. Species analyzed for pesticide residues were gizzard shad (Dorosoma cepedianum), river carpsucker (Carpiodes carpio), com- mon carp {Cyprimis carpio), channel catfish (Ictaluriis punctatus), white crappie (Pomoxis annularis), large- mouth bass (Micropterus salmoides), and walleye (Sti- zostedion vitreum). Specimens were grouped by collec- tion date, location, species, and body length. An at- tempt was made to collect small specimens and to avoid large, old fish of each species. Small fish were selected on the assumption that most of their life occurred after impoundment, and that they would be less likely than old fish to have migrated between sampling stations. With few exceptions, all fish selected for sampling were subadult, and many were young-of-the-year. Mean total lengths ranged from 137 mm for gizzard shad to 232 mm for walleyes (Table 1). Fish in the same group were ground together in a hand grinder and then mixed manually in an effort to obtain a homogeneous mixture. Subsamples were then wrapped in aluminum foil and frozen until analysis. Because preliminary analyses indicated that atrazine, alachlor, cyanazine. dieldrin, p.p'-DDE, p.p'-TDE, p.p'-DDT, and heptachlor epoxide were present in water or fish, these substances were selected for study. Con- centrations of pesticides in water are listed in Table 2. TABLE 2. Mean weekly dissolved pesticide concentrations (ng/liter) at eacli Des Moines River station where fish were collected, September 1977 to November 1978 ' Station Chemical 1 Mean Atrazine 225 (<10-1356) 221 (0-1167) Alachlor 115 (0-1450) 80 (0-1125) Cyanazine 71 (0-500) 90 (0-6601 Dieldrin 3 (0-14) 3 ( SOUND ^,ibVj'/ilJt ^ W 7i'jo' 7rio' 71* 7crW FIGURE 1. Sites along Buzzards Bay for the sampling of shellfish contaminated with PCBs. ANALYTICAL METHODS PCBs were quantitatively determined in pooled tissue homogenates. All chromatographic reagents, glassware, and equipment contacting the samples were copiously rinsed with reagent grade, redistilled solvents (Fisher Scientific Co.), in the following sequence: methanol, acetone, toluene, and hexane. The shucked clams including mantle cavity water were homogenized (Polytron R. Kinematica GmbH), lyo- philized, and extracted three times with hexane — one 50-ml portion and two 25-ml portions. The extracts were filtered through a column of powdered sodium sulfate (NaoSOj) to remove residual water and particu- lates and then concentrated to 1 ml for column chromatographic cleanup. The cleanup columns were packed with 10 g of 200-mesh alumina and 8 g of 60-200-mesh silica gel, both deactivated 5% with water. The columns were first eluted with 15 ml hexane. PCBs were then collected in a 50-ml hexane-toluene (80 + 20) elution and quantitatively concentrated for gas-liquid chromatographic (GLC) analysis. GLC in- strument parameters and operating conditions were as follows: Chromatograph: Detector: Column: Temperatures: Pulse interval: Carrier gas: Detector purge: Chart speed: Hewlett-Packard, 7620A •'■^Ni electron-capture glass, 6-ft long by 2-mm ID, packed with a mixture of 1.5% OV-17 and !.95% QF-1 on 100-200-mesh Chromosorb W(AW) injection port 225°C oven, isothermal 190°C detector 300°C 50 mseconds a mixture of 95% argon and 5% methane flow- ing at 20 ml/min 40 ml/min 0.5 inches/min | PCBs were quantitated by comparing the summation of eight individual peak areas with a separately injected Aroclor 1254 or 1242 standard. The limit of detection, 124 Pesticides Monitoring Journal based on (he studies of shellfish by Goldberg et al. (6), was 0.001 ppm dry weight. Recovery of PCBs from samples spiked with Aroclor 1254 before extraction was 80% -90% or better. PCBs were confirmed by glass capillary gas chromatographic/ mass spectrometric (GCMS) analyses at the Woods Hole Oceanographic Institution Laboratory using a Finnigan Model 1015 SL system modified for glass capillary GC. Results PCBs reported as Aroclor 1254 were detected in all samples, ranging from 4.19 ppm dry weight in sam- ples collected adjacent to the harbor down to 0.232 ppm in samples collected approximately 3 nautical miles from the harbor (Table 1 ) . Samples from Westport TABLE L Aroclor 1254 concentrations in Mercenaria mercenaria and Crassostrea virginica, 1978 Av. CONCN Corrected for 80% Extn AV. CONCN Av. CONCN Efficiency, X 10-e g/g X 10-« E/g X 10-« g/g Sampling Site Dry Wt ■ Wet Wt Dry Wt Mercenaria i mercenaria 1 4.19 0.524 5.24 2 1.36 0.170 1.70 3 1.75 0.218 2.19 4 0.443 0.055 0.553 5 1.54 0.192 1.92 6 1.42 0.177 1.77 7 0.290 0.036 0.362 8 0.625 0.078 0.781 9 0.537 0.067 0.671 10 0.232 0.029 0.290 11 1.04 0.130 1.30 12 0.879 O.IIO 1.10 13 0.008 0.001 0.010 Crassostrea virginica 14 0.560 0.070 0.700 15 2.57 0.321 3.21 16 2.28 0.284 2.84 17 1.47 0.184 1.84 1 Samples were analyzed at Southeastern Massachusetts University Laboratories. Harbor, Massachusetts (Site 13), containing 0.008 ppm PCB were considered indicative of background con- centrations. Examination of the data suggests a gradient of decreas- ing concentration from point-source contamination sim- ilar in pattern to that reported from the upper Hudson River (/). The lower concentrations found in protected coves and estuaries indicate minimal PCB input from urban runoff. The Commonwealth of Massachusetts has prohibited commercial fishing north of a line drawn from Ricket- son's Point, Dartmouth (41°34'38"N; 70°56'19"W), to Black Rock, Fairhaven (41°34'41"N; 70°51'45"W). Sampling sites south of this closed fishing area, how- ever, showed PCB concentrations comparable to those within the restricted area. High PCB concentrations at Sites 6 and 8 may be due to transport paralleling the mass flow of water in Buzzards Bay (14). The ele- vated PCB concentration of Site 1 1 may be due to tidal flushing along the major shipping channel away from the harbor. A few samples were analyzed in more detail in the Woods Hole Oceanographic Institution Laboratory. These analyses showed that the PCBs were composed of a mixture of components similar to Aroclor 1242 or 1016 and 1254. In addition, authors analyzed a sample of scallops {Aeqiiipecten irradians Lamarck) from Cleveland Ledge Light (Figure 1 ) supplied by the Falmouth, Massachusetts, shellfish warden. The data from these analyses are presented in Table 2. TABLE 2. Mixture of Aroclors 1242 and 1254 in selected samples from New Bedford Harbor and Buzzards Bay, Massachusetts, 1978 Residues x 10-« g/g Dry Wt i Site Organism 1242 1254 1.46 0.20 0.185 3 Mercenaria mercenaria 1.59 10 Mercenaria mercenaria 0.22 Cleveland Ledge Aeqiiipecien irradians 0.093 ' Samples were analyzed at Woods Hole Oceanographic Institute. Discussion In compliance with the U.S. Toxic Substance Control Act, the manufacturing facilities abutting New Bed- ford Harbor have severely curtailed the discharge of PCBs into harbor waters. AH PCB use was, in fact, suspended as of September 1978 (Private Communica- tions: Anonymous. 1978. Aerovox Inc. spokesperson; Robinson, W. 1978. Cornell Dubilier, Inc., spokes- person, both of New Bedford, Mass.). However, the discharge of large amounts of PCBs over the last 38 years, coupled with the affinity of PCBs for sediments (8), has resulted in severely contaminated sediments in this area. The literature reveals little data for PCBs in sediments from this area. Harvey and Steinhauer (9) reported 8.4 x 10"« g PCB/g dry weight in outer New Bedford Harbor sediment samples in 1973. Gilbert et al. (,5), reported values of 0.175- 0.543 X 10-6 g/g dry weight for concentrations of PCBs in surface sediments from eight stations in Buz- zards Bay outside New Bedford Harbor. deLappe and Risebrough (i) analyzed mussels (Mytilus ediilis L.) from inner New Bedford Harbor and re- VoL. 15, No. 3, December 1981 125 ported a phenomenally high concentration of 110 x 10"^ g PCB/g dry weight. They also analyzed water from the area and found concentrations up to 580 x 10"'-' g PCB/ liter of dissolved and particulates combined. Critical questions of the size of the reservoir of PCBs in the sediments of the harbor and the extent to which they are a source for contamination of other areas of Buzzards Bay remain and are being pursued. Samples of shellfish, bottom fish, and sediments from the New Bedford Harbor area were analyzed in 1976 and 1977 for PCBs. Concentration ranged as follows; 0.5-620 X 10 " g PCBs/dry weight sediments; up to 11.7 X 10'' g PCBs/g wet weight of lobster {Hoinarus americanus Milne-Edwards) edible tissue; and up to 20.0 X 10"6 g PCBs/g wet weight black back flounder (Pseudopleuronectes americanus, Walbaum) edible tis- sue (unpublished data: Commonwealth of Massachu- setts, Department of Environmental Quality Engineer- ing, 1976-77). These data led to the closure of the New Bedford Harbor area as previously noted. Summerhayes et al. (14) and Stoffers et al. (72) in- vestigated trace metal contamination of New Bedford Harbor sediments. They found up to 1% Cu in sur- face sediments in the inner harbor and concluded that the harbor area was slowly leaking trace metal-contam- inated sediments to nearby Buzzards Bay. Processes active in movement of trace metal-contaminated sedi- ments are likely to be active in the movement of PCBs in the same sediments. Thus, even though PCB discharges by industry have been curtailed, harbor sediments contain high concen- trations of PCBs and can act as a source of PCB con- tamination of the harbor for some time to come. Young et al. {16) clearly demonstrated that PCB-contaminated sediments can be a source of PCB contamination for shellfish. Rhoads (11) showed that tidal influences in Buzzards Bay result in resuspension of surface sedi- ments in some areas with the resulting probability of transport to other areas of the bay. Disturbance of the sediments in New Bedford Harbor by natural events such as tidal movement or storms or by man-induced activities such as dredging will probably result in con- tamination of other Buzzards Bay areas. This may be the reason PCBs were detected in the bay sediments by Gilbert et al. (5) and in scallops at Cleveland Ledge Light in the present study. However, PCBs are so ubiquitous in coastal regions near indus- trialized areas that authors cannot be certain at present of the origin of the low concentrations of PCBs at Cleveland Ledge Light and Buzzards Bay surface sedi- ments. Data on PCBs in New Bedford Harbor are sufficient to identify this area as one of high PCB concentration in both sediments and biota. However, the exact mag- nitude of the problem has not yet been investigated. The few higher-resolution measurements available to us at this time indicate that there is a substantial con- centration of the di, tri- and tetrachlorobiphenyls in the area compared with the amounts of penta- and hexachlorobiphenyls usually found in environmental samples. This indicates a proximity of the samples analyzed to source of input via efl^luents. The di- and trichlorobiphenyls are more reactive than the penta- and hexachlorobiphenyls and, as distance and time between input and measurement increase, there is a greater probability that the less-chlorinated biphenyls will undergo reaction (15). The electrical component manufacturers in New Bedford used primarily Aroclor 1242 and 1016 mixtures. Thus, the input of the less- chlorinated analogs is expected. The New Bedford Harbor and Buzzards Bay ecosystems provide a sys- tem to study the biogeochemistry of the various PCB isomers and authors are currently pursuing this investi- gation. Our data on the PCBs in oysters from the Slocum River estuary (Table 1 ) may suggest a second problem with PCBs in the greater New Bedford area. PCB con- centrations in C. virginica from the Slocum River es- tuary are in excess of those in M. mercenaria collected off the river mouth. It is possible that lateral transport of contaminated sediments from the New Bedford Harbor area to a point upstream in the adjacent Slocum River would exceed transport to a point off the mouth of the river. This is unlikely but cannot be ascertained because of lack of knowledge about sediment transport in the area. A second possibility is the release of PCBs from a landfill site to the aquifer feeding the Slocum River. It has been established that there are over 200,000 kg of PCBs buried in the New Bedford munici- pal landfill located on the aquifer feeding the Slocum River valley. A few preliminary measurements have shown that some PCBs are present in waters draining from the landfill (13). Extensive contamination of groundwaters was not found, based on a few measure- ments. However, time series measurements and mass flow calculations have not been made (13). This prob- lem merits more extensive study because the aquifer represents the primary source of drinking water for the town of Dartmouth, Massachusetts. Recent measurements of PCBs in the common blue mussel (Mytihts ediilis) and in oysters (Crassostrea virginica) collected around the coast of the United States have shown that the northeastern U.S. coastal area is more contaminated with PCBs on a regional 126 Pesticides Monitoring Journal basis than most other areas of the coast (6). The data and discussions presented here suggest that the New Bedford Harbor area should be considered along with the Hudson River and Chesapeake Bay as one of the sources of these regionally elevated concentrations. Acknowledgments Authors thank the officials and scientists of the Com- monwealth of Massachusetts, Office for Environmental Affairs, and its various departments for making avail- able unpublished file data and discussions. LITERATURE CITED (!) Berle, P. A. A. 1978. The Hudson River: A reclama- tion plan. 15 pp. New York State Department of En- vironmental Conservation, Albany, N.Y. (2) Courtney, W. A. M., and G. R. W. Denton. 1976. Persistence of polychlorinated biphenyls in the hard clam (Mercenaria mercenaria) and the effect upon the distribution of these pollutants in the estuarine en- vironment. Environ. Pollut. 10(l):55-64. (i) deLappe, B. W., and R. W. Risebrough. 1980. The sampling and measurement of hydrocarbons in natu- ral waters. Pages 29-68 in Hydrocarbons and Halo- genated Hydrocarbons in the Aquatic Environment. B. K. Afghan and D. Mackay (Eds.). Plenum Press, New York, N.Y. (4) Duke, T. W., J. I. Lowe, and A. J. Wilson, Jr. 1970. A polychlorinated biphenyl (1254) in the water, sedi- ment and biota of Escambia Bay, Florida, Bull. En- viron. Contam. Toxicol. 5( 1) : 171-180. (5) Gilbert, T., A. Clay, and A. Barker. 1973-74. A site selection and study of ecological effects of disposal of dredged materials in Buzzards Bay, Massachusetts. New England Aquarium Report to U.S. Army Corps of Engineers, New England Division, 70 pp. (6) Goldberg, E. D., V. T. Bowen, J. W. Farrington, G. Harvey, J. M. Martin, P. L. Parker, R. W. Rise- brough, W. Robertson, E. Schneider, and E. Gamble. 1978. The mussel watch. Environ, Conserv, 5(2): 101-105, (7) Hammond, P. B., I. C. T. Nisbet, and A. S. Sarofin. 1972. Polychlorinated biphenyls — environmental im- pact. Environ. Res. 5(1) :249-262. (5) Haque, R., D. Schmedding, and V. H. Freed. 1974. Aqueous solubility, adsorption and vapor behavior of polychlorinated biphenyl Aroclor 1254. Environ, Sci, Technol. 8(2) ; 139-142. (9) Harvey, G. R., and W. G. Steinhauer. 1976. Environ- mental Biogeochemistry, Vol. I, Chapter 15, Ann Arbor Science Publishers, Inc, Ann Arbor, Mich, (10) Jensen, S. 1966. Report of a new chemical hazard. New Sci. 32(512) :612-615. (//) Rhoads, D. C. 1974. Organism-sediment relations on the muddy sea floor. Oceanogr. Marine Biol. Rev. 12:263-300. (12) Staffers, P., C. Suminerhayes, U. Forslner, and S. R. Patchineclam. 1977. Copper and other heavy metal contamination in sediments from New Bedford Har- bor, Massachusetts: A preliminary note. Environ. Sci. Technol. 1 1 (9) :819-821. (13) Stralton, C. L., K. L. Tullle, and J. M. Allan. 1978. Final Task Report, Research Request No, 4, Contract No, 68-01-3248, U, S, Environmental Protection Agency, Washington, D.C, {14) Summerhayes, C. P., J. P. Ellis, P. Sloffer, S. Briggs, and M. G. Fitzgerald. 1977. Fine-grained sediment and industrial waste distribution and dispersal in New Bedford Harbor and western Buzzards Bay, Massa- chusetts, Tech, Rept, No, 76-115, Woods Hole Ocean- ographic Institution, Woods Hole, Mass. (15) U . S. Environmental Protection Agency. 1976. Criteria document for PCBs, Massachusetts Audubon Society, prepared by U.S. Department of Commerce, National Technical Information Service, PB-255-397, (16) Young, D. R., T. C. Heesen, and D. J. McDermolt. 1976. An offshore biomonitoring system for chlori- nated hydrocarbons. Marine Pollut. Bull. 7(8):156- 159. Vol. 15, No. 3, December 1981 127 Nationwide Residues of Organochlorine Compounds in Wings of Adult Mallards and Black Ducks, 1979-80 Brian W.Cain' ABSTRACT Organochlorine residues in wings of adult mallards (Anas platyrhynchos) and black ducks (Anas rubripes) were mon- itored nationwide from birds harvested during the 1979-80 hunting season. DDE residues were found in all samples. DDT residues had declined from levels reported in 1976 on a flyway basis but the decline was significant fP < 0.05} only in the Pacific Flyway. Levels of DDT, DDE, TDE, and dieldrin were low on a flyway basis, and all but DDE declined significantly fP < 0.05) in the percent occurrence. Polychlorinated hiphenyls (PCB) levels were lower in mal- lard wings from all flyways compared with 1976 data, but percent occurrence had significantly IP < 0.05) increased. Pools from Alabama and New Mexico continued to show higher DDE residues than pools from other areas. relation between DDT residues in the wing and those in breast skin, breast muscle, brain, kidney, liver, and other tissues from captive mallards and scaup ducks (1). This paper presents results from the mallard and black duck wings collected during the 1979-80 hunting sea- son and includes the mean residue levels for each state. The percentage of the pools from each flyway that con- tain a particular contaminant residue is presented and compared with the 1976-77 hunting season. The mean value of organochlorine residues in wings by major fly- ways is presented and compared with the 1976 col- lection. Introduction During the 1965-66 hunting season, the Fish and Wild- life Service, U.S. Department of the Interior, as part of the National Pesticide Monitoring Program (2), began to monitor organochlorine pesticides in duck wings collected by hunters. Justification for this method of collection was given by Johnson et al. (5). The black duck ranges over a large part of the Atlantic Flyway and the mallard is found throughout the rest of the contiguous 48 states. Thousands of wings collected each year by cooperating hunters are sent to collection sites in each of the four flyways. Waterfowl migrate twice a year within four major flyways that consist of states or parts of states in which the birds feed or rest for short periods of time. Millions of waterfowl spend the winter months in the southern portions of these fly- ways, and may be exposed to environmental contami- nants different from those found in northern nesting areas. Heath and Prouty (4) successfully tested the monitor- ing methodology in 1965 using mallard and black duck wings collected from New York and Pennsylvania. A later report showed there was a highly significant cor- Methods WING COLLECTIONS ' Fish and Wildlife Service, U.S. Department of the Interior, Patuxent Wildlife Research Center, Laurel, MD 20811 During the 1979-80 hunting season, cooperating water- fowl hunters mailed approximately 11,660 wings from adult mallards or black ducks to a regional collection point within each of the four flyways. Each wing was sent in a separate envelope that listed the date, county, and state where the bird was harvested. The wings were held in frozen storage until March or early April 1980 when biologists determined the sex and maturity of each bird. Only adult wings were used for the pesticide monitoring program to maintain the sampling consis- tency established by Heath and Hill (i). Wings from each state were sorted randomly into pools of 25 wings, and random samples of these pools were made by using a random numbers table. The number of pools taken was such that about 50% of the wings submitted from a state were selected for organochlorine analyses. Each pool of 25 wings was wrapped in aluminum foil, tagged with a coded number, frozen, and shipped to Raltech Scientific Services, Inc. (formerly WARF Institute, Inc.) in Madison, Wisconsin. There were 24 pools of black duck wings and 29 pools of mallard wings from the Atlantic Flyway, 64 pools of mallard wings from the Mississippi Flyway, 54 pools of mallard wings from the Central Flyway, and 44 pools of mallard wings from the Pacific Flyway. 128 Pesticides Monitoring Journal ANALYTICAL PROCEDURES Wings in eacli pool were trimmed by removing most of the feathers and the distal joint with a pair of scissors. Remaining portions were homogenized in a Hobart grinder, and approximately 10 g was removed, weighed, and placed in a preweighed 150-ml beaker. The beaker and sample were oven-dried 2 weeks at 40°C and reweighed, and the sample dry weight was recorded. Approximately 40 g homogenized sample was weighed into a 250-ml beaker and mixed with 100 g anhydrous sodium sulfate, placed overnight in a hood, and then transferred to a 43-mm by 123-mm prewashed What- man extraction thimble plugged with glass wool. The thimble was placed in a desiccator overnight and then extracted for 8 hours in a Soxhlet apparatus with a mixture of 150 ml each of ethyl ether and petroleum ether. This solution was then concentrated on a steam bath, and the residue was transferred to a 50-ml volu- metric flask and diluted to volume with a mixture of dichloromethane-cyclohexane (15 + 85). A 5-ml aliquot of the extract was placed in an Auto- Prep 1001 gel permeation chromatograph that had been standardized for chlorinated insecticides and PCB com- pounds. The column was glass, 600 mm by 25 mm, and packed with 60 g of 200-400-mesh Bio-Beads (SX-3). The solvent was dichloromethane-cyclohexane (15 + 85) at the flow rate of 5.5 ml/min. The resulting solu- tion was concentrated on a flash evaporator to approxi- mately 1 ml in the presence of 5 ml iso-octane and diluted to 25 ml with petroleum ether. A 10-ml aliquot of this gel permeation extract was placed in a 25-g silica-gel 60 column and three elutions were prepared. The first was eluted with 90 ml petroleum ether and contained hexachlorobenzene (HCB) and mirex; the second was eluted with 200 ml petroleum ether and contained PCB compounds and DDE; and the third was eluted with 150 ml of a mixture of acetonitrile-hexane- dichloromethane (1 + 19 -f 80) and contained the remaining chlorinated insecticides. Fraction three was concentrated on a flash evaporator to I ml and diluted to 10 ml with petroleum ether. Four microliters from each fraction was injected into a gas chromatograph equipped with an electron-capture detector. Instrument parameters and operating conditions ap- plied to all samples except where difTerences are noted: Column: 2 m by 4 mm Packings: (1) organochlorine pesticides and PCBs: a mix- ture of 1.95% OV-n and 1.5% QF-I on 100-200-mesh Supelcoport (2) chlordane isomers: 3% OV-1 on 80-100- mesh Gas-Chrom Q Temperatures, °C column 200 injector 250 detector 300 Carrier gases: a mixture of 95% argon and 5% methane Flow rates (1) 33 ml/min (2) 32 ml/min Lipids were determined by using a 5-ml aliquot of the Soxhlet extract in a preweighed 2-dram vial. The vial was placed in a 40°C oven for 3 days to remove the solvent and then reweighed, and the amount of the lipids was calculated. All residues are expressed as ppm wet weight and may be converted to an approximate dry or lipid weight by dividing by 0.60 or 0.14, the mean proportions of dry or lipid material in the samples, respectively. Mean residue values were calculated by using 0.00 as the value for samples in which no residue was reported at the 0.01 -ppm sensitivity level. The recovery percentages from spiked samples were DDE, 85; TDE, 125; di- eldrin, 98; heptachlor epoxide, 90; and Aroclor 1254, 118. Analytical results have not been corrected for re- covery. Residues in 5% of the pools were confirmed by mass spectrometry. The percentage occurrence of the organochlorines in wings from each flyway were compared with the 1976 collection data by using a test for two population pro- portions. Mean residue levels of DDE. DDT, TDE, dieldrin, and PCBs were compared on a flyway basis with the published 1976 data of White (8) by using only those samples with a detectable residue level. A /-test comparison was made on each data pair that had detectable residues in at least 50% of the pools col- lected. A P < 0.05 was necessary for significance for all statistical comparisons. Results and Discussion Residues of DDE, DDT, TDE, dieldrin, and PCBs in the duck wings from the 1979-80 hunting season are presented in Table I. These data, collected from 5,268 wings (215 pools), are presented as mean values for each state in a flyway and are arranged in a North to South direction. Data in Table 1 should not be inter- preted on a statewide basis alone because waterfowl migrate and may cover a wide area and range of habi- tats in many states. Samples from some localities (i.e., Alabama and New Mexico) continue to show higher residues of DDT and DDE than do samples from the other localities. This situation in Alabama was reported earlier (3, 7, 8), and a possible source of the contami- nation was described by O'Shea et al. (6). The highest DDE level, 3.28 ppm, was detected in a pool composed of wings from Arizona and New Mex- ico, and the lowest level of DDE residue, 0.02 ppm, occurred in pools from Florida and Kentucky. DDE residues occurred in all wing pools; however, DDT, TDE, and dieldrin were found in fewer pools in the 1979-80 wing collection than in the 1976-77 collection Vol. 15, No. 3, December 1981 129 m u h a a a Q a I I O C o "^^ o m tr. C O o — o rj rj d odd do d +1^+1 +1 +l^+l+l^+lr 1"^ I I I I — rJ "Tt r- d d d d . o — o o o o o c o ii+ig+ig+i +1 +1 +1 c: O d d -H r- w-1 ' D Z I I Q Z D a z z g 8S d do .09 + (2) 01 + 03 + c o o Q Z a z Q z +1 +1 ? T 1 (N — (-J — f , — D d d d> d d d d d d d d d d <6 (6 E 3 I * ' aj 1> « > Z 2 O J= >• s z a.Z 1^ n c c "■ ■S o ? ■§ ff !5 S <« ;; I-' u M - -5 •= ? DS > S z M O ? I I ? ? C O i O Ov o c 5 c! <: dodd_^°'^ rj — (N d ~ ^. "^ d d d d — o c U-l — o o o r~- o o o 0^0 d d do '^ ^ "^ '^' W-l — — Ov r) ■,00 ^ ;_; d d ci c d 0 d 1 g Q D Q 0 z z z z sS 8 d d d d d + rJ +1+ M + ? =f Q Z z — r- ^ C Q z z Q Z DO zz 1 1 1 "f 1 ^ ? 5 ? =i- 1 1 1 _ 0 d 1 r', 0 d Q Z 0 d a z D Z 0 D Q DD D Z Z Z ZZ Z 000 — c 0 0 c 0 0 0 0 0 q 0 0 d d d d d d d d d d +1 +1 +1 y^ +1+' 5+1 rs +' r; +1- +i- rJ rJ — rj "" rr. r^i n "" 0000 0 C 0 0 0 0 d d d d d d d d d d 1115 112 2 3 ^ O 1-1 O O ^c o c; rj d d d 8 d 8 8 g q . d d d d d d d d d d d d d d o o o ■fl +1 +1 +1^+1 +!+l^+l5+^5+g+l5+!5+l+'5+lg+l5+l «v _-..~.* ,^,1 ^ XT) ^m r- e-4 y-< — m q ddddddddd — * o m (S c (N m d d d d d d d ^ ^ (S ^ ^ z s — " o c -a c c » c £ w 002 Z ^ aj rt > Z Q S ^Z 130 Pesticides Monitoring Journal =f 9 ?■ — rj i 5 2 « J Tj- r< — ^ (N ■ +i;^ +l«+li^ +lm +lm +|C rJ — 3 ? 2 fS — r'. ;+i£+i5+i5+i£ CT- 00 -■ ^^ 1/1 ""^ n .u o J n S S S £ = o_-^oo — o — — — rJ fN *g- ", /-\ in Q w^ r^. rl ooqq^q^oqq ddddZdZodd +|Tf +|>c +lTf +|Tr +|v^ +|so +|^+|m +|i- +|t~ Q Z D Z +1- +lg+l§ Q Q D z z z Q z +trr+i::: 9 a z Q Z ?■ ?■ ?■ ? 1 ? a D Q Q a a z Z Z Z z z Q Q a D Z Z z Z +i„ +i?l+i; +1- +1; (N l-H +i^+i;^+i^+i^+!» +is+i;;r+ip;+iP+'P 2 s z Q » Z § — O o '^ o — ■ ■- + |oo +1^5- +|cc +1^ ? ? =f Q Q Q Z Z Z Q Z 0 0 0 0 0 0 d d d +li^+l - +tS ^ ^0 ""e Q Z +1:^ 2 2 a z Z z Q Z 0 0 0 d d d _ +l?^+l?r+IS 7 ? =f 00 r»-, ^ — — C +l» +15+1 » +IC Vol. 15, No. 3, December 1981 131 CQ u 0. H Q Q Q D +1 UJ o 5 c S 0. Q — *o ^ rJ r^ q o o o o Z d o d d o +[^+|vD +lr< +|N +|c^ +|r D Z o o o o S Q Z D D Z Z D a z z D z D Z Q Z Q Z r- — =r ■? t V-, \D -^ O O — O •— O O ■-; o d d o d d .-^ +1 r7 +; 3" +1 (N +' IN +1 (^ +1 r 132 Pesticides Monitoring Journal (Table 2). The highest level of dieldrin was 1.18 ppm in a pool from Alabama (Table I ) . PCBs were detected in all pools from the Atlantic Flyway and were found in at least 90% of the pools from the other three fly- ways (Table 2). This is a significant increase (P < 0.05) in the percentage occurrence of PCBs over that re- ported for the 1976-77 hunting season (Table 2). The highest residues of PCBs were 1.80 ppm in a pool of black duck wings from New York and 1.62 ppm in a pool of mallard wings from North Carolina. Three pools from the Pacific Flyway, two from the Central Flyway, and one from the Mississippi Flyway did not have PCB residues at the 0.01 -ppm limit of detection (Table 1). In addition to the organochlorine compounds listed in Table 1, heptachlor epoxide, chlordane isomers, and hexachlorobenzene (HCB) were found in duck wings, but less frequently. Residues of these three compounds seldom exceeded 0.1 ppm, so these data were not in- cluded in Table 1. The percentage occurrence of these three compounds and the percentage occurrence of mirex and endrin are presented in Table 2 and com- pared with the 1976-77 wing data. Hexachlorocyclo- hexane, lindane, and toxaphene residues were found in only three pools at the 0.01 -ppm level. Means of DDE, DDT, TDE, dieldrin, and PCBs in the 1976 and 1979 collections are presented by flyways in Table 3. To compare these residues with the data pre- TABLE 2. Comparison of ihe percent occurrence of organochlorine residues in duck wings by flywav for the two collection periods of 1976-77 and 1979-80 Year of Collection No. OF Pools Organochlorine Residues, ppm Wet Weight Species DDE DDT TDE Dieldrin PCBs Hepta- chlor Epoxide Mirex Endrin HCB Chlor- dane Isomers ATLANTIC FLYWAY Black duck Black duck Mallard Mallard 1976-1977= 1979-1980 1976-1977 1979-1980 32 24 20 29 100, s 100. 100, 100, 69, 38, 60. 52b 66. 84, 29, 58„ 50. 85. 17„ 62„ 100. 100, 100. 100. 34, 4, 50. 14,, 19, 13. 50. 3b 3. 0, 5. 3, 16, 21 „ 10. 3h 59. 58, 55. 48b MISSISSIPPI FLYWAY Mallard Mallard 1976-1977 1979-1980 69 64 100, 100, 87. 28b 38. 78, 61, 13b 64b 98b 45, 28b 29, 2b 4. 8b 7, 2b 22. 16, CENTRAL FLYWAY Mallard Mallard 1976-1977 1979-1980 56 54 100, 100, 79. 22b 45, 64. 13, 2b 22b 90b 48, 30b 14, Ob 2. 0. 9, 4b 14, 7b PACIFIC FLYWAY Mallard Mallard 1976-1977 1979-1980 50 44 100. 100, 92. 57b 58. 62, 14, 7b 39b 93b 32, 23b 4, 0, 0, 0. 24, 23. 14. 5b 1 Detection limit ^0.01 ppm. ^ Data taken from White (8). 3 1979-80 percent occurrence is significantly different (P<0.05) than 1976-77 percent occurrence where subscript letters (a or b) differ. TABLE 3. Means and standard errors of organochlorine residues in waterfowl wing pools by major flyway 1976 and 1979 Residues, ppm Wet Weight Species Flyway Year Pools DDE DDT TDE Dieldrin PCBs Black duck Atlantic 1976^ 32 1979 24 Mallard Atlantic 1976 20 1979 29 Mallard Mississippi 1976 69 1979 64 Mallard Central 1976 56 1979 54 Vlallard Pacific 1976 50 1979 44 0.39 -I- 0.07 (32) 0.32 ± 0.04 (24) 0.32 ± 0.07 (20) 0.27 ± 0.03 (291 0.25 ± 0.04 (69) 0.17 ± 0.03 (64) 0.28 + 0.17 (56) 0.10 ±0.02 (54) 0.22 ± 0.04 (50) 0.35 ± 0.08 (44) 0.06 -1- 0.01 0.03 H- 0.00 (22) (21) 0.02 -*- 0.00 0.04 + 0.03 (9) (7) 0.07 -1- 0.01 0.02 + 0.01 (12) (10) 0.02 -t- 0.0 1 0.01 + 0.00 (15) (5) 0.07 -1- 0.01 0,05 + 0.03 (60) (26) 0.05 + 0.01 0.05 -1- 0.02 (18) (8) 0.05 -t- 0.01 0.04 -1- 0.01 (44) (25) 0.03 -*- 0.01 0.02 ■+■ 0.00 (12) (1) 0.06 -t- 0.01 = 0.03 + 0.00 (46) (29) 0.02 + 0.01 0,02+0.01 (25) (3) 0.04 -^ 0.01 (27) 0.03 ± 0,01 (14) 0.06 + 0.03 (17) 0.05 ± 0.03 (18) 0.05 ± 0.01 (54) 0.05 ± 0.03 (41) 0.03 ± 0.01 (36) 0.02 ± 0.00 (12) 0.02 ± 0.00 (31) 0.02 ± 0.00 (17) 0.52 ± 0.08 (32) 0.63 -I- 0.09 (24) 0.52 ±0.18 (20) 0.45 ± 0.07 (29) 0.23 ± 0.03 (42) 0.11 ±0.02 (63) 0.15 ±0,01 (7) 0,06 ± 0.01 (49) 0.16 ±0.04 (7) 0.07 ± 0.02 (41) VOTE: Values in parentheses are actual number of pools containing residues; means were calculated using these values. Data taken from White (8). ■Significant difference (P < 0.05). v'OL. 15, No. 3, December 1981 133 sented from the 1976 collection (8), the author calcu- lated the mean values by using only the wing pools that contained the residues. A trend toward lower mean values for most of these residues in both the mallard and black duck wings was not significant (F > 0.05). The only significant decline (P < 0.05) was DDT residues in mallard wings from the Pacific Flyway (Table 3). Residues of DDT, TDE, and dieldrin were all low in the four flyways, and the percentage occur- rence of these contaminants has declined significantly (P < 0.05) since 1976. PCB residues were low in mal- lard wings from the Mississippi, Central, and Pacific Flyways, but their percentage occurrence increased sig- nificantly (P < 0.05) above the 1976 level (Table 2). Conclusions Mean values of DDE residues in mallard and black duck were not significantly (P > 0.05) lower than those reported for 1976 in all flyways. DDT, TDE, and dieldrin residues in duck wings have declined sig- nificantly (P < 0.05) in the percentage occurrence in all flyways. The decline of PCB residues in mallard wings from all flyways was not significant (P > 0.05). PCBs. however, occurred in a significantly (P < 0.05) larger percent of the 1979-80 pools than in the 1976 pools. A cknowledgnienls The author thanks the following people in the U.S. Fish and Wildlife Service for their help in the wing col- lections: Samuel M. Carney, Michael F. Sorensen, and Elwood M. Martin from the Office of Migratory Bird Management; Environmental Contaminant Evaluation Stall Specialist James B. Elder in Region 3: Eugene W. Hansmann in Region 6; and David J. Lenhart in Re- gion 1 . Biological aides Ellen PafTord and Lynn Palmer helped prepare the wings for shipment. Christine Bunck provided the statistical advice and computations, and Patty McDonald compiled the tables. E. H. Dustman and D. H. White reviewed the manuscript. LITERATURE CITED (/) Dimial. D. L., and T. J. Peterle. 1968. Wing and body tissue relationships of DDT and metabolite residues in mallard and lesser scaup ducks. Bull. Environ. Contam. Toxicol. 3(1 ):37-48. (2) Hcatli. R. G. 1969. Nationwide residues of organo- chlorine pesticides in wings of mallards and black ducks. Pestic. Monit. J. 3(2): 115^123. (.?) Healh. R. G ., ciiiJ S. A. Hill. 1974. Nationwide organo- chlorine and mercury residues in wings of adult mal- lards and black ducks during the 1969-70 hunling season. Pestic. Monit. J. 7(.^/4) : 153-164. {4) Heath. R. G., and R. M. Proiity. 1967. Trial monitor- ing of pesticides in wings of mallards and black ducks, Bull. Environ. Contam. Toxicol. 2(2): 101-110. (.5) Johnson. R. E.. T. C. Carver, and E. H. Dustman. 1967. Indicator species near top of food chain chosen for assessment of pesticide base levels in fish and wild- life— clams, oysters, and sediment in estuarine environ- ment. Pestic, Monit. I. 1(1) :7-13. (6) O'Shea. T. J.. IV. J. Flemin.i; III. and E. Cromartie. I9S(). DDT contamination at Wheeler National Wild- life Refuge. Science 209:509-510. (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. (T>0,005 ^'g/g exiractable lipids). ' Calculations based on samples with residues >0.01 fxi/i extractable lipids. = DDT - 1.115 DDE + 1.11 TDE. 136 Pesticides Monitoring Journal followed by p,p'-DDT and p-BHC. Total equivalent DDT ranged from 1.21 to 35.09 times the practical limit (1.25 ^ig/g, lipid basis) recommended by FAO/ WHO for DDT alone or combined with TDE and DDE in cows' milk (26); the mean concentration of p,p'-DDT was 1.98 ^ig/g, 1.58 times the FAO/ WHO limit. The concentrations of p,p'-DDE ranged from 1.08 to 28.81 times the limit. Therefore, concen- trations of DDT-derived compounds in all samples were higher than the FAO/ WHO practical limit. The mean concentration of (3-BHC (1.63 \ig/g) was equivalent to 8.15 times the limit of 0.2 |.(g/g recommended by FAO/WHO for the ^-isomer (lindane) in cows" milk (26). p-BHC was above this limit in all samples. The results of the present study and similar surveys in other countries are presented in Table 3. It is evident that the higher values for p.p'-DDE. p-BHC, and total equivalent DDT in human milk correspond to levels found in other developing countries such as Guatemala, Portugal, Argentina, and Chile. Several other studies (9, 19} have indicated that high concentrations of organochlorine residues in human milk may adversely affect neonates. Other investigators have shown the effects of the chronic ingestion of low levels of some pesticides are more severe in young and mal- nourished animals (6, 16). The finding of residues of the cyclodienic compounds dieldrin, heptachlor epoxide, and endrin in the human milks analyzed, although at low levels, is a matter of concern. These pesticides are being increasingly used in Mexico, even though their persistence and toxico- logical effects have caused their use to be severely re- stricted in other countries. Mother's milk is an important source of nutrition for infants in the region studied, especially in the low socio- economic groups in which malnourishment of mother and child is also frequent. In view of the high values obtained for organochlorine pesticide residues in human milk in the present study, further related research in this region and throughout Mexico is essential. Also noteworthy is the presence of hexachlorobenzene residue, which heretofore has only been reported in de- veloped countries (1. 17, 22, 23). The mean value (lipid basis) of p,p'-DDE calculated as DDT (11.81 ^ig/g) represented 89.60% of the aver- age total equivalent DDT. This could indicate that most of the DDT-derived material in the human milks analyzed originated in the food chain due to excessive past use of DDT in the region (5). In general, the organochlorine residue levels found in the present study of human milk would be unacceptable in cows' milk in other countries. A cknowledgments This work was carried out at the laboratory of Environ- mental Chemistry of the Department of Chemistry, CIEA-IPN, with instruments donated by the Organiza- tion of the American States. We thank V. W. Kadis from the Food Laboratory, Edmonton, Canada, and J. R. W. Miles from the London Research Station, Agriculture Canada, Ontario, Canada, for technical ad- vice; J. F. Thompson from U.S. EPA, Research Tri- angle Park, N.C., for providing the pesticide standards; M. E. Cabrian, of the School of Medicine, Torreon, for his interest and general help; and G. Massieu and J. E. Herz from CIEA-IPN for their continued support and encouragement. TABLE 3. Average concentrations of some organochlorine pesticide residues in human milk from various countries, 1965-79 Year Concentrations in Whole Milk, ^g/m! COUNTRY' /3-BHC p,P -DDE P.p'-DDT Total Equiv. DDT United States (27) 1965 0.08 0,12 Holland >.25) 1971 0.004 0.03 0.016 — Australia {23) 1975 — 0.080 0.015 Sweden {27) 1972 — 0.059 0.020 United States )14) 1977 0.003 0.035 0.008 — Canada (New Brunswick) (78) 1974 — 0.035 0.013 — Canada (77) 1979 0.002 0.035 0.006 __ New Guinea (Sepik) (7J| 1972 — 0.096 0.181 New Guinea (Saidorl (7.i) 1972 — 0.002 0.001 Portugal (Lisbon! {12) 1974 — 0.223 0.100 0.323 Portugal (Bragan<;al (72) 1974 — 0.040 0.023 0.063 Guatemala (La Bomba) {20) 1973 — 1.02 1.00 2.15 Guatemala (La Bomba! {20) 1976 — — — 0.587 Guatemala (Guatemala City) (?.') 1976 — — — 0.233 Argentina (70) 1974 0.042 0.092 0.046 0.140 Chile (24) 1978 — 0.15 0.092 0.25 Mexico (This Study) — 0.030 0.202 0.049 0.266 Vol. 15, No. 3, December 1981 137 LITERATURE CITED (/) Acker, L.. and E. Schulte. 1970. Uber das Vorkom- men von Chlorierten Biphenylen und Hexachlorbenzol (/^j neben Chlorierten Inzecticiden in Humanniilch und Menschlichem Fettgewebe. Naturwissenschaften 57 (10);497-498. {16) (2) Albeit. L„ F. Mendez, M. Cebridn. and A. Portales. 1980. Organochlorine pesticide residues in human adi- pose tissue in Mexico: Results of a preliminary study (//) in three Mexican cities. Arch. Environ. Health 35(5): 262-269. (J) Albert. L.. and R. Reyes. 1978. Plaguicidas Organo- chlorados II. Contaminacion de Algunos Que'os Mexicanos por Plaguicidas Organochlorados. Rev. Soc. ( IS) Quim. Mex. 22(2):65-72. (4) Albert. L.. R. Reyes, and S. Saval. 1975. Pesticide residue problems in Mexico. Rev. Soc. Quim. Mex. 19(5):216. (5) Bordas. E. 1973. El Empleo de los Insecticidas Agri- (/9) colas y la Contaminacion en el Ambiente Rural Mexi- cano. Memoria de la 1 Reunion Nacional sobre Problemas de Contaminacion Ambiental. 11:1111- {20) 1117. (6) Boyd, E. M. 1972. Protein deficiency and pesticide toxicity. Charles C. Thomas, Springfield, 111. (7) Canada National Health and Welfare. Health Pro- [21) tection Branch. 1973. Analytical methods for pesticide residues in food. (S) Chan. A. S. Y. 1972. Analytical methods for waters {22) and wastewaters. Environment Canada, Ottawa, On- tario, Canada. (9) Fahim M. S., R. Bennett, and D. G. Hall. 1970. {23) Effect of DDT on the nursing neonate. Nature 228:1222-1223. {10) Garcia Fernandez. J. C. 1974. Estudios y Comentarios {24) sobre Impregnacion Humana por Plaguicidas Organo- clorados en la Repiiblica Argentina. Medicina 34{4): 393-4)0. (//) Goulden. R.. E. S. Goodwin, and L. Davies. 1963. {25) Improvement of identification in the gas-liquid chro- matographic analysis of agricultural samples for residues of some chlorinated pesticides. Analyst 88: {26) 941-958. (72) Graca, /., A. M. S. Silva Fernandez, and H. C. Mou- rao. 1974, Organochlorine insecticide residues in human milk in Portugal. Pestic. Monit. J. 8(3):148- (27) 156. (13) Hornabrook, R. W.. P. G. Dyment. E. D. Gomes, and J. S. Wiseman. 1972. DDT residues in human milk (28) from New Guinea natives. Med. J. Austr. 1:1927- 1300. (14) yo/mo/i, I'., G. J. K. Lin, J. Armbrnster, L. L. Kettel- hut, and B. Drucker. 1977. Chlorohydrocarhon pesti- cide residues in human milk in Greater St. Louis, Missouri— 1977. Am. J. Clin. Nutr. 30: 1 106-1 109. Lam perl, L. M. 1964. Rapid separation of fat for pesticide residue analysis of mi.k products. J. Dairy Sci. 1013-1014. Lu. F. C. D. C. Jessiip, and A. Lavallee. 1965. Tox- icity of pesticides in young versus adult rats. Food Cosmet. Toxicol. 3:591-596. Mes, J., and D. J. Davies. 1979. Presence of poly- chlorinated biphenyl and organochlorine peslicide residues and the absence of polychlorinated terphenyls in Canadian human milk samples. Bull. Environ. Contam. Toxicol. 21:381-387. Miisial, C. J., O. Hutzinticr, V. Zitko, and J. Croker. 1974. Presence of PCS. DDE and DDT in human milk in the provinces of New Brunswick and Nova Scotia, Canada. Bull. Environ. Contam. Toxicol. 12:258-267. O'Leary, J. A., J. E. Davies, W. F. Edmun.wn. and G. A. Reich. 1970. Transplacental passage of pesti- cides. Am. J. Obstet. Gynecol. 107( 1 ) :65-68. Olszyna-Marzys, A. £., M. de Campos, M. Taghi- Farvar, and M. Thomas. 1973. Residues de Plagui- cidas Clorados en la Leche Humana en Guatemala. Bol. Of. Sanit. Panam. 74:93-107. Qninbv, G. E.. J. F. Armslroni;, and W. F. Dnrliam. 1965.'dDT in human milk. Nature 207(4998) :726- 728. Siyali, D. .S. 1973. Polychlorinated biphenyls, hexa- chlorobenzene and other organochlorine pesticides in human milk. Med. J. Austr. 2( 17):815-81S. Stacey. C. I., and B. W. Thomas. 1975. Organo- chlorine pesticide residues in human milk. Western Australia— 1970-71. Pestic. Monit. J. 9(2):64-66. Tapia. R., R. Bocic. and N. Dimitroff. 1978. Niveles de DDT y DDE en Tejido Adipose y Leche Humana por Chromatografia de Gases. Thesis, University of Chile, Santiago de Chile. Tninslra. L. G. M. Tli. 1971. Organochlorine insecti- cide residues in human milk in the Leiden Region. Neth. Milk Dairy J. 25(l):24-32. t/iV Food and Ai-riciilliire Ori^'unizalion/World Health Organization. 1974. Recommended international toler- ances for pesticide residues. CAC/RS 65-1974. Rome, Italy. Westoo. G., and K. Noren. 1972. Levels of organo- chlorine pesticide and polychlorinated biphenyls in Swedish human milk. Var Foda. 24(4) :41-54. Winter, A/., M. Thomas. S. Wernick, S. Levin, and M. Taghi-Farvar. 1976. Analysis of pesticide residues in 290 samples of Guatemalan mother's milk. Bull. Environ. Contam. Toxicol. 16:652-657. 138 Pesticides Monitoring Journal WATER ],2-Dibromo-3-chloropropane Residues in Water in South Carolina, 1979-80 George E. Carter. Jr., and Melissa B. Riley = ABSTRACT During 1979-80. a total of 236 water samples were col- lected from 205 sites in South Carolina. Well water, surface water (lakes, ponds, and rivers), and municipal water were sampled and analyzed for the soil fumigant 1 .2-dibromo-3- chloropropane (DBCP). DBCP levels ranged from non- detectable to 0.05 fig/liter (ppb) in an area of noniise (background). No municipal water .samples in the state exceeded the background level. In the area of high use of DBCP, 37% of the surface water samples exceeded the background level, but none exceeded 0.4 fig/liter. Twenty- seven percent of the well water samples from the high-use area exceeding the background level, and 10.2% of the samples exceeded 1 fig/ liter. All samples exceeding I ng/liter came from a small area within one county. The possible mode of contamination was not determined. Introduction Soil fumigation for nematode control is a key factor in a program against peach tree short life, a condition that has decimated southeastern peach orchards (I, 5). Both pre- and postplant treatments are required for growing healthy peach trees (Prunus persica (L.) Batsch) (3). l,2-Dibromo-3-chloropropane (DBCP) is the postplant nematicide used to control ring (Macro- Dosthonia xenoplax Raski) and root-knot (Meloidogyne ^pp.) nematodes. Peach trees have no resistance to either nematode, DBCP is the only pesticide cleared for aostplant treatment of orchards, and no other pesticide las been effective for controlling the nematodes well inough to prevent premature death of peach trees. Low ;oncentrations of DBCP have been reported in Cali- wnia groundwater samples {4), which led to questions 5f groundwater contamination in South Carolina. The Jurpose of the present study was to determine the This research was partially funded by grants from the Southern legion Pesticide Impact Assessment Program and the U.S. Environ- nental Protection Agency. Contribution No. 1944 of the South Caro- ina Agricultural Experiment Station. Department of Plant Pathology and Physiology, Clemson University :iemson. SC 29631 levels of DBCP present in water samples collected in South Carolina. Materials and Methods WATER SAMPLE COLLECTION Three areas of South Carolina were selected for their DBCP usage: (I) Piedmont area, non-use; (2) Coastal area, scattered agricultural use; and (3) Sandridge area, extensive agricultural use. During 1979-80, three types of water samples were collected from each area as follows: well water from privately owned wells; sur- face water from ponds, rivers, and lakes; and water from homes supplied by municipal sources. Samples were collected in new canning jars which were discarded after one collection. Jars were rinsed with glass-distilled, pesticide grade ethyl acetate, covered with ethyl acetate- rinsed aluminum foil, and closed with jar caps and rings. Jars were filled to the top from home taps (well and municipal) or by submerging into ponds, rivers, and lakes, leaving no head space, and were placed in ice immediately after collection. The location of the sample and any information on the agricultural prac- tices of the area were recorded at the time of collection. Sites yielding samples containing over 1 ppb DBCP were resampled to verify results. EXTRACTION This procedure was obtained from the California De- partment of Food and Agriculture (2) and was modi- fied by the addition of a centrifugation step. Five glass beads, rinsed with ethyl acetate, were combined with a I60-ml water sample and 10-ml gla.ss-distilled, pesticide- grade ethyl acetate in a round-bottom boiling flask that was attached to a modified Stark and Dean trap and condenser. The flask was placed in a heating mantle; full voltage was applied until the mixture began to bofi and then was reduced to one-third maximum. The mixture was allowed to reflux 15 minutes or until the ethyl acetate was distilled over to the trap. The /OL. 15. No. 3, December 1981 139 heating mantle was turned off and the condenser was washed with distilled water. After 5 minutes, the dis- tillate was removed and centrifuged 10 minutes at 17, 500g in a Sorvall RC2-B refrigerated centrifuge. The ethyl acetate layer was transferred to an ethyl acetate-washed, screw-cap tube to which a small amount of anhydrous sodium sulfate was added. An aluminum foil liner rinsed with ethyl acetate was placed between the test tube and the screw cap. Samples were kept in the freezer after extraction and before gas chromato- graphic analysis. Glassware blanks were run by placing 30 ml ethyl acetate in the boiling flask of the extraction apparatus and refluxing it 15 minutes. A 10-ml quantity was then collected to be used as a glassware blank. Glass- ware was cleaned by placing it overnight in sodium dichromate-sulfuric acid cleaning solution, and then rinsing it three times with distilled water and ethyl ace- tate. GAS CHROMATOGRAPHY The concentration of DBCP in water samples was de- termined by use of a Varian 3700 gas chromatograph connected to a CDSlll chromatography data system and recorder. Instrument parameters and operating con- ditions were as follows: Detector ; Column Temperatures Carrier gas; Retention time: Detection limit ; '■'Ni electron-capture 2 m by 2 mm glass, packed with 10% OV-101 on 80-inO-mesh Chromosorb W-HP column: 1I10°C for 3 min, tlien increased column: 4°/min for 7 min, tlien increased column: 18°/min for 5.66 min, and then held column: at 230°C for 4.33 min injector 220'C detector 280°C nitrogen llowing at 30 mlmin 5.7."; minutes for DBCP 0,008 ppb Recovery percentage was determined from the mean value of four fortified samples (50 ng DBCP added to 160 ml distilled, deionized water). This value, 88%, was used to calculate DBCP present in the samples. Levels of DBCP were calculated by the data system, using an external standard method of calibration. DBCP standards were prepared in ethyl acetate, using a 99.6% pure analytical standard (AMVAC Chemical Corp.); standards and sample extracts were kept in different freezers. The gas chromatograph was cali- brated using a 5 pg DBCP/ul standard as the first sample every day. Ethyl acetate blanks were run after every sample containing DBCP. Either of the following apparatus and operating con- ditions was used to confirm the presence of DBCP: Column: 2 m by 2 mm glass, packed with 3% OV-216 on 80-100-mesh Chromosorb W-HP 140 1 emperatures, °C DBCP retention time: OR Column; Temperatures, °C DBCP retention time: Carrier gas (both columns): Detection limit (both) column 75 injector 270 detector 250 2,1 min 2 m by 2 mm glass, packed with 2% DEGS on 80-100-mesh Chromosorb W, A/W column 100 injector 250 detector 250 1.2 min nitrogen flowing at 40 ml min 0,008 ppb MASS SPECTROMETRIC ANALYSIS FOR DBCP Selected samples were taken to Research Triangle In- stitute in Research Triangle Park, North Carolina, for analysis. Methane-enhanced negative ion chemical ioni- zation mass spectrometric analysis was conducted on one of two gas chromatograph-mass spectrometers un- der the following conditions: CiC MS: Column: Temperatures. "C: Electron energy: Box current ; Accelerating voltage; OR GC MS: Column: Temperatures, ' C : LKB 2091 25-m WCOT SE-30 capillary column: 1(I0°C for 4 min. then 240°C injector 210 ion source 210 50 eV 250 ^A 3.5 kV Electron energy: Finnigan Model 4000'PPNICI 25-m SP2I00 capillary column 70° for 1 min. then 8° /min to 250°C injector 250 ion source 250 70 eV The appearance of the characteristic ions (m/z 79, 81, 158, 160, and 162) in the correct retention window was used to confirm the presence of DBCP in the samples. Tentative confirmation was based on the observation of the m/z 79 and 81 ions in the correct retention window. Selected samples were concentrated before analysis by placing the sample in ice with a stream of nitrogen flowing over it. Results and Discussion Distribution of the 236 water samples is shown in Table 1. Samples from the Piedmont area (non-use of DBCP) appeared to contain a background level of DBCP or a compound indistinguishable from DBCP at levels from 0.008 ppb (limit of detection) to 0.05 TABLE I. Distribiiiion of waler samples analyzed for DBCP in Soiilh Carolina 1979-80 No, OF AREA Type of Water No, OF Sites Samples Piedmont well 8 8 (Non-use) surface 15 18 municipal 3 3 Sandridge well 49 63 (High use) surface 46 60 municipal 8 8 Coastal well 24 24 ( Scattered usel surface 33 33 municipal 19 19 Pesticides Monitoring Journali MUNICIPAL VA/ATEn 3 SITES WELL WA TE R 8 SITES SURFACE WATER IS SI TE S FIGURE 1. Percentage of sites showing DBCP contami- nation (pph) in Piedmont area of South Carolina. Detection limit = 0.008 pph. ND represents no detectable residue of DBCP. ID u led MUNICIPAL WATE R IB SITES V/VELL WATER Sa SITES SURFACE WATER 33 SITES 10 UJ U TO I IV1UNICIPAL VA/ATEP a SITES I I L_ SURFACE \A/ATER ae SITES \A/ELL WATER as SITES D Ul PP B FIGURE 3. Percentage of sites showing DBCP contami- nation (pph) in Sandridge area of South Carolina. Detection limit = 0.008 pph. ND represents no detectable residue of DBCP. Original Sample Neighbors of Original Sample Neighbors of Second Samples 226 22) 222 223 22t 229 220 Verification Samples Verified by 216. 217. Confirmed by GC/MS Verified by 221. Confirmed by GC/MS Verified by 213. 220 Confirmed by GC/MS Verified by 219. Confirmed by GC/MS 207 2oe 209 210 212 verified by 211, Not conf 1 nned by GC/HS FIGURE 2. Percentage of sites showing DBCP contami- nation (pph) in Coastal area of South Carolina. Detection limit = 0.008 pph. ND represents no detectable residue of DBCP. [*) Samples containing above 1 opb FIGURE 4. Treatment of original water samples contain- ing above 1 ppb DBCP (numbers indicate sample numbers). Vol, 15, No. 3, December 1981 141 ppb (Figure 1 ). Although the compound was tested un- der two sets of gas chromatographic conditions and at significantly different polarities, and on the mass spec- trometer, the low level prevented positive identification. Levels of DBCP up to 0.05 ppb were therefore con- sidered to be background levels. In the coastal area of South Carolina (scattered use of DBCP). no well water or municipal water sample and only one surface water sample exceeded the background level (Figure 2). Samples were obtained in the Sand- ridge area of South Carolina (high use of DBCP) showed a greater variability in DBCP concentrations (Figure 3 ) . No municipal water sample exceeded the background level, but surface and well water samples varied from none to more than 1 ppb. Seventeen sur- face water samples in the Sandridge area contained DBCP, but none were above 0.04 ppb, and 10 were below 0.1 ppb. Five well water samples contained greater than 1 ppb DBCP. All of these samples were verified by resampling at a later date. Two of the sites were located in a ran- dom survey, and the remaining three were found when the nearest neighbors to the original samples were sam- pled, as shown in Figure 4. When the samples contain- ing more than 1 ppb DBCP were tested by mass spec- trometry, four of the five were confirmed to contain DBCP. This study indicates that low levels of a material that is indistinguishable from DBCP may exist in ground- water where no agricultural use has occurred. This pos- sibility must be considered when data concerning trace amounts of DBCP are analyzed. One must consider whether the material is authentic DBCP and, if so, whether it resulted from agricultural use. Most samples from the high-use area did not exceed the background levels found in samples from the non- use area, but several well water samples from the high- use locality did exceed the background levels. Hydrol- ogy of the area, the nature of well construction, and use patterns of DBCP in the vicinity of the wells were not studied. Therefore, it is impossible to conclude that contamination in this area was due to agricultural ap- plication of products containing DBCP. Further study is necessary to identify the source of contamination in these five wells. A cknowledgments Authors appreciate the assistance of Edo Pellizzari and Ken Tomer of the Research Triangle Institute in con- ducting the mass spectrometer analyses. LITERATURE CITED (/) Chandler . W. A.. J. //. Owen, and R. L. Livingston. 1962. Sudden decline of peach trees in Georgia. Plant Dis. Rep. 46(12):831-834. (2) Jackson. T., and S. Frederickson. 1978. Determination of DBCP in crops, soil, water, bark, and leaves. Memorandum, California Department of Food and Agriculture, October 24. (i) Managing Peach Tree Shori Life in the Southeast. I97S. J. A. Brittain and R. W. Miller, Jr., Eds. Clem- son University Extension Service Circular 585, De- cember. 1.4) Peoples, S. A.. K. T. Maddy, W. Ciisick, T. Jackson, C. Copper, and A. S. Frederickson. 19S0. A study of samples of well water collected from selected areas in California to determine the presence of DBCP and certain other pesticide residues. Bull. Environ. Contani. Toxicol. 24(4):611-618. (5) Zehr. E. /., R. W. Miller, and F. H. Smith. 1976. Soil fumigation and peach rootstocks for protection against peach tree short-life. Phytopathology 66(5) :689-694. 142 Pesticides Monitoring Journal APPENDIX Chemical Names of Compounds Discussed in This Issue ^ACHLOR .DRIN anochlorine pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by age group PEsncints Women 18-25 Years Old (58 Cases) Women 26-34 Years Old (42 Cases) Detected Range Arithmetic Mean SE Range Arit HMETIC MI;AN SE Total BHC 6.9-278.3 32.97 16.89 2.0-507.84 45.79 5.90 Lindane* 1.28-78.69 10.27 2.18 3.10-175.73 14.99 1.23 r.p'-DDE 1.02-850.0 12.33 1.98 2.05-78.14 23.10 4.75 p.p'-DDU ND^8.21 5.84 1.25 ND-48.21 8.01 2.85 P.p'-DDT' ND-140.0 7.30 2.32 ND-57.52 22.13 2.37 SDDT' 2.73-1029.85 59.65 25.51 4.59-149.62 51.18 8.51 *, ** Statistically significant (P<0.05 and 0.005, respectively). 2DDT = total DDT equivalent. TABLE 2. Organochlorine pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by dietetic habit Pesticides Vegetarian Diet (36 Cases) Nonvegetarian Diet (64 Cases) Detected Range Arithmetic Mean SE Range Arithmetic Mean SE Total BHC 6.9-278.43 38.3 7.29 2.0-507.84 35.64 3.13 Lindane 1.28-78.68 12.47 0.34 1.8-175.73 11.41 1.10 P.p'-DDE 1.02-850.0 15.33 3.26 1.9-150.0 20.53 4.39 p.p'-DDD ND^8.21 6.55 1.85 0.89-32.09 8.49 1.80 p.p'-ddt ND-55.56 14.89 3.05 1.78-140.0 17.08 3.55 i;DDT 4.03-1029.85 62.22 8.50 2.73-240.41 50.07 7.78 TABLE 3. Organochlorinc pesticides detected (ppb) in cord blood collected at term from 100 pregnant women, by area of residence . LIrban Population (48 Cases) Rural Population (52 Cases) Detected Pesticides Range Arithmetic Mean SE Range Arithmetic Mean SE Total BHC 2.0-507.84 47.38 13.87 3.0-76,97 27.06 2.31 Lindane** 1.28-175.73 16.94 0.72 1.8-33.43 8.88 1.63 p.p-DDE 1.02-257.50 22.81 7.05 2.2-850.0 15.48 4.38 P.p'-DDD ND^8.21 7.33 3.88 ND-32.09 6.25 1.43 p.p -DDT 0.5-50.23 13.71 2.19 ND-140.0 17.08 4.43 vDDT*** 2.73-338.43 41.60 10.88 7.14-1029.85 68.23 13.84 •* Siaiistically significant (P<0.05, 0.05, and 0.005, respectively). 144 Pesticides Monitoring Journah Information for Contributors The Pesticides Monitoring Journal welcomes from all iources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators issociated with pesticide monitoring, research, and Jther programs concerned with pesticides in the environ- Tient. Other subscribers work in agriculture, chemical Tianufacturing, food processing, medicine, public health, ind conservation. ^rticles 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 Estuaries. The sixth is a general heading; the seventh encompasses t)riefs. 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. 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