, BOSTON PUBUC LIBRARY I GOVSRNMENT OOCUMtNTS UEPARTMfMT Rf^CRIVED D" 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 Technical Services Division, Office of Pesticide Programs, U.S. Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies represented on the Monitoring Panel which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and articles. However, pertinent data in summarized form, together with discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institutions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not 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 Milton S. Schechter, Agricultural Research Service Herman R. Feltz, Geological Survey Address correspondence to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, DC. 20460 Editor Martha Finan CONTENTS Volume 12 June 1978 Number 1 SOIL Page DDT moratorium in Arizona — agricultural residues after seven years 1 G.W. Ware, Betty J. Estesen. N.A. Buck, and W.P. Cahill FISH, WILDLIFE, AND ESTUARIES Organochlorine insecticide, polychlorinated hiphenyl. and metal residues in some South Dakota birds, 1975-76 4 Yvonne A. Greichus, Brian D. Gueck, and Barbara D. Ammann Organochlorine pesticide residues in Florida birds of prey , 1969-76 ° David W. Johnston Shell thinning and pesticide residues in Texas aquatic bird eggs. 1970 16 Kirke A. King, Edward L. Flickinger, and Henry H. Hildebrand Organochlorine insecticide and polychlorinated hiphenyl residues in woodcock wings, 1971-72 22 M.A. R. McLane, E.H. Dustman, E.R. Clark, and D.L. Hughes Chlorinated hydrocarbons and mercury in birds of Lake Pdijdnne, Finland — 1972-74 26 Jukka Sarkka, Marja-Liisa Hattula, Jorma Janatuinen, Jaakko Paasivirta, and Risto Palokangas Dieldrin, DDT. polychlorinated biphenyl. and mercury levels in freshwater mullet from the upper Great Lakes, 1975-76 . 36 Mary E. Zabik, Barbara Olson, and Teiko M. Johnson GENERAL Mirex incorporation in estuarinc animals, sediment, and water, Mississippi Gulf Coast — 1972-74 40 Armando A. de la Cruz and Kuang Yang Lue APPENDIX 43 Information for Contributors 44 SOIL DDT Moratorium in Arizona — Agricultural Residues After Seven Years ' George W. Ware. Betty J. Estesen, Norman A Buck, and William P. Cahill ABSTRACT The moratorium on agricultural use of DDT in Arizona that began in January 1969 proved very effective during the first 7 years of enforcement. Residues on green alfalfa declined sig- nificantly to a probable inherent level of 0.02 ppm wet weight. Soil residues of ^DDT-related degradation products declined significantly, averaging 23 percent: residues in desert soils declined 60 percent. The ^DDT half-life in irrigated soils was about 7 years: it decreased to 2.5 years in nonirrigated soils. Introduction The moratorium on agricultural use of DDT in Arizona began in January 1969 (2, 4, 5). This is the fourth and probably last report on the status of DDT residues and SDDT-related degradation products, after 18 years of unrestricted use and 4 years of restricted use in Arizona. TABLE 1 IDDT residues in green alfalfa. Baseline Rd., Maricopa Co., Arizona, 1967-75 XDDT Residues, PPM 1967 1968 1969 1970 1971 1972 1975 Sample Aug. Sept Sept Sept. Sept. Sept Oct ■) 0.220 0,038 0050 0.020 0.023' 0.009' i 0283 _ 0027 0030 — 0025' 0.007' 4 0 170 0.120 0038 0 037 0.031 0.022 0016' 5 — 0.060 0,020 0 024 0.011 0.029« 0009' 6 0,277 0035 0.022 — 0.008" — 8 0,794 — — 0.027 0,038 0,013' 0,023 9 _ 0076 0034 0.IM2 0,020 0,029' 0,027 10 0.350 0092 0,054 0 162 0 027 0.031 0.022' Jl 0453 0.580 0,064 0.047 0085 0.056 0.027' 12 0299 0.077 0 025 0.038 — 0.023' 0.014' 13 0.606 — — 0.021 0.027 — 0008' Means 040449 0030 0.025 0007 — 0011 0015* 6 0 113 0064 0060 0051 — 0045" 0041* 7 0082 00,34 0023 — — 0055 021 8 0125 0.056 — — — — — 9 0085 0044 0 101 — — — — 10 - — 0.080 0.059 — — — Means 0 117c 0051b 0.063b 0036b - 0.39b 0.023a Pinal County. AUZONA 1 0047 0042 00J4 0 055 0041* 2 0047 0 031 0059 0 036 — — 0068' 3 0 142 0 187 _ _ _ — 0006* 4 0 231 0076 0 071 0.072 — 0025 — 5 0092 0 130 0045 — — 0.025' _ 6 0038 0 058 OMS _ — — — 7 0 079 0 118 0 059 0 038 _ 0.044 0023* 8 0068 0 071 0.031 0.034 — 0.018 0.077' 9 0.054 0.068 0.057 0.060 — — aooe* Means 0088b 0086b 0030a 0.049a - 0.031a 0.0361 Yuma Countv AUZONA 1 0.047 0.373 0.120 0.025 0.032 0016' 2 0039 0098 — — 0010* 0017» 0008' 3 0049 0 256 0084 0.270 0073* 0040* 0040 4 0 057 0 093 _ _ 0055' 0075' 0025 5 0057 0545 0063 0 -340 0047* 0290* 0030' 6 0044 0317 — — 0035' 0300* 0.032' 7 0059 0 241 — — 0026* 0 190* 0034' 8 0 036 0 045 0 034 0 031 0039* — 0005' 9 0021 0056 — — 0015> — — 10 0.046 0.074 0051 0050 0.028 0.045 0006 Means 046a 0210b 0.058a 0 162b 0.035a 0.123b 0.022a NOTE: — = no samples analyzed. * = subadtule adjacenl Ttelds. Means with saiitc letter arc not significanlly difTcicnl ul the 0 0^ level Pesticides Monitoring Journal TABLE 3. 1,DDT residues in soils during 1969-75 DDT moratorium . Arizona 1969 Jan PPM Residues 1972 Sept . ppm Residues 1975 Oct PPM Residues Field DDE o.p'- P.P'- Total DDE o.p'- py- Total DDE o.p'- p.p'- Total No. DDT DDT DDT DDT DDT DDT Ma>icop« County 1 0.35 0.04 0.12 0 54 0 40 0 04 0 II 0.55 0.43 0.10 0 13 0.66 2 0 48 0 17 0.78 1 54 0 98 0 18 0.47 1.63 3 0 33 0.07 0 16 0.59 1.24 0 13 0 32 1.69 10 0 10 0.23 1 33 4 0.49 0 05 0 17 0.74 0 58 0.05 0.23 0 86 0 40 0,03 0 12 0 55 5 0 29 0.05 0 09 0 44 0.17 0 01 005 0.23 0 17 0 01 0.02 0 21 6 2.10 0.43 1 10 3 93 2 58 0 28 0 96 3 82 2 24 0 31 0 58 3 13 7 0 84 Oil 0 23 1 22 0 92 0 09 029 1 30 0 68 0 06 0 14 0 88 8 2 22 0 38 1 29 4 00 2 37 0.27 1.21 3.85 1 96 0 24 0 98 3 18 9 1 18 0 21 0 91 2 41 1 12 0.17 0.77 2 06 0 83 0 14 0 55 1 51 10 — — — (0.24) 0.31 0.04 0.07 0.42 0 24 0.02 0 06 0.32 Means 0.92 0.17 0.54 1 57a 1.07 0 13 0.45 1 64a 0.883 Oil 0 31 1 31b Desert 1 0 08 <0.01 0 03 0 13 0 43 0 07 0 09 0 59 0 04 0 00 0 02 0 06 2 0.24 0 02 0 06 0 35 0 28 0.03 0.58 0 89 0.04 0.01 0 02 0 06 3 0.44 0.04 0 15 0 67 0.18 0 02 0 04 0.24 0 06 0 01 0.02 0 10 4 — — — 12 39) 0.54 0 08 0 06 068 0 69 0 10 0 19 0 98 Means - - - 0.89a 0.36 0.05 0.19 0.60a 0.21 0.03 0.06 0.30b Pinal County 1 0.64 0 48 2.43 3 77 0 74 0.34 2 64 1.72 0.59 0.24 2 51 3.34 2 0 27 0 15 1 03 1.52 0 41 0 13 0 96 1.50 0.37 0 09 1 03 1 49 3 1 05 0 32 1 38 2 75 1 16 0 16 080 2.12 0 64 0 09 0 42 1 16 4 0 99 0 27 1 04 2 30 1.40 0 18 0.74 2.32 1.60 0.21 0,25 2 05 5 0 16 0.02 0 21 0 41 0 25 0.02 0 16 0.43 0.19 0 02 0 10 0 31 6 0 06 0 01 0 07 0.14 0 07 0 01 0.04 0.12 0.04 0 00 0.05 0 08 7 1 09 0 28 1 37 2 74 1 63 0 20 0 80 2.63 1 32 0 16 0 31 1 79 8 0 09 <0 01 0.04 0 14 0 08 0 01 0.02 Oil 0.05 0 00 0.01 0 06 9 0 67 0 09 0 29 1 06 0 74 0.03 006 0.83 0 59 0 05 0.08 0 72 10 0 66 0 14 0 36 1 16 1 19 0 15 0 39 1.73 0 91 0 09 0.08 1.08 Means 0.57 0 18 0 82 1 60a 0 69 0 12 0 66 1 55a 0.63 0 10 0.48 1 21b Desen 1 0 09 <0 01 0 06 0 16 0 17 0 02 0 12 0 31 0 04 0 00 0 01 0 06 2 0 18 0 01 0 11 0 32 0 21 0 02 0 21 0 44 0 07 0 00 0 02 0 09 3 0 05 0 03 0 10 0.21 0.06 0.01 0.02 0.09 0,04 0 01 0.01 0 06 4 0.09 0 03 0 10 0.25 0.77 0.07 0.09 0.93 0 49 0 05 0 07 0.61 Means 0.10 0.02 0 09 0.24a 030 0.03 0.11 0.44a 0 16 0.02 0.03 0 20b Yuma County 1 0 10 <001 0 07 0.17 0 12 0 02 0.03 0 17 0 06 0 01 0 01 0 08 2 0 24 0 05 0.25 0 54 0 20 0 03 0 07 0.30 0.24 003 0 06 0 33 3 0 72 0 16 0 72 1 60 0 79 0 16 0 49 1 44 071 0 15 0 29 115 4 0 59 Oil 0 47 1 17 0 98 0 15 0.46 1 59 0.84 0 13 0.22 118 5 0.48 0 05 0.30 0 83 075 0 12 0 34 1.21 0 54 0 10 0.15 0 79 6 0 29 0 16 0.74 1 19 0 48 0 10 0,43 1 01 045 0 08 0 29 0 81 7 1 29 0 07 037 1 73 111 0 09 0 50 1 80 0 91 0 06 0 01 0 97 8 0 06 0 01 0 01 0 08 0 05 <0 01 <0.01 007 002 0.00 0.00 0 02 9 0 00 0.00 0 00 0 00 <0 01 <0 01 <001 0.03 0 00 0 00 0 00 0 00 10 0 26 0.02 0.03 0 31 0 17 001 0.02 0 20 0.08 0.00 0 01 0 10 Means 040 0 06 0.30 0.76a 0.47 0.07 0.25 0 78a 0 39 0.06 0.10 0 54b Desert 1 0 27 0 02 0 07 0 36 0 24 0 06 0 09 0 39 0 10 0.03 003 0 16 2 0 03 0 01 0 02 0 06 0.02 0 01 0 02 0 05 0 02 000 0.01 0 03 3 0.02 0 01 0 03 0.06 0 02 0 01 0.02 0 05 0 02 0.00 0.02 0 05 4 0 00 0 00 0 01 0 01 0 79 0.07 0.15 1 04 0 00 0 00 0 00 0 01 Means 008 0 01 0.03 0 12a 0.27 0 04 0.08 0.38b 0.035 0.01 0.02 0 06a NOTE — = no sample analyzed. Figures in pareniheses are missing values calculated by randomized blocks missing value formula. Means wiih same tetier are not significantly different a( ihe 0 05 ppm level 12, No. 1, June 1978 nSH, WILDLIFE, AND ESTUARIES Organochlorine Insecticide, Poly chlorinated Biphenyl, and Metal Residues in Some South Dakota Birds, J 975-76 ' Yvonne A. Greichus, Brian D. Gueck, and Barbara D. Ammann ABSTRACT Chlorinated hydrocarbon insecticide, pnlychlorinaled biphenyl (PCB). and metal residues nere measured in tissues of common crows (Corvus brachyrhynchos), American coots (Fulica americana). starlings (Sturnus vulgaris), and Franklin's gulls (Larus pipixcan). of South Dakota in 1975-76. Insecticides and PCBs were analyzed by column, thin-layer, and gas-liquid chromatography . Metals were analyzed by atomic absorption spectrophotometry. DDE was the most prevalent residue: it was delected in 93 percent of all samples and averaged 66 percent of the total residues in the carcass. Average values ranged from 0.04 ppm to 0.54 ppm. Dieldrin was delected in 61 percent of all samples and averaged < 0.01 ppm to 0.15 ppm. TDE and DDT were found in 27 percent and 15 percent, respectively, of all samples. and the averages for both ranged from < 0.01 ppm to 0.06 ppm. Heptachlor epo.xide and lindane were delected in some samples. PCBs were not found above the minimum delectable level. 0.1 ppm. in any sample. Gulls had higher insecticide and metal residues than had cools, starlings, or crows. Arsenic values averaged 1.4 ppm dry weight in carcass samples from the four species of birds. Cad- mium, copper, manganese, lead, and zinc averaged 0.10. 0.94. 4.8, 1.0, and 69 ppm dry weight, respectively, and were no higher than values reported in some birds from other areas. Introduction Organochlorine insecticides have been used in South Dakota since 1946 for the control of noxious insects (4). Although many of these insecticides have been banned or limited, residues of some of the more persistent compounds such as DDT, dieldrin, and lindane are still commonly found in birds of South Dakota (6, 7). ' Slalion Biochemistry Section. Chemistry Dcpanmenl. South Dal(Ola Stale Univer- sity. Brooltings. SD 57UU7 This paper is being published with the approval of the Director of the South Dakota Agricultural Experiment Station as Publication No 1515 of the journal article series Four common species of South Dakota birds with distinctly different feeding habits were analyzed in 1975-76 for eleven insecticide residues, six metals, and polychlorinated biphenyls (PCBs) to determine present levels of these chemicals so that comparisons could be made in future studies. Methods and Materials INSECTICIDE AND PCB ANALYSIS Seven common crows (Corvus brachyrhynchos), six American coots (Fulica americana), six starlings (Sturnus vulgaris), and six Franklin's gulls (Larus pipixcan) were analyzed. Organochlorine insecticide and PCB residue levels were measured on a wet-weight basis in brain, liver, feather, and carcass samples from each bird. Metal levels were measured on a dry-weight basis for each bird. Sam- ples were analyzed for lindane, heptachlor, heptachlor epoxide, dieldrin, aldrin, methoxychlor, endrin, tox- aphene, DDE, TDE, DDT, zinc, cadium, lead, copper, arsenic, and manganese. All birds were killed by shotgun. Gulls were collected September 2, 1975, approximately three miles west of Nunda, South Dakota, while feeding in a freshly plowed field. Coots were collected September 15. 1975, approxi- mately five miles southeast of Arlington, in a marsh. Starlings were obtained February 14, 1976, near Crocker. South Dakota Game, Fish, and Parks personnel collected crows April 6, 1976, near Richmond Lake in Brown County. All specimens collected appeared to be normal and healthy. Authors had intended to use only adults for the study but could find no literature on estimating the age of crows and starlings. They selected the seven heaviest crows for study and they analyzed all starlings collected because only six had been taken. Coots were aged by leg color (9) and gulls by plumage (15). All coots and five of six gulls analyzed were judged to be adults. Pesitcides Monitoring Journal Each specimen was necropsied to remove tissue samples and to determine sex, stomach contents, and general body condition. Technicians removed 5 g of feathers, finely cut them, and wrapped them with aluminum foil. Brains and livers were removed, weighed, and stored in glass jars. Carcass samples consisted of the entire body minus beak, legs, stomach contents, and the samples of feather, brain, and liver previously removed. After necropsy, the car- casses were wrapped and frozen in aluminum foil: several days later they were homogenized by grinding with a Toledo meat chopper, and frozen in glass jars for later analysis. All glassware used for storage and later insec- ticide analysis was washed in detergent, rinsed with dis- tilled water, and baked at 425°C for at least 3 hours to remove organic contamination. Samples were extracted and purified for chlorinated hy- drocarbon residues analysis by a Florisil column method (/6) as modified by Greichus et al. (8). Methods for separating PCBs and insecticides and quantitating PCBs have been described by Greichus et al. (5). One gram of carcass and liver and 0.5 g of brain and feathers were analyzed. Gas chromatograph; Detectors: Recorders: Columns: Packing: Carrier gas: Column temp.; Injector temp.: Detector temp.: Varian Aerograph Model 2100 "■'Ni and Sc'H electron-capture Beckman Ten Inch. I mv 6-ft X 1/16-inch borosilicate glass 15 percent QF-1 silicone (Fluoro) or 1:1 mixture of 15 percent QF-I and 10 percent DC-200 silicone, both on 60- lOO-mesh Chromosorb W (HP). acid-washed and dimethylchlor- osilane-treated Nitrogen at 40 ml/minute 210° C 220° C 280° C Identity of individual insecticides was verified by using thin-layer chromatography (2, 4). Insecticides and PCBs were recovered at 89 percent and 95 percent, respectively. Minimum detection limits were set at 0.01 ppm and 0.1 ppm for insecticides and PCBs and were corrected for percent recovery but values for metals were not corrected. METAL ANALYSIS Zinc was determined with a Perkin-Elmer Model 303 flame atomic absorption spectrophotometer. Lead, arsenic, cad- mium, copper, and manganese were determined with a Perkin-Elmer Model 503 atomic absorption spec- trophotometer equipped with a heated HGA-2100 graphite furnace and a Sargent-Welch Model SRLG recorder. A Perkin-Elmer deuterium arc power supply Model 560 background corrector was used in conjunction with the spectrophotometer when necessary. Operating conditions of the instrument were essentially the same as those given by the manufacturer. Before analysis. 0.5 g dry weight of each sample was digested in 10 ml of concentrated nitric acid on a micro-Kjeldahl digestion apparatus until 2 ml of solution remained. An additional 5 ml of nitric acid was added, and the solution was boiled until I ml remained. Samples were reconstituted to 10 ml with distilled water and analyzed directly. Average recoveries for metals were copper 87, cadmium 91, manganese 82. arsenic 73. lead 79. and zinc. 94 percent. Minimum detection limits used for heavy metals were 0.01 ppm for cadmium. 0.1 ppm for arsenic and lead. 0.5 ppm for copper and manganese. 1.0 ppm for zinc. In calcula- tions of averages and totals, less than (<) values were included and given one-half the stated value; that is. a value of less than 0. 1 ppm is recorded as 0.05 ppm. Results and Discussion INSECTICIDES AND PCBs Average insecticide residue concentrations for common crows, starlings. American coots, and Franklin's gulls are given in Table 1. Endrin. heptachlor. methoxychlor, al- drin, and PCBs were not detected above the minimum detectable levels in any of the 100 samples analyzed. Toxaphene detected in starling feathers was judged to have been an inadvertent contaminant from a container used to carry the birds. Lindane was found in only two crows and was not used in the calculation of average total insec- ticides. One crow had carcass and liver residues of 0.01 ppm and 0. 1 1 ppm lindane, respectively: another crow had a carcass residue of 0.01 ppm. Heptachlor epoxide was detected in crow carcass and liver samples and in one crow brain. Dieldrin residues were found in all species, all four tissue types, and in 61 percent of all samples, except the coot. Dieldrin was either absent from the tissues of the coot, or present in the liver at the limit of detection, 0.01 ppm. Dieldrin concentrations in the brain and feathers of the four species were usually below or slightly above the 0.01 ppm lower analytical limit. DDT and its metabolites were the residues found most consistently. DDE was the most prevalent of the DDT complex and was found in 93 percent of all samples. TDE and DDT were detected in 27 percent and 15 percent, respectively, of all samples. Starlings reflect the general environmental levels of or- ganochlorine insecticides and metals available to them in South Dakota because they are often year-around terrestrial residents. Coots and Franklin's gulls do not reflect true South Dakota contamination levels because they are sum- mer resident only and are subject to migratory contamina- tion in other areas. The low levels of TDE and DDT may reflect the decreased use and eventual banning of DDT in Vol. 12. No. 1, June 1978 TABLE 1. Organochlurinc iiisecliciJf residues in Sonih Dakota birds. 1975-76 Heptachlor Epoxide Average Residues, ppm (Mg'g) Wet Weight Total tiNSECTICIDES Crow Cool Slarling Gull 0 06 <0,0I <0 01 <0 01 0.13 <0.01 0.02 0.15 0.54 0.04 0 05 0.44 0.U4 <0.01 <0.01 0.06 0.06 <0.0I <0.01 <0.0I 0 84 0.06 0.10 0.66 Crow Cool Starling Gull 0 10 <0 01 <0 01 <0.0I 0,05 0 01 0 04 0.04 0.41 0.02 0.06 0.10 0.04 <0 01 <0.01 0.04 0.02 <0.01 <0.01 <0.01 0 61 0,05 0,12 0.20 BRAIN Crow Cool Starling Gull <0,0I <0,0I <0,0I <0,0I 0,07 <0 01 <0 01 <0,01 0,05 0.01 0.02 0.02 <0 01 <0 01 <0.01 <0 01 <0 01 <0.01 <0.0I <0.0I 0.13 0 04 0 04 0.04 FEATHERS Crow Cool Starling ' Gull <0.01 0 06 0,04 <0.01 <0 01 0.11 <0,0I <0 01 0.02 <0.01 <0,0I 0.04 Note: Seven crows and six each of cools, starlings, and gulls were analyzed ' Starling feathers were contaminated with loxaphene at bird-collection site; no residues are reported here. the United States in 1973, altiiough DDE is still common in the environment. Nationwide monitoring of mallard and black duck wings by the Fish and Wildlife Service. U.S. Department of the Interior, since 1965 has shown DDE to the the predominant residue (10. II). Results of the monitoring in 1965-66 showed DDE to be the predominant residue, followed by DDT, TDE, dieldrin, and heptachlor expoxide; in 1969, DDE was followed by PCBs, DDT, dieldrin, TDE, and heptachlor epoxide. In both studies, organochlorine resi- dues were generally highest in the Atlantic and Pacific flyways and lowest in the Central flyway of which South Dakota is a part, and in the Mississippi flyway. Total insecticide residues were consistently higher in crows than in other species. Franklin's gulls had the second highest total residue level, followed by starlings and American coots. In brain samples, however, all three species had approximately equal concentrations. Carcass samples usually had the highest insecticide levels, fol- lowed by livers; brains and feathers were about equal. Martin {13) analyzed carcasses of starlings from 128 areas of the United States in 1967-68 and found DDT, its metabolites, and dieldrin in all sites. At four South Dakota sites, the average residues for 1967-68 ranged from 0.103 ppm to 1.925 ppm DDE. 0.013 ppm to 0.018 ppm TDE. 0.018 ppm to 0.030 ppm DDT, and 0.012 ppm to 0.080 ppm dieldrin. Heptachlor epoxide and lindane were occa- sionally found at all South Dakota sites. Average total insecticide residues were 0.234, 0.201, 2.054, and 0.334 ppm at the four sites (/.?). Starlings monitored for the present study in 1976 had lower average total insecticides, 0.10 ppm, than had birds in any of the four South Dakota sites studied by Martin (13). Average concentrations of metals in carcasses of crows, coots, gulls, and starlings are reported in Table 2. Values are given on a dry-weight basis but can be converted to the approximate wet weight by multiplying the value by 0.43, which was the average dry weight of 1 g of bird carcass. Arsenic levels were similar in all four types of birds. Converted to wet weight, arsenic residues were greater than those reported by Martin and Nickerson (14). Starl- ings collected from 50 sites in the United States contained < 0.05 ppm wet weight arsenic except for one sample with 0.21 ppm arsenic ( Z-^). Gulls averaged 0.21 ppm cadmium, higher than residues in other birds of this study but lower than some values reported for starlings by Martin and Nickerson (14). TABLE 2. Metal residues in South Dakota bird carcasses, 1975-76 Average Residues, ppm iMg/g) Ohm Weight' Metal Arsenic Cadmium Copper Manganese Uad Zinc Gulls Coots Starlings Crows 16 1.5 1.6 1.0 0 31 0.08 0.10 0.03 1.8 0,75 0.51 0.75 4.5 9.8' 4.0 4.2 3.2 = 0 86 0.77 0.72 82.0 71 0 75,0 52.0 Note: Seven crows and six each of cools, starlings, and gutis were analyzed ' Residues can he convened (o wet weighi by multiplying each value by 0 43. (he average dry wcighi of 1 g of bird carca>s. ' Two birds were analyzed Pesticides Monitoring Journai Gulls also had higher concentrations of lead than had coots, starlings, or crows. The gulls could have been contaminated in areas other than South Dakota because they are migratory. A possible cause could be the ingestion of shot. Waterfowl are susceptible to shot ingestion in wetland areas; upland birds are susceptible to a lesser extent in terrestrial areas (/). Lead residues in South Dakota starlings averaged 0.36 ppm in 1971 (14), which is close to 0.33 ppm wet weight found among starlings in the present study. Manganese, copper, and zinc are essential dietary elements and are not usually considered contaminants. Levels of copper and zinc (Table 2) reported for the four types of birds were not unusual. Considerably higher levels of copper (21 ppm wet weight) and zinc (76 ppm wet weight) have been found in livers of white pelicans (12). Man- ganese concentrations of 9.8 ppm were more than twice as great in coots than in other birds, possibly because their diet contains aquatic plants rich in this element. Some aquatic plants have comparatively high levels of man- ganese (660 ppm dry weight) (3). LITERATURE CITED (J) Bagley. G. E.. L. N. Locke, and G. T Nightiiiaale . 1967. The occurrence of lead in tissues of wild birds. Bull. Environ. Contamin. Toxicol. 2(5):297-305. (2) Breidenbach, A. W.. J. J. Lichtenherg, C. F. Henke. D. J. Smith. J. W. Eichelberger, Jr.. and H. Slierle. 1964. The identification and measurement of chlorinated hy- drocarbon pesticides in surface waters. Rev. Ed. U.S. Depl. Health, Educ. Welfare, Publ Health Serv Publ. 1241:63-69. (3) Funk. W. H.. R. W. Rabe. R. Fithy. and J. I. Parker. 1973. The biological impact of combined metallic and organic pollution in the Coeur D'Alene-Spokane River drainage system. Natl. Tech. Info. Serv. No. PB-222 946. (4) Greenwood, R. J., Y. A. GreUhus. and E. J. Hugghins. 1967. Insecticide residues in big game mammals of South Dakota. J. Wildl. Manage. 3l(2):288-292. (5) Greichus. Y. A.. A. Greichus, B. D. Ammann. D. J. Call. K. C. D. Hamman, and R. M. Poll. 1977. Insecticides, polychlorinated biphenyls and metals in African lake ecosystems. I. Hartbeespoort Dam, Transvaal and Voelvlei Dam, Cape Province, Republic of South Africa. Arch. Environ. Contamin. Toxicol. 6(I):1-12. (6) Greichus. Y. A.. A. Greichus. and R. J. Emerick. 1973. Insecticides, polychlorinated biphenyls and mercury in wild cormorants, pelicans, their eggs, food and environ- ment. Bull. Environ. Contam. Toxicol. 9(6):321 -328. (7) Greichus. Y. A.. A. Greichus. and E. G. Reider. 1968. Insecticide residues in grouse and pheasant of South Dakota. Pestic. Monit. J. 2(2):90-92. (8) Greichus. Y. A.. D. Lamb, and C. Garrett. 1968. Effi- ciency of extraction of metabolically incorporated HEOD (carbon-14) from pheasant tissues, eggs and faeces. Analyst 93:323-325. (9) Gullion, G. W. 1952. Sex and age determination in the American coot. J Wildl. Manage. 16(2): 191- 197. (10) Heath. R. G. 1969. Nationwide residues of organochlorine pesticides in wings of mallards and black ducks. Pestic. Monit. J. 3(2):1I5-123. (in Heath. R. G.. and S. A. Hill. 1974. Nationwide or- ganochlorine and mercury residues in wings of adult mal- lards and black ducks during 1969-70 hunting season. Pestic. Monit. J. 7(3/4): 153-164. (12) Koeman. J. H.. J H. Pennings. J. J. M. DeGoeij. P. S. Tjioe. P. M. Olindo. and J. Hopcrafl. 1972. A prelimi- nary survey of the possible contamination of Lake Nakuru in Kenya with some metals and chlorinated hydrocarbon pesticides. J. Appl. Ecol. 9:411-416. (13) Martin, W. E. 1969. Organochlorine insecticide residues in starlings. Pestic. Monit. J. 3(2): 102-1 14. (14) Martin. W. £., and P. R. Nickerson. 1973. Mercury, lead, cadmium, and arsenic residues in starlings — 1971. Pestic. Monit. J. 7(l):67-72. (15) Robbins. C. S.. B. Brunn. and H. S. Zim. 1966. Birds of North America. Western Publishing Co., Inc., Racine, Wl. 340 pp. (16) Slemp. A. R.. B. J. Liska. B. E. Langlois. and W. J. Sladelman. 1964. Analysis of egg yolk and poultry tissues for chlorinated insecticide residues. Poult. Sci. 43(0:273-275. Vol. 12, No. 1, June 1978 Organochlorine Pesticide Residues in Florida Birds of Prey, 1969-76 David. W Johnston ABSTRACT Chlorinated hydrocarbon pesticide residues, especially DDT and its metabolites, were determined in 71 individuals of 14 species of predatory birds obtained in Florida between 1969 and 1976. Of the 71 birds. 68 contained p.p -DDE or another DDT metabolite; 34 contained dieldrin. DDE was found in 93 percent of the 57 adipose tissue samples, all the 9 brain samples, and 89 percent of the 62 uropygial gland samples. Of the 65 birds taken since 1972, 61 contained DDE in at least one of these three tissues The annual average of 'S.DDT in adipose tissue and uropygial gland over the 6-year span was approximately 5 ppm wet weight. From 1973 to 1976, no significant increase or decrease in pesticide burdens was detected. Some birds had no DDE whereas others contained up to 76 ppm IDDT. None of the data suggest thai any of the birds of prey had died of DDT or DDT metabolite poisoning. Introduction For approximately two decades in North America, much public and scientific interest has been focused on popula- tion declines of various birds of prey including eagles, osprey (Pandion haliaetus), and peregrine falcon iFaIco peregrinus). In some species, correlations have been made or suspected between pesticide burdens, especially DDE, and mortality, population declines, or altered physiological processes resulting in impaired reproductive performances (8, IH). Eggshell thinning is now believed to be a result of high DDE burdens, both in captive and feral birds of prey {13, 14. 17). One might anticipate high pesticide burdens in birds of prey because they are usually terminal members of food chains, and thus can concentrate the fat-soluble chlorinated hydrocarbon pesticides. In most published ac- counts dealing with these birds, pesticide residues were extracted from eggs or nestling birds or from birds experi- mentally fed DDT (4. 13, 14); there are few published ' Deptrtmenl of Zoology, Universily of Florida, Gainesville, FL .'i2611 Research supported in pan by Gram GB 25R72 from the National Science Foundation. Washington. OC accounts of body burdens in adults except for a limited number of autopsied birds found dead and suspected of pesticide poisoning. In fact, virtually nothing has been published on body burdens in feral adult birds of prey which reportedly produced thin eggshells. Thus, to date, pesticide burdens at levels presumably not impairing re- production are poorly documented (2). In the present re- port, some organochlorine pesticide residues extracted from birds of prey obtained recently in Florida are quanti- tated. Sampling Methods The birds analyzed were obtained between 1969 and 1976, chiefly in northcentral Florida near Gainesville. Most birds were fresh roadkills or were illegally shot by hunters. A few were picked up alive in a weakened condition or were having convulsions; they were kept in an aviary, and died within 24 hours. With the possible exception of the latter birds, the present report includes birds dying accidentally, that is, there was no a priori suggestion that any pesticide burden contributed to death. The sample includes two orders (Falconiformes: vultures, kites, hawks, falcons, osprey, caracara; Strigiformes: owls). In all, 6 families, 12 genera, 14 species, and 71 individuals were analyzed. Analytical Procedures From each specimen, whether fresh or previously frozen in individual plastic bags, samples of subcutaneous adipose tissue (fat) and/or the entire uropygial gland and/or the cerebrum were removed for analysis. Recently, a number of investigators have indicated the possibility oi using the unique avian uropygial, or preen, gland as an indicator of pesticide burdens in birds (3. 4. II). In feral, migratory songbirds, Johnston (//) reported a high correlation. Pesticides Monhorinc; Journal r = 0.7568. of SDDT between adipose tissue an(J uropy- gial gland. In the present study, birds varied in the degree of obesity; in some, essentially no fat could be located, so only the gland or brain was used for analysis. For 59 samples of fat, the mean sample weight was 1.1224 g; for 62 samples of uropygial glands, the mean weight was 0.5590 g; and the mean brain weight taken from 9 birds was 4.1375 g. Each sample was individually thoroughly homogenized in sodium sulfate, and extracted for at least 12 hours with petroleum ether in a Soxhlet apparatus. The lipid extract was evaporated to dryness, weighed, and partitioned with acetonitrile and hexane. Detector: electron-capture Column: 6-ft x Vj-inch glass, packed with a mixture of 6.4 percent OV-210 and 1.6 percent OV-17 1 1 + 1 ) on Chromosorb W Temperatures: injection port 210° C column 212° C detector 215° C Carrier gas: nitrogen flowing at 45 nil/minute Recoveries for the organochlorine compounds ranged from 75 percent to 95 percent. Sensitivity was approximately 0.01 ppm. Rexultx All samples were an alyzed on a Model 600-D Varian gas chromatograph w th the following instrument parameters Table 1 contains the results of analyses for the 71 birds of and operatin gc onditions: prey. Tissues analyzed for the Individ ual biriJ s were not TABLE 1 . Chlorinated pesiicide burdens in Florida birds of prey. 1969-76 Tissue ^ and Residues. PPM Wet We GHT County Date Age ' Weight, g p.p'-DDE SDDT DiELDRIN CATHARTES AURA (TURKEY VULTURE) Alachua Nov 71 UNK A (2 0751) 3 37 3.55 0 Lev, Apr 73 M A (3.0238) B (6 0752) 1 32 0 17 3.00 0,17 0.07 0 Alachua Apr 73 FA (4 0514) B (5,5159) 0 78 0,11 1 32 0,11 0.46 .0 Levy May 73 MA 1,59 2.28 0.07 Levy May 73 Leon May 73 Sepi 74 CORAGYPS ATRATUS (BLACK VULTURE) Alachua 'Marion [Contimied next page) Vol. 12, No. 1, June 1978 Jan 72 May 73 May 73 M F (2 0323) F A (2 8724) U (1,0003) F A (2 2551) B (5 6169) 6,39 3 83 10,50 1 26 0.10 II 75 6 87 15 25 1 49 0 II 1 18 0.22 0.50 0.04 0 TABLE 1 (continued). Chlorinaled pesticide burdens in Florida birds of prey. J 969-76 Date Tissue * and Sex/ Sample Age ' Weight, g Residues, ppm Wet Weight p.p'-DDE SDDT CORACYPS ATRATUS (BLACK VULTURE)— Continued May 73 A 3.06 7 68 (3 0264) U 5,44 6.84 (0 8266) A 1 1 56 25.43 (0 9518) U 9 33 14 74 (0 8682) 0 66 0,24 2 02 0 69 ELANOIDES FORFICATUS (SWALLOW-TAILED KITE) May 75 U (0 6269) ACCIPITER STRIATUS (SHARP-SHINNED HAWK) A (0 3009) U (0.0637) 16 62 19.62 17 12 19.62 ACCIPITER COOPERII (COOPER S HAWK) Alachua Sept 73 V (0.2763) BUTEO J A MAICENSIS (RED-TAILED HAWK) July 73 July 74 IMF IM IM A 6.25 6 25 (1.8650) U 0 10 0 10 (0 4830) A 3 49 3.73 (1 0422) U 0 11 Oil (0.4788) A 0 37 0 48 (0.7617) U 0 39 0.50 (0.7570) A 0 59 1.32 (1 6963) U 0 21 0 21 (0.4846) A 0 37 0.37 (0.5357) U 0 0 (0.4527) A 4.26 5 86 (0 4694) U 0 38 0 38 (0 3936) A 6 14 7 19 (0 5699) U 1 05 1 05 (0.2852) 0 0 0 89 0 0.04 0 0 0 0 0 0 85 U 0 38 0 38 0 (0 3936) Madison Jan 76 IM A (0 5699) 6 14 7 19 2.37 U 1 05 1 05 0 18 (0.2852) BUTEO LINEA TUS (RED-SHOULDERED HAWK) Alacliua Jan 72 F A (1 3596) 0 64 1 04 006 U 0 18 0.18 0 (0.2853) Alachua Sept 73 IM A (0 3310) 0.45 1.21 0 U 0 24 0 60 0 (0 3104) Alachua Jan 76 AD A (0 1888) 7,15 7 15 0 V 0 39 0 39 0 (0.2552) Pinellas Jan 76 F A (0 2615) 34 42 61 76 38 24 U 0 80 1 80 0 80 (0 2514) Baker May 76 F U (0 6186) 1 21 121 0 (Continued next page) 10 Pesticides Mon ITORING JOURNAI TABLE 1 (continued). Chlorinated pesticide burdens in Florida birds of prey. 1969-76 Sex/ AOE ' Tissue ^ and Sample Weight, g Residues, ppm Wet Weight p.p'DDE PANDION HALIAETUS (OSPREY) Apr 73 Sepi, 74 Apr 75 May 76 A (0 3864) U (2.4581) A (2 8327) U (4 1778) A (0 3S401 U (1 1643) A (0 7767) U (0 6309) U (0 4922) A (0 4861) U (3.7545) 0.13 1.55 0.55 0 41 0 0.09 0 33 0.32 13.21 1 65 0 53 IDDT 0.26 1.79 1.29 0.62 0 0.09 0.33 0 32 15 85 1 87 0.71 0 0 0 0 0 0 0 0 0.91 0 0 Pinellas May 76 M A (0.4264) 1.52 2.46 0 U 1 39 1.39 0 CARACARA CHERIWA l" (CARACARA) Glades July 75 ADF A (0 1416) 2.47 2.47 0 U 1.25 1.25 0 (0 5854) Highlands July 75 IMF A (0 0805) I 24 1.24 0 U 0.48 0.48 0 (0 6235) Highlands Apr 76 IM F A (0.1229) 3 25 3.25 0 U 2.44 2.44 0 FALCO SPARVERIUS (AMERICAN KESTREL) Mar 73 Mar 73 Mar 73 Mar 73 Jan 74 Jan 75 Nov. 75 M M A (0 2810) U (0 0954) A (1.1978) A U A (0 1588) U (0.0788) A (0.1399) U (0.0602) A (0 0551) U (0.0833) U (0 0653) A (0 0980) U (0 0258) A (0.0262) U (0.0302) A U U (0 0486) B (1.0756) U (0.0459) 14 59 3.15 1 77 20 57 4 63 0 79 0 63 2 14 1.66 9.07 1 80 0 0 1 94 0 0 7 61 1 44 4 12 0.42 7.63 16 37 3.15 2.09 22.71 4 63 0 79 063 2.14 1.66 9.07 1.80 0 0 1 94 0 0 8.03 2.20 4 12 0.42 18 53 0 36 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3.09 0.70 4.36 {Continued next page) Vol. 12, No. I.June 1978 11 TABLE 1 (continued). Chlorinated pesticide burdens in Florida birds of prey, 1969-76 Residues, ppm Wet Weight Tissue ^ and Sex/ Sample Age ' Weight, g p.p'-DDE XDDT DiELDRIN FALCO SPARVERWS (AMERICAN KESTREL) Pinellas ' B (1.1574) U (0 0486) B (12114) A (0.0790) U (0 0505) 0.30 2 06 1 03 0 0 0.74 2 06 1,03 0 0 0.82 1 03 0.37 0 0 TYTO ALBA (BARN OWL) May 76 A (0.9538) U (2.1913) U (0 3550) 8 28 1.31 0 9.27 1.31 0 1 68 0 0 OTVS ASIO (SCREECH OWL) Levy Indian Riv Pinellas > Pinellas ' Sepl. 73 May 75 Jan 76 May 76 F A 6 19 (1.1317) U 1 17 (0.I20I) UNK A (0.3585) 0,26 U 0 (0 1454) UNK A (0 6573) 0 30 U 3 48 (0 1435) UNK U (0.0378) 10 58 M U (0 0502) 49.80 M U (0 0748) 1 34 6.19 1 17 U 26 0 0 30 3 48 10 58 49,80 1.34 BUBO VIRGINIANVS (GREAT HORNED OWL) Diiie Maruin Dec. 75 May 76 UNK A (3.0278) 2 06 U 8 24 (0 6823) F A (0 6460) 5 42 U 3 28 (0.7466) UNK U (0 4400) 17.05 MF A (0 2821) 9 75 U 0 81 (0 5537) 3 59 8 68 9 21 4 28 17 05 12 05 0 81 0.08 0 3 02 0 47 0 6 20 0 STRIX VARIA (BARRED OWL) Alachua Alachua Apr. 73 May 74 Dec 75 UNK A (1.5201) U (0.7385) U (0 5460) A (0 22S6) U (0.5321) A (O.II83) U (0 6588) A (0.1830) U (0.5843) 5 76 5 08 74.18 1 09 0.37 7.61 I 44 1 09 0 73 6 90 5 69 75 93 1 09 0.37 8.03 2 20 1 09 0,73 0,21 0 14 0 0 0,40 0 0 0 0 ' M~ftdull male. F=idult female, AD= adult of undetermined sex, UNK = bird of unknown sex or age, JUV= juvenile, IM = immature. Sex of juvenile and immature birds was not always recorded ' Tissue abbreviations A = adipose tissue. U~uropygial gland. Bahrain ^ Birds that reportedly died in captivity and exhibited convulsions 12 Pesticides Monitoring Journal always perfectly uniform because birds were obtained in different ways by different persons, and it was frequently inconvenient or impossible to take samples of brain, fat, and the uropygial gland from every bird. Furthermore, due to its relatively superficial position, the uropygial gland was sometimes damaged, and quite often a specimen was so lean that no fat could be found for pesticide analysis. Even so, a number of important features emerge from the data in Table 1. All taxa (family, genus, and species) had some birds containing p,p' -DDE or other DDT metabolite. Dieldrin, on the other hand, was not present in all taxa. Of the 71 birds, 68 (96 percent) contained DDE but only 34 (48 percent) contained dieldrin in at least one of the three tissues. In the three tissues analyzed 93 percent of the fat samples contained DDE, 100 percent of the brains con- tained DDE, and 89 percent of the uropygial glands con- tained DDE. These values indicate a nearly universal oc- currence of DDE in the birds studied and in the three tissues sampled. In the 45 birds of prey in which both adipose tissue and uropygial gland were analyzed and in which one or both samples contained DDE, 40 (89 percent) had DDE in both tissues, 3 (7 percent) had DDE in adipose tissue only, and only 2 (4 percent) had DDE in the uropygial gland alone. However, Figure 1 shows a poor correlation (/■ = 0.3398) of SDDT, in ppm wet weight, between these two tissue types. Of 46 birds, 40 had higher concentrations of 2DDT in the adipose tissue than in the uropygial gland. For the species analyzed, the mean ratio of SDDT in adipose tissue to uropygial gland was 2.6:1, a higher ratio than the 2.2; I reported by Johnston (//) for a sample of other feral species such as loons, cormorants, herons, and gulls. Figures 2 and 3 show SDDT found, respectively, in the adipose tissue and uropygial gland through the sampling period. In both samples, median values were calculated for all the species in a given year; these values are indicated by f^ OS,. 5 - SOLID LINE CONNECTS MEDIAN ANNUAL VALUES FIGURE 2. ^DDT in adipose tissue of Florida birds of prey. 1971-76 '^ O * ::(.: 1974 12 1975 15 1976 14 > ? Q. a> O » tr — -, », h- a. a " o ■ • • 1= 0.3398 • Y=0.I4X-H.75 %^ • m • • .• • • • • • • • I DDT IN ADIPOSE TISSUE (ppm wet weight) FIGURE 1 . Relationship of IDDT in adipose tissue and uropygial gland in Florida birds of prey. 1969-76 FIGURE 3. XDDT in uropygial glands of Florida birds of prey. 1971-76 a solid line. The lines might not indicate realistic trends because the numbers of a given species available for analysis varied from year to year, as indicated by raw data in Table 1 . Discussion Of the 14 species examined here, there is no assurance that any bird was a permanent resident where collected except for the caracaras and juvenile osprey. Any or all the birds might have been transient or migratory at some time during their lives, so pesticide burdens determined for these birds Vol. 12, No. 1, June 1978 13 were not necessarily accumulated in Florida, but could have come from prey consumed on a wintering area south of the state, from a breeding area in the north, or in intervening areas during migratory nights. It is likely, however, that most of the four owl species were Florida residents because they tend to migrate less than the other birds of prey studied here. Subspecific information was determined only for the American kestrel. These small falcons were all representa- tive of the northern subspecies ( Faico s. sparverius) which migrates into Florida from the northern United States and winters in large numbers in the state. The author was unable to obtain samples of the local resident Florida subspecies. F. s. pautus. for analysis. Data on the vul- tures. Catharles and Coragyps. are presented in Table I and appear to be the first residue findings published on these species. Because vultures are terminal members of food chains, they might be expected to have exceptionally high DDT levels, but this does not appear to be true of Catharles. Only I of 10 turkey vulture fat samples exceeded 10 ppm SDDT; the mean was 4.76 ppm. However, the mean for the fat of 5 Coragyps was 10.64 ppm SDDT; one bird had 25.43 ppm. Both vultures scavenge road-killed animals such as the nine-banded armadillo. Virginia opossum, dogs, and various smaller mammals, birds, and reptiles in Florida, most of which are nonmigratory. Why Coragvps should have a higher mean burden of SDDT than do Catharles is unclear. The Accipiter hawks, also called bird hawks, have pes- ticide burdens as high as or higher than most other species studied (Table 1). The small sample size precludes generalizations, but it is noteworthy that in 1972 Henny reported that the Cooper's hawk "is in serious jeopardy in the northeastern U.S." ( 6 ) . Some species listed in Table 1 are largely insectivorous (5), namely, Etanoides forficutus. FaIco sparverius. and Otus asio. At least three of the 14 specimens of Falco had SDDT burdens exceeding 10 ppm; one contained 18.53 ppm in the uropygial gland, and the 2DDT burden in adipose tissue probably exceeded 50 ppm. Two of six Otus specimens had exceptionally high levels in their uropygial glands; 10.58 ppm and 49.80 ppm. For this species, 10 ppm DDE dry weight in the diet produced thin eggshells (13). Although dietary levels of DDT may not be directly related to levels in the adipose tissue or uropygial gland, it is significant that 5 ppm DDT wet weight in the diet of Falco sparverius resulted in the classical eggshell-thinning syndrome (17). However, carcass (17) and breast muscle (8) analyses of dead or dying American kestrels in the northern United States had generally higher DDT burdens than those found in the present study (/). For this species, it is significant that three individuals contained no DDT or metabolite (Table I ). Henny et al. presented data on eggshell thicknesses and populations of red-shouldered hawks (Buteo lineatus) from a refuge in Maryland (7). The authors thought it "doubtful that the relatively low pesticide levels in the eggs had a detrimental effect on the reproductive performance of the population." Except for a single bird containing 61.76 ppm 2DDT and 38.24 ppm dieldrin. organochlorine resi- dues in this species were generally low (Table 1 ). The osprey (Pandion haliaeius) was studied intensively in the 1960s because its population had declined precipitously in some areas (6). As with other species discussed in this paper, presticide levels in eggs and nestlings have been published but data for adults are scarce. Wiemeyer et al. reported brain and carcass analyses of dead birds in Con- necticut and Virginia (18). DDE residues in carcasses averaged 23 ppm wet weight, generally, exceeding the levels in adipose tissue and uropygial gland in Florida birds reported here. Because different tissues were analyzed, it is difficult to compare previously published data on red- tailed hawks and great horned owls with those reported here. For three nestling red-tailed hawks, Seidensticker found an average of 21.50 ppm 2DDT wet weight, in breast muscle (15). Seidensticker and Reynolds reported 1.40 ppm wet weight iDDT in nestling red-tail hawk muscle and 9.29 ppm XDDT in the muscle of a great horned owl ( 16). Two generalities emerge from the data in Table 1 and Figures 2 and 3. There is no firm evidence for this sample of birds of prey from Florida that DDE and dieldrin burdens diminished in 1971-76. In both the adipose tissue and uropygial glands, the data indicate an approximate average of 5 ppm over the 4-6 year span. Small migratory songbirds, on the other hand, showed a dramatic decrease of DDE in adipose tissue from 1964 to 1973 (9, 10). That decrease was correlated with the decreased use of DDT in the United States during the same time. Presumably, the ban on DDT use in the United States imposed by the U.S. Environmental Protection Agency (EPA) December 31. 1972. should have reduced the amount of DDT in natural ecosystems. The birds of prey studied here are significant, especially those analyzed after 1972. because a large pro- portion did contain DDT or a metabolite. How would a hawk, owl, or vulture obtain significant quantities of DDT in 1976? It is plausible that a long-lived bird could have accumulated small pesticide quantities for years and simply stored them in adipose tissue. Unless these deposits were totally depleted for energy resources, the pesticides might not have been mobilized into the bird's bloodstream or eliminated except in very small quantities. The data on uropygial glands presented in Table 1 indicate that birds of prey eliminate smaller quantities of pesticides through this gland than do other types of birds (.?. 4). A second possible explanation for the DDT burden in birds of prey after the EPA ban in 1972 is that at least eight species analyzed here might have migrated to Florida from 14 Pesticides Monitoring Journai the West Indies or Central America where they could have obtained DDT-contaminated foods. This is probably simi- lar to the situation of the migratory American kestrels discussed by Lincer and Sherburne {12). They suggested that this species obtained pesticide-laden foods chiefly from the wintering grounds rather than from nesting sites in the northern United States. They state: "The disastrous role played by the far-removed, but inordinately contami- nated, winter prey once again dramatically points out the global nature of the biocide problem." Still, the presence of DDT in tissues of the caracara, which is a resident of southcentral Florida, is an enigma. Since 1973, the SDDT burdens in adipose tissue of two species examined here, osprey and American kestrel, were very low (0-2 ppm). A cknowledgments O. L. Austin, Jr., P. Brodkorb, R. L. Crawford, D. J. Forrester, T. Gilyard, R. Heath, Jr., H. W. Kale, II, S. A. Nesbitt, and J. M. Whittier assisted in collecting birds. Birds from Leon County, Florida, were provided by per- sonnel at the Tall Timbers Research Station. I thank the following for help in laboratory analyses: R. Bull, G. Cause, A. Meylan, and M. Raum. An earlier draft of the manuscript was critically examined by W. H. Stickel. Illustrations were prepared by E. Belcher. LITERATURE CITED (1) Bernard. R F. 1962. Secondary DDT poisoning in a sparrow hawk. Auk 79(2):276-277. (2) Cade. T. J.. C. M. While, and J. R. Haugh. 1968 Peregrines and pesticides in Alaska. Condor 70(2): 170- 178. (3> Charnelski. W. A., and W. E. Stevens. 1974. Or- ganochlorine insecticide residues in preen glands of ducks; possibility of residue excretion. Bull. Environ. Contam. Toxicol. 12(6):672-676. (4) Dindal. D. L. 1970. Accumulation and excretion of CI"' DDT in mallard and lesser scaup ducks. J. Wildl. Manage. 34(l):74-92. (5) Grossman. M. L., and J. Hamlei. 1964. Birds of Prey of the World. Chas. N Potter, Inc. New York, NY. 496 pp. t6) Henny. C. J. 1972. An analysis of the population dynamics of selected avian species, with special references to changes during the modern pesticide era Wildl Res. Rep. 1, U.S. Department of the Interior. Fish and Wildlife Service, Bureau of Sport Fisheries and Wildlife, Wash- ington, DC. (7J Henny. C. J.. F. C. Schmid. E. M. Martin, and L. L. Hood. 1973. Territorial behavior, pesticides, and the population ecology of red-shouldered hawks in central Maryland. 1943-1971. Ecology 54(3);545-554. (8) Hickey. J. J. (ed.) 1969. Peregrine Falcon Populations. Their Biology and Decline. Univ. Wise. Press, Madison. Wl. 596 pp. (9> Johnston. D. W. 1974. Decline of DDT residues in migra- tory songbirds. Science 186 (4166):841 -842 (10) Johnston. D W. 1975. Organochlorine pesticide residues in small migratory birds. 1964-73. Pestic. Monit. J. 9(2):79-88. (11) Johnston. D. W. 1976 Organochlorine pesticide residues in uropygial glands and adipose tissue of wild birds. Bull. Environ. Contam. Toxicol. 16(2): 149-155. (12) Lincer. J. L.. and J . A. Sherburne. 1974. Organochlorines in kestrel prey: a north-south dichotomy. J. Wildl Man- age. 38(3):427-434. (13) McLane. M. A. R.. and L. C. Hall. 1972. DDE thins screech owl eggshells. Bull. Environ Contam. Toxicol. 8(2):65-68. (14) Porter. R. D.. and S. N. Wiemeyer. 1969. Dieldrin and DDT: effects on sparrow hawk eggshells and reproduction. Science 165 (3889): 199-200. (15) Seidenslicker, J. C. IV. 1970. A biopsy technique to obtain tissue for pesticide residue analysis from fal- coniform birds. Bull. Environ. Contam. Toxicol. 5(5):443-446. (16) Seidenslicker. J. C. IV. and H V. Reynolds III. 1971. The nesting, reproductive performance, and chlorinated hydrocarbon residues in the red-tailed hawk and great horned owl in south-central Montana Wilson Bull. 83(4):408-418. (17) Wiemeyer. S. N.. and R. D. Porter. 1970. DDE thins eggshells of captive American kestrels. Nature (London) 227:737-738. (18) Wiemeyer. S. N.. P R. Spitzer. W. C. Krantz. T. G. Lamont. and E. Cromartie. 1975. Effects of environmental pollutants on Connecticut and Maryland ospreys. J. Wildl. Manage. 39(1): 124-139. Vol. 12, No. I.June 1978 15 Shell Thinning and Pesticide Residues in Texas Aquatic Bird Eggs, 1970 Kirke A. King,' Edward L Flickinger.' and Henry H. Hildebrand ' ABSTRACT Significant decreases in eggshell ihicliness were found in 15 of 22 species of aquatic birds in Texas in 1970. Shell thickness reductions of 9 to 15 percent were found in while pelicans (Pelecanus erylhrorhynchos), brown pelicans (P. occidentalis), and great blue herons (Ardea herodias). DDT family compounds were found in all eggs, and mean residues ranged from 0.4 ppm in while ibis (Eudocimus albus) to 2i.2 ppm in great egrets (Casmerodius albus). IDDT residues were negatively corre- lated with shell thickness in five species: PCBs were negatively correlated in two. Residues in marine birds were generally lower and more uniform than levels in birds feeding in fresh and brackish water. DDT and dieldrin residues were higher in eggs from colonies near agricultural areas where these insecticides were heavily used: higher PCB residues were consistently as- sociated with urban and industrial areas. Populations of five species have declined and deserve continued study: brown peli- can, reddish egret (Dichromanassa rufescens). white-faced ibis (Plegadis chihi), laughing gull (Larus atricilla), and Forster's tern (Sterna forsteri). Population trends of four other species were undetermined and should he followed closelv in future years Introduction Eggshell thinning has been noted in a number of declining populations of fish-eating birds in the United States (2, 6. 19, 20). Laboratory investigations show that the DDT family compounds. SDDT, primarily DDE. induce shell thinning in some wild birds and their eggs (15. 16. 2H). The recent decline in brown pelicans, reddish egrets, and an apparent decline in white-faced ibis on the Texas Gulf Coast prompted the present study to determine the extent of eggshell thinning and the impact of pesticide contamination on these and other fish-eating birds breeding in Texas. The authors present information on shell thickness changes and * Pith and Wildlife Service, U S Oepanmenl ol (he Inlenor. PaluxenI Wildlife Research Center. Gulf CoaM Field Slalion. P O Bo» 2iOb. Victoria. TX 77901 ' Department of Biology, Texas A&i University, Kingsville, TX 78363 chemical residues in eggs of 22 species of aquatic birds. Sources of contamination and species threatened by expo- sure to pesticides are identified. Study Area and Methods From March through July 1970. 1,043 eggs were collected in 30 locations on the Texas Coast. One egg was taken randomly from each nest sampled in a pattern distributed as evenly as possible throughout each colony. Whole eggs were weighed and measured, wrapped in aluminum foil, and frozen. Contents were later removed, stored in jars prerinsed with acetone, and immediately refrozen until analysis. Five to 20 eggs of each species were analyzed at the Denver Wildlife Research Center Laboratory, Denver, Colorado. Chemical analyses were completed in 1970 and 1971. Except for brown pelican eggs which were addled, only fresh eggs were analyzed for pesticide residues. The authors biased selection of eggs for chemical analysis by singling out thin-shelled eggs from each species. Ran- dom samples of white-faced ibis, black-crowned night heron, and Forster's tern eggs were also analyzed. Mercury levels were determined in 10 white-faced ibis and 10 great blue heron eggs. Organochlorine residues and polychlorinated biphenyls (PCBs) were determined by using methods described by Peterson et al. (25). The methods measure SDDT, aldrin, dieldrin, endrin, heplachlor epoxide, and lindane at 0.1 ppm wet weight, and chlordane and toxaphene at 0.5 ppm wet weight. PCBs were not separated from pesticides be- fore measurement. When found. PCBs were identified on two separate columns and by visual comparison of chromatograms with standard Aroclors. The PCB residues were quantitated by averaging peak responses and com- paring them with Aroclor 1254 standards. Detection limit of the procedure for PCBs was 0.5 ppm. Mercury residues 16 Pesticides Monitoring Journai- were determined by using methods described by Okuno et al. (24). No corrections were made for possible moisture loss. The authors compared shell thicknesses of eggs collected in 1970 with those of museum eggs collected before wide- spread use of DDT. Data on white and brown pelican eggshells collected before 1947 are from Anderson and Hickey (2); data on white-faced ibis eggshells were supplied by A. J. Smith and J. O. Keith (personal com- munication. 1971). All other measureinents of eggshells collected before 1943 were obtained from the Western Foundation of Vertebrate Zoology, Los Angeles. Califor- nia, and Welder Wildlife Foundation. Sinton. Texas. An- derson and Hickey (/). showed that eggshell thickness for a particular species varies significantly over broad geo- graphic areas particularly with latitude. Whenever possi- ble, museum eggs from the Texas Coast and other southern latitudes were selected for shell thickness measurement. Results and Discussion EGGSHELL CHANGES Fifteen of 22 species sampled showed a signficant negative change in eggshell thicknesses from their museum mean (Table 1). The species with the greatest average thinning were the white pelican (15 percent), great blue heron (13 percent), and brown pelican (11 percent). No collapsed eggs were found in the nests of these species. Although the average thinning of white-faced ibis eggshells was only 4 percent, numerous collapsed, dented, and cracked eggs were found in and around ibis nests. In 1971. continued sampling showed that about 3.5 percent of the white-faced ibis eggs in marked nests had denied or cracked shells; the incidence of cracked eggs of other species was less than I percent. Numerous field studies have shown that eggshell thinning of less than 10 percent seldom incurs egg break- age {3. 6, 10). Egg loss becomes evident with thinning of 10-15 percent (19), and serious breakage, usually accom- panied by population decline, occurs when eggshell thin- ning exceeds 15 percent (2. 20). The degree of shell thin- ning among the white and brown pelicans and great blue heron approaches thai found in other populations in which shell thinning adversely affected reproduction. Average shell thinning was greatest in the Lower Laguna Madre-Green Island region (Figure I). Shell thickness did not vary significantly among heronries sampled elsewhere on the Texas Coast. ORGANOCHLORINE RESIDUES Residues of 2DDT, primarily DDE, were found in all sam- ples. The highest averages were in eggs of the great egret, 23,2 ppm; Caspian tern, 15.1 ppm; and laughing gull, 10.4 ppm (Table 2). SDDT in the eggs of the remaining species TABLE 1. Eggshell changes of several Te. Kas fish-eating hirds, pre- 1943 and in 1970 Shell Thickness, mm Change Spectes Pewod'-' No. MeAN±SE % While Pelican pre-IM? 102 0,6765:0005 Petecanus er\throrh\nchos 19711 2S O577±00O8' -15 Great Blue Heron pre- 1943 32 0 413*0,005 Ardfa herodias 1970 74 O.M9±0,G03' -13 Brown Pelican pre- 1947 43 0.557*0,006 P occidenialis 1970 14 0 497*0 013' -11 Snowy Egret pre- 1943 38 0 241 ±0,003 Egretta thula 1970 79 0 220*0,002' _9 Royal Tern pre-1943 18 0358*0.004 Thalnsseus maximus 1970 12 0,330±0,007' _g Olivaceous Cormorant pre-1943 30 0347*0005 Phalacrocorax olivaceus 1970 24 0 323*0,006' _7 Louisiana Heron pre-1943 31 O,238±O,0O3 Hydranassa tricolor 1970 58 0.225*0 002= -5 Little Blue Heron pre-1943 31 0,243 ±0.002 Florida caerulea 1970 32 0, 232*0003'' _3 Great Egret pre-1943 30 0295*0,004 Casmerodtus alhu.K 1970 113 0 282±O,0O2' -4 White Ibts pre. 1943 38 0 363±0 0O4 Eudocimus albus 1970 48 0 .347±0,003' -4 White-faced Ibis pre. 1943 18 03I2±0,006 Plegadis chihi 1970 86 0 301 ±0 002' -4 Blacl(.CTOwned Night Heron pre-1943 79 0 278 ±0 003 Sychcorax nycncorm 1970 74 0 266*0 003' _4 Black Sbmmer pre-1943 28 0 249*0 0O4 RyrK-hops nigra 1970 48 0240±0.002> -4 Oullbilled Tern pre-1943 31 0 239±0,002 Gelochtlidon nilolica 1970 58 0,231 ±0,002' -3 Laughing Gull pre-1943 27 0,270*0,003 Lan^ alrtctlla 1970 65 0 263*0 002' -3 Sandwich Tern pre-1943 25 0 286*0,004 Sterna sand\'tcensis 1970 19 0 277±0,005 -3 Anhinga pre-1943 31 0328±0004 Anhinga anhinga 1970 8 0,318*0.007 -3 Roseate Spoonbill pre-1943 32 O426±0.0O8 .Ajma ajaja 1970 53 0415*0.004 -3 Reddish Egret pre-1943 47 0 270*0.002 Dichroiruinassa rufexcens 1970 54 0 267±0,003 -1 Least Tern pre- 1943 22 0 156*0,003 S albifront 1970 15 0 154*0,004 -1 Foraler's Tern pre-1943 26 0,219±0,003 5 forsten 1970 41 0218±0,003 0 Caspian Tem pre-1943 15 0 336*0,005 S caspta 1970 32 0 339±0,0O3 -t-l ' Pre- 1947 while and brown pelican data are from Anderson and Hickey (2), • All pre-1943 eggs are from the Texas Coast except white pelican, western United Slates; black. crowned night heron, South Carolina, Florida, and California; snowy egret, little blue heron, great egret, and anhinga. Gulf Coast. Florida, and South Carolina ';><0 001 (Student's /-test). 'p<0 01 'p<0,05 ranged from 0.4 ppm in white ibis to 9.7 ppm in black skimmer. Consistently higher levels of 2DDT and the greatest amount of shell thinning were found in eggs from the lower coast near the intensively cultivated Rio Grande Valley. iDDT compounds were found in eggs of species that feed in all habitats: freshwater, brackish, and marine. Dieldrin residues, found in 14 species, were highest in the snowy egret, white-faced ibis, and great egret (Table 2), species that feed primarily in freshwater and brackish marshes. Little dieldrin was found in eggs of ocean-feeding birds such as brown pelican, royal tern, and Sandwich tern. Greatest dieldrin residues were in eggs from colonies adja- cent to the Texas rice belt where aldrin had often been used to treat rice seed. Vol. 12, No. I, June 1978 17 -RIO GRANDE RGURE 1 Location of colonies of wading birds sampled for eggshell thinning, Texas Gulf Coast — 1970 PCB residues were found in all but two species; highest levels occurred in the olivaceous cormorant, Caspian, Forster's, and royal terns (Table 2). Except for the royal tern, these birds feed most frequently in freshwater and estuarine areas. The colonies associated with highest PCB contamination are Vingtun Island near the sprawling urban-industrial complex of Houston-Baytown, Texas, and Dressing Point, south of Freeport, Texas; both areas have numerous oil refineries and petrochemical plants. Insecticide and PCB residues in marine birds were gener- ally lower and more uniform than levels in birds feeding in freshwater and brackish habitats. iDDT and dieldrin resi- dues were higher in eggs from colonies near agricultural areas where insecticides were heavily used. Higher PCBs were consistently associated with urban and industrial areas. RESIDUl- CORRKI.ATIONS WITH hOCSHEl.l. THICKNESS SDDT or DDE was negatively correlated with shell thick ness for the great blue heron {r = -0.66; p < 0.01), white-faced ibis (r = -0.64; p < 0.01), gull-billed tern (r = -0.936; p < 0.02), reddish egret (r = -0.74; p < 0.05), and brown pelican (r = -0.61; p < 0.05). PCB residues were negatively correlated only for the red- dish egret (r = -0.72; p < 0.05) and the brown pelican (r = -0.53; p < O.I); no correlation was found between 18 any of the remaining insecticide residues and eggshell thickness. Other insecticides and industrial pollutants may affect shell thickness because many pollutants are capable of altering food chain composition, ecosystem energy flow, and ulti- mately the bioenergetics of individual populations of birds. The many environmental factors and physiological proc- esses that result in eggshell thinning are not well under- stood. However, the chemical pollutant most frequently identified with shell thinning is DDE. The authors' data support the findings of others who have reported that DDE is the principal agent correlated with eggshell thinning in wild birds (J, 7, 16. 26). SOURCES OF CONTAMINATION This study indicates that DDE and dieldrin levels detected in egg samples are related to food habits of adult birds. Flickinger and King (/2) found wet-weight residues of iDDT from 0.2 to 1.6 ppm and dieldrin from 0.4 to 2.8 ppm in three species of freshwater fish that are commonly consumed by fish-eating birds. Maximum SDDT residues of 9.3 ppm were found in menhaden [Brevooriiu sp.) and 6.4 ppm in anchovies (Anchoa sp.) collected from 1967 through 1969 from rivers, bays, and estuaries in Texas (9). Potential effects of these residue levels in food items are evident from results of other studies showing that 3^ ppm wet-weight DDE in the diet will cause eggshell thinning in certain species of birds (16. 22. 23. 30). DDT was found in the eggs of six species; great egret, white-faced ibis. Sandwich tern, least tern, gull-billed tern, and roseate spoonbill. Low DDT residues, less than 0.8 ppm, were found in all roseate spoonbill eggs. Frequency of contamination in the other five species ranged from 4 percent in the white-faced ibis to 40 percent (two eggs) in the Sandwich tern. The highest DDT residue found was 1 .3 ppm in a Sandwich tern egg. Local contamination through the food chain is possible since DDT residues have been found in a pooled sample of 76 sailfin molly {Poecilici lalipinna) and in crawfish (Procambarus clurki), two common foods of aquatic birds in Texas (12). Birds mig- rating to Mexico have been contaminated also since DDT still was widely used there in 1970. DDT residues occurred in all five species that regularly migrate to Mexico: roseate spoonbill, white-faced ibis, snowy egret. Sandwich tern, and least tern. SIGNIFICANCE OF RESIDUES DOE — DDE-induced shell thinning has been summarized for numerous birds (2. 2«). Residues in eggs reported in the present study are comparable to levels found in wild populations that have experienced reproductive failures. Some laboratory studies indicate that harmful effects other than shell thinning are possible Longcore (22) found re- duced survival of ducklings (Anas ruhripes) hatched trom Pesticides Monitoring Journal TABLE 2. Insecticide and PCB residues in eggs of Texas wading birds, 1970 Mean Resioues±SE Wet Weight Speoes IDDT ' DiELDMN PCBs Lipid. % Great Egret Caspian Tern Laughing Gutl Black Skimmer Least Tern Louisiana Heron Olivaceous Cormorant Great Blue Heron White-faced Ibis Gull-billed Tern Royal Tern Roseate Spoonbill Snowy Egret Brown Pelican Reddish Egret Black-crowned Night Heron Forster's Tern White Pelican Little Blue Heron Sandwich Tern White Ibis 10 10 10 5 5 5 5 20 16 10 5 10 10 II 10 10 10 5 5 5 5 23.24±3.61 I5.13±2.25 10 35±3 90 9 68±3 02 6 94±3.52 5 50±2 17 6 22±2 08 5.55*1.05 5.33±2.92 4 89±2.73 4 28±0 88 3,85±0,88 3 26±l.30 3 23±0.20 2 52*0.60 I 76*0 58 1 74±0 20 1 38±0 30 1 20±0.75 1 12±0 36 0 41±0-12 0 63*0.14 (10) ND 0 52±0.34 (5) ND ND 0 16*0 12 (2) 0 30 (1) 0.14*0.09 (i) 0.8I±0.22 (12) 0 18*0 15 (•<) ND TR (2) 1 06±0 67 (S) ND ND TR «) 0.47 (/> ND 0 12*0.05 (4) 0 72 (I) TR (5) 16 50*4 51 (10) 3 00±2 13 (2) 5.40±1 89 (5) 2.60*0.81 (•«) 2 40*0.81 (4) 32 00*5 83 (S) 5 54*1 02 120) 3 00*2 13 («) 1.25±0.33 (6) 11 60±2 84 (5) 2.10*0.28 (10) 2.03±l 24 (7) 9.73*1 38 (10) 1 50*0 29 UO) ND 12 50±4 76 (7) 0 98*0,97 (5) 1 40*0 37 (5) 1.40*0.24 (5) ND 5 6 8.5 10 6 110 17,2 8.5 4.7 5.4 6,2 9 3 12.7 5.4 6 2 4 8 5 9 5.4 9.1- 4 7 6.5 15 2 110 NOTE: ND = not detected TR = trace Numbers in parentheses represent number of eggs with residues, ' IDDT residues found in all eggs sampled eggs of hens which had consumetJ food treated with 10 ppm and 30 ppm DDE. Haegele and Hudson (15) also re- ported increased mortality of young and reduced clutch size in ring doves (Slreptopelia risoria) fed 40 ppm DDE. DDE fed at 10 ppm and 40 ppm to mallards (.Anas platyrhynchos) reduced hatching of eggs, although survival of hatchlings to 14 days was unaffected {16). nificantly lower in eggs of hens that received dieldrin through the egg. Dieldrin above 1 ppm in the eggs of golden eagles (AquiUi chrysaetos) may cause reproductive problems (28), and dieldrin residues of 0.54 ppm are lethal to brown pelican embryos (7). In view of the great varia- tion in toxicity of dieldrin to different wildlife species, egg residues greater than 1 ppm must be viewed as hazardous. Dieldrin — Dieldrin levels found in the present study are lower than those reported in several studies investigating reproductive success and survival of young birds. Fowler et al. (U) reported normal hatching success of purple gal- linule {Porphyrula niw-tinica) and common gallinule {GalUiuda chloropus) eggs containing average dieldrin residues of 3.8-17.5 ppm. Pheasants (.Phasianus col- chicus). fed varying amounts of dieldrin. showed no ef- fects on fertility, hatching, or survival associated with yolk fresidues of up to 52 ppm (4). Dieldrin residues in whole eggs would normally average about 26 ppm. Chickens fed up to 5 ppm dieldrin showed no effects on clutch size, hatching, or survival of young associated with egg residues ,of 4-5 ppm (14). In contrast, Baxter et al. (5) found [second-generation effects; fertility and hatching were sig- PCBs — Laboratory experiments indicate that PCB levels found in the present study do not reflect acute exposure of fish-eating birds, but results of reproductive studies are not so conclusive (17, 26). One important consideration is the wide range in species sensitivity to PCBs; Heath et al. (17) found a fourfold difference in sensitivity between two gal- linaceous species. The complex problems associated with the wide range of sensitivity to PCBs and the varying toxicities of different Aroclors were reviewed by Stendell (27). These differences emphasize the difficulties in drawing conclusions about the meaning of residues in eggs of fish-eating birds. But al least five species in this study have sufficiently high egg levels of PCBs to warrant addi- tional research; olivaceous cormorant, Caspian tern, Fors- ter's tern, royal tern, and brown pelican. Vol. 12, No. I.June 1978 19 Mercury — A pooled sample of 30 while-faced ibis eggs contained 0.18 ppm wei-weighl mercury, and 10 great blue heron eggs averaged 0.30 ppm. Fimreite ( // ) reported sig- nificanlly lowered hatching success in pheasant eggs con- taining 0.5-1.5 ppm mercury, and Borg et al. (iS) found similar effects at levels of 1.3-2.0 ppm. However. Heinz {18) found no significant effects on mallard reproduction associated with egg residue levels of 1 .0 ppm. Herring gull iLtinis arficnuitus) chicks hatched from each of 24 clutches that contained mercury between 0.5 ppm and 2.0 ppm (29). Thus it seems unlikely that mercury residues in white-faced ibis and great blue heron eggs were high enough to affect reproduction adversely. White-faced ibis eggs were expected to contain high mer- cury residues because ibis feed in flooded rice fields where mercury-based fungicides were used on seed, but levels were low compared with those found in other studies dS'. //, /S. 29). Great blue heron feed in various freshwater and brackish habitats and had slightly but not significantly greater mercury residues than had ibis. This indicates that mercury is found throughout the coastal environment, at least in feeding areas of both species in the Texas rice belt. THREATENED SPECIES One objective of the present study was to identify popu- lations possibly threatened by pesticide contamination. On the basis of recent population trends, residue levels, and shell thinning, the authors believe that the brown pelican, white-faced ibis, reddish egret, laughing gull, and Forster"s tern warrant immediate attention. Popula- tions of white pelican, olivaceous cormorant, great blue heron, and great egret showed weak or undetermined population trends and should be watched closely in future years. Results of a Texas brown pelican study were re- cently published (21) and ibis data are being prepared for publication. (3) Anderson. D. W.. J. J. Hickew R W. Risebrough. D. F. Hughes, and R. E. Chrisiensen. /y6y Significance of chlorinated hydrocarbon residues to breeding pelicans and cormorants. Can Field-Nat. 83{2):9I-1 12. (4) Atkins. T. D.. and R L Under 1967. Effects of dieldrin on reproduction of penned hen pheasants. J. Wildl. Man- age. .■(!(4):746-753- {5) Baxler. W. l... R. L. Under, and R. W. Dahlgren. 1969. Dieldrin effects on two generations of penned hen pheas- ants, J Wildl Manage, 33(I);96-I02, t6) Bius. L J 1970. Measurements of brown pelican eggshells from Florida and South Carolina, BioScience 20(I5):867~869. (7) Blus. L. J.. B S. Neely. Jr.. A. A. Belisle. and R M. Prouty. 1974. Organochlorine residues in brown pelican eggs; relation to reproductive success. Environ. Pollut. 7:81-91. (Sj Borg, K.. H Wannlhrop. K. Erne, and E. Hanko. 1969. Alkyl mercury poisoning in terrestrial Swedish wildlife. Vellrevy 6(4):301-379. (9) Childress. R, 1970. Levels of concentration and incidence of various pesticide residues in Texas. Texas Parks and Wildlife Dept., 58 pp , Unpublished report. ilO) Coulter. M. C. and R W. Risebrough. 1973. Shell- thinning in eggs of the ashy petrel (Oceanodrama homo- chroa) from the Farallon Islands Condor 75(2);254-255. (//) Fimreite. N. 1971. Effects of dietary methylmercury on ring-necked pheasants. Canadian Wildlife Service, 37 pp. Occasional Paper No 9 (12) Flickinger. E. L . and K ,A King. 1972. Some effects of aldrin treated rice seed on Gulf Coast wildlife J, Wildl. Manage, 36(3):706-727, (13) Fowler. J. F.. L D. Newsome. J. B. Graves. F. L. Bonner, and P E Schilling. 1971 . Effects of dieldrin on egg hatchability, chick survival, and eggshell thickness in purple and common gallinules Bull Environ Contam. Toxicol, 6(6):495-501 Acknowledgment The authors thank Robert E. White, Iwao Okuno, Dennis L. Meeker, and Ronald E. Powers of the Chemical Re- search and Analytical Section, Denver Wildlife Research Center, for chemical residue analyses. They express ap- preciation to Lawrence J. Blus, Eric G. Bolen, James O. Keith, Lowell C. McEwen, and Donald H. White for manuscript review. LITERATURE CITED (1) Anderson. D W.. and J J Hiikey 1970. Oological data on egg and breeding characteristics of brown pelicans. Wilson Bull 82(1)14-28 (2) Anderson. D. W.. and J J. Hickev 1972. Eggshell changes in certain North American birds. Pages 514-540 in K. H. Voous, ed., Proc XVth Inter Ornithol. Congr. E J Brill. Leiden, The Netherlands (14) Graves. J B.. F L Bonner. W F McKnight. A. B Watts, and E. A. Epps 1969 Residues in eggs, preening glands, liver, and muscle from feeding dieldrin contami- nated rice bran to hens and its effect on egg production, egg hatch, and chick survival. Bull. Environ. Contam. Toxicol, 4(6):375-383. (15) Haegele. M. A . and R. E Hudson 1973. DDE effects on reproduction of ring doves Environ. Pollut. 4:53-57. (16) Heath. R G . J W. Spann. and J. F Kreitzer. 1969. Marked DDE impairment of mallard reproduction in con- trolled studies. Nature 224(52l4):47-48. (17) Heath. R. G . J W Spann. J F Kreitzer. and C Vance. 1972. Effects of polychlorinaled biphenyls on birds. Pages 475-485 in K. H. Voous, ed., Proc XVth Inter. Ornithol. Congr. E. J. Brill, Leiden, The Netherlands tlS) Heinz, G. 1974. Effects of low dietary levels of methyl mercury on mallard reproduction. Bull Environ Contam. Toxicol. I l(4):386-392. 20 Pesticides Monitoring Journai (19) Hickey. J J., and D W. Anderson. 1968. Chlorinated hydrocarbons and eggshell changes in raptorial and fish- eating birds. Science 162(3850):271-273- (20) Keith. J. O.. L A. Woods, and E. G. Hunt. 1970. Reproductive failure in brown pelicans on the Pacific Coast. Trans. N. A. Wildl. Nat. Res. Conf. 35:56-64. (21) King. K. A.. E L Flickinger. and H H Hihiehrand. 1977 . The decline of brown pelicans on the Louisiana and Texas Gulf Coast. Southwest Nat. 21(4):417-431 . (22) Longcore, J. R . F B Samson, and T. W. Whitiendale. Jr. 1971. DDE thins eggshells and lowers reproductive success of captive black ducks. Bull. Environ. Contam. Toxicol. 8(2):65-68. (23) McLane. M. A. R.. and L C Hall. 1972. DDE thins screech owl eggshells. Bull Environ. Contam Toxicol. 8(2):65-68 (24) Okuno. /., R. A. Wilson, and R. E White. 1972. Determi- nation of mercury in biological samples by flameless atomic absorption after combustion and mercury-silver amalgamation. J Assoc. Off Anal. Chem 55( 1 ):96-IOO. (25) Peterson. J. E.. K. M. Slahl. and D L. Meeker. 1976. Simplified extraction and cleanup for determining or- ganochlorine pesticides in small biological samples. Bull. Environ Contam. Toxicol. 15(2); 135-139. (26) Risebrough. R. W.. and D W. Anderson. 1975. Some effects of DDE and PCB on mallards and their eggs. J. Wildl. Manage 39(3):508-5l3. (27) Stendell. R. C. 1975. Summary of recent information regarding effects of PCBs on birds and mammals Proc. Nat. Conf. PCBs, U.S. Environmental Protection Agency. EPA-560/6-75-004, Chicago, IL, pp. 262-267 (2S) Stickel. L. F. 1973. Pesticide residues in birds and mam- mals. Pages 254-312 in C. A Edwards, ed.. Environ- mental Pollution by Pesticides, Plenum Press, London and New York (29) Vermeer. K 1971 . A survey of mercury residues in aquatic bird eggs in the Canadian Prairie Provinces. Trans. N. A. Wildl. Nat. Res. Conf. 36:138-150. (30) Wiemeyer. S. N.. and R. D. Porter 1970. DDT thins eggshells of captive American Kestrels. Nature 227(5259):737-738. Vol. 12. No. I.June 1978 21 Organochlorine Insecticide and Polychlorinated Biphenyl Residues in Woodcock Wings, 1971-72 M. Anne R. McLane,' Eugene H. Dustman,' Eldon R. Clark,' and Donald L. Hughes ■* ABSTRACT Pesticide residues in wings of adult woodcock (Philohela minor) were used to monitor regional differences in a 1970-71 survey of DDT. DDE. TDE. dieldrin. mirex, and PCBs in Maine. New Hampshire . New York, New Jersey. Pennsylvania. North Carolina. South Carolina, Georgia, Lousiana. Michigan, and Wisconsin. In 1971-72, wings were sampled again to compare levels of organochlorine insecticide residues with those of the previous survey and to delineate differences in residue values between adult and immaiure woodcock. Three additional states. Massachusetts. Minnesota, and Vermont, and one additional organochlorine insecticide, heptuchlor epoxide, were included in the second survey . Residue levels in the 197 1 -72 wings showed the same pattern as thai observed in 1970-71: organochlorine insecticide residues were highest in wings collected in the southern states and in New Jersey; residues were lowest in samplings taken in the northern and midwestern stales Residues of DDT. TDE, and dieldrin in the 1971-72 wings were slightly lower than those found in 1970-71 . DDE. PCB. and mirex residues were signifi- cantly lower (P<0.05. P 22 Hunion St . Calais. ME (M6I9 * WARF Institute, Inc. (now Raltech Scientific Services. Inc }, Madison. Wl 53701 by cooperating hunters. Thus wings are in ample quantity tor other studies. The same wings can be used to assess quantities of pollutants which the birds have acquired, largely from their food. The woodcock occurs near or at the top of a terrestrial food chain and subsists on animal material, primarily earthworms (7, 10). Earthworms con- centrate an array of persistent environmental pollutants in their tissues and are important in the diets of a number of avian species (2, 3. 4. 5. 6). Woodcock wings were first monitored for environmental pollutants in 1970-71. Regional differences were clearly demonstrated and baseline measurements were obtained for later comparisons (8). An expanded sampling of wings was undertaken in 1971-72 to compare residues with those found in 1970-71, and to determine whether residues in the wings of adult and immature woodcock differed. This paper reports the findings of the 1971-72 survey . Methods Wings were collected in 15 states: Connecticut, Georgia, Louisiana, Maine, Massachusetts, Michigan, Minnesota, New Hampshire. New Jersey, New York. North Carolina, Pennsylvania, South Carolina, Vermont, and Wisconsin. These states provided a suitable geographic distribution and offered the best chance for collecting adequate num- bers of wings. Because wings from North Carolina. South Carolina, and Georgia were too few to provide a sample from each state, the wings from these states were combined into one tri-state area sample. Wings from adult and im- mature woodcock from each state and from the tri-state area were sorted into groups of 25. Five of these groups from each state and five from the tri-state area were randomly selected for analysis. Wings were plucked and the distal joint was removed. The part remaining was ground in a hand grinder and 22 Pesticides Monitoring Journai homogenized with the group of 25 which made up the complete sample. A 20-g aliquot was taken for analysis. Organochlorine pesticides and polychlorinated biphenyls (PCBs) were determined at WARF Institute, Inc.. Madi- son, Wisconsin, by the following procedures: The 20-g aliquot was dried at 40° C for 96-120 hours, and then ground with sodium sulfate and extracted for 8 hours on a Soxhlet extractor with 105 ml of ethyl ether and 250 ml of petroleum ether. The extract was concentrated on a steam bath and diluted to 50 ml with petroleum ether. A 10-ml aliquot of the extract was cleaned and separated into two fractions by elulion through a Florisil column with mixtures of ethyl ether and petroleum ether (5-1-95 and 15 -(-85). An aliquot of the final elation was passed through a standardized silicic acid column as described by Armour and Burke (J). Temperatures: Carrier gas: Chromatograph: Column: Temperatures: Carrier gas: injector 225° C column 205° C detector 245° C purified nitrogen fllowing at 80 ml/minute Barber-Coleman Model 500U 4-ft X 4-mm glass, packed with 3 percent OV-17 on 100-120-mesh Gas-Chrom Q injector 215° C column 200° C detector 250° C purified nitrogen flowing at 80 ml/minute The sensitivity level of this method was 0.05 ppm or- ganochlorine pesticide and 0.10 ppm PCBs on a lipid basis. Recovery for organochlorine pesticides ranged be- tween 80 and 95 percent, and PCB recoveries ranged be- tween 75 and 85 percent. None of the residue data has been adjusted for rates of recovery. The pesticides and PCBs were determined by electron- capture gas chromatography under the following condi- tions: Chromatograph: Column: Barber-Coleman Model 5360 Pesticide Analyzer 4-ft X 3-mm glass, packed with 5 percent DC-200 on 80- 100- mesh Gas-Chrom Q Results and Discussion Table 1 shows the ranges and the means as ppm lipid weight for DDT, DDE, TDE, PCBs, dieldrin, mirex, and heptachlor epoxide residues in adult woodcock wings from 12 states and the tri-state area arranged in approximate geographic order from south to north. DDT and its State TABLE 1 . Ranges and geometric means of organochlorine insecticide residues in adult woodcock wings from 15 easternlmidweslern states. 1971-72 REStDUES, PPM Lipid Weight Heptachlor DDT DDE TDE PCB DtELDRtN MiREX Epoxide Louisiana Tri-slate area New Jersey Pennsylvania Connecticut New York Massachusetts New Hampshire Vermont Maine Michigan Wisconsin Minnesota 1.88-5 45 2 74 2.35-11 12 5 90 3,27-8,20 4 90 0 29-1 37 0 60 1 28-5 61 2 36 0,29-2,87 1 12 0,51-5 41 2 16 0,68-8,47 1 92 0,25-0 67 1,36 0.36-0 94 0,77 0.24-0 68 0,50 ND-0 18 0,10 0 16-0.47 0 30 5 74-13,09 9 20 6 99-27,00 18 69 10 11-25 80 16 96 2,11-4,71 3 59 3,38-7.12 6 23 4 16-13 07 6 32 8,28-22 65 15,63 5 96-11 56 8 47 2 63-3 57 3,33 3.24-7,20 5 13 2 28-6 96 3 53 2,60-4 23 3 15 1 12-3 34 1,74 0 52-1 40 0 91 0 64-2 02 1 42 0 76-2,34 1 25 ND-0 17 0,03 0 16-0,65 0 35 0,14-0 26 0 19 0 11-073 0 33 ND-0 47 0,31 0 07-0 13 0,12 0 06-0 25 0,18 0 06-0 32 0,18 1 65-4 10 2.21 2,63-4 22 3,24 1.97-4,04 2,92 0 94-2 07 1 39 1 52-4.38 2 66 1,37-1,84 1 60 4 03-9,58 5 84 1 44-1,90 1 69 1,54-2 02 1.75 0 96-1 26 1 12 1 02-2 21 1 39 0,46-1,22 0.77 ND-0 48 0 08 1.27-5 56 1.90 1,22-4 04 1 88 0 27-0 77 0 43 0,12-2.99 0 30 0 12-1.12 0,36 0,15-0.21 0.18 0.05-0,91 0 15 0.14-0.59 0 27 0,08-0 II 0,09 0,06-0,12 0,08 0 07-0,11 0 09 0,09-0,82 0,18 0.05-0,06 0,05 4,70-8,49 5 20 I 66-5 27 3 14 ND-2 12 0 58 0,24-0 78 0 48 ND-0, 38 0,50 0 28-0,96 0,54 ND-0, 91 0 24 ND-0 92 0.45 0,24-1.25 0,54 0.34-1 44 0,87 0.59-5 01 1,34 ND-1 78 0 85 ND-0. 74 0,21 0,52-1 13 0 70 0 21-1 48 0 58 ND ND ND ND ND NOTE Tn-state area = North Carolina, South Carolina, and Georgii ND = not detected. Vol. 12, No. 1, June 1978 . Wings from three slates were combined because not enough were available from any one state 23 metabolites are distributed in a similar pattern: geometric means of DDT and its metabolites were highest in the tri- state area (DDT. 5 90 ppm; DDb, 18.69 ppm; TDE, 1.42 ppm) and second highest in New Jersey (DDT, 4.90 ppm; DDE. 16.96 ppm; TDE. 1.25 ppm). Differences in con- taminant residues levels were determined by one-way anal- ysis of variance with Duncan's multiple range test. Aver- age TDE residues in woodcock wings from the tri-state area and New Jersey were significantly higher {P<0.01) for the tri-state area than for all other states except New Jersey. Massachusetts, and Louisiana. The average level of DDE was significantly lower (/'<0.01) for Minnesota than for all other states. The average PCB residue in woodcock wings (5.84 ppm) was significantly higher (P<0.01) for Massachusetts than for all other states: PCBs in wings were higher (P<0.01) for the tri-state area than for all other states except New Jersey, Connecticut, and Louisiana. The average PCB level was significantly lower (P<0.01) in Minnesota than in all other states. Average dieldrin residues in wings from Louisiana and the tri-state area (1.90 ppm and 1.88 ppm, respectively) were significantly higher than those in all other states. Min- nesota had the lowest average residues (0.05 ppm). Heptachlor epoxide residues were found in adult wings in only two areas: Louisiana and the tri-state area. These two areas were included in the fire ant {Solenopsis saevissima) eradication program which used heptachlor in the 1950s. Mirex was substituted for heptachlor in the early 1960s. Heptachlor epoxide residues found in adult wings from Louisiana ranged from 0.52 to 1.13 ppm: the geometric mean was 0.70 ppm. Residues in adult wings from the tri-state area ranged from 0.21 to 1.48 ppm: the geometric mean was 0.58 ppm. Woodcock wings from the two southern areas, Louisiana and the tri-state area, had consistently higher or- ganochlorine residues other than PCBs. PCB residues were highest in Massachusetts and second highest in the south- ern areas. Wings from Minnesota had the lowest or- ganochlorine residues except for DDT. Wisconsin had the lowest DDT residues: Minnesota had the second lowest. Eleven of the 13 states, including those in the tri-state area, were sampled in both 1970-71 and 1971-72 (Table 2). Generally, residues were lower in the second sampling period. DDE, mirex, and PCB residues were significantly lower in 1971-72 than in 1970-71 (P<0.05, P<0.01, and P<0.01, respectively). The relationship of residue levels among states for the two years was tested by a two-way analysis of variance (Table 3). Residues in both sampling periods were consistently highest in the southern states and in New Jersey. Residues were lowest in the northern and midwestern states. Table 4 shows ranges and geometric means of or- ganochlorine insecticide residues found in immature wood- cock wings. Immature wing residues follow the same pat- tern as residues in adult wings in all but three instances. Mirex residues were higher in immature wings from the tri-state area than in immature wings from Louisiana. Av- erage PCB residues in immature wings were lowest in New Jersey, Louisiana, and the tri-state area: this is the opposite order of residues in adult wings. Heptachlor epoxide resi- dues were found in adult and immature wings from Louisiana and the tri-state area: heptachlor epoxide was also found in two pools of immature woodcock wings from New Jersey. TABLE 2. Geometric means of organochlorinaled insecticide residues in woodcock wings from easternlmidweslern states, 1970-71 and 1971-72 GeoM- Mean PPM Lipid Weight Residue 1970-71 1971-72 DDT 1.48 1.26 DDE ' 8.79 6 82 TDE 1.41 1 42 Dieldrin 0.31 131 Mirex ' 1.54 1 09 PCB = 5.58 1.64 NOTE; See Table 3 for list of slates sampled. 'Significani al/'<0 05 '■ Significani al P <0 01 TABLE 3. Comparison of organochlorine insecticide residues in adull woodcock wings, 1970-71 and 1971-72 State Geoim. Mean of Residues, ppm Lipid Weight DDE DDT TDE PCB [)lELDiUN Mirex 4 7ld 078de 0 19c 2 18c 008b 1.04c 7 58cd 1 6lcd 0 25c 3 08bc 0 19b 063c 5 92cd 0.77de 0 15c 3 27b 0 19b 1 04c 4 07d 0 70de 0 lie 2 51bc 0 17b 046c 16 01«b 5.15ab 081b 4 16a 0 53ab 0 63c 28 56a 9 19a 2.27a 5 24a 2.25a 3 lib 1083bc 2 33bc 066b 3 36b I98> 1025a 4.65d 0.63e 0.16c 2 43bc 0.15b 1.39c 5.05d 033e 0.51c 2.14c O.lSb I.Otc Maine New Hampshire New York Penrnylvania New Jertey Tnsiatc area ' Louisiana Michigan Wiiconsin NOTE. VaJue^ with the \8me letter are not significantly difTercni ' Sec Table 1 for cxplanatiDn 24 Pesticides Monitoring Journ.'M TABLE 4. Ranges ami geometric means of organochlorine insecticide residues in immature woodcock wings from seven easternlmidwestern states. ]97l~72 Residues, ppm Lipid Weight Maine Michigan New Jersey Tri-stale area ' NOTE: ND = nol detected 'See Table 1 for explanation Heptachlor DDT DDE TDE PCB DiELDRIN MiREX Epoxide 0 51-2.28 2 56-5 28 0 16-0 41 0.75-1.07 0 06-0.83 ND ND 1 19 4.07 0.25 0 89 0 16 — — 0 46-4.33 1 90-9.77 0 12-2.04 0 95-1 52 0 07-0.35 ND ND 0 92 3 16 0 23 1 18 0 20 — - 3 10-27 04 9 40-18,01 0 46-2 84 1 93-4 28 0 61 -1 07 ND ND-0,42 6 41 13 64 1 11 2.55 0 88 - 0 13 2 89-18 10 15 29-47 47 0 64-4.09 ND-3 93 0 76-2 70 1 80-3 98 0 26-1 23 6 82 26.03 1 46 2.04 1 64 2 87 0 51 1.93-4 01 7 42-12 53 0 46-0.95 1.27-3.68 1.32-10.20 1 43-3 72 0 45-0.96 2.97 9 80 0.72 2.23 2.46 2 48 0.69 Mirex levels in wings of adult and immature woodcock from Louisiana are clearly different; the residues in wings from adults were significantly higher t,P<0.Q5). Mirex residues in adult wings ranged from 4.70 to 8.49 ppm: the geometric mean was 6.20 ppm. In immature wings, mirex residues ranged from 1.43 to 3.72 ppm; the geometric mean was 2.48 ppm. Mirex residue levels from all other states were very low. No significant difference in residue levels were found between adult and immature woodcock in other states, nor among other organochlorine insec- ticides. The authors conclude that woodcock wings can be used to help determine the levels and trends of a variety of en- vironmental pollutants in the eastern United States. Periodic assessment of residues in the wings of this species will provide important monitoring information at nominal cost. LITERATURE CITED (I) Armour. J. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Assoc. Off. Anal. Chem'. 5.1(4);761-768. (2) Barker. R. J. 1958. Notes on some ecological effects of DDT sprayed on elms. J. Wildl. Manage. 22(3):269-274. (3) Boxkins, E A. 1966. DDT residues in the food chains of birds. Ati. Nat. 21(l):l8-25. (4) Gish. C D. 1970. Organochlorine insecticide residues in soils and soil invertebrates from agricultural lands. Pestic. Monit. J. 3(4):24I-252. (5) Korschgeii. L. J. 1967. Soil-food chain-peslicide wildlife relationships. Missouri Pesticide Studies, Federal Aid Proj- ect 13-R-21. Missouri Department of Conservation. Jeffer- son City, MO (6) Krohn. W. B. 1970. Woodcock feeding habits as related to summer field usage in central Maine. J. Wildl. Manage. 34(4);769-775. (7) McLane. M.A.R.. L. F. Slicket. E. R. Clark, ami D. O. Hughes. 1973. Organochlorine residues in woodcock wings. 1 1 states— 1970-71. Pestic. Monit. J. 7(2);IOO-103. {8} Sheldon, W . G 1967 . The book of American woodcock. University of Massachusetts Press, Amherst, MA, p. 227. Vol. 12, No. 1, June 1978 25 Chlorinated Hydrocarbons and Mercury in Birds of Lake P'dij'dnne, Finland — 1972-74^ Jukka Sarkka,- Marja-Liisa Hattula,^ Jorma Janatuinen.- Jaakko Paasiviria,' and Rislo Palokangas- ABSTRACT The levels of mercury, PCBs, DDT and its analogs, lindane, and dieldrin were examined in aquatic birds nesting on the shores of Lake P'aifanne, the second largest lake in Finland, which is polluted hy a wood-processing industry and urban sewages. The primary food of the 10 species examined was fish. In muscle of about 350 individuals, the highest average residues were PCBs: in livers, mercury was the highest Lindane was found in some individuals: dieldrin appeared in none. The differences among levels in 1972, 1973, and 1974 were not significant. Some regional differences were found, particularly for mercury. Some PCB contamination was observed near the town of Jyvaskyla. DDT was distributed evenly. A stronger correlation existed between residues of PCBs and DDT than between residues of any other compounds . In some gulls, males had higher average residues than had females. The DDT:PCB ratio generally corresponded to that of the North Atlantic Ocean, hut the difference among species was great. Higher mercury. PCB, and DDT values existed in adults than in juveniles: higher mercury values existed in livers than in mus- cles. Black-throated divers had highest mercury residues: in herring gulls. PCBs and DDT were highest. The levels gener- ally correspond to those found in other studies. Introduction Authors undertook the present study to discover the levels of chlorinated hydrocarbons and mercury in the aquatic birds of Lake P'aij'anne, Finland. Simultaneously, the methods of chemical analysis and the chemical structures of the compounds were developed. Data on the birds were collected by the University of Jyvaskyla as part of a monitoring study of the chlorinated hydrocarbons and mer- cury in the food webs of Lake Faij'anne, in which residues were analyzed in the higher aquatic plants, plankton, bot- tom fauna, sediment, fishes, and aquatic birds. Adults and juvenile birds were analyzed separately. Juveniles were birds of the same summer, ranging in age from a few days to several weeks. Muscle and liver tissues were analyzed separately. Concentrations of different residues were analyzed ac- cording to age, location on the lake, and species. Attention was also paid to the differences between and ratios of residues in liver and muscle, and to the correlations of different residues to muscle:liver ratios, differences of residue load between the sexes, and the 1DDT:PCB ratios. The significances of the differences were statistically tested. Sampling and Collection Lake Faij'anne. the second largest lake of Finland (1100 km-), has been the object of limnological investigations since 1968 (32). It receives waste principally from the three origins shown in Figure 1. The sulphite and sulphate pulp mill wastes of A'anekoski come from the north in the upper part of the watercourse, approximately 40 km up- stream from Lake Faij'anne. Wastes are also discharged into the northern part of the lake from the town of Jyv'as- kyl'a via Lake Jyv'asjarvi (station 1); these effluents contain urban sewages and paper mill wastes. The third source of wastes is in the center of the lake near station 4, which receives effluents from a sulphite pulp mill and two paper mills of Jamsa, as well as a minor amount of domestic waste. At the northern end of the lake, the content of human sewages is greater than in the center which is contaminated almost exclusively by the wood-processing industry. When flowing from the north to the center (sta- tion 3), the water becomes cleaner. Water extending from the central part of the lake (station 4) to the southern part (station 6) is quite clean. Study supported by a grant from the Academy of Finland. Helsinki ' Dcpanment of Biology, University of Jyvaskyri, SI-40I0U Jyvaskyfa 10. Finland ' Oepinmenl of Chctnislry. University of Jyvaskyla. SF-40100 Jyvaskyla 10. Finland. The main sampling sites of the study were stations 1, 4, 5, and 6. From stations 2 and 3, a few birds were obtained for supplementary study. Station I is polluted by domestic 26 Pesticides MoNiroRiNc Journal AANEKOSKI Pulp mills Paper mill Mai n inflow JTVASKYLA,/ Town JP ^ M 1 " O SampI in g Stat ions ^ Inflows FIGURE 1. Lake Paijdnne with sampling stations. birds were conserved by freezing in plastic bags which did not contain PCBs. Species analyzed were black-throated diver {Gavia arclica L), great crested grebe (Podiceps cristatus L.), goldeneye (BucephaUi clangula L.), redbreasted merganser ( Mergus serrator L.), sandpiper (Tringa hypoleucos L), lesser black-backed gull (Larns fuscus L.), herring gull (Larus argentatus L.), common gull (Larus canus L.), black- headed gull (Larus ridibundus L), and common tern (Sterna hirundo L.). Species were chosen to represent aquatic birds, especially those which feed at Lake Paijanne in the summer. This is why such species as mallard (Anus platyrhynchos) and other common game birds were not sampled. All species, however, are migratory, spending only about one third of the year in Finland. The number of birds analyzed for total mercury was 344; for methyl .nercury, 32; and for chlorinated hydrocarbons, 301. Analytical Procedures CHLORINATED HYDROCARBONS The frozen sample was thawed and 5-10 g breast muscle or liver was weighed. The sample was ground in a mortar with acid-washed sand (Merck) and anhydrous sodium sulphate, 4 g of the latter for each gram of wet tissue. The homogenized mixture was transferred to a glass container and dried at room temperature for 48 hours. The extraction was performed by Soxhiet in thimbles which had been washed ultrasonically in a 1:1 mixture of acetone and diethyl alcohol. The homogenate was trans- ferred to the thimble and extracted for 6 hours in a mixture of diethyl ether, petroleum ether (boiling point 40°-60° C), n-hexane, and acetone in quantities of 1:9:2, 5:5, 5 (v/v). All solvents were pesticide analytical (pa.) grade and redistilled. This solvent system has been statistically proved to be the most effective for extracting animal tissue {14). sewages and paper mill effluents. Until 1968, effluents from the paper mills and the Aanekoski pulp mills con- tained mercury originating from slime-preventing chemi- cals (12). Water at stations 2 and 3 gradually becomes cleaner as it moves south. Water at station 4 is affected by a wood-processing industry whose effluents contained mercury until 1968. Water at station 5 becomes cleaner as it approaches station 6, which is almost limnologically pure (28). Adult birds were collected by shooting and young birds were caught live. No individuals were found dead. The adults were all caught after eggs had been laid. The whole The extracted fat was weighed and cleaned by the follow- ing methods: shaking with concentrated sulphuric acid (2), thin-layer chromatography (75), and a column chromatog- raphic method (16). In routine analyses, if extracted fat exceeded 20 mg, it was made into a I percent solution in n-hexane and divided into halves. One half was shaken with concentrated sulphuric acid for determining total PCBs, lindane, and DDE. The residues were extracted in hexane which was ready for gas chromatography. The hexane was shaken again with chromic acid for determin- ing DDE (35). The second half was applied on a thin-layer plate for determining TDE, DDT, dieldrin, and endrin. When extracted fat was 10 mg or less, thin-layer Vol. 12, No. I.June 1978 27 chromatography was the only cleanup method used. The column chromatographic method was used mainly for analyzing bird material because residues were greater than in the rest of the samples and required dilution from 10 mg fat. which is the maximum amount accommodated by the column, (0 10 ml fat for proper gas chromatography. The cleanup methods have been tested to determine the highest values of the chlorinated hydrocarbons per fresh weight of tissue ( /5). The highest value of PCBs is the only recovery criterion available at present. The sulphuric acid cleanup produced a statisfactory measurement of PCBs in a fat reference sample of the Organization for Economic Coop- eration and Development (OECD). The equipment used in determining the residues was a Varian Model 600 D gas chromatograph with an H' electron-capture detector. The length of the glass column was 1.5 m and the inside diameter was 1.5 mm. In the routine analyses the column filling was a mixture of 65 parts of 8 percent QF-I and 35 parts of 4 percent SF-96 on Chromosorb W 100-120 mesh. Occasionally SF-96 on Chromosorb W 100-120 mesh was also used for control purposes. The carrier gas was nitrogen (99.999 percent). The column temperature was 180° C, the detector and injector were 190° and 225° C. respectively. The following pesticide standards, all 100 percent pure. were used: aldrin. p.p'-TDE, p,p'-DDE, p,p'-DDT, o.p'-DDT, dieldrin, endrin, and lindane. The PCB stand- ard was Clophen A 60 by Bayer because the PCB contami- nation in Finland had been statistically tested and proved to be that type (13). The final concentration in chromato- graphing was 10 ng/ml for pesticides and 100 ng/ml for the PCBs. The calculation was carried out as described by Gaul (10) and the PCBs were calculated by summing nine peaks (total 13 peaks) which did not interfere with the pesticides. Injection of 50 pg pesticides or 500 pg PCBs produced peak heights of approximately 50 percent of full-scale deflection. TOTAL MERCURY Total mercury was determined by cold vapor atomic ab- sorption using a Coleman MAS-50 mercury analyzer. A sample of 0.5-1 g was homogenized in an Erienmeyer flask with 0.5 ml water, and 10 ml concentrated sulphuric acid was added while the flask was kepi in an ice bath. The flask was then covered with plastic film and kept in a 60° C water bath for 4 hours. After cooling. 15 ml 6 percent solution of KMnOj was added from a buret, the bottle was kept in an ice bath and shaken well, and the sample was diluted to 100 ml. To reduce mercury II ions to mercury metal. 2 ml 20 percent hydroxylamine hydrochloride and I ml stannous chloride (40 percent solution in 5 percent sulphuric acid) were added and the measurement was taken immediately. The standard was HgCI^ and a standard curve was made daily after treating the standard as described above. METHYL MERCURY Methyl mercury was identifieil by gas chromatography using the following conditions: Chromatograph: Varian Aerograph 2400 Deleclor: H ^ Irilium Column glass. 18 in long and 6 mm ID. packed with 10 pcrcenfCar- bowax 20M on Chromosorb W 80-100 mesh Temperatures: column: 140° C injector: 180° C detector: 210° C in a Sorvall Omniinixer. 1-5 g material was homogenized in 26 ml 29 percent KBr. Then 3.5 ml 47 percent HBr that had been prewashed with benzene was added to the homogenate which was then centrifuged and the liquid was decanted. The homogenate was treated again with KBr and HBr. The liquid phases were combined in a 250-mI separatory funnel and 50 ml redistilled benzene was added. Methylmercury bromide was added to the benzene. The water phase was extracted again with 25 ml benzene and the extracts were combined; then 8 ml 20 percent cysteine acetate (dried with Na2S04) was added and the solution was shaken to bind the methylmercury bromide to cysteine. Five ml of the water phase was shaken with 1 ml 47 percent HBr and 10 ml benzene to extract the methylmer- cury bromide in benzene. The benzene phase was chromatographed and the peak heights of the sample and the standard were calculated. Injection of 50 ^g Hg as methylinercury bromide produced a peak height of full- scale deflection. Results Table 1 shows the average levels of the residues studied in muscles and livers of both adult and juvenile birds. Differ- ences among species, areas, and years are not considered in this table. The table shows that in muscles, the residues of highest concentration are PCBs; in the livers, mercury appears at the highest levels. Concentrations of TDE and DDT are very small compared with those of DDE; all three are combined in subsequent tables as SDDT. Lindane was present in only a few individuals, accounting for minute TABLE 1. Average chlorinated hydrocarbon and mercury con- cenrralion.s In muscles and livers of aquatic birds. Lake Paijanne. Finland — 1972-74 Average CONCENIRAriON mo/kg Wet Weight MUSCI ES Livers Compound Adui TS Juveniles Adui ts Juveniles Total Hg 2.729 0.777 7.900 2,312 Methyl Hg 2 697 0.275 — — PCB 4 970 1 135 5 734 0,961 DDE J .173 0 708 4 187 0,821 TDE 0.012 0 000 0,015 0,000 DDT 0.002 0,000 0,007 0,000 SDDT 3 387 0.708 4,209 0,821 Lindane 0 002 0 001 0 000 0 000 Dieldrin 0 000 0 000 0 000 0,000 28 Pesticides Monitoring Journal residue averages. Dieldrin was not present in any indi- vidual at concentrations above 0.0005 mg/kg wet weight. The material of each year of study consists of different numbers of samples from different sampling areas, so results for the different years were not compared with parametric statistical tests. The yearly differences of the average concentrations of total Hg, PCBs, and SDDT were examined separately in different bird species for the mus- cles and livers of the adults and juveniles, using non- parametric Friedman two-way analysis of variance or Wil- coxon matched-pair signed-rank tests {29). No significant differences among the years were observed. Tables 2-5 present the corresponding residues in birds at different areas of the lake. Because residues vary broadly TABLE 2. Average concentrations of total Hg, PCBs. and XDDT in muscles of adult birds. Lake Pdifdnne. Finland Stody are* 1 Am* 2 A«ea 3 Aie* 4 A«e* 5 Ama 6 Species Statistic Ho PCB ZDDT Hg PCB iDt)T Ho PCB SDDT Ho PCS SDDT Ho PCB IDDT Ho PCB TDUl Residues, mg/kg wet weighl Black-lhroaled diver M — — — _________ |2 80 3,53 5 66 14,57 181 6.81 SD 0,00 2,88 2 59 0,00 0,37 4.34 N 13 3 13 3 Greal crested grebe M 2 88 3 99 3 74 — — — — — — 178 133 3 54 ______ SD 1 13 3 11 2 76 0,80 1 02 3 11 N 8 8 8 4 4 4 Goldeneye M — — — ______ o 24 0 22 0 14 — — — — — — SD 0,06 0 17 0,03 N 4 3 3 Merganser M ___ _ ________ 5,48 2,16 1,28 5 42 185 3 22 SD 0.00 0.00 0.00 141 141 4 36 N 1113 3 3 Sandpiper M ____________ o,31 0,28 0,71 0,63 3.30 5.41 SD 0.00 0.00 0.00 0.00 000 000 N 1 I 1 1 1 I Black-backed gull M 3.00 7.97 1 II 3 44 14 32 5 87 2 43 _ _ 2 74 3 64 5 22 3 27 7 15 7 02 3,66 5 10 6 60 SD 0.00 0,00 0 00 124 4.72 193 0,60 _ — 158 3 09 3 79 106 4 91 3 54 1,29 3 29 4.46 N 1115 5 5 3 9 9 9 17 17 17 15 12 12 Hemnggull M 0 10 6 69 I 79 _ _ _ _ _ _ 4,00 19 54 20,38 2,80 20 49 6 90 2 97 8,46 6 89 SD 000 0.00 0,00 125 2 06 2,36 1 10 12 31 5 10 192 5 33 3,92 Nlll 222555 12 88 Commongull M 2 64 8,98 5.88 2,05 7 16 2 61 3 16 1177 14 29 2 03 4 04 2 41 2 01 3 33 2.58 1,70 3 18 2 40 SD 0 00 0,00 000 0,15 3 15 2 86 0,00 0,00 0 00 I 15 4 54 2,18 148 2 57 2 41 1,01 3 26 184 N 1 1 15 5 5 1 1 1 20 20 20 14 14 14 16 16 16 Black-headed gull M 178 4 67 1 58 2 73 4 89 0 87 _ _ _ 0 96 2 28 0,69 1 17 2 60 0 48 _ _ _ SD 088 4 17 3 38 1,55 2 53 0,32 0 54 5 84 1,07 0 35 0 14 0,13 N 17 16 16 4 4 4 18 18 18 2 2 2 Common teiT. M 3 01 6,18 2,36 2,68 4,53 0.66 5,94 _ _ 3 48 2 91 137 4 38 2.92 1,32 5,08 4 27 1.53 SD 1,60 4,38 5,18 2,19 3,03 0 29 0,51 2,28 1,92 150 132 1,52 0,94 1,61 3 92 156 N 13 12 12 5 5 5 2 16 16 16 7 6 6 7 6 6 NOTE: See Figure 1 for location of study areas, M = mean. SD = standard deviation. N = number of observations. TABLE 3. Average concentrations of total Hg, PCBs, and ^DDT in muscles of juvenile birds. Lake Pdifdnne, Finland Study Area 1 Area 2 Area 4 Area 5 Area 6 SPEOES Statistic Hg PCB IDDT Ho PCB IDDT Ho PCB XDDT Ho PCB XDDT Ho PCB XDDT Residues, mg/kg wet weight Black-throated diver M ____________ 8.15 — — SD 0.00 N 1 Great creasted grebe M 0 53 1,25 0 30 _ _ _ 0.38 0 19 0,11 _ _ _ _ _ _ SD 0 19 0.81 0 15 0 12 0 15 0 04 N 6 3 3 3 2 2 Goldeneye M ______ 0,07 _ _ 024 015 0 16 _ _ — SD 0,00 0,00 0 00 000 N 1111 Merganser M ____________1.32 0.18 0.78 SD 0,48 0,00 0,00 N 4 11 Black-backed gull M 198 7 70 4,39 0,87 4,06 0,82 _ _ _ 0,92 I 10 0 51 0 69 2.28 5,00 SD 0 00 0,00 0,00 0,00 0 00 0 00 0,23 1 14 0 44 0,41 2,30 5.31 N llllll 733433 Hemnggull M 0.04 0.67 0.36 _ _ _ 0.94 5 44 2,57 0,79 2,97 0,96 0,64 2,85 1,52 SD 0.00 0,00 0,00 0,00 6,86 3,25 0,00 0,00 0,00 041 2,47 0,84 N 111 222111 11 33 Commongull M 145 103 0 40 _ _ _ 0 76 0 33 0 13 1,00 0 43 0,51 0,85 1,32 0,59 SD 000 000 0,00 032 0,00 0,00 0,39 0,51 1,08 0.20 1,90 0,79 N 111 3 1 1 13 12 12 6 4 4 Black headed gull M 0,45 0,52 0,10 _ _ _ 0,35 0.36 0,15 ______ SD 0 28 0,33 0,05 0,32 0 37 Oil N 9 8 8 11 11 II Common tern M 0,50 0.95 0 16 _ _ _ 1.12 1.06 0 67 0.34 1.00 0.41 0,45 0,68 0.25 SD 0.09 0,22 0.04 0,65 0 59 0 62 0.07 0,35 0 12 0,02 0.00 0,00 N 544 444333222 NOTE, See Figure 1 for location of study areas, M = mean. SD = standard deviation. N = number of observations. Vol. 12, No. 1, June 1978 29 TABLE 4. Average concentrations of total Hg, PCBs, and IDDT in livers of adult birds, Lake P'aifanne, Finland Study aipa I Area 2 Akea 3 Aaea 4 Area S Area 6 Sncm Statistic He PCB ZDDT Ho PCB SDDT Ho PCB SDDT Ho PCB ZDDT He PCB XDDT Ho PCB ZDDT BUck-throalcd diver M SD N Great crusted grebe M SD N Goldeneye M SD N Merganser M SD N Sandpiper M SD N Black-backed gull M SD N Hemng gull M SO N Common gull M SD N Black-headed gull M SD N Common tern M SD N Residues, mg/kg wet weight — — — — — — — — — — — — 4380 3 79 — 82 33 6.10 24.91 000 000 000 0.00 000 0.00 1 I I I II 562 6.37 5 23 —— — — — — 60] 282 8,71 _ — — — __ 2 19 3.99 4.03 2 90 185 7 59 8 8 8 4 4 4 — — — — — — — — — 2 19 0.30 0 12 200 0 35 0 13 — — — 132 0.05 0.04 0 00 0 00 0 00 4 3 3 111 — — — — — — — — — — — — 24.00 2 16 128 22 97 180 3.78 0.00 OOO OOO 854 0.39 1.93 I I I 3 3 3 — — — — — — — — — — — — 0 38 0 16 0.44 123 0 44 0 25 000 OOO 0.00 0.00 000 0.00 1 I I I I I 7 20 683 3 19 8 74 1997 1640 8 42 4 60 4 97 7 98 9.39 9.33 9.74 5.91 8.54 10.62 3.72 7.82 000 OOO 000 209 16 28 10.99 0 78 2 86 3 55 4.36 8.64 6.% 4.10 5.32 5.22 4 35 3.78 6.34 I I 15 5 5 3 3 3 9 9 9 17 17 17 15 12 12 0.21 0.77 2 49 — — — — — — 1065 2516 1996 761 1362 6.53 7.39 346 4.48 0.00 0.00 000 361 611 123 2 80 9 87 4 96 511 2 66 3 62 III 222555 12 55 6 75 5.33 105 6.29 14 16 5 82 10 00 10 07 10 99 5 65 4.45 4 08 6 17 2 48 2 67 5 36 4 58 3 32 0 00 0.00 0 00 0 72 13 91 2 87 0 00 0 00 0.00 2.74 3.98 4.75 4.38 3 97 3.36 4.45 4 15 3 73 1 1 13 5 3 I I I 20 19 19 14 14 14 16 16 16 4 65 6 86 1 II 6 04 4 59 2 34 — — — 2 65 2 03 0 66 2 28 2 21 0.65 — — — 2 72 5 17 072 3 51 194 2 21 136 174 0 61 0 74 0 28 0 07 17 17 17 4 4 4 18 18 18 2 2 2 7 79 6 19 1 14 6 34 10 35 2 09 13 30 7 10 1 38 8 36 3 87 1 62 15 52 2 62 104 14 6 5 35 1 80 3.06 4.01 087 468 8 03 127 0 28 0 40 0 26 6.32 2 65 161 9 52 143 0 53 4 32 4 17 192 13 13 13 5 3 5 2 2 2 16 15 15 7 7 7 7 7 7 NOTE: See Figure 1 for location of study areas. M = mean. SD = standard deviation, N = number of observations. TABLE 5. Average concentrations of total Hg, PCBs, and IDDT in livers of juvenile birds. Lake P'aifanne, Finland STATtsnc Study area 1 AltEA2 Area4 Area5 AREA6 Sncas Ho PCB XDDT Ho PCB £DDT He KB XDDT Ho PCB IDDT Ho PCB ZDDT Residues, mg/kg wet weight Black-throated diver M SD N M — — — — — — — — 1920 000 12.62 000 642 000 Great crested gicbe 1 00 1 40 0.29 2.21 071 3 55 SD 0 II 0.34 0.10 0.93 0.48 3.31 N 2 2 2 3 3 3 GoWcneye M SD N 0.22 0.09 2 0.24 003 2 0 13 008 2 049 001 3 040 0 17 3 0 30 036 3 Merganser M SD N " " " " " " " ' " " " " 2.78 063 2 1 81 2.60 3 177 2.70 3 Sandp^n M SD N ~ ~ " " " " " ~ ~ " III 004 2 Bkck-bKkedguU M SD N M — — — 2.30 0.00 1.91 0.00 063 000 — — — — — — 2 10 OOO — — Haiiii(giiU 0.26 046 0 14 '_ _ 1 32 034 0 18 1,77 SD 0.00 0.00 0.00 000 000 000 1 64 N 1 1 1 1 1 1 5 M — — — — 3.11 1 20 042 350 043 072 343 0.96 0.37 SD 1.43 0.00 0.00 1.22 048 104 1 01 1.33 0.31 N 4 1 1 8 7 7 4 3 3 Black-headed gull M SD N 145 0.77 4 058 036 4 0 12 009 4 " " " 0.56 0.48 6 0 14 0.13 6 007 007 6 " " " M SD N 041 0.02 2 0 15 0.02 2 NOTE: See Figure 1 for location of study areas. M^iocan. SD = standard deviation. N = number of observations. amont different species, locations, and sampling years, the nonparametric Friedman two-way analysis of variance was used here, too, for comparing the different areas. In areas I, 4, S, and 6 (Figure I) and in the black-backed gull, herring gull, common gull, and common tern, significant regional differences occurred with iDDT in the livers of 30 Pesticides Monitoring Journal the adult birds but with no other compounds. The greatest concentration of SDDT was in area 4 and the smallest concentration was in area 1 . Table 6 presents averages and standard deviations of total mercury, PCBs, and 2DDT for the muscles and livers of adults and juveniles. Table 7 presents means and ranges of concentrations in different bird species. From these tables, comparisons between different species, between muscles and livers, and between adults and juveniles can be made. Because lindane was present in only three individuals, the data on this compound appear separately in Table 8. TABLE 6. Average Hg, PCB, and iDDT concentrations in muscles and livers of aquatic birds. Lake Pdijanne, Finland Muscles Livers Residue Adulis Juveniles Adults Juveniles M 2.73 0.78 7.90 231 TouJHg SD 1.95 0.86 7.64 2,83 N 242 101 243 50 M 4.97 1 14 5.73 096 PCB SD 5.32 1,75 6,33 2,08 N 229 72 230 40 M 3-39 071 4.21 0,82 SDDT SD 394 1 58 541 1 68 N 229 72 230 40 NOTE: M = mean. SD = standard deviation. N- number of observations. The ratios of residues in muscle to residues in liver were compared with those of other studies (1 . 4. 9, 17, 18). For mercury, this ratio varied in different bird species between 0.112 and 0.577 in adults, and between 0.278 and 0.573 in juveniles. The muscle:liver ratio for PCBs in adults was between 0.540 and 5.917; in juveniles the ratio was be- tween 0.100 and 8.258. The SDDT ratio in adults ranged from 0.383 to 8.884, and in juveniles, from 0.044 to 9.919. These values are approximately the same as those found in the investigations cited above. Table 9 presents the correlation coefficients of different residues. Coitipounds whose residues correlated most fre- TABLE 7. Concentrations of total Hg. PCBs, and IDDT in muscles and livers of aquatic bird species, Lake Paijanne. Finland Muscles LlvBts Juvemiles Mean Range Mean Range Mean Range Mean Range Black-throated diver Residues, mg/kg wet weight lot^ Hg 13.69 1280-14.57 PCB 2,67 1,32- 6,79 IDDT 624 2.90-11.82 64.07 494 16.27 45.80-82 33 3 79- 6 10 7.63-24.91 1920 12.62 6.42 1920 12.62 6.42 Great crested grebe total Hg 251 0,90- - 4.76 0.48 0.30- 0.75 5.75 1 15 - 8.50 1.73 0.92- 2.80 PCB J. 10 054- -1068 0.83 0.09- 2 18 5.18 0.41 -10,00 0.99 016- 1.65 IDDT 3.67 0 19- - 7.58 0.22 0.08- 046 639 0.06 -1755 2.25 0,22- 6.89 Ooldeneye total Hg 0 24 0 16- - 0.28 0 16 0.07- 0,24 2.15 0.72 - 3.42 038 0 15- 050 PCB 0,22 0.06- - 0.40 0.15 0 15 0.31 0.25 - 0.36 0,34 021- O60 IDDT 0 14 013- - 0.17 0.16 0.16 0.12 009 - 0 16 0,23 008- 0.71 Merganser toulHg 5.44 3.80- - 6.40 1 32 0.93- 1.97 23.23 1600 -32.50 2.78 2,33- 3.22 PCB 193 059- 3 38 0.18 0 18 1.89 1.45 - 2.23 1 81 0 30- 4.82 IDDT 2,73 056- 8,25 008 008 3.16 1.28- - 5 95 1 77 0 20- 4.89 Sandpiper total Hg 0.47 031- 063 _ _ 0.82 0.38- - 1.25 _ PCB 179 0.28- 3 30 — - - 030 0.16- - 044 — — IDDT 3.06 0.71- 541 — - - 0.34 0.25 - 0 44 — - Black-backed gull total Hg 3,25 1,32- 656 0.93 0 10- 1 98 946 4.50- -22,20 2.20 2 10- 2.30 PCB 671 0,27- 18.87 2.74 038- 7,70 8,00 0 84-47,83 1 91 1.91 IDDT 6,27 008- 16.83 2.75 0.23- 1097 9,04 1 54 -34,41 0.63 0.63 Herring gull total hg 289 0,10- 6.55 065 004- 1 74 753 021- -18.00 149 026- 4.62 PCB 13 49 0,68- 37.71 3,30 0.59- 19.29 11.27 0.77- -29.48 0.40 034- 046 IDDT 826 1.04- 22.05 1 60 0.27- 4.87 7.50 0.21- -20.83 0.16 0.14- 0 18 Common gull total Hg 1 97 0.45- 5.36 095 0.30- 1 59 585 1.22- -1660 338 1.42 -5 56 PCB 4 12 0 19- 1745 0,66 0 15- 4,15 498 033- -37 90 064 0.09 -2.50 IDDT 2.73 0.12- 1429 050 0.11- 3.93 3,73 0,02- -1628 0.60 009 -2.41 Black-headed gull total Hg 1 48 0.18- 4.36 0.40 0.10- 1.22 3.79 0.64- - 9 90 0.92 0 19- 2.52 PCB 351 0.09- 24.52 0.43 0.06- 1 34 4.29 0.36- -19.13 0.32 0.05- 1.09 IDDT 1 06 0.02- 1413 0 13 0.04- 0,42 1 01 0.09- - 5.52 0.09 0.02- 0.21 Common tern total Hg 3 73 069- 800 0,64 030- 1 92 10 10 068- 35 60 111 108- 1 14 PCB 4,15 043- 1592 095 3 24- 1 77 5 31 0 76- 24,38 041 0 40- 043 IDDT 1,57 0 16- 18.75 0,39 0.12- 1,55 1,47 0.18- 6.55 0.15 0.13- 0.16 Average of all species total Hg 2,73 0 10- 14.57 0,78 0.04- 1.98 7.90 0.21-82.33 2.31 0.15- 19.20 PCB 497 0.06- 37.71 1.14 0.06- 10 29 5,73 016-47 83 096 005- 12.62 IDDT 339 0.02- 22.05 0.71 0.04- 1097 4,21 002- 34.41 0.82 0.02- 689 Vol. 12, No. 1, June 1978 31 TABLE 8. Lindane residues in muscles of three individual birds. Lake P'aijanne. Finland Specibs/aob Common gull , juvenile Common gull, juvenile Merganser, adult (male) Study A«E» Date mg/kg Wet Weight 1-8-73 1-8-73 5-6-73 0.019 0 058 0.362 NOTE: See Figure I for location of study areas. TABLE 9. Correlation coefficients Ir) of different residues in muscles and livers of adult and juvenile birds. Lake P'aijdnne, Finland Tissue Residue Total Methyl Hg PCBs Muscles Adult methyl Hg PCBs ZDDT + 0.287'«« + 0.2I4*" + 0.237"* + 0.049 + 0.026 + 0.565"* Muscles Juvenile methyl Hg PCBs ZDDT + 0.039 + 0 114 + 0,074 -0.018 -0 012 +o.7oa«" Livers Adult PCBs ZDDT + 0 131* + 0.3I7**' + 0,644<«» Livers Juvenile PCBs ZDDT + 0.819'" + 0,543«'« + 0689«'« NOTE: • = p < 5 percent. ••• = p < 0 1 percent quently in the greatest number of birtis were PCBs and SDDT. Table 10 presents the percentage of total mercury which is methyl mercury. Percentages varied in different species between 91 and 117. indicating inaccuracy of analytical methods, since the correct value must be below 100 percent. TABLE 10. Ratios of methyl mercury to total mercury in muscles of adult birds from study areas I and 4, Lake Paifanne, Finland — 1972 Methyl Hg: Ratios. Species N' Total Hc,%' Range Great crested grebe 6 91 67-110 Black-backed gull 4 117 107-126 Herring gull 1 100 100 Common gull 2 111 107-115 Black-headed gull 7 93 66-127 Common tern 10 107 69-160 NOTE: See Figure 1 for location of study areas. ' N^number of individuals sampled ' Percentages over 100 indicate inaccuracy in analytical methods. Table 1 1 lists t-test findings which indicate that average concentrations of residues in males and females differed significantly. Muscles and livers in adults of each species were tested. In some gull species significant differences were found, and in all cases the average residue concentra- tion in males was higher than in females. Table 12 presents the ratio of 2DDT:PCBs among different bird species for comparison with corresponding values in earlier studies (4, 5, 23. 27. 34). Generally, birds which have been nesting in industrial areas contain more PCBs in relation to DDT than do individuals nesting far from such areas (27). In Lake Paijanne, these ratios never reached the high levels of 9:10 found in more remote areas of the globe, but the average levels do correspond to those of the North Atlantic (4). In many species the ratio SDDT;PCBs parallels the values for birds in Greenland (5). Great differences exist in the SDDT:PCB ratios of the different bird species of Lake Paijanne. Discussion The nonparametric tests showed no regional differences of concentration patterns among the birds sampled except for XDDT in liver. If the material sampled from the different areas is combined on this ground and t-tests are used to search the yearly differences for every species, only the PCB contents of the black-backed gull seem to have de- creased. If the absence of any significant variations be- tween the sampling years is regarded as a basic fact, then the regional differences can be examined for every species from material in which the results of the different years are combined. Such an examination indicates that the different gull species and the common tern contain significantly more mercury at areas 3, 5, and 6 than elsewhere; PCBs appear most often at area 1; and in all species, 2DDT appears in comparatively even amounts at the different sampling areas. Thus for mercury, the regional maximums are not found in the locations of greatest pollution, areas 1 and 4. The same paradox applies to certain other trophic levels of the lake (24). An explanation of this might be that mercury is retained within the sediment at the low- oxygenated areas 1 and 4; it does not pass through the food chain as effectively as it would in sediment which is farther from the sources of pollution. TABLE 1 1. Significant t-test differences between residues in adult male and female birds. Lake Paifanne, Finland Content Tissue Males Females SiGNIF.' OF DiFF Species M SD N M SD N Black-backed gull total Hg total Hg muscle liver 3.51 10.19 1.30 4,24 25 25 2 80 8.19 1 05 3.36 22 22 o Herring gull total Hg liver 10.19 4,41 8 5.76 3.98 12 • Common gull total Hg total Hg DDE ZDDT muscle liver liver liver 2.28 6.99 4 63 4.63 1,13 3.75 4.24 4.24 35 36 35 35 1 46 3.88 2.24 2.24 098 2.46 3.26 3.26 22 21 21 21 • * • • • NOTE: M = mean; SD = standard deviation; N = number of observations. ' Significances: •=-p> Coinmon gull 0663 0 763 0.750 0933 Black-headed gull 0300 0.301 0.235 0,277 Common tern 0.379 0.409 0.278 0.353 Average 0681 0.624 0.734 0.854 PCBs seem to enter the watercourse from the town of Jyv'askyfa but their exact origin is unicnown. Otherwise there is little regional difference of PCB and IDDT con- tamination in the waterways around Lake Paijanne. indi- cating that the residues detected in the birds originate primarily in the wintering regions or along the migration routes, or that they reflect the global levels of contamina- tion. The differences between the average residues in adults and those in juveniles show that bioaccumulation occurs as individuals age (Tables 6, 7). Within each species the contents of mercury, PCBs, and DDT were significantly higher in adults than in juveniles. This was seen in all species that had sufficient material for statistical comparison. Canada; and for the common gull, mercury content was lower than in Norway. For the grebe, PCB levels were lower in Lake Paijanne than in Great Britain; and for the black-backed gull, levels were lower than in the Faeroe Islands north of Scotland. For the merganser, juvenile herring gull, and common tern, SDDT levels were lower in Lake Paijanne than in the United States; and for the black-headed gull, SDDT residues were lower than in the Po Delta of northern Italy. In Lake Paijanne, mercury residues for the black-throated diver were greater than in Aberdeen in eastern Scotland, and Canada; and for mergansers and herring gulls, residues were greater than in Canada. In Lake Paijanne, mercury content was higher for mergansers than elsewhere in Fin- land; higher for black-backed gulls and herring gulls than in the Faeroes; higher for the herring gulls than at Fife, Scotland; and higher for the black-headed gulls than in Norway and Great Britain. Mercury was present in equal concentrations among mergansers in Lake Paijanne and goosanders in the Baltic Sea. For the black-backed gull in the Faeroes and the black- headed gull of the Po Delta, PCB concentrations were lower than in Lake Paijanne. For the black-headed gull and the common tern, SDDT concentrations were greater in Lake Paij'anne than in the Po Delta. For the herring gulls from the Faeroes and the common tern from the Po Delta, PCB levels were equal to those of Lake Paijanne. Tables 6 and 7 also show that mercury levels are higher in liver than in muscle, and these differences are significant in all species having sufficient material for statistical com- parison according to t-tests. Conversely, PCBs and 2DDT do not accumulate in the liver more than in pectoral muscles. Correlations between the different pesticide contaminants (Table 9) do not reveal any causes but they do, to a certain degree, illustrate the possible common origin of the differ- ent residues, possible similar bioaccumulation in the food chains, or possible similar behavior in metabolism. The high significant positive correlation between the levels of PCBs and 2DDT indicates that these fat-soluble contami- nants behave similarly. Authors referred to the published literature to compare residue levels of Lake Paijanne birds with levels in the same species in other countries (/. 3-7. 9, 17-23, 25-27, 33, 34, 36 ). It must be remembered, however, that mate- rial from Lake Paij'anne did not contain birds that were dead. This excluded from the sample those individuals that may have been fatally poisoned by pesticides. For the goldeneye, merganser, herring gull, and common tern, mercury levels were lower in Lake Faij'anne than in Lindane occurred at about the same concentrations in many individual birds from Lake Paij'anne as in those from other locations. Fat of aquatic birds of Greenland averaged 0.40 mg/kg of lindane (5); aquatic bird eggs of Ireland averaged 0.045 mg/kg (8); cormorants in the United States averaged 0.05 mg/kg in liver and whole bodies (//). Black-headed gulls in the Po Delta averaged 0.049 mg/kg in the muscle and 0.495 mg/kg in the liver; for the same individuals, maximum values were 0.1 10 mg/kg for muscle and 1.87 mg/kg for liver (34). Although average concentrations of lindane in Lake Paij'anne birds were almost zero, the maximum levels were similar to those in the other coun- tries mentioned. Dieldrin, which did not appear at all in Lake Paij'anne birds, has been reported in aquatic birds elsewhere (8. II, 18, 22, 30 34, 37). Values as high as 0.348 mg/kg have been observed in aquatic birds of Utah, although maximum levels range generally from 0.01 to 0. 10 mg/kg {30). Comparison of concentrations in various bird species shows that mercury residues are highest in the diver, merganser, common tern, and common gull. PCB contents are highest in the herring gull and common gull, and SDDT is highest in the herring gull, black-backed gull, and diver. Considering SDDT concentrations in liver Vol. 12, No. I, June 1978 33 alone, residues arc highest in the diver. Differences among the bird species may depend principally on feeding habits, although duration of life, migration routes, and wintering regions also cause differences. The gulls, especially the black-headed gull and the herring gull, feed on garbage as well as fish, and the black-headed gull also eats terrestrial animals living in arable lands. LITERATURE CITED (1) Adiey. F.E.. and D.W. Brown. 1972. Mercury concentra- tions in game birds. Slate of Washington — 1970 and 1971 . Pestic. Monit. J. 6(2):91-93. (2) Ahling. B.. and S. Jensen. 1970. Reversed liquid partition in determination of polychlorinated biphenyl (PCB) and chlorinated pesticides in water. Anal Chem. 42(13): 1483- 1486. (3) Bagge, P. 1975. Pesticide residues in some Baltic ani- mals— a review of selected literature. Pure Appl. Chem. 42(1-2):129-137. (4) Bourne, W.R.P , and J. A. Bogan. 1972. Polychlorinated biphenyls in North Atlantic seabirds. Mar. Pollut. Bull. 3(1I):I71-175. (5} Braeslrup. L.. J. Clausen, and O. Berg. 1974. DDE, PCB and aldrin levels in arctic birds of Greenland. Bull. Envi- ron Contam Toxicol 1 1(4):326-332. (6) Date. I.M.. M.S. Baxter. J A. Began, and W.R.P. Bourne. 1973. Mercury in seabirds. Mar. Pollut. Bull. 4(5):77-79. (7t Dimond. J.B.. A.S. Geichell. and J. A. Blease. 1971. Accumulation and persistence of DDT in a lotic ecosystem. J. Fish Res. Board Can. 28(12): 1877-1882. (8) Eades. J.F. 1966. Pesticide residues in the Irish environ- ment. Nature 2IO(5036):65O-652. (9) Fimreite. N. 1974. Mercury contamination of aquatic birds in northwestern Ontario. J Wildl. Manage. 38(1):120- 131. (10) Gaul, J. A. 1966. Quantitative calculation of gas chromatographic peaks in pesticide residue analysis. J. Assoc. Off. Anal. Chem. 49(2):389-399. (11) Greichus. Y.A., A. Greichus. and R.J. Emerick. 1973. Insecticides, polychlorinated biphenyls and mercury in wild cormorants, pelicans, their eggs, food and environ- ment. Bull. Environ. Contam. Toxicol. 9(6):321-328. (12) H'as'anen. E., V. Mieitinen, O. Ojala, and J. Rautap'aa. 1972. The use and replaceability of mercury in industry and agriculture in Finland. Kem. Teollisuus 29(8):530- 533. (13) Hallula. ML 1973. Analysis of DDT- and PCB-type compounds at low level in fish with reference to pike, perch and bream in Lake Paijanne. Univ. Helsinki, EKT series 301:1-147. (14) Hallula, M.L. 1974. Some aspects of the recovery of chlorinated residues (DDT-type compounds and PCB) from fish tissue by using different extraction methods. Bull. Environ. Contam. Toxicol. 12(3):301-306. 34 (15) Hallula. M. L. 1974. Simultaneous clean-up of fish fat containing low levels of residues and separation of PCB from chlorinated pesticides by thin-layer chromatography. Bull. Environ Contam. Toxicol. 12(3):33l-337. (16) Holden. A.V.. and K Marsden. 1969 Single-stage cleanup of animal tissue extracts for organochlorine resi- due analysis. J. Chromatogr. 44:481-492. (17) Holl. G. 1969. Mercury residues in wild birds in Norway. Nord. Veteringermed. 21(2): 105-1 14, (IS) Johnson. L.G.. R.L. Morris, and R. Bishop. 1971 . Pes- ticide and mercury levels in migrating duck populations. Bull. Environ. Contam. Toxicol. 6(6):513-516. (19) Karlog. O . I. Kraul. andS. Dalgaard-Mikkelsen. 1971. Residues of polychlorinated biphenyls (PCB) and or- ganochlorine insecticides in liver tissue from terrestrial Danish predatory birds Acta Vet Scand. 12(2):3 10-312. (20) Karppanen. E.. K. Henriksson. and M. Helminen. 1970. Mercurv content of game birds in Finland. Nord. Med. 84(35):'l097-ll28. (21) Koivusaari. J.. I. Nuuja. R. Palokangas. and M.L. Hal- lula. 1976. Chlorinated hydrocarbons and total mercury in the prey of the white-tailed eagle (Haliaetus albicilla L.) in the Quarken Straits of the Gulf of Bothnia, Finland. Bull. Environ. Contam. Toxicol. 15(3):235-241 . (22) Mulhern. B.M.. W.L. Reichel, L.N. Locke, T.G. Lamonl, A. Belisle. E Cromarlie. G.E Bagley. and R.M. Prouty. 1970. Organochlorine residues and autopsy data from bald eagles, 1966-68. Pestic. Monit. J. 4(3):141-144. (23) Nelson. N.. P.B Hammond, and I .C T . Nisbel. 1972. PCB's environmental impact. Environ. Res. 5(3):249-362. (24) Paasivirta. J.. ML. Hallula. and J. S'drkka. 1975. The residues in the food webs of Lake Paijanne. Jyv'askyla. 156 pp plus Appendix (104 pp). (25) Presli. I . D J. Jefferies. and N .W . Moore. 1970. Polychlorinated biphenyls in wild birds in Britain and their avian toxicity. Environ. Pollut. l(l):3-26 (26) Risebrough. R.W.. D.B. Menzel. D.J. Martin. Jr.. and H.S. Olcoll. 1967. DDT residues in Pacific sea birds: a persistent insecticide in marine food chains. Nature 2I6(51I5):589-59I. (27) Risebrough. R.W.. P. Rieche. D B Peakall. S G. Her- man, and M.N. Kirven. 1968. Polychlorinated biphenyls in the global ecosystem. Nature 220(5172): 1098-1 102. (28) S'drkka. J . 1975. Effects of the pollution on the profunda! meiofauna of Lake Paijanne. Finland. Aqua Fennica 1975: 3-11. (29) Siegel. S. 1956. Nonparametric Statistics for the Be- havioral Sciences McGraw-Hill Book Co., Inc., New York. 312 pp. (30) Smith. FA.. R.P Sharma. R.I. Lvnn. and J B. Low. 1974. Mercury and selected pesticide levels in fish and wildlife of Utah: II Levels of mercury. DDT, DDE, diel- drin and PCB in chukars. pheasants and waterfowl. Bull. Environ. Contam. Toxicol. 12(21:153-157. (31) Talion. JO G. and J. HA. Ruzicka. 1967. Or- PESTICIDES MONtTORlNG JOURNAL ganochlorine pesticides in Antarctica. Nature 215 chloride pesticides in the fish and birds of the Po delta. (5099):346-348. Rev. Int. Oceanogr. Med. 35-36, 79-90. (32) Tuunainen P.. K. Granherg, L. Hakkari. and J. Sdrkk'a. 1972. On the effects of eutrophication on Lake Paijanne, Central Finland. Verh. Int. Ver. Theor. Angew. Limnol. '-^^^ Westoo. G.. and K. Noren. 1970. Determination of or- 18( 1 ) 388— 40"* ganochlorine pesticides and polychlorinated biphenyls in animal foods. Acta Chem. Scand. 24(5):I639-I644. (33) Vermeer. K.. F.A.J. Armstrong, and D.R.M. Hatch. 1973. Mercury in aquatic birds at Clay Lake, Western Ontario. J. Wildl. Manage. 37:58-61. (36) Woodwell, G.M.. and C.F. Wurster. and PA. Isaacson. 1967. DDT residues in an east coast estuary: a case of (34) Viviani, R.. G. Crisetig, P. Cortesi, and E. Carpene. biological concentration of a persistent insecticide. Science 1974. Residues of polychlorinated biphenyls (PCB) and I56(3776):821-824. Vol. 12, No. I.June 1978 35 Dieldhn, DDT, PCBs, and Mercury Levels in Freshwater Mullet from the Upper Great Lakes, 1975-76 • Mary E. Zabik,^ Barbara Olson,- and Teiko M. Johnson - ABSTRACT Freshwater mullet harvested commercially during various sea- sons of 1975-76 from the upper Great Lakes were analyzed for organochlorine pesticides , PCBs. and mercury. Species analyzed were Catostomus commersoni, C. catostomus. and Moxostoma erythruran. Whole ground fish, mechanically de- honed flesh, head, middle, and tail steaks, and various muscles were analyzed for pesticides and PCBs: only edible flesh was analyzed for mercury. Dieldrin ranged from none detected to 0.23 ppm in deboned and whole ground samples, the DDT range was a trace to 0.30 ppm, and PCBs ranged from 0.06 ppm to 0.79 ppm. Levels were also higher in head sections and in high fat-containing medial muscle and belly flap. Mercury levels ranged from 0.03 ppm to 0.28 ppm in the flesh of mullet from Lake Michigan. Introduction Freshwater mullet from the lakes surrounding Michigan have received little attention as significant sources of human food. In their native form, these fish are frequently considered unattractive to consumers because of their in- tramuscular bony structure and/or their muddy flavor which is characteristic of fish with their particular eating habits. Estimates indicate, however, that mullet could be harvested from Michigan waters at an annual rate ap- proaching one million kg. Two species of the genus Catostomus comprise most of the mullet population in Lakes Huron, Michigan, and Superior. The white mullet iCaloslomus commersoni) is widespread in Lakes Huron and Michigan, the longnose mullet (C. catostomus) pre- dominates in Lake Superior, and the golden redhorse mul- let ( Mo.xosloma erythruran) is available in commercially harvestable quantities from Lake Huron. 'Michigan Agricultural ExperimenI Slition Journal Article No 8142 Research supported hy Upper Great Lakes Regional Commission Technical Assistance Project No 10520239 ' Department of Food Science and Human Nutrition. Michigan State University. East Laming. Ml 4S824 In addition to their muddy flavor, these fish have been unpopular with consumers because of the numerous Y bones throughout the fleshy portion of the fish. Recently, however, mechanical means have been developed for separating meat from bone, yielding a boneless minced flesh product. This minced flesh can be used in various consumer products. However, before commercial products can be developed, it has been necessary to determine the levels of environmental contaminants, their seasonal varia- tion, variation of environmental contaminants within dif- ferent muscles, and location of the fish in representative species from the three lakes concerned. Sampling Procedures Mullet were harvested by commercial anglers from Lakes Huron (Saginaw Bay, Standish. and Au Gres. Michigan), Michigan (Epoufette Bay, Epoufette, Michigan), and Superior (Whitefish Bay, Brimley, Michigan) during dif- ferent seasons of 1975-76. They were readily available from commercial anglers in Saginaw Bay. The fish were less readily available in the upper Lakes Superior and Michigan, so seasonal variation could not be determined specifically. Fish were ice-packed and transported to the laboratory for processing and analyses, usually arriving the day after the catch. Following heading and gutting, fish to be deboned by machine were split into halves and run through the Bibun deboner (Type SD x 13, 5-mm holes), resulting in a minced flesh product separated from bone, skin, and scales. Whole headed and gutted mullet (.15^0 cm long) were coarsely ground three times in a Hobart food cutter fitted with chopper attachment. Other whole dressed mullet were filleted into the ventral, dorsal, medial, and belly flap muscles or sectioned into head, midsection, and tail cross slices. Two mullet, 35^0 cm long, were used for each muscle or section study for each catch date for each lake. Muscles or sections were homogenized sepa- rately in an Osterizer blender and all samples were frozen 36 Pesticides Monitoring Journal and held at -23° C in glass jars before being thawed overnight at 4°-5° C for residue analyses. Analytical Procedures PESTICIDES AND POLYCHLORINATED BIPHENYLS (PCBs) Two samples of each fish variable were extracted sepa- rately with hexane-acetone (2:1), partitioned with acetonitrile, and subjected to Florisil-Celite column cleanup according to the method of Yadrick et al. (7). Solids were determined by drying 2-g samples under vac- uum at 90° C to constant weight; lipid was estimated by evaporating an aliquot of the hexane extract to dryness at 70° C under vacuum. Gas chromatographic analyses were performed with a Tracor 560 gas-liquid chromatograph (GLC) equipped with a ^'Ni electron-capture detector and interfaced with a Dig- ital PDP-8e-Pamila GC data system. Instrument parameters and operating conditions follow. Column Temperatures: Carrier gas: 1 83-m X 4.0-mm ID Pyrcn. packed with 3 percent OV-1 on 80-IOO-mesh Chromosorb W-HP column 190° C injection port 230° C detector 300° C nitrogen nowing at 40 ml/minute Standards were prepared with 99-1- percent pure recrystal- lized dieldrin, p,p'-DDT. and p.p'-JDE, and Aroclor 1248 in Nanograde hexane. Quantitations were based on peak area for pesticides; the area of three peaks was used to quantitate the PCBs. Standards were run every morning and after every eight or nine samples. Recoveries with this method of extraction and quantitation were 85±2 percent for PCBs and 92±1 percent for dieldrin and DDT com- pounds; limits of detection were 0.01 ppm for PCBs and 0.001 ppm for dieldrin and DDT compounds. Data pre- sented in this paper are not corrected for recoveries. Presence of these residues was confirmed by mass spec- trometric analysis on a pool of all extracted samples from each lake. The chromatograph used was a Beckman GC-65 interfaced with a DuPont 21-490 mass spectrometer which in turn was interfaced with a Digital PDP-12-LDP com- puter. Mass spectra were obtained at an ionizing voltage of 70 eV with a source temperature of 210° C. MERCURY Mercury was determined from duplicate edible flesh sam- ples for each catch from each lake as total elemental mercury by using flameless atomic absorption spec- trophotometry as described by Gomez and Markakis (2). Concentrated sulfuric acid was used to digest the samples as described in their Digestion 1 procedure. Recovery was 95 ±1 percent, and the limit of detection was 0.005 ppm. Values presented are not corrected for recovery data. Results Fat, solids, pesticides, and PCBs in whole ground and mechanically deboned mullet from the upper Great Lakes are presented in Tables 1 and 2. Dieldrin content ranged from none to 0.23 ppm. 2DDT in white mullet caught in Lake Superior in June ranged from a trace to 0.30 ppm. PCBs varied from 0.06 ppm to 0.79 ppm. All levels are below the tolerances for these environmental contaminants established by the Food and Drug Administration (FDA), U.S. Department of Health, Education, and Welfare, al- though dieldrin levels in the mullet from Lake Michigan are closest to their tolerance level, 0.3 ppm. Seasonal variation appears to be minor. As much variation occurred in the levels of contaminants themselves as in the levels as they related to the different catch dates. The Great Lakes Environmental Contaminant Survey analyzed two freshwater mullet under 16 inches long from Lake Huron in 1974 and four in 1975 {3, 4). Values reported there are similar to those in the current study. An earlier analysis of a freshwater mullet revealed 1.14 ppm DDT (5). Thus DDT levels may be decreasing. Similar DDT levels were reported in freshwater mullet from Lakes TABLE 1 . Fat. solids, pesticides, and PCBs in whole ground freshwater mullet. Upper Great Lakes. 1975-76 Date of Dl ELDKIN ZDDT PCBs AS AKOCLOit 1248 Wet Wet Wet Lake Type Caich Fat. % SOUDS, % Tissue Fat Tissue Fat Tissue Fat White February 75 2.63 23 43 Residues, PPM Huron 0 03 1 10 0 06 2,03 0 54 10 03 White May 75 1 20 21 30 0 10 8 84 0,06 4 26 0,54 43,40 While August 75 2.70 24 40 0 09 3,15 0,08 2,89 0.79 29 36 Redhorse August 75 7 90 31 70 0,11 1,45 0 08 098 0.70 8.86 White December 75 2 30 21.30 0 16 3 97 0 30 13,31 0.12 5.30 White February 76 2 30 23 90 0 04 1 92 0 08 3,57 0.15 6 28 Michigan Longnose June 75 4,20 25 25 0 21 5,01 0,23 3 12 0,62 14 05 Longnose August 75 5 55 25,65 0 23 4 31 0,27 4.49 0.71 12 67 White June 76 115 24 00 0 03 2 77 0.03 2.82 0.16 12.99 Superior White June 75 2,05 22,35 — — Tr' — 0.06 3.12 Longnose December 75 3 95 24,25 0,09 2 33 0-14 3.46 0,26 6.55 ' Tr = 0 005 -0.009 ppm Vol. 12, No. 1, June 1978 37 Ontario and Erie, although dieidrin levels were less than 0.01 ppm(/). Variation in levels of environmental contaminants from head to tail is summarized in Table 3. The head slices which contained the most fat had the highest levels of environmental contaminants. On a fat basis, however, the distribution was more uniform. have little benefit because residues in the loin muscles were also high. Mercury levels in the edible flesh (Table 5) were highest in fish from Lake Michigan. Values reported for fish from Lake Huron are close to those reported by the Great Lakes Environmental Contaminants Survey {3, 4). Variation in contamination according to muscle content is shown in Table 4. The high-fat medial muscle and belly flap contained the highest amounts of residues. Because the residues are fat-soluble, trimming would be a feasible method of reducing contaminants if the deboned flesh ever exceeded FDA tolerances. Reinert and Bergman (6) also found that these areas had higher levels of contaminants in Coho salmon, but they concluded that trimming would Acknowledgment The authors thank Estes Reynolds, Food Science and Human Nutrition Department, Michigan State University, for procuring the fish, and Drs. Dawson, Price and Reynolds for help with fish processing. Appreciation is also expressed to Matthew Zabik, Pesticide Research Cen- ter, for mass spectrophotometric analyses. TABLE 2. Fat, solids, pesticides, and PCBs in mechanically deboned freshwater mullet, upper Great Lakes, 1975-76 Date OF Dl ELDRIN IDDT PCBs AS AIOCLOE 1248 Wet Wet Wei Lake Type Catch Fat. % Solids. % Tissue Fat Tissue Fat Tissue Fat While February 75 2,07 22,37 Residues. PPM Huron 001 0.62 0.03 1.84 0.29 14 13 While May 75 1 50 19 83 0 06 4.27 0.06 4.14 0 50 33 39 While August 75 1 60 19 75 0 07 4.16 0 08 4.63 0 41 2501 Redhorse August 75 5 50 24,85 005 096 0.04 0.69 0 18 3.22 While December 75 2,75 20,70 0 15 5.22 0 20 6 99 0 70 24 38 While February 76 2 95 20 25 0 07 2.47 0 10 3 26 0.17 5 88 Michigan Longnose August 75 5,23 23,90 0.13 2.37 0.16 2.93 0 49 9 29 While June 76 1,83 19 75 0.03 1 90 0.03 1.87 0 26 14 06 Superior While June 75 2,15 18.20 Tr' — 0.01 0.56 006 2.93 Longnose December 75 3 00 21 15 0 07 2.28 0.12 3 88 0.70 23.32 ' Tr = 0 005-0 009 ppm TABLE 3. Pesticides and PCBs in sections of freshwater mullet, upper Great Lakes, 1975-76 Mean Fat Mean Solids Mean DlELDEIN Mean XDDT Mean PCBs as AloCLoa 1248 Wet Tissue Fat Wet Tissue Fat Wet Tissue Fat Lake Section (Range). % (Range). % (Range) (Range) (Range) (Range) (Range) (Range) Head 5 80 27,77 Residues, ppm Huron ' 0.16 3.35 0.24 4.84 0.86 15 06 (3.65-955) (23 65 33 55) (0.02-0.68) (0.45-13 31) (0.03-0.98) (1 75-19.25) (Tr'-l 92) (Tr-32 40) Middle 3 14 24 13 006 2.66 0 07 2 91 039 15 54 (1.72-7 60) (22 55-30.00) (0.01-0 21) (0 58-9 40) (0 02-0 19) (0 36-8 09) (0 14-1 10) (302-37 36 Tail 2.04 26 21 003 2 34 0 04 2 97 0 18 12 94 (0.65-5.25) (23 00-30 00) (Tr-0 09) (Tr-6 68) (Tr-0 13) (Tr-6 85) (Tr-0. 34) (Tr-23.29) Michigan ' Head 4 77 26 22 0 09 2.25 0 10 2 18 056 1509 (2.25-8 20) (23 20-30 10) (0 05-0 11) (1.33-3 10) (0 05-0 17) (1 94-2 53) (0 49-0.61) (8 07-18.78) Middle 3.82 24 30 009 2 17 0 12 2 13 0 29 11 61 (1.15-7 05) (21.05-26 70) 10 02-0 14) (1 62 2 94) (0 03-0 17) (1 94-2 43) (023-035) (8 56-16 90) Tail 2.13 23.07 0.06 2 58 0 06 2 09 0 26 15 55 (1.24-3 80) (21 10-24 70) (0. 02-0. 08) (1 58-3 95) (002-0 08) (1 94-2 25) (0 10-0 46) (7 40-30.58) Superior* Head 2.65 23.70 0 06 1 68 0 13 3 34 0 24 7 29 (2.05-3.25) (21 90-2550) (Tr-0 II) (Tr 3 36) (Tr-0. 23) (Tr-6 68) (0 08-0 39) (3 16-11 41) Middle 2.10 24 15 0 02 0 84 0.03 1 17 0 15 6 66 (1.70-2 50) (22.20-26 10) (0.00-0 04) (0 00-1 68) (Tr-0 06) (Tr-2 34) (0 08)-0 22) (4 42-8 89) Tail 1.70 22 48 003 1 21 0 06 2 56 0 14 7 80 (1 20-2.20) (20.70-24.25) (Tr-0.05) (Tr-2.42) (0.00-0. II) (0.00-5.11) (0.07-0.21) (5.76-9.84) J oa six CBichci from Feburary I97S to February 1976. 'Tr - 0 005 -0 009 ppm ' Bucd on (hree caichet from June 1975 (o June 1976 ' Bucd on two calcbci from June 1975 to r>ccembcr 1975. 38 Pesticides Monitoring Journal TABLE 4. Pesticides and PCBs in muscles of freshwater mullet, upper Great Lakes. 197 5 -It Lake Michigan ^ Superior* Ventral Lateral line Dorsal Belly nap Ventral Lateral line Oonal Belly flap Ventral Lateral line Dorsal Belly nap Mean Fat Mean Solids (Range). % (Range). » 0.83 (0 55-1 03) 5 44 (1-50-8 25) 1.10 (0.50-1 90) 3 51 11.15-7 05) I 04 (0.60-1 45) 8.13 (2.49-13 95) 1.32 (0,52-2 30) 6.13 19 94 (17.25-22.20) 24.26 (17.25-29.45) 20 II (17.05-21 65) 21 55 (19 00-26 90) 20 59 (19 85-21 30) 26 70 (21 30-31 45) 20 53 118 85-21,40) 23 88 (1. 85-11. 90) (19.45-29,40) 159 1968 (0.87-2.30) (1790-21.45) 8 50 28 95 16 80-10 20) (2675-31.15) 145 19,73 (0 85-2 05) (18.60-2085) 3 93 24.13 (2.00-5.85) (2000-28.25) ' Based on six catcfies from ■ Tr = 0 005-0 009 ppm ' Based on three catches froi ' Based on two catches from Febritary 1975 to February 1976. n June 1975 to June 1976 June 1975 to December 1975 Mean Dieldrin Mean ZDDT Wet Tissue (Range) 0.02 (Tr^-O 05) 0 08 (0 01-0.18) 0.02 (Tr-0 05) 0 10 (0 01-0 24) 0.06 (0.02-0.10) 0,22 (0,15-0 28) 0 05 0.02-0.10) 0.26 (0.19-0 34) 0 04 (Tr-0,08) 0 12 (0 02-0,22) 0 02 (Tr-0 04) 0,09 (0 02-0,15) Fat (Range) Wet Tissue (Range) Fat (Range) 3 39 (Tr-ll 20) 2 18 (0,36-5,78) 2.45 (Tr-7.10) 3.24 (0 70-6.36) 6 00 (4 04-9 83) 3.92 (I 57-5.52) 4 50 (1.60-8.5 1) 5 98 (2.13-7.92) 1.33 (Tr-2.66) I 24 (0,35-2.13) 1 06 (Tr-2 12) I 86 (0.71-2.95) Residues, ppih 0.07 (0 01-0 28) 0 10 (0.05-0 18) 0.06 (Tr-0. 20) 0.13 (0,03-0.36) 0,06 (0 03-0 II) 0,28 (0 16-0 41) 0,22 (0,16-0.34) 0.37 (0.13-0 55) 0 07 (Tr-0 14) 0.37 (0 03-0 70) 0.04 (0.01-0 06) 0 13 (0.01-0 24) 10 06 (1 22-38 69) 2 43 (0 62-5.39) 5.27 (0.63-20.47) 3 91 (1 67-6 29) 6,32 (3 28-11,11) 4,32 (I 99-6.00) 6 91 (I 80-13 36) 7,77 3,62-11.95) 2.37 (Tr-4.74) 3,74 (0 56-6 91) 2.22 (1.52-2.87) 2 48 (0 62-4 34) Mean PCBs as Aioclou 1248 Wet Tissue (Range) Fat (Range) 0 18 (Tr-0 52) 0,80 (0,19-1 17) 0 09 (Tr-0 17) 0 69 (0,24-1 53) 0,30 (0 09-0.46) 1.22 (1.13-1. 31) 0 21 (0.02-0 34) 1 33 (0.35-2.44) 0 08 (0 06-0 10) 0,42 (0,27-0 57) 0 08 (0 08-0 08) 0,21 (0,13-0,28) 32 20 (Tr-120 02) 16 93 (9 44-23,45) 10 83 (Tr-16,43) 21 03 (7 06-41 19) 29,20 (16,59-40.42) 22.10 (9.47-40.84) 15.12 (3.44-23.38) 24 49 (10.22-49.20) 7,85 (4 92-10.77) 5.71 (2 75-8.66) 7,32 14 73-9 91) 6.92 (6.70-7.13) TABLE 5. Mecury levels in freshwater mullet, upppr Great Lakes. 1975-76 Lake Date of Catch Michigan Superior While Fcbruarv 75 While Mav 75 While August 75 Rcdhorse August 75 White December 75 White February 76 Longnose June 75 Longnose August 75 White June 76 While June 75 White December 75 Mercury. PPM 0 03 0 06 0.09 0.07 0 06 0 05 0.21 0.12 0.28 0 10 0 06 LITERATURE CITED (1) Frank. R.. A. E. Armstrong. R G. Boelens. H E Braun. and C. W. Douglas. 1974. Organochlorine insecticide resi- dues in sediment and fish tissues, Ontario, Canada Pestic Monit. J. 7(3/4):I65-180. (2) Gomez. M. I., and P. Markakis. 1974. Mercury content of some foods. J. Food Sci. 39(4):673-675. (3) Great Lakes Environmental Contaminants Survey. 1974. Michigan Department of Agriculture, Lansing, MI. p. 35. (4) Great Lakes Environmental Contaminants Survey. 1975. Michigan Department of Agriculture, Lansing. MI. p. 25. (5) Reineri. R. 1970. Pesticide concentrations in Great Lakes fish. Pestic Monit. J. 3(4):233-240. (6) Reinert. R. E.. and H. L. Bergman. 1974. Residues of DDT in Lake Trout (Salvelinus namoycush) and Coho salmon (Oncorhynchus kisutch) from the Great Lakes. J Fish Res Board Can 31(2):191-I99. (7) Yadrick. M. K.. K. Funk, and M. E. Zabik. 1971 . Dieldrin residues in bacon cooked by two methods. J. Agric Food Chem 19(3):491^94. Vol. 12, No. 1, June 1978 39 General Mirex Incorporation in Estuarine Animals, Sediment, and Water, Mississippi Gulf Coast — 1972-74 ' Armando A. de la Cruz- and Kuang Yang Lue' ABSTRACT Analysis of mirex residues in esiuarine animuls, seJimeins. unci waters collected from the Mississippi Gulf Coast in 1972-74 showed the following ranges of concentrations: seston, 200- 3000 pph: molluscs. 36-500 pph: fish. 0-259 ppb: sediment. 3-5 ppb: and water. 0-0.01 ppb. These data indicate that mirex in aquatic environments is localized in animal tissues and bot- tom substrate and that only a negligible amount is incorporated in the water Introduction In 1971-74. the authors conducted a series of studies on the toxicity and ecological and physiological effects of mirex on nontarget organisms. The three areas of study included residue monitoring and toxicity, effects of mirex on certain ecological processes of plants and animals, and physiological effects on enzyme systems. The results of these studies are cited in a literature review by Lue (4). The ecological aspect of this project emphasizes the incor- poration of mirex in the environment through leaching of the insecticide from decaying fire ant bait in the field (2, /O). Mirex residues were recovered from seafood from the Atlantic and Gulf Coastal states (7), in terrestrial and aquatic invertebrates from Louisiana (S), and in other selected organisms (//). During these studies, therefore. the authors routinely collected samples from different habitats (Q). This paper reports mirex residues detected in samples collected from an estuarine environment on the Mississippi Gulf Coast. The animal samples were collected in the fall of 1972. the sediment samples during summer 1973. and the water samples in 1972 and 1974. Materials and Procedures COLLECTION OF SAMPLES The animals were collected manually from the substrate in St. Louis Bay marsh during low tide. Those from Missis- sippi Sound were collected by using a shrimp trawl. The specimens were rinsed of mud or debris, blotted dry. wrapped in aluminum foil, and frozen until analysis. Water samples were collected in clean, hexane-rinsed lO-liter jugs by directly filling the jugs a few centimeters beneath the water surface. Water samples for mirex analysis were refrigerated when not immediately processed. Waters in- tended for seston analysis were promptly filtered through AA millipore filters (0.8-;j.m porosity) in a millipore vacuum-filtration apparatus. Seston is particulate matter suspended in water including plankton, organic detritus, and inorganic silt. Sediments were collected by an Ekman dredge from St. Louis Bay and by a Petersen dredge from Mississippi Sound. The samples were placed in clean, hexane-rinsed wide-mouth specimen jars and refrigerated until extraction. EXTRACTION OF SAMPLES Single or pooled (2-10 specimens) whole-body samples of animals were extracted for residue analysis according to the procedure of Naqvi and de la Cruz (9). Only the fleshy tissue of molluscs was extracted. Specimens were rinsed with distilled water to remove salt and briefly dipped in hexane to remove any external insecticide contamination. Samples were ground in nanograde hexane and shaken vigorously, and the decanted solvent was evaporated to dryness. Prior to gas-liquid chromatography, the extracts were cleaned by using activated alumina. ' Sludy lupponcd by Agricullural Rcseirch Servkt. U S Dcpsnmcnl of Agncul lure. Coopcrilive Agrecmcm No 12- 14-1001093}. ' I>cpartment of Biological Sciences. Mi»%isMppi Slate Univcr&ily. P O Drawer Z Mittisiippi Slale. MS 39762 ' Depailment of Biology, Taiwan National Normal University. 88 Sec 5, Taipei. Taiwan 117, Republic of China Seston samples were extracted according to the procedure in the Pesticide .Aiuilyticat Manual {3) for small samples. The filter paper holding the seston was ground in a tissue grinder with acetonitrile. The filter paper was free of mirex when checked for contamination. The extract was concen- trated and reduced to a suitable volume for analvsis. 40 PhSIK IDKS MONl TURING JoUKNAl Water was extracted with nanograde hexane in 250-ml separatory funnels; 150 ml samples were shaken vigorously with 50 ml hexane three successive times. 3 minutes each time. The three hexane extracts were combined and evaporated to a volume suitable for gas chromatographic analysis. Samples of 150 g sediment were extracted with 300 ml hexane-isopropanol mixture (3:1) according to the proce- dure of Markin et al. (6). The extract was filtered through Na2S04 and concentrated to 10 ml. CHROMATOGRAPHY Extracts of all samples were analyzed in a Barber-Colman Pesticide Analyzer Model 5360 equipped with an electron-capture detector. A 152.4 mm x 3.2 mm glass column was used. Standard injection techniques were used consistently for all samples. Extract volumes (2 ju.1) were injected. Information about operating parameters of the analyzer can be obtained from the Physiological Labora- tory, Department of Zoology, IVississippi State University, Mississippi State, Mississippi 39762. The concentration of mirex was calculated with the following formula: mirex residue = Vwd2lWvd \ where W = weight of the sample in grams, V = volume of final extract in milliliters, v = volume of extract in- jected in /xl, w = weight of the standard injection in nanograms, d \ = peak height of standard solution, rfa = peak height of extract. A second column (1.5 percent SP-250, dimethylchlorosilane-treated and acid-washed) was used to confirm the mirex residues recovered from the field samples. Results and Discussion Mirex residues in seston and animals collected from St. Louis Bay and Mississippi Sound are summarized in Tables 1 and 2. Concentrations in seston filtered from Mississippi Sound water (1000-3000 ppb) is one order of magnitude higher than in seston from St. Louis Bay (200-800 ppb). Residues in the animals were all below 1 ppm except in the fiddler crab Uca (1.3 ppm). The molluscs, i.e., snails, clams, and mussels, from St. Louis Bay, which are ba- sically filter feeders, had slightly higher levels of mirex (36-500 ppb) than did the other invertebrates from Missis- sippi Sound (0-133 ppb). In an earlier study, Naqvi and de la Cruz (9) found 70-410 ppb mirex in snails and clams collected from a similar estuarine habitat. Residues in the fish ranged from 0 to 259 ppb. The residue levels of sediments from bay and sound were essentially similar (Table 3) and fairly low (2.8-4.6 ppb). These values are, however, much higher than the residue levels detected in the water samples (0.001-0.010 ppb) from Mississippi Sound, St. Louis Bay, and from the TABLE 1 . Mirex residues in seston ' and animals ^ from Si. Louis Bay marsh-estuary. November 1972 BlOMASS Extracted, G Residues .ppb' Specimen Col. I Col. n Seston 0.07 817.7 9206 0 26 204 1 235 0 0.19 2159 199 7 0.10 408.8 376,9 Rangia cuneata (Clam) 8.10 331.3 247,5 3.00 490.2 450,0 Modiolus liemissus (Ribbed mussel) 4 60 183.8 159 8 3.00 367 71 3 Melampus bldeniolus (Snail) 3.80 339 2 265,2 2 90 471.4 415,2 0 65 81 8 0.0 0.45 118,2 0.0 Littorina irrorala (Snail) 0.40 130 9 0 0 0.80 499 9 31,3 0.70 75.9 89 3 0.70 37,9 0,0 0.60 66,5 35 7 Vca sp (Fiddler crab) 0.30 1302,0 2661,0 Strong\lura marina 13,80 50,9 47,4 (Atlantic needlefish) ' Seslon includes suspended paniculate matier consisting of plankton organisms, organic detritus, and inorganic sediment filtered from 300 ml of water with 0 8 /im Millipore acetate filter ^ Animals were pooled from 2-10 individuals of about the same size. Biomass represents whole tissue, excluding shells and molluscs * All analyses were done with two columns to verify the mires residue TABLE 2. Mirex residues in seston^ and animals^ from Mississippi Sound, September 1972 Sponge Luidia claihraia (Starfish) LoUiguncula hrevis (Squid) Palaemonetes sp. (Grass shrimp) Callmectes sapidus (Blue crab) Squilla empusa (Mantis shrimp) Bairdiella chrysura (Silver perch) Bagre marinus (Gafflopsail catfish) Porichlhys porisissimus (Atlantic midshipman) Eiropus crossotus (Fringed flounder) S\mphurus plagiusa Blackcheek tonguefish) Cynoscion arenarius (Sand seatrout) Sirongylura marina (Atlantic needlefish) BlOMASS Residue! i. PPB G Col 1 Col. II 0,01 3038 4 2396.8 0 03 1507 8 26298 0 03 1001,4 4150 5 0,23 1172,7 1321.1 0,01 3260,7 2007 4 0,02 2291,8 28149 0,01 2677,2 2677.2 0.01 3243 4 3003,7 0.61 133 5 231 0 7.24 28 1 37,0 8.68 24 0 0,0 5.40 0,0 0,0 S.97 13 6 0 0 2.77 0,0 0,0 3.39 0,0 0,0 15.84 7 6 106 0 20,80 3,7 0,0 18,00 6 4 6,4 1.10 1280 207,8 1.30 22,0 0 0 8.30 4 8 0,0 6.60 1 1 1 8 11,70 81,6 97,0 9.70 15 9 9.6 9.20 7.2 _ 11.30 12 5 11,7 12.80 110 16 5 45.00 0,0 0,0 19 30 259 1 245 4 18.00 179.9 132,0 ' Seston includes suspended particulate matter consisting of plankton organisms organic detritus, and inorganic sediment filtered from 300 ml of water with 0.8 ^m Millipore acetate filter ' Animals were single speciments; whole-body tissue was analyzed, ' All analyses were done with two columns to verify the mirex residue. Vol. 12, No. 1, June 1978 41 Jordan and Wolf Rivers thai empty into the bay (Table 4). Spence and Markin (10) found that the highest mirex level in natural water was 0.02 ppb. In a separate study (5). the authors found 0.01 ppb residue in samples of water col- lected from a farm pond. The residue data reported in this paper indicate that mirex in aquatic environments is lo- calized in bottom sediments, animal tissues, and in par- ticulate matter, i.e., seston, suspended in the water, and TABLE 3. Mirex residues in esluarine sediment. Mississippi Gulf Coast — 1973 Residues. Collection Date Amount Extracted, G PPB ' Location Col Col. II St, Louis Bay ' 5/29/73 6/18/73 8/26/73 100 ino ion 2.8 3.9 3 5 5 0 5 9 5 3 Mississippi Sound ' 7/17/73 7/19/73 100 100 4-6 3 5 2 2 5 2 ' All analyses were done with two columns to verify the mirex residue, * Collected by an Ekman dredge from the mouth of Catfish Bayou on the western side of the bay * Collected by a Petersen dredge about 3 km off the Biloxi-Ocean Spring coastline TABLE 4. Mirex residues in esluarine water, Mississippi Gulf Coasi— 1972-74 Sampling Site St Louis Bay Mi&sissippi Sound Amount Residue .5. ppb' Collection Extracted, DATE ML Col I Col n 3/1/74 4.000 0,007 0,000 6/20/74 4.000 0,005 0000 0,009 0,003 0,004 0,000 snnA 4.000 0001 0,001 7/31/74 4.000 0,004 0,001 0.007 0,000 5/1/72 4.000 0000 0 000 4/4/72 500 0,000 0000 11/15/72 500 OOOO 0000 5/15/73 4,000 0,030 0 001 6/12/73 4,000 0000 0000 2/22/74 4.000 0,010 0 003 0000 0001 0004 0 000 0,000 0000 3/1/74 4.000 0004 0 002 4/6/74 4.000 0,000 0,000 9/23/72 4.000 0,000 0,000 O0O4 0,000 4/6/74 4,000 0000 0 000 ' All analyses were done with two columns to verify the mirex residue, ' Samples collected a few kilometers inland from St, l^uis Bay, that only negligible amounts of mirex are incorporated in the water (/. 10). LITERATURE CITED (I) Alley. E.G 1973. The use of mirex in control of the imported fire ant. J. Environ. Qual. 2( 1 ):52-61 . (2i de la Cruz. A. A., and K. Y. Lue . I97S. Mirex incorpora- tion in the environment. In situ decomposition of fire ant bait and its effects on two soil macroarthropods. Arch. Environ. Contam. Toxicol. 7(1):47-6I. (3) Food and Drug Administration. 1970. Pesticide Analytical Manual. Vol. 3, U.S. Department of Health, Education, and Welfare, p. 40. (4) Lue. K. Y. 1977. Decomposition properties of mirex and bait and its ecological effects on selected biotic systems. Ph.D. Dissertation. Mississippi State University. Missis- sippi State. MS. 89 pp. (5) Lue. K. Y.. and A. A. de la Cruz 1978. Mirex incorpora- tion in the environment: Toxicity in Hydra. Bull. Environ. Contam Toxicol. 19(14):412-4I6. (6) Markin. G. P.. J. H. Ford. J P. Hawthorne. J. H. Spence. J. Davis. H. L. Collins, and C. D. Loftis. 1972. The insecticide mirex and technique for monitoring. U.S. Department of Agriculture-APHIS 81-3, 19 pp (7) Markin. G. P.. J. C Hawthorne. H. L. Collins, and J. H Ford. 1974. Levels of mirex and some other organo- chlorine residues in seafood from Atlantic and Gulf Coastal states. Pestic. Monit. J. 7(3/4): 139-143. (8) Markin. G P.. H L. Collins, and J Davis. 1974. Resi- dues of the insecticide mirex in terrestrial and aquatic invertebrates following a single aerial application of mirex bait, Louisiana— 1971-72. Pestic Monit. J. 8(2): 131-134. (9) Naqvi. S M.. and A. A. de la Cruz. 1973. Mirex incor- poration in the environment: residues in nontarget organisms— 1972. Pestic, Monit J, 7(2):104-l 1 1. (lOj Spence. J. H., and G. P Markin. 1974. Mirex residue in the physical environment following a single bait applica- tion, 1971-72. Pestic, Monit. J. 8(2): 135-139. (II) Wolfe. J. L., and B. R. Norment. 1973. Accumulation of mirex residues in selected organisms after an aerial treat- ment, Mississippi— 1971-72. Pestic. Monit. J. 7(2):112- 116. 42 Pesticides Monitoring Journai APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN AROCLOR 1248 DDD DDE DDT DIELDRIN ENDRIN HEPTACHLOR EPOXIDE LINDANE MIREX PCBs (polychlorinated biphenyls) TDE Hexachlorohexahydro-endo. exo-dimelhanonaphthalene 95% and related compounds 5% PCB. approximately 48% chlorine See TDE Dichlorodiphenyldichloroelhylene (degradation product of DDT) Dichlorodiphenyltnchloroethane Hexachloroepoxyoctahydro-endo, exo-dimethanonaphlhalene 85% and related compounds 15% Hexachloroepoxyoctahydro-endo, endo-dimethanonaphthalene 1 ,4.5.6.7,8.8-Heptachloro*2.3-epoxy-3a,4,7.7a-tetrahydro-4.7-melhanoindane Gamma isomer of benzene hexachloride ( 1,2,3.4.5,6-hexachlorocyclohexane) of 99+% purity Dodecachlorooctahydro- 1 ,3.4-metheno- 1 H-cyclobuIa[cd]pentalene Mixtures of chlorinated biphenyl compounds having various percentages of chlorine Dichlorodiphenyldichloroethane Vol. 12, No. 1, June 1978 43 Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators associated with pesticide monitoring, research, and other programs concerned with pesticides in the environ- ment. Other subscribers work in agriculture, chemical manufacturing, food processing, medicine, public health, and conservation. Articles are grouped under seven headings. Five follow the basic 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. 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. 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For further information on Journal scope and manuscript prepara- tion, see Information for Contributors at the back of this issue. Editorial Advisory Board members are: John R. Wessel, Food and Drug Administration, Chairman Robert L. Williamson, Animal and Plant Health Inspection Service Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Gerald E. Walsh, Environmental Protection Agency G. Bruce Wiersma, Environmental Protection Agency William H. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Herman R. Feltz, Geological Survey Address correspondence to; Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, D.C. 20460 Editor Martha Finan CONTENTS Volume 12 - September 1978 Number 2 Page SOIL Biomacil and diiiroii residue levels in Florida citris soils , 47 David P. H. Tucker FISH, WILDLIFE, AND ESTUARIES Residues of peslieides and PCBs in estnarine fish. 1972-76 — National Pesticide Monitoring Program 51 Philip A. Butler and Roy L. Schutzmann Residues of organochlorine insecticides and polychlorinated hiphenyls in fisli from Lakes Huron and Superior, Canada— 1968-76 60 Richard Frank, Micheline Holdrinet, Heinz E. Braun, Douglas P. Dodge, and George E. Spangler Residues of organochlorine in'^ecticides and polychlorinated hiphenyls in fish from Lakes Saint Clair and Erie. Canada~196S-76 69 Richard Frank, Heinz E. Braun, Micheline Holdrinet, Douglas P. Dodge, and Stephen J. Nepszy Organochlorine residues in aquatic environments in Iran. 1974 S A. Sodergren, R. Djirsarai, M. Gharibzadeh, and A. Moinpour Chloriiuited hydrocarbon pesticide residues in Pacific oysters (Crassostrea gigas) from Tasmania. Australia — 1973 _ 87 Colin Edward Sumner FOOD AND FEED DDT residues in butter and inf(mt formula in India. 1977 91 G. S. Dhaliwal and R. I . Kaira GENERAL Organochlorine pesticides iu\d polychlorinated hiphenyls on sediments from a subarctic salt marsh, Jimtes Bay, Canada — 1976 94 W. A. Glooschenko and R. C. J. Sampson APPENDIX 96 liijorntalion for Coiilribulors 97 SOIL Bromacil and Diuron Residue Levels in Florida Citrus Soils^ David P. H. Tuckers ABSTRACT The widespread use of herbicides in Florida citrus f,>rores raises the possibility of residue uccuinulalion following repeated applications. To determine residue levels of com- monly used herbicides, soil samples were taken from larf>e experimental plots in commercial furores in Polk and Hardee Counties. Bromacil and diuron had been applied in com- bination at both locations for 7-8 years. Analyses of san\ples showed low levels of both herbicides at various soil depths to 60 cm. Only a small amount of bromacil was detectable one year after application, but diuron levels were higher. Continuous applications at recommended rates and frequen- cies have resulted in ma.ximum bromacil and diuron levels of 3.9 percent and 13.1 percent, respectively, of their total application. Introduction Integrated weed control programs used on large acreages of citrus in Florida include herbicides, various cultiva- tion practices, limited hand labor, and naturally occur- ring weed pathogens and insect pests. Herbicides have been widely used for the past decade, and have been applied annually to a large percentage of nonbearing and young-bearing acreage. Herbicides are now used on older groves to control rapidly increasing annual and perennial vines which thrive under tree canopies. This widespread use of predominantly soll-sterilant herbi- cides has caused concern about their accumulation with repeated application. Therefore, continued monitoring of their residual levels in major citrus-growing soil types is warranted. Bromacil and diuron are degraded in the soil by bio- logical and nonhiological means, and they may be 'University of Florida, Cooperative Extension Service, Institute of Food and Agricultural Sciences, Agricultural Research and Education Center, Lake Alfred, FL 3.1850. -Extension Horticulturist, University of Florida, Agricultural Researcli and Education Center, Lake Alfred, FL 33850. altered by one or more mechanisms including microbial decomposition, adsorption, volatilization, leaching, chemical degradation, and plant uptake {2,5,7,8). A number of review papers on this general subject have been presented (3. 4). The persistence of soluble herbicides in soils in forms to.xic to plants is likely to be less serious in humid areas such as Florida than in more arid citrus-growing regions. The amount, frequency, and intensity of rainfall is important to herbicide lon- gevity in soil since moisture atfects herbicide efficacy and mode of dissipation. Tucker and Phillips (9) sampled the major citrus- growing soil types which had received repeated applica- tions of herbicides. Analyses of these samples for bromacil, terbacil, dichlobenil, and trifluralin showed a fairly predictable annual rate of dissipation from the top 45 cm of the soil profile. The results precluded the possibility of any substantial tcxicity to citrus trees due to accumulation in the soils following repeated applica- tions at recommended rates. The present paper presents additional data showing levels of bromacil and diuron following their commercial application to two soil types at two grove locations over 7-8 years. Residue levels are shown at different locations under the tree canopy and at various depths. Sampling and Aiutlysis In 1969 and 1970, paired lO-acre blocks of citrus were selected in commercial groves in Polk and Hardee Counties. Soil types were Astatula fine sand (95 per- cent sand, 0.42 percent organic matter, pH 7.8) and Mayakka fine sand (99 percent sand, 0.38 percent organic matter, pH 7.3), respectively. Annual rainfall at both locations averaged 114-127 cm. The Hardee County grove has a permanent overhead irrigation system with supplemental irrigation averaging 30-50 cm/year. The Polk County grove receives only occa- sional supplemental irrigation. At each site, weeds were controlled by tillage in one block and by broadcast Vol, 12, No. 2, September 1978 47 herbicides in the other. Generally, weed control was satisfactory with one application ot herbicide each year. However, in some years, herbicides were rc-applied when weed growth resumed before the end of the season. Herbicides were sprayed by a machine-mounted boom to the entire grove floor area rather than in strips down tree rows. Wettable powder formulations of bromacil ( 5-bromo-3-sec-butyl-6-methyluracil) and diuron [3- (3.4-dichlorophenyl)-l,l-dimethylurea] in tank mixes or as a chemically blended combination were used throughout the experimental period. Soil samples were collected with a 2.2-cm-ID soil tube from 0- to 15-cm and 15- to 30-cm depths at both locations except at one sampling time when samples were also taken from 30- to 45-cm and 45- to 60-cm depths. Each sample was a composite of 10 subsamples. Samples were taken in row middles between trees, at the drip line or tree canopy edge, and under the tree canopy. There were three separate sampling times in Polk County and two in Hardee County. Care was taken in obtaining the lower depth samples to avoid the top soil layers falling into the holes. To assure this, samples were taken during optiniLmi soil moisture conditions. Samples were stored at — lO'F before shipment for residue analyses by the Dupont Company. Samples were analyzed for bromacil by the microcoulometric gas chromatographic method of Pease (6), and for diuron colorimetrically after chromatographic cleanup by the method of Dalton and Pease (/). Results and Discussion The data in Table 1 show that concentrations of bro- macil and diuron at depths sampled are very low in both locations compared to the total amoimts applied over the 7-8-year experimental period. The levels, as per- centages of the total amounts applied, range from 0.3 to 3.9 for bromacil and from 3.7 to 13.1 for diuron. As percentages of the last application only, they range from 2.5 to 31.0 for bromacil and 33.6 to 84.6 for diuron. This indicates that a substantial part of the residues remains from the latest application within one year of sampling. Residues of diuron remained at considerably higher levels in the soil than did those ot bromacil. This is influenced primarily by their relative water solubilities: 800 ppm for bromacil and 42 ppm for diuron. Residue levels do not appear to be influenced by the location of sampling. Since precipitation is greater on the tree drip line due to the umbrella elTcct of the tree canopy, leaching would also be greater, resulting in an earlier breakdown in weed control. Other factors which may influence residue levels at various sampling locations include photodecomposition of diuron, probably greatest in the row middles due to the high light intensity. Under tree canopies, where sunlight breakdown and precipitation would be less, adsorption of herbicides by organic matter and break- down by microorganisms would be greater. Another factor to consider is that spray coverage is frequently poorer in areas where tree canopies hinder equipment movement. Inadequate spray coverage in the tree row also is frequently due to poor overlap of spray patterns. In most cases, bromacil was more evenly distributed throughout the profile depth sampled than was diuron where higher concentrations were consistently found in the sLirface layers. Again, this is a reflection of the much lower solubility of diuron and hence its slower movement through leaching. Overall residue levels of both herbicides were higher in the Mayakka fine sand of Hardee County than in the Astatula fine sand of Polk County. Bromacil levels in control samples taken from cultivated plots are at or very close to the lower end of the detec- tion limit of the test procedure. Siich background levels are not unusual in analyses of soils for herbicide residues. The levels of diuron are, however, more finite, and an explanation of these levels in the nontreated soil sample is more difticult. Contamination of soil in the cultivated blocks may have occurred when sandy soils were blown in during the dry windy season or washed in during heavy rains. Equipment movement throughout the experimental areas may also account for some move- ment of herbicides in the surface soil. The fact that diuron remains in the sLirface of the soil profile for longer periods would allow for greater movement than bromacil which is more rapidly moved into the lower soil profile. From the data presented, it is evident that bromacil and diuron levels are relatively low in the ()-60-cm layers of the soil types sampled. Since soil was not sampled below 60 cm, the extent of residue movement through leaching into the lower soil profile is unknown. However, the data suggest that residue levels do decrease with depth. Although soil samples were not collected yearly, the data indicate that the degree of accumulation would not lead to cumulative levels toxic to citrus at rates used in commercial practice. This statement is supported by the fact that the tree foliage has not exhibited phyto- loMcity symptoms throughout the experimental period. Rather, residues are steadily dissipating through leaching and ileizradation. 48 Pesticides Monitorinc, Jol'knai o H 1 s W-, ri so gPl O rt o o c Ol — »/^ (N CO r>-j — — S^i? -0 = 0 ^ S?I 0 r- 00 — so t r4 r'l 0 0 CN ■— pi 0 ri — o c o C O ^ •— o — o V o V O O O O o o o o vv 0000 vvv 0 ^ 0 " 0 0 0 0 ^ 0 ^ 0 V 0 0 V 0 o — S ^ SO rj m fS ^ — r-l Tt o -^ r- 00 so m rj ■ ^ d: d d ^ O W-, O W^ >/^Ou-iO inOu^Q mow-iO "^ — f. ^^ — m'*sO — n-, ^sD •— iiTi iiil I"'"' ow^ou-t Cw^c:u-j omow^ O O "'"1 O *ri O ""^ mo \n O mo O m O m d w-i d E s o ai ~3 ri 5 Q 2 = + i" + I TO + U + Q + + ?j + a + + •; + + U 03 ii u m Q + I i U 05 Vol. 12, No. 2, September 1978 49 LITERATURE CITED (/) Dulton. R. L.. and H. I.. Pease. 1962. Delerminution of residues of diuron. monuion, fenuron, and neburon. J. Assoc. Off. Agric. Chem. 45( 2 ) :377-38l. (2) Ganlincr, J. A., et al. 1969. Synthesis and studies with 2-C'^-labeled bromacil and lerbacil. J. Agric. Food Chem. 17(5) :980. (.?) Geisshiililer, //.. and G. Vos.^. 1971. MetaboMsm of substituted urea herbicides. Pages 305-322, in A. S. Tahori (ed.). Pesticide Terminal Residues. Interna- tional Union of Pure and Applied Chemistry Sym- posium, Tel-Aviv, Israel. (4) Coring, C. A. I., D. A. Laskowski. J. W. Hanutker, and R. W. Meikle. 1974. Pages 135-172 in Riswanul Haque and V. H. Freed (eds.). Environmental dynam- ics of pesticides. Proc. Symp. Environ. Dynami(;s Pestic, Los Angeles, CA. {5) Hill. G. D., et al. 1955. The fate of substituted urea herbicides in agricultural soil. Agron. J. 47:93-104. (6) Pease, H. L. 1966. Determination of bromacil residues. J. Agric. Food Chem. 14(l):94-96. (7) Rhodes, R. C. I. J. Belasco. and H. L. Pease. 1970. Determination of mobility and adsorption of agri- chemicals in soils. J. Agric. Food Chem. 18(3) :524— 528. (cS) Torgc.son, D. C, and H. Mee. 1976. Microbial degra- dation of bromacil. Proc. NEWCC 21:584. (9) Tucker. D. P., and R. L. Phillips. 1969. Movement and degradation of herbicides in Florida citrus soils. Fla. State Hort. Soc. 81:72-75. 50 Pesticides MoNriouiNc. Journal FISH, WILDLIFE, AND ESTUARIES Residues of Pesticides and PCBs in Estuarine Fish, 1972-76 — National Pesticide Monitoring Program Philip A. Butler' and Roy L. Schiitzmann^ ABSTRACT This report .summarizes 1524 analyses of juvenile fish col- lected semiannually in 144 estuaries nationwide from July 1972 through June 1976. Pooled samples of 25 whole fish were screened for 20 common pesticides and polychlorinated biphenyls (PCBs). The three most common residues. DDT. PCBs, and dieldrin, were found in J9, 22, and 5 percent of the samples, respectively. Data indicate that estuarine pollution levels continue to decline. [iitroiliiclioil The economic and aesthetic importance of estuaries prompts many investigations to determine the causes and effects of imbalances in these sensitive ecosystems. The most comprehensive program was the monthly surveil- lance in 1965-72 for pesticide pollution of molkiscan populations (4). The nationwide study identified the widespread contamination of estuarine fauna with DDT and demonstrated that DDT levels had peaked and were declining. The persistence of DDT and other synthetic organo- chlorines made it desirable to continue monitoring estuarine areas, but it was necessary to reduce the ana- lytical workload of the monitoring program. Unfortu- nately, residue data from molluscan populations are best understood when obtained contintially. The animals purge themselves rapidly when pollution loading is intermittent (i). The literature on accumulation and long storage of synthetic compounds by fish indicated that fish could be sampled less frequently than mollusks. However, little information was available on the sensitivity or selectivity ^Ecological Monitoring Branch. Technical Services Division, U.S. En- vironmental Protection Agency, Gulf Breeze. FL .tZSbl. = Ecological Monitoring Branch, Pesticides Monitoring Laboratory, U.S. Environmental Protection Agency, Bay St. Louis, MS 39529. of different species of fish in acquiring residues of specific pollutants or combinations of pollutants. Also, it was difficult to determine when and where migratory species acquired residues. Sample Selection ciitd Collection Many species of estuary fish spend only their first year within a single estuary; other species may spend their lifetime in an estuary. Presumably, fish less than a year old would reflect pollution levels during the preceding few months at or near where they were caught. So, each estuary was monitored at 6-month intervals in the spring and fall. The geographic e.xtent of this program meant that com- parisons of residues in ditTerent species would be ques- tionable. Consequently, in a given estuary, the same two species of fish were collected for the duration of the pro- gram. The two species represented different food webs, e.g., a carnivore and a particle feeder. This manner of sampling made it possible to detect pollution trends over the 4-year period. Fish were collected with trawls and beach seines in 144 primary and secondary estuaries in 19 coastal states, Puerto Rico, and the Virgin Islands. Monitoring in Alaska, Hawaii, and Mississippi was limited to one year, but in most areas, si.K to eight semiannual collec- tions were made during five calendar years. The 154 species collected represent 52 of the 175 families of marine fishes of North America (/). Some species and estuaries were monitored only once to identify possible problem areas. More than 60 species were sampled at least three times, and 22 species were collected in the estuaries of three or more states (Tables 1,2). About 38,000 fish were analyzed in groups which made up 1524 samples. Vol. 12, No. 2, September 1978 51 TABLE 1 . Suiniiuiry of cstuariiie fish colh ■clions. July 1972-Junc 1976 Number Number Number Number OF Years OF OF Fish OF Coastal Area MoNnoRED Estuaries Species Samples' Alabama 3 3 4 13 Alaska 1 8 17 37 California 4 7 17 82 Conncclicul 4 4 3 39 Delaware 4 3 11 57 Florida 3 11 22 66 Georgia-' 4 9 15 74 Hawaii 1 8 14 22 Louisiana 2 14 14 51 Maryland 4 8 8 140 Mississippi 1 4 6 21 New Yorl< 4 3 4 46 North Carolina 4 19 28 251 Oregon 3 5 13 178 Puerto Rico- 3 5 14 25 Rhode Island 4 1 2 32 South Carolina- 4 6 5 99 Texas 4 9 8 51 Virginia 3 3 5 55 Virgin Islands- 2 8 19 28 Washington stale 4 6 3 157 TOTAL 144 154'- 1524 'Each sample consisted ol" 25 Hsh less than one year old. -Some monitoring data for 1972-74 have also been published for these four coastal areas (see literature references //. I2i. ■Different species, some species were collected in more than one slate. Sample Prefuiraiioii Earlier laboratory investigations indicated that analyses of 15 randomly selected fish would cover the range of individual variations in pesticide concentrations in experimentally exposed fish populations (2). In the present study, 50 yearling fish were collected semi- annually and analyzed in pools of 25 each. Whole fish samples were homogenized, and an aliquot was blended with a desiccant as described in the molluscan program (4). The prepared samples were shipped unrefrigerated to the Pesticides Monitoring Laboratory, U.S. Environ- mental Protection Agency, Bay St. Louis, Mississippi, for analysis. Analylical Procedure Desiccated samples were shaken with acctonitrile for 4 hours, and partitioned and cleaned by the Mills method (8); methylene chloride and hexanc were used to elute the Florisil cokinin (9). The extract was analyzed by flame photometric detector before Florisil cleanup to avoid possible loss of organophosphorus compounds (6). Polychlorinatcd biphenyls (PCBs) were separated from other chlorinated compounds by the silicic acid method (7). Instrument parameters and operating conditions used for gas chromatographic analysis and confirmation are given in Table 3. Samples were routinely screened for residues of the synthetic compounds listed in Table 4. The recovery range for organochlorines was 75-85 percent, and for organophosphatcs, 85-95 percent. Results and D ISCIISSK'll i;Di)i DDT is persisteni in sediments with high organic content; its presence long after ils use has been lerminated is not 52 surprising. However, DDT residues found recently in fish a few months old are not so easily explained. Of the states and territories monitored, DDT was absent only from Alaska, Hawaii, and the Virgin Islands (87 sam- ples). In 595 samples, 39 percent, DDT was detected at levels of lO-H /j.g/kg (Table 5). In many areas, DDT residues were consistently present in small amounts in fish only a few months old. However, these low levels probably are biologically insignificant. Some samples from California, Delaware, Florida, and New York had DDT residues in the 1 000-4000-/,g/kg range. DDT burdens this high could cause physiological stress and lessen reproductive capacity in fish populations (5). The larger residues surpass levels observed in oysters in the same estuaries in 1965-72 when DDT was still being used. The fact that the half-life of pesticide residues is much shorter in mollusks than in fish may explain this paradox. Coastal areas are ranked in the order of frequency and magnitude of -DDT residues in Table 6. Not surpris- ingly, the 10 areas with the highest frequency of positive fish samples are essentially the same coastal areas which had the highest frequency of -DDT-positive molluscan samples during 1965-72. However, there was a 30 per- cent decline in the overall frequency of DDT-positive samples of fish compared to mollusks in the 13 states where both were monitored. This decline was not uni- form; in Delaware, the frequency remained at 75 per- cent, and in Washington state it declined from 1 1 to 4 percent. Examination of the percentage distribution of DDT and its metabolites, TDE and DDE, in residues indicates to some extent the movement of DDT in the estuarine en- vironment in recent years (Table 7). There has been a well defined shift from the large proportion of DDT in 1972 to its absence from fish samples collected in 1976 and the concomitant increase in levels of DDE. Yet, there has been no significant change in the mean residues of i:DDT present during the 4-year period (Table 8). This suggests that DDT is continually recycled in the food web since it occurs in juvenile fish, and, in moving along biological pathways. DDT is gradually metabolized to the more stable compound. More important, it indi- cates that DDT is no longer being introduced into the estuarine environment and th;it a pollulani can be con- trolled nationwide by enforcing legislation. POl ^CHLOUlNATKD lilPHHNIlS (PCBs) PCBs were identified in 331 samples, 22 percent of the total analyzed. Residues were quantitated by compari- son with standards of Aroclors 1242, 1254, and 1260. In the data tabtilations, PCBs are reported as a single entity regardless of the standard used to quantitate them. Thus, residues consisting of more than one PCB are not fully identified, :tnd reported dal.i oi the actual amounts may vary. Pesticides Monitorinc. Journ.m. X X X X XX X X XXX X XX X xxxx XX X xxxx XX X XX XX XX XX X X X X X X XX XX X XXX XXX X XXX XXX XX X X XX X X X X 5 n -o ■S £ tT c 'J c e: tfi i-s a-s << c c c c < < < < rt ^ x> '^ c 75 ^ u a; 5J c tj- CQ m m m o oa ■^ o. c 03 n — uuu IHW u. OOOOO I 5 -5 S ji _g - I i 2 2 - :§ = g o o u .. u o ^ j= -C S^ tn c -a zh-3 2 X r.i, n >, u ^ ^ o c 13 C -o CI O •a D — -J - •5 y , " 'r ■■ J c a E '" >- 5 1: -^ anSx:.i:=oa.aaa52ii5 HH Vol. 12, No. 2, September 1978 53 X XXX X XXX X X •^ ^ ^ -S ^ s ^ I- !o' O ^ § sil l£ ^ ^ V iJ V ^ it i. 'aZ'L'S.'s. S.^ = 54 PCBs were not found in samples from Alaska and Mis- sissippi. In 1 1 states, Puerto Rico, and the Virgin Islands, Aroclor 1254 was the only standard used. In the remain- ing six coastal areas, standards of Aroclors 1242 and 1260 were occasionally required as well for the quanti- tation of residues (Table 5). The annual incidence of PCB-positive samples is summarized in Table 8. Data indicate a gradual decline in both the ma.ximum residues observed in most years and the average concentration of the PCB residues. The changes were e.xpected in view of the general curtailment in production and use of the compounds. Their chemical persistence suggests, how- ever, that they will continue to contaminate the environ- ment for several years. Only at one station each in Delaware and Washington state did PCB residues frequently exceed 1000 Mg/kg. Such data do not indicate high PCB levels in the ambient water since residues are cumulative and fish may have had up to one year of exposure. However, controlled experiments show that PCB concentrations as low as 1.0 Mg/kg are sufficient to cause fin rot and increased mor- tality in chronically exposed fish (10). Coastal areas are ranked in order of the frequency and magnitude of PCB residues in estuarine fish (Table 9). These residues were found in 19 of the 21 areas moni- tored, but in only tour states were they present in more than half the samples. In contrast. DDT residues were found in 18 areas and were present in more than half the samples from nine states. This indicates a much broader contamination of the environment with DDT than with PCBs. The incidence of PCB residues in fish cannot be com- pared with the much lower frequency observed in mol- lusks in 1970-72. PCBs are an industrial pollutant and are not usually found where shellfish are harvested. DIELDRIN Residues of dieldrin were delected in 74 samples, 5 per- cent of the total samples, ranging from 10 Mg^kg to 145 Mg/kg. Positive samples were collected in some of the estuaries of 12 states and the Virgm Islands (Table 10). About halt the positive samples were collected in sec- ondary estuaries in the Maryland section of Chesapeake Bay. Samples from this area conlained dieldrin in 1972- 74, but not in 1975. Dieldrin was found in a variety of fish species, but its presence had no apparent correlation with their different feeding patterns. In 1972-74, diel- drin was found in about 7 percent of Ihe fish samples; but in 1 975-7(1, less than I percent of the samples con- tained detectable levels (Table 8). During the 1965-72 monitoring of mollusks, dieldrin was found in 15 percent i>f the samples at levels approximately double those de- tected in the juvenile tish. Pesticides Monitoring Journal TABLE 3. Operating parameters for analyzing estiiarine fish for pesticide and PCB residues— 1972-76 Detector CoLUM^ Electron- Glass, 1.8 m long x 4 mm ID, packed with capture 3 percent DC-200 on 80-100-mesh Supelcoport Electron- Glass, 1.8 m long X 2 mm ID, packed with capture a mixture of 1.5 percent OV-17 and 1.95 per- cent OV-210 on 80-100-mesh Supelcoport Electron- Glass, 1.8 m long x 2 mm ID. packed with capture 5 percent OV-210 on 80-UIO-mesh Supelcoport Flame Glass, 1.8 m long x 4 mm ID, packed with photometric 3 percent OV-IOI on 80-100-mesh Chromosorb W-HP Column Temperatures, °C Detector Carrier Gas, Flow Rate 188 300 250 Argon/methane 50 ml/minute 193 200 230 Nitrogen 30 ml/minute 173 200 230 Nitrogen 30 ml/minute 177 184 230 Nitrogen 50 ml/minule TABLE 4. Coinpoiimls detected by gas cliromatograpluc analysis of estiiarine fish tissue — 1972-76^ Organochlorine ORUANOPHdSPHATE Aldrin Chlordane DDT Dieldrin Endosulfan Heptachlor Lindane Methoxychlor Mirex PCBs Toxaphene Trifluralin Azinphosmcthyl Carbophenothion DEF Demeton Diazinon Ethion Malathion Parathion Phoraic NOTE: See appendix for cllcmical names of compounds. 'Lower delcclion Hmit is 10 ;ig kg for all compounds except the fol- lowing: endosulfan. 20 /ig'kg: methoxychlor and ethion, M ^g, kg; mirex, PCBs. toxaphene, carbophenothion, and DEF, 50 ng kg. PESTICIDES OCCASIONALLY DETECTED Despite the fact that all samples were routinely screened for 21 synthetic hydrocarbons and their oxygen analogs, few were detected. DDT and its metabolites, dieldrin, and PCBs were the most common residues. Only si.x other pesticides were found in measurable amounts (Table II). These were detected in 48 samples or about 3 percent of the total. A majority of these residues occurred in fish from the upper end of Chesapeake Bay and along the Texas coast. The insecticide endrin and the herbicide Dacthal (DCPA) were also identified in fish from a heavily farmed area in the Texas Rio Grande river basin. This area was monitored monthly and the data will be presented in a separate publication. DATA INTERPRETATION The data are organized on a seasonal and geographic basis, i.e., by state boundaries, in an effort to make the large group of heterogenous samples more manageable. Unfortunately, some details of localized pollution pat- terns are lost in the process. For example, data from only one river basin in Rhode Island can be compared with data from 3-19 river basins in other states. Or, as in Washington state, data from one polluted estuary were averaged with five other relatively clean areas in the state. In Table 9, the frequency of PCB residues is shown as 17 percent in Washington. Actually, all 27 samples from the Duamish River were contaminated, but none of the 128 samples from the other five estuaries contained PCB residues during the 4-year period. PCB residue data from the Duamish River samples illus- trate the importance of sampling continuity to determine localized pollution patterns and trends. The Pacific stag- horn sculpin and English sole were both collected seven times in the 4-year period. Quantitation of the PCB residues required three different standards (Table 12). The residues were probably mixtures of two or more PCBs, but the data indicate both a shift in the kind of pollution and a decline in pollution levels. There must always be some ambiguity in the compari- son of residue data from ditTerent species in the absence of controlled experiments on their ability to accumulate pesticides. In the Duamish River samples, the consis- tently higher residue levels in English sole probably were due to a ditTerence in age rather than in species. Sole populations sampled were usually about 6 months older than Ihe sculpins. Comparisons of residue data in a single fish species dis- tributed over a wide geographic range permit valid judg- ments of regional pollution differences. The bay anchovy was the most widely distributed species in the present program. It was collected in 37 estuaries in the 1 1 states from Delaware to Texas over a 3-year period. Samples from three estuaries in Georgia and three in Louisiana contained no detectable DDT or PCBs. in contrast, 42 bay anchovy samples collected in Delaware and Chesa- peak Bay during this 3-year period contained residues of DDT ( 10-467 Mg/kg, mean 77) and PCBs (90-996 /ig/kg, mean 340). On the basis of such data, it is pos- sible to identify regional pollution patterns when juvenile fish of the same species are monitored periodically. In general, residue data from all the estuaries in a single state were strongly skewed because only one or two estu- aries were highly polluted. In Washington state, less Vol. 12, No. 2, September 1978 55 TABLE 5. Residues of ^Dl^T and PC lis in wliolc-hody samples of juvenile esluiirine fisii, 1972-76 Residues, ^c/kg Wet Weight JDDT PCBs Coastal Area, Number of Year Samples Alabama 1972 2 1973 2 1975 3 1976 6 Alaska 1972 7 197.1 30 California 1972 6 1973 21 1974 17 1975 18 1976 20 Connecticut 1972 4 1973 7 1974 15 1975 5 1976 8 Delaware 1972 6 1973 12 1974 14 1975 9 1976 16 Florida 1972 25 1973 15 1974 19 1975 7 Georgia 1972 12 1973 17 1974 10 1975 18 1976 17 Hawaii 1972 8 1973 14 Louisiana 1975 24 1976 27 Maryland 1972 22 1973 45 1974 45 1975 28 Mississippi 1972 5 1973 16 New York 1972 6 1973 10 1974 12 1975 6 1976 12 North Carolina 1972 30 1973 80 1974 70 1975 41 1976 30 Oregon 1973 77 1974 66 1975 35 Number PoSlltVE Maximlim Residue Geometric X OF Positive Samples Number Positive Maximum Residue 4 19 15 15 18 6 12 13 8 4 8 4 17 5 14 26 35 6 3 5 10 5 10 29 34 26 18 18 21 22 3 82 17 35 49 213 667 1422 1349 2588 63 68 43 97 1425 636 1194 1146 1015 170 18 1640 23 65 14 32 16 108 23 184 345 694 714 16 159 174 115 11)6 4082 11)4 140 357 322 78 140 125 221 12 67 17 20 35 69 75 69 79 95 43 68 26 25 220 85 109 181 471 25 13 36 21 26 13 32 16 52 23 55 73 51 251 14 135 71 49 34 188 39 43 39 39 24 33 29 32 11 0 2 5 6 12 4 7 14 5 4 0 0 16 1 14 12 16 9 5 2 10 2 10 15 1 3 1 2 271) 512 432 400 592 678 1065 497 289 4504 2671 823 1566 1258 614 104 508 137 305 256 788 1046 878 940 310 235 301 694 447 786 120 174 173 538 277 247 288 163 229 224 210 254 313 321 406 252 172 1469 802 258 720 649 62 104 508 137 244 256 351 318 287 267 231 149 165 471 295 258 120 131 173 527 130 1 79 236 (Continued next page) 56 Pesticides Monitoking Journal TABLE 5 Cconfd.). Residues of SPPT and PCBs in whole-body samples of juvenile estuarine fish. 1972-76 Coastal Area, Number of Year Samples Puerto Rico 1972 4 1973 8 1974 4 1976 9 Rhode Island 1972 4 1973 g 1974 8 1975 8 1976 4 South Carolina 1972 12 1973 25 1974 21 1975 22 1976 19 Texas 1972 7 1973 9 1974 11 1975 18 1976 6 Virginia 1973 26 1974 11 1975 18 Virgin Islands 1972 6 1973 13 1974 9 Washington state 1972 21 1973 48 1974 48 1975 24 1976 16 Number Positive 2 1 0 5 0 0 5 4 0 7 13 6 2 0 5 5 8 12 4 20 10 7 0 0 0 0 1 1 0 4 Residues, /io/kg Wet Weight 2DDT Maximum Residue 157 172 86 78 20 60 33 29 12 52 188 223 59 70 124 60 821 25 11 38 Geometric X OF Positive Samples 100 172 24 17 29 16 19 11 38 S2 65 23 37 39 39 115 25 11 32 Number Positive 2 2 4 0 4 4 8 4 4 1 0 0 0 0 3 0 4 4 1 PCBs Maximum Residue 201 416 579 477 797 524 241 356 182 267 240 265 157 438 456 2549 166 809 4903 3363 2028 2639 900 Geometric X of Positive Samples NOTE: Samples from Alaska conlained no PCBs. 181 316 238 451 464 231 230 275 182 136 95 150 157 214 254 850 142 615 2552 1577 1515 2057 668 ,,.,,;,, . , ,-,,„ ^.-. Aroclor 1 254 was used as the slandard in all olher coaslal addii ons. Aroclor 126(1: Cahlornia, Connecticut. Delaware. Maryland, North Carolina, and Washin.i Maryland. North Carolina, and Washington state. asning. areas with the following occasional on state; Aroclor 1242: Delaware, TABLE 6. Frequency and average concenlration of IDDT residues in juvenile estuarine fish by coasted area. 1972-76 Average Frequency Concen- Coastal OF Coastal tration, Area Residues, % Area /IG/KG ' California 87 Delaware 213 Delaware 75 Maryland 108 New York 72 Puerto Rico 10(1 Alabama 69 California 77 Virginia 67 New York 76 Texas 67 Mississippi 75 Maryland 58 Virginia 64 Florida 52 Texas 49 North Carolina 48 Connecticut 41 Puerto Rico 32 Louisiana 38 Connecticut 31 North Carolina 36 Mississippi 29 Alabama 35 South Carolina 29 Florida 24 Rhode Island 28 Oregon 24 Oregon 26 Washington state 23 Louisiana 12 Georgia 1? Georgia 10 Rhode Island 21 Washington slate 4 South Carolina 19 Alaska 0 Hawaii 0 Virgin Islands 0 NOTE: Comparisons are limited in that the number of samples, nun ber of sampling stations, period (years) of sampling, and species of fish differ for each coastal area. •Arithmetic average of geometric means of positive samples in all collection years. than 4 percent ot the samples collected in 5 years con- tained measurable residues of DDT. The geometric means of the positive samples, along with the maximum residue detected and the number of positive samples, is the best summary of actual pollution levels. Conversely, the geometric means of the residue data from year to year in a given state were normally distributed, and the arithmetic means were used to compare pollution levels in ditTerent geographic areas (Tables 6, 8. 9). Plans are finder way to store sample and analytical data in a com- puter data bank to provide more precise data analyses in stLidies of localized polkition problems. TABLE 7. Percentage distribution of metabolites in ZDDT residues in juvenile estuarine fisli by coastal area, 1972-76 Year Number of Positive Samples Distribution. % DDT TDE DDE 1972 1973 1974 1975 1976 90 167 173 97 68 23 12 5 1 0 37 30 36 21 14 40 58 59 78 86 Vol. 12, No. 2, September 1978 57 TABLE 8. Annual iiicUlciwe of ZDDT, PCB, and dielilrin residues in juvenile whole fish samples, 1972-76 No. OF Samples Residues, /ig/kg DDT PCBs DiELDRIN Year PosnivE Maximum Residue Average Residue' Positive Maximum Residue Average Residue' % Positive Maximum Residue Geometric X 1972 1973 1974 1975 1976 187 483 380 284 190 48 34 46 34 36 1425 667 1640 4082 2588 62 58 42 69 88 34 12 29 20 22 4903 3363 2028 2639 1258 540 429 320 460 351 7 6 8 1 0 140 140 145 15 21 30 12 14 ' Arithmclic average of the geomelric means of positive samples from each coastal area. Conclusions Juvenile fish arc satisfactory tools for gauging pesticide pollution trends in estuaries provided at least 25 indi- viduals. 6-12 months old, of the same species are sam- pled annually at a specific location. AnaUses of the same species of fish at different geographic locations permit valid comparisons of pollution levels. Existing i;DDT residues are the result of biotic recycling, and probably little, if any. DDT has been introduced recently into the cstuarine systems monitored in this study. The magnitude and frequency of biotic residues of DDT, dicldrin, endrin, and toxaphene declined substantially between 1965-70 and 1972-76. Data from this study warrant annual monitoring of juve- nile fish in the nation's estuaries. Aclinowledginent The autht)rs arc greatly indebted to many people for the success of this monitoring program. We thank espcciall>' TABLE 9. Frequency and average concentration of PCB residues in juvenile estiiarine fish by coastal area, 1972-76 Average Frequency Concen- Coastal OF Coastal tration, Area Residues. % Area ;iG/KG' Connecticut 87 Washington state 1674 Rhode Island 75 Delaware 780 New York 63 Virginia 439 Delaware 51 Virgin Islands 379 Virginia 38 Rhode Island 330 Maryland 36 Connecticut 323 Puerto Rico 32 Georgia 323 California 31 Maryland 306 Florida 26 New York 262 Texas 24 Louisiana 256 Alabama 23 Puerto Rico 245 Virgin islands 18 Hawaii 244 Washington state 17 North Carolina 242 Hawaii 14 California 229 Oregon 10 Oregon 182 North Carolina 9 South Carolina 182 Georgia 3 Alabama 163 Louisiana 2 Texas 135 South Carolina 1 Florida 83 Alaska 11 Mississippi 0 NOTE; Comparisons arc limited in ihal (he number of samples, num- ber of sampling Malions, periods (years) of sampling!, and stpccics of lish difTcr lor each coastal area. ^Arithmetic average of jieumeiric means of positive samples in all collection years. TABLF 10. Geographic incidence of ilieldrin residues in juvenile estuarine fish, 1972-76 Number Mean Coastal OF Number Residue. Area Samples Positive liC/KC California 82 2 34 Connecticut 39 3 15 Delaware 57 2 59 Florida 66 12 10 Georgia 74 T 60 Louisiana 51 1 15 Marvland 140 35 30 Mississippi 21 2 17 New York 46 2 24 North Carolina 251 4 20 Texas 51 6 20 Virginia 55 2 10 Virgin Islands 28 1 10 June Hartsfield for helping to summarize the data and for typing the manuscript, and Michael Reuschel for help with the tables. We thank Charles D. Kennedy for countless analyses, and we thank Stanley S. Mecomber at the Pesticides Monitoring Laboratory. Fish samples were collected through the cooperation of state, federal, and university marine laboratories. These agencies and their principal investigators are: University of Alabama Marine Sciences Program, G. Crozier; National Marine Fisheries Service, Auke Bay, Alaska Laboratory, H. S. .Sears; California Department of Fish and Ciame, W. Griffith; National Marine Fisheries Ser- vice, Connecticut Biological Laboratory, A. Calabrese; University of Delaware College of Marine Studies, R. W. Smith; University of South Florida Marine Science Insti- tute, R. Baird; University of Miami School of Marine and Atmospheric .Science, B. Yokel; National Marine Fisheries Service, Panama City Laboratory, E. Naka- nuira; University of Georgia Marine Institute, R. J. Reimold (also made collections in Puerto Rico and the Virgin Islands); University of Hawaii Institute of Marine Biology, J. H. Bardach; University of Southwestern Louisiana. H. D. Hoese; University of Maryland Chesa- peake Biological Laboratory. 1 . Ritchie; Gulf Coast Re- search Laboratory. T. I-. Lytic; University of North Carolina Institute of Marine Science, A, F. Chestni.it; University of Oregon Marine Science Center. R. S. Cald- well; University of Puerto Rico Department of Pharma- cology, T. Morales-Cardona; University of Rhode Island Oceanograph\ Department, D. R, Sheehy; South Caro- 58 Pesticides Monitorinc, Journ.m State TABLE 1 1. Pesticide residues occasionally detected in juvenile estuarine fish, 1972-76 Chiordane Heptachlor Epoxide TOXAPHENE Ethyl Parathion Methyl Parathion Carbophenothion Ethion Alabama 1-13-133 Connecticut 1-39-10 Hawaii 6-22-290 Louisiana 1-51-504 Maryland 22-140-118 3-140-15 Mississippi 2-21-388 New York 2^6-207 North Carolina 1-251-12 Texas 3-51-75 3-51-75 2-51-47 1-51-103 1-51-83 NOTE: Data in columns represent incidence, number of samples, and mean residue, Mg/kg, respectively. lina Wildlife and Marine Resources Department, M, H. Shealy, Jr.; Texas Parks and Wildlife Department, R. Childress; Virginia Institute of Marine Science, R. J. Huggett; State of Washington Department of Fisheries, B. Pattie; and University of Washington Fisheries Re- search Institute, B. Miller. TABLE 12. Treiuls in PCB residues ill Englisli sole and Pacific stai>liorn scittpin. Dininiisli River, Waslungton state, fall 1972-spring 1976 Most Similar Aroclor St ^NDARDl Date Species 1254 1260 1242 Fall 1972 E P 3346 2202 Spring 1973 E P 2111 2065 Fall 1973 E P 1683 1129 Spring 1974 E P 1927 1477 Fall 1974 E P 1733 825- Spring 1975 E F 2541 1832 Spring 1976 E 888 1241 P 506 492 NOTE: E = English sole, P ~ Pacific staghorn sculpin. ^ Data represent average of two sample pools of 25 fish each (.wet weight, ^g/kg). -Only one sample. LITERATURE CITED (/) Bailey, R. M., J. E. Fitch, E. S. Herald. E. A. Laciuter, C. C. Lindsey, C. R. Robins, and W. B. Scott. 1970. A list of common and scientific names of fishes from the United Slates and Canada. Third ed. Am. Fish. Soc. Spec. Publ. No. 6, Washington, D.C. 150 pp. '■?) Butler, P. A. 1969. Significance of DDT residues in estuarine fauna. Pages 205-220 in Chemical Fallout. Charles C Thomas, Springfield, 111, (.?) Butler, P. A. 1971. Influence of pesticides on marine ecosystems. Proc. Roy. Soc. London B. 1970: 321-329. (4) Butler, P. A. 1973. Organochlorine residues in estuarine mollusks, 1965-72 — National Pesticide Monitoring Program. Pestic. Monit. J. 6(4) :238-362. (5) Butler, P. A., A. J. Wilson. Jr., and R. Childress. 1972. The association of DDT residues with losses in marine productivity. Pages 262-266 in Marine Pollution and Sea Life Fishing News Ltd. Books, London, England. (6) Luke, M. A., J. E. Frobcrg, and H. T. Masumolo. 1975. Extraction and cleanup of organochlorine, organo- phosphate, organonitrogen, and hydrogen pesticides in produce for determination by gas-liquid chromatog- raphy. J. Assoc. Off. Anal. Chem. 58(5) : 1020-1026. (7) Masumoto, H. T. 1972. Study of the silicic acid pro- cedure of Armour and Burke for the separation of PCB's from DDT and its analogs. J. Assoc. Off. Agric. Chem. 55(5): 1092-1 100. (S) Mills, P. A., J. H. Onley. and R. A. Gaither. 1963. Rapid method for chlorinated pesticide residues in nonfatty foods. J. Assoc. Off. Agric. Chem. 46(2): 186-191. (9) Mills, P. A.. B. A. Bong, L. R. Kanips. and J. A. Burke. 1972. Elution solvent system for Florisil cleanup in organochlorine pesticide residue analyses. J. Assoc. Off, Agric. Chem. 55(1) :39-43. (10) Nimmo, D. R., D. J. Hansen, J. A. Couch, N. R. Cooley, P. R. Parrish. and J. 1. Lowe. 1975. Toxicity of Aroclor 1254 and its physiological activity in sev- eral estuarine organisms. Arch. Environ. Contam. Toxicol. 3(l):22-39. (//) Reimold, R. J. 1975. Chlorinated hydrocarbon pesti- cides and mercury in coastal biota, Puerto Rico and the U.S. Virgin Islands— 1972-74. Pestic. Monit. J. 9(l):39-43. {12) Reimold, R. J., and M. H. Shealy, Jr. 1976. Chlori- nated hydrocarbon pesticides and mercury in coastal young-of-the-year finfish. South Carolina and Georgia — 1972-74. Pestic. Monit. J. 9(4) : 170-175. Vol. 12, No. 2, September 1978 59 Residues of Organochlorine Insecticides and Polychlorinated Biphenyls in Fish from Lakes Huron and Superior, Canada — 1968-76 ' Richard Frank," Micheline Holdrinet,- Heinz E. Braiin,- Douglas P. Dodge,' and George E. Sprangler' ABSTRACT Five species of fish from Lake Superior and 12 species from Lake Huron were analyzed for ori;anoclilorinc pesticides and polychlorinated biphenyls (PCBsj between 1968 and 1975. Mean residues of ^DDT peaked at 1 .72 ppm and 7.60 ppin in lake trout (Salveliniis namayciish) from Lakes Superior and Huron, respectively. By 1975, the mean level of '^DDT had decreased in lake trout and was liighest in bloaters (Coregoniis hoyi) from both lakes: 1.06 ppm and 1.87 ppm. respectively. Dieldrin levels in fisli from Lake Superior changed little over the .same period. However, in 1969-70. dieldrin levels in fish from Lake Huron exceeded the 0.3 ppm tolerance level set by Health and Welfare Canada or the Food and Driit; Administration, U.S. Department of Health. Education, and Welfare in 5 percent of lake whilefish (Core- gonus cliipeaformis) and 10 percent of bloaters. By 1975. 50 percent of bloaters caught in Georgian Bay and North Channel hud dieldrin levels above 0.3 ppm. PCB residues declined in lake trout and lake whitefish caught in Lake Superior between 1971 and 1975, but increased slightly in bloaters and white sucker (Caloslomus commcrsoni ). .Mean PCB residues in bloaters caught in Lake Huron in 1969-71 and 1975-76, and splake (Salveliniis fonlinalis and S. namaycush) and ci.sco (Coregonus arledii) caught in 1975 exceeded the 2 ppm tolerance level. IiUrociiiclion The Great Lakes are surrounded b> land ihal is highly developed for urban, industrial, agricultural, and recrea- tional activities. Since outflow of the Circat Lakes is limited, chemical discharges into the lakes are very per- sistent. For the past decade organochlorines have been identified as a serious contaminant in fish, resulting in long-range detrimental effects to private and commercial fishing. 'Partial fundinK fur ihc l'*75-75 samplint; and analysis provided by the Intcrnaiiunal Ji>int (Vimmission under Task Force D of the Pollution from Land Use Activities Reference Group. •Provincial Pesticide Residue Tesiinp laboratory. Ontario Ministry of Auriculiurc and food, c o University of Guelph. Guclph, Ontario. NIG 2WI. ■■ Fisheries Branch. Ontarin .Ministry of Natural Resources. Queens Park. Toronto, Ontario. 'Fish and Wildlife Research Dramh. Ontario Ministry of Natural Resources, South Bay. Ontario. Organochlorine insecticides and polychlorinated bi- phenyls (PCBs) have been identified in fish caught in Lakes Huron and Superior. Reinhert reported residues of 0.2-7.4 ppm i.DDT and 0.01-0.05 ppm dieldrin in several species of fish caught in Lake Superior in 1967- 68 (7). Reinke et al. reported that two fish species caught in 1970 from the same lake had mean residues of 0.2 ppm and 1.3 ppm -DDT and 0.06 ppm dieldrin (9). Four species, also caught in Lake Superior in 1974- 75, cited by the Upper Great Lakes Reference Group, contained mean residues of 0.2-4.4 ppm -DDT and 0.0 1 -0. 1 5 ppm dieldrin ill). Residues of chlordane, lin- dane, and PCBs were also reported in these four species. Reinhert found mean residues of 0.8-6.9 ppm -DDT and 0.02-0.1 1 ppm dieldrin in nine species of fish from Lake Huron in 1967-68 l7). Reinke et al. reported mean residues of 0.5-16.4 ppm IDDT and 0.01-0.31 ppm di- eldrin in the same major fish species in Lake Huron in 1970 1 9). The Upper Great Lakes Reference Group cited considerably lower residues of -DDT in three fish species caught in 1974-75 111), but levels of dieldrin. lindane, chlordane, and PCBs were similar to those found in other studies. Studies on the distribution of organochlorines in water, sediment, and scston in Lakes Superior and Huron reveal that these compounds are widespread in the Great Lakes ecosystem l3). Miles and Harris reported that the Mus- koka River discharged large amounts of -DDT to Georgian Bay 16). Peak discharges of 5.4 kg/week occurred in May 1971, but the i^uantity declined rapidly from May to October, averaging 0.9 kg -DDT/week. r-rank et al. found that fish in the Muskoka Lake- Muskoka River system contained some of the highest residue levels founti in fish from inland lakes of Ontario l2). Fourteen species had mean residues of 0.22-22.4 ppm -DDT; sediments in this lake-river system con- tained -DDT residues as high as 2.9 ppm. Ihc present study, begun in 1968, was originally in- tended to idenlily ami measure organochlorine residues 60 Pesticides Monitoring Journal LAKE SUPERtOft 9 »iNLi' M' 9 SH(s>«fp BREPAR.-\TION Fish were measured, weighed, and where possible, the sex was determined. Heads and viscera were removed and the remainder of the fish was macerated in a Hobart meat grinder. A 150-200-g subsample was stored in a sealed glass jar at — 20"C: storage time varied from a few days to four months. Individual fish were analyzed when the sample size was not limiting. Alewife. shiners, smelt, and other small fish were prepared as composites of similar sized fish. They were weighed and measured individually before being ground. Vol . 12, No. 2. September 1978 61 ANALYTICAL PROCEDURE Ten grams of tissue homogenate was ground with 100 g anhydrous sodium sulfate and 25 g Ottawa sand. The mixture was extracted with 300 ml hexane for 7 hours In a Soxhiet extractor. Solvent was evaporated by rotary vacuum and the percentage fat was determined gravi- melricalh. A one-step Florisil column cleanup method described by Langlois et al. <5) was used to isolate organochlorine in- secticides and PCBs. A maximum of I g fat was mixed with conditioned Florisil and placed above another layer of Florisil. The column was eluted with a 300-ml 1:4 mixture of dichloromethane-hexane. Solvent was evap- orated by rotary vacuum. PCBs. Hexachlorobenzene (HCB), and organochlorine insecticides were separated on a charcoal column accord- ing to the method described by Holdrinet (4). Analyses were performed with a Tracor Model 550 gas-liquid chromatograph (GLC). Instrument parameters and oper- ating conditions follow. Deleclor: Column: Temperature: Carrier gas: Injection volume: •"Ni 15 cm y 0.64 cm OD glass, packed with a mixture of 4 percent SE-30 and 6 percent QF-I on 80-100-mesh Chromosorb W I80°C nitrogen flowing at 60 ml/minute 5 ti\ was equivalent to I ng fat sample Two-dimensional thin-layer chromatography was used on random samples for confirmation. Samples were re- moved, redissolved. and re-injected into the GLC column. Recoveries were checked periodically by fortification of tissue homogenates prior to extraction. Average recov- eries were: was included in 1973 but was discontinued because of the low level and incidence of HCB found in the sam-. pies. The analysis and confirmation for cis- and irans- chlordane was refined in 1975; analyses for mirex and oxychlordane were introduced in 1976. Results LAKE SUPERIOR -DDT — None of the five fish species caught in Lake Superior contained annual mean residues in excess of the 5 ppm tolerance level established by Health and Welfare Canada or the Food and Drug Administration, U.S. De- partment of Health, Education, and Welfare. The high- est mean residue of 2.7 ppm was found in lake trout caught in 1968. However, of 18 lake trout analyzed, three contained residues of -DDT that exceeded 5 ppm (Table 1): a 1 544-g fish caught in Shesheep Bay con- tained 14.1 ppm: a 2906-g fish caught off Thunder Cape contained 7.9 ppm; and a 3314-g fish caught in Finlay Bay contained 5.2 ppm (Figure I). Lake trout caught in 1971 and bloaters caught in 1971 and 1975 contained the second highest mean -DDT residues of 1.16 ppm and 1.06 ppm. respectively, but no individuals exceeded the tolerance level. Residues of -DDT declined in both lake trout and lake whitefish (Coregoniis cliipeaformis) between 1971 and 1975. but no trend was apparent in either bloater or white sucker (Coregoniis commersoni). The ratio of DDE plus TDE to -DDT increased in lake trout and lake whitefish from 1971 to 1975. indicating a metabolic breakdown of o.p'- and /7./)'-DDT; this was not so appar- ent in bloaters and white sucker (Table 2). The decline is more evident in lake trout when similar weight classes are compared (Table 3). In spite of higher fat content in fish caught in 1975. -DDT is only a fraction of the resi- due found in 1968-70. Residue % Residue % o,p'_DDT 91 Dieldrin 89 P,P'-DDT 89 c(5-Chlordane 98 P,P-TDE 94 /rtmA-Chlordane 90 P,P'-DDE 96 PCBs 85-90 The data were not corrected for recoveries. Detection limits were 0.005 ppm for organochlorines and 0.05 ppm for PCBs. PCBs were identified by comparing them with mixtures of Aroclors 1254 and 1260 and checking for a resemblance to peaks VII, VIM, and X on sample chro- matograms according to Reynolds (10). Analysis was begun in 1968 when the known main con- taminants in fish were /j./)'-DDT and its analogs plus di- eldrin and heptachlor epoxide; PCB values prior to 1970 were estimated. With the iniroduction of a column frac- tionation technique in 1970 for the separation of PCBs from organochlorine insecticides, ihc measurement of PCB residues became more precise. Analysis for HCB Dieldrin — No fish species contained mean residues that exceeded 0.08 ppm dieldrin, and no individual fish con- tained residues which exceeded the 0.3 ppm guideline set by FDA. The highest level of dieldrin found in an individual fish was 0.26 ppm in a lake trout caught in 1968. In general, levels of dieldrin were low, but the rate of disappearance of dieldrin since 1971 also has been slow. On the basis of a -DDT/dieldrin ratio, -DDT declined more rapidly than dieldrin between 1971 and 1975 (Table 2). Lake trout exhibited a decline in the ratio between 1968 and 1975 of 91 to 5. The ratio of PCBs to dieldrin changed little between 1971 and l'>75. This was borne out when similar weight classes t)f lake trout were compared (Table 3). PCBs — None of the five fish species caught in Lake Superior contained mean residues of PCBs greater than the 2 ppm tolerance level set by Health and Welfare Canada (Table I). However, two individual trout caught 62 Pesticides Monitoring Journal TABLE 1. OrganocMorine residues in five fish species caught in the Canadian waters of eastern Lake Superior, 1969-75 Year No. OF Analyses Mean AND Range Mean Con TENT AND RANGE OF Contaminants in Fish P UREE, PPM».= Weight. G Fat. Species DDE TDE DDT 2 DDT Dieldrin PCBs Caloslomidae White sucker 1971 5 1102 -) 1 0.08 0.01 0.04 0.13 0.01 0.2 988-1202 0.9-5.0 <0.0!-0.15 <0.01-0.02 <0.01-0.07 0.01-0.24 <0. 1-0.5 1975 8 946 3.1 0.14 0,01 0.05 0.20 0.02 0.3 696-1154 0.7-7.1 0.03-0.46 <0 .01-0.03 <0.01-0.15 0.08-0.59 <0.01-0.06 0.1-0.7 Esocidae Northern pike 1971 5 2044 1.2 0.23 0.03 0.14 0.40 <0.01 0.3 1474-2752 0.8-1.8 0.08-0.48 0.01-0.07 0.02-0.41 0.11-0.96 0.1-0.6 Salmoiiidae Bloater 1971 4(19) ■ 149 9.7 0.68 0.07 0.41 1.16 0.02 0.6 145-175 9.4-10.0 0.56-0.75 0.06-0.08 0.34-0.45 0.96-1.36 0.01-0.06 0.5-0.7 1975 10 169 10.2 0.52 0.07 0.47 1.06 0.04 1.0 112-268 3.1-18.7 0.07-1.76 0.02-0.16 0.12-1.39 0.22-3.23 0.0I-O.09 0.3-3.7 Lake Irout 1968 18 2016 8.0 1.44 0.24 1.04 2.72 0.08 0.7 455-5506 1.3-14.7 0.16-7.11 0.01-1.32 0.02-5.68 0,27-14.1 0.01-0.26 <0. 1-2.0 1969 20 734 6.4 0.43 0.12 0.43 0.98 0.03 0.3 409-171X) 1.7-14.4 0.20-0.75 0,04-0.20 0.19-0.77 0.43-1.69 <0.0 1-0.05 0.1-0.6 1971 5 1901 17.4 0.9S 0.09 0.65 1.72 0.03 1.8 1572-2728 15.7-22.1 0.59-1.25 0.06-0.11 0.38-0.82 1.03-2.18 0.02-0.05 1.1-2.3 1975 10 1121 20.7 0.11 0.01 0.05 0.17 0.04 0.4 555-1432 14.7-29.4 0.09-0.16 <0. 01-0.03 0.02-0.09 0.10-0.24 0.03-0.05 0.3-0.6 Lake whilefish 1971 5 959 12.0 0.35 0.04 0.35 0.74 0.04 0.8 895-1060 8.5-14.2 0.29-0.45 0.03-0.05 0.. 10-0.43 0.6.3-0.93 0.03-0.05 <0. 1-1.0 1975 11) 1135 10.8 0.16 0.02 0.06 0.24 0.07 0.3 766-1400 6.2-12.2 0.09-0,29 0.01-0.03 <0.01-0.16 0.12-0.48 0.04-0.11 0.1-0.7 1 In 1975 traces (0,004 ppm ) of cis- and /rflM5-chlordane were detected in st.>me bloater, while sucker, lake Iroul. and lake whitefish. -<0.01 ppm represents a trace of contaminani above the level of detection (0.001 ppni ) but uelow 0.010 ppm. ■'Composite of 19 fish. off Grass Cap Point in 1971 ha(i resi(iues of 2.2 ppm and 2.3 ppm PCBs and two bloaters caught commercially in I97.'> had residues of 2.1 ppm and 3.7 ppm. Mean resi- dues for lake trout in 1971 and bloaters in 197.S were 1.8 ppm and 1.0 ppm, respectively. TABLE 2. Ratios of organochlorinc contantinants in four species of fisli cauglit in Luke Superior, Luke Huron, and Georgian Bay, 1968-76 Year DDE+TDE ^DDT i;DDT PCBs :cddt PCBs Species Dieldrin DnU-DRlN Lake Superior Bloater 1971 0.65 2.0 50 30 1975 0.56 1.1 30 25 While sucker 1971 0.69 0.5 21 20 1975 0.75 0.8 10 15 Lake trout 1968 0.62 3.9 91 9 1969 0.56 3,3 33 10 1971 0.62 0.9 50 60 1975 0.70 0.4 5 10 Lake whilefish 1971 0.53 0.9 19 20 1975 0.75 0.8 3 4 Lake Huron (Mt MM Lake ) Bloater 1969 0.74 3.5 69 20 1970 0.52 1.8 29 16 1971 0.64 2.1 94 44 Cisco 1969 0.66 6.1 61 10 1976 0.95 1.0 6 7 Coho salmon 1968 0.54 0.5 26 50 1969 0.68 2.5 51 20 1970 0.60 1.6 25 15 1971 0.61 1.2 19 17 1975 0.91 0.4 7 16 Lake whitelish 1969 0.36 3.6 9 -) 1972 0.60 1.4 9 1 1973 0.60 1.2 8 7 1976 0.80 0,6 "> 3 Georgian Bay Bloater 1971 0.66 1.0 24 24 1975 0.61 0.7 5 7 Cisco 1969 0.38 3.2 159 50 1976 0.62 0.7 8 12 Mean PCB residues declined in lake trout and lake whitefish between 1971 and 1975 but increased in bloat- ers over the same period. Comparison of lake trout by weight class revealed no significant decline in PCB resi- dues (Table 3). The i:DDT/PCB ratio in all species de- clined, suggesting the disappearance of XDDT. The PCB/dieldrin ratio indicates that dieldrin is more per- sistent in fish tissues than are PCBs. Other organochloriiu's — Trace quantities (<0.01 ppm) of CIS- and traiis-chlordane were detected in some bloaters, white sucker, lake trout, and lake whitefish caught in 197.^, but no o.xychlordane, endrin. or heptachlor epox- ide was detected in fish caught in I9(iS-73. LAKE HURON -DDT — Three fish species caught in Lake Huron and Georgian Bay contained mean residues that exceeded 5 ppm. These included walleye (5.05 ppm) caught in southern Lake Huron in 1970, lake trout (7.60 ppm) caught in Georgian Bay in 1969, and bloaters (5.18 ppm) caught in 1971 in Georgian Bay (Table 4). Individual fish of five species contained -DDT residues in excess of 5 ppm including; bloaters (1970 and 1971), coho salmon (1970), and walleye (1970), caught in the southern half of Lake Huron; and bloaters (1971). rainbow trout (1968), lake trout (1969), and walleye (1969 and 1970) caught in Georgian Bay (Table 4, Figure 1). i;DDT residues declined noticeably between 1968-71 and 1975-76 in six species including alewife (Alosa pscudoharengiis), smallmouth bass (Micropterus dolo- itiiciii). Cisco fCoregoniis artedii). coho salmon, rainbow Vol. 1 2, No. 2, September 1978 63 TABl F. 3. Comparison of organocMorinc residues in Iwo weiglil classes of splake, lake trout, and lake whitefish cauglit in Lake Huron and Lake Superior, 1969-76 Spi cii s 0.5-1.0 KG Class L0-L5 KG Class AND No. OF Weight. Fat. 2 DDT. DiELDRIN, PCBs. No. OF Weight. Fat, 2 DDT, DiELDRIN, PCBs, Location Year Fish G '■/o PPM PPM PPM Fish c % PPM PPM PPM Splake Lnkc Huron 1969 3 821 6.8 1.61 0.06 0.2 5 1351 6.9 0.86 0.03 0.3 1970 3 784 13.2 1.16 0.06 1.6 8 1220 17.6 1.35 0.07 1.5 1972 3 787 10.8 0.87 0.05 0.7 1973 10 690 6.6 0.77 0.03 0.6 4 1108 12.2 0.75 0.06 0.9 1974 1 526 3.3 0.11 730 5.4 0.40 0.05 0.1 1 1180 3.7 0.25 0.03 <0.I 1972 12 813 8.2 0.55 0.07 0.3 7 1142 12.3 0.87 0.09 0.6 1973 7 1172 17.1 0.64 0.08 0.4 1976 2 850 3.7 0.08 0.03 0.1 10 1237 6.3 0.12 0.07 0.2 North Channel 1969 6 936 3.2 0.14 0.01 <0.1 8 1187 6.1 0.89 0.10 0.1 1970 1 980 8.6 0.80 0.05 0,4 2 1285 10.6 0.71 0.07 0.4 Georgian Bay 1969 4 939 4.5 0.44 0.01 0.1 6 1131 3.7 0.54 0.01 0.2 Lake Troui Lake Superior 1968 8 698 4.8 0.818 0.046 0.21 4 1566 10.6 4.94 0.128 1.19 1969 1(1 619 3.8 0.731 0,1124 0.25 10 1308 8.8 1.25 0.040 0.34 1970 4 1694 17.9 1.75 0.033 1.88 1975 3 768 18.6 0.192 0.037 0.33 7 1272 21.6 0.17 0.037 0.49 smelt iOsntcrus inordu.x}. and walleye from the main waters of Lake Huron, and bloaters from Georgian Bay. -DDT mean residues were erratic or unchanged in cisco, splake (Salveliniis foniinalis and 5. nainaycush). and walleye caught in Georgian Bay and in splake and lake whitefish caught in the main lake. To determine whether -DDT residues in splake and lake whitefish had declined, similar weight classes were com- pared (Table 3). 2;DDT levels in splake with an average weight of 1250 g declined between 1971 and 1974 from I. .35 ppm to 0.15 ppm. A similar decline in 2;DDT residues in lake whitefish was noted between 1972 and 1976. Cisco, coho salmon, and lake whitefish all showed a marked increase in the DDE + TDE/2;DDT ratio dur- ing the present stud\ (Tabic 2), suggesting a lower intake of the parent compound and 'or degradation to metabo- lites; this decline was not evideiil in bloaters. Dietdrin — Mean residues for all species investigated did not exceed the 0.3 ppm tolerance level set by FDA. However, individual fish of three species exceeded the level. One of 20 lake whitefish caught in the North Channel in 1969 contained 0.58 ppm dieldrin; one of 10 bloaters caught in Lake Huron in 1970 had a residue of 0.44 ppm dieldrin: five of 10 bloaters caught in Cieorgian Bay in 1975 contained dieldrin levels of 0.34-0.50 ppm; 10 of 20 bloaters caught in the North Channel in 1975 contained residues of 0.3 -0.6 ppm dieldrin; and two large splake caught in Lake Huron contained residues of 0.43 ppm and 0.53 ppm dieldrin. The 10 bloaters caught in the North Channel during 1975. which had residues above the tolerance level, weighed an averace 64 of 333 g and contained an average of 0.40 ppm dieldrin. The remaining 10 bloaters, which averaged 236 g, con- tained a mean residue of 0.19 ppm dieldrin. In this in- stance, and in the case of the splake, higher dieldrin residues were associated with larger fish, but this rela- tionship was not apparent in the 10 bloaters caught in Georgian Bay in 1975 (Table 4). Dieldrin levels increased in alewifc, bloaters, cisco. yel- low perch iPcrca flavcsccns). coho salmon, and splake during l9(iS-71 and 1975-76; levels in other species showed little change. Assessment of dieldrin levels on the basis of similar weight classes of lake whitefish and splake indicate that residues declined in lake whitefish and increased in splake (Table 3). A marked decline was noted in the -DDT dieldrin ratio in four species: in cisco, for example, the ratio declined from 61 to 6 be- tween 1969 and 1976. The PCB/dieldrin ratio also declined in the same four species suggesting declining PCB residues and static or increasing dieldrin residues (Table 2). PCBs — Three fish species contained mean PCB residues which exceeded the 2 ppm tolerance level set by Health and Welfare Canada. Bloaters from the main lake (1970 and 1971), from Cieorgian Bay (1971 and 1975). and from the North Channel (1975) contained mean residues of 2.2-5.2 ppm. Individual bloaters hatl resi- dues as high as 5.0 ppm and 6.4 ppm (Table 4). Cisco netted in Georgian Ba\ during 1975 contained a mean PCB residue of 2.2 ppm and a high level of 4.6 ppm in individual fish. Two large splake taken from the main waters of Lake Huron in 1975 contained levels of 5.5 ppm :nid (\4 ppm PCBs. Pisrii ini s MoNiroKiNC. Joi'knai, TABLE 4. Organochlorine residues in 14 fish species caught in the North Channel, Georgian Bay, and Canadian waters of Lake Huron, 1968-76 Year Location No. OF Anal- YSESl Mean and Range Mean 1 roNTENT AND Range of Contaminants in 1 Fish Puree, Weight, Fat. 0 Tc PPM = Species DDE TDE DDT 2 DDT Dieldrin PCBs Catosromidae White sucker 1972 Huron 5 723 2.5 0,08 0.01 0.02 o.u <0.01 0.1 550-909 1.8-3.3 0,05-0.13 <0.0 1-0.03 <0.0 1-0.06 0.06-0.22 <0,l-0.2 1973 Georgian 4 131 0.7 <0.0I <0.01 <0.01 0.01 <0.01 0.1 Bay 66-212 0.2-1.0 <0.01-0.02 <0.01-0.03 <0.1-0.2 1976 Huron 10 977 0.6 0.06 <0.01 0.02 0.09 <0.01 O.l 738-1 83-i ' 0.1-1.1 <0.01-0.20 <0.01-0.14 <0.0 1-0.37 <0.1-0.2 Centrachidae Smallmouth 1968 Huron 3 499 3.1 0.68 0.76 0,53 1.97 <0.01 0,9 bass 429-630 2.0-4.9 0.12-1.69 0.15-2,02 0.12-1.23 0.30-4.94 0.2-2.0 1972 Huron 5 353 3.7 0.12 0.01 0.03 0.16 0,01 0.4 298-437 2.6-4.5 0.11-0.13 0.02-0.04 0.15-0.18 <0,0 1-0.03 0.3-0.5 1972 Georgian 6 281 2.8 0.05 0.01 <0.01 0.07 <0.01 0.01 Bay 270-300 1.6^.0 0.04-0.07 0.01-0.02 0.06-0.10 0.1-0.1 1975 Georgian 9 364 3.2 0.17 0.01 0.03 0.21 0.03 0.6 Bay 275-562 1.7-4.5 0.09-0.28 <0.01-0.04 <0.01-0.08 0.12-0.36 <0.0 1-0.09 0.4-0.9 Clupeidae Alewife 1970 Huron 8(21) 33 7.5 0.76 0.23 0.64 1.63 0,08 1.1 26-40 1.5-13.2 0.16-1.40 0,04-0,52 0.22-1.48 0.27-3.40 0,01-0,22 0.5-2.0 1976 Huron 5(23) 23 10.7 0.44 0.10 0.26 0.80 0.14 0.3 3-49 5.8-16.9 0.04-1.08 0,01-0.12 0.01-0.54 0.06-1.74 <0.01-0.25 0.1-0.6 Osmeridae Rainbow smelt 1970 Huron 8(21) 22 6.5 0.36 0.12 0.32 0.80 0.04 0.7 12-67 4.0-8.4 0.06-0,97 0.01-0.25 0.02-0,80 0.11-1.86 <0.01-0.15 0.2-1.0 1970 N. Channel 5(24) 26 3.6 0,12 0.04 0,15 0.31 0.02 0,1 18-44 2,8-4.4 0,05-0.20 0.03-0.05 0,08-0,20 0.15-0.45 <0.01-0.03 1976 Huron 7(32) 14 2.7 O.II 0.02 0.02 0.15 0.01 0.01 7 -.30 1.2-3,9 0.05-0.19 0.01-0.02 <0.0 1-0.03 0.08-0.23 <0.0 1-0.02 <0. 1-0.2 Percidae Yellow perch 1968 Huron 5 335 0.8 0.20 0.12 0.20 0.52 <0.01 0.2 118^26 0.5-1.0 0.06-0.61 0.02-0.47 0.08-0.51 0.1^1.59 <0.1-0,5 1969 N. Channel 20 201 1.4 0.03 0.01 0.03 0.07 <0.01 <0,1 167-341 0.5-2.4 <0.01-0.08 <0.01-0.03 <0.01-0.05 <0,01-0,13 1972 Huron 5 67 4.4 0.07 0.01 0.03 O.U 0.01 0.1 64-74 3.8-5.3 0.06-0.08 0.01 0.02-0.03 0.09-0.12 <0.0 1-0.02 1975 N. Channel 10 175 6.1 0.36 0.03 0.09 0.48 0.05 0.9 150-197 3.5-8.6 0.13-0.57 <0.0 1-0.05 <0.01-0.17 0.1-3-0.72 0,02-0,09 0.4-1.4 1976 Huron 17 236 2.5 0.21 0.03 0.08 0.32 0,02 0,2 66-481 0.7-5.4 0.06-0.68 0.01-0.08 0.01-0.55 0.07-1.31 <0.0 1-0.05 <0. 1-0.4 Walleye 1968 Huron 3 409 0.8 0.12 0.04 0.13 0.29 <0.01 0,1 390-426 0.6-0.9 0.06-0.22 0.02-0.07 0.08-0.21 0.16-0.50 <0. 1-0.1 1969 Georgian 15 2073 2.6 1.05 0.24 1,08 2.37 0.02 1.5 Bay 792-4190 0.6-6.0 0.23-3.53 0.06-0.81 0.23-4.03 0.54-8.36 )\ the present study shows mean levels of 0.98 ppm iDDT and 0.04 ppm dieldrin for 41 coho salmon caught in the same area. -DDT levels in rainbow trout caught in soLithern Georgian Bay vary considerably from those reported previously. Reinkc et al. reported a mean of 8.7 ppm -DDT in rainbow trout caught in 1970 [9), but only 1.75 ppm IDDT was found in the same species caught in the same location in 1968 for the present survey. This discrepancy may be due to local dilTerences in -DDT use. Despite the number of variables which are associated with a sampling study of this kind, it is remarkable that such close agreement is found between ditTcrent studies in different time frames for such large bodies of water as Lakes Superior and Huron. Other factors that cause fluctuations in contaminant concentrations in fish tissues are spawning times and changes in fat content. Acknowledgment The assistance of the field staff of the Ontario Ministry of Natural Resources in collecting the fish for this study is gratefully acknowledged. Particular thanks are given to J. .S. Ball, J. Collms, VV. R. Hesson, F. Mantec, J. No- vak, R. Payne, and L. Thurston. Technical assistance was provided by J. Stanck and Y. P. Lo in preparation of samples for analysis. LITER.-\TURE CITED (1) American Fisheries Society, Committee on Names of Fislies. 1970. A list of common and scientific names of fish from the United States and Canada (3rd ed.). Am. Fish. Soc. Spec. Publ. 6. Washington. D.C. 150 pp. (2) Frank. R.. A. E. Armstroni;, R. G. Boelens. II. E. Braan. and C. W. Doii.vlas. 1974. Oiganochlorine in- secticide residues in sediment and fish tissue, Ontario, Canada. Pestic. Monit. J. 7(3/4) : 165-180. (3) Clooschenko. W. A., W . M. J. Slruchan, and R. C. J. Sampson. 1976. Distribution of pesticides and poly- chlorinated biphcnyls in water, sediments, and seston of the Upper Great Lakes — 1974. Pestic. .Monit. J. I0(2):61-67. (4) Holdrinet, M. 1974. Determination and confirmation of he.xachlorobenzene in fatty samples in the pres- ence of other halogenated hydrocarbon pesticides and PCBs. J. Assoc. Off. Anal. Chem. 57(3 ) :580-584. (5i Lan.vlois, E. B., A. P. Stcmp, and B. J. Liska. 1964. Analysis of animal food products for chlorinated in- secticides. J. Milk Food Technol. 27(7 ) :202-204. (6} Miles. ]. R. W., and C. R. Harris. 1973. Organochlo- rine insecticide residues in streams draining agricul- tural, urban-agricultural, and resort areas of Ontario, Canada— 1971. Pestic. Monit. J. 6(4) : 363-368. {7) Rcinlicrt. R. E. 1970. Pesticide concentrations in Great Lakes Fish. Pestic. Monil. J. 3(4) :233-240. (8) Reinhert, R. £., and H. L. Bergman. 1974. Residues of DDT in lake trout (Salveliniis namaycush) and coho salmon (Oneorliynchus kisatch) from the Great Lakes. J. Fish. Res. Board Can. 31 (2 ): 191-199. (9) Reinkc. J.. J. F. Vthe. and D. Jamieson. 1972. Or- ganochlorine pesticide residues in commercially caught fish in Canada— 1970. Pestic. Monit. J. 6(l):43-49. [10) Reynolds, L. M. 1971. Pesticides residue analysis in the presence of polychlorinatcd biphenyls (PCB's). Residue Rev. 34:27-57. (11) Upper Great Lakes Reference Croup. 1976. The waters of Lake Huron and Lake Superior, Vol. 1. Summary and recommendations. International Joint Commission, Windsor, Onliuio. pp. 115-125. 68 Pesticides Monmoring Journal Residues of Organochlorine Insecticides and PoJychlorinated Biphenyls in Fish from Lakes Saint Clair and Erie, Canada — 1968-76 ' Richard Frank,' Heinz E. Braun,- Micheline Holdrinet,^ Douglas P. Dodge,' and Stephen J. Nepszy ' ABSTRACT Eighteen species of fish from Luke SainI Ckiir unci 19 species from Lake Erie were unalyzed for organochlorine pesticides and polychlorinuted biphenyls (PCBs) between 196S and 1976. Mean residues of ':^DDT peaked at L19 ppm in longnose gar (Lepisosteus osseus) caught in Lake Saint Cluir in 1970-71 , but had declined in all species by 1975-76. Dieldrin levels in fish tissues increased over the same period. White bass (Morone chrysops). caught in 1975 in Lake Eric, had the highest mean residue of dieldrin at 0.17 ppm. PCB residues increased in some species and decreased in others. PCB residues exceeding the tolerance level of Health and Welfare Canada were found in the following: from Lake Saint Clair, smallniouth bass (Micropterus dolomieui) in 1975 and channel catfish (Ictakiriis piinctatus) in 1971 : from Luke Erie, coho salmon (Oncorhynchus kisutch) /;; 1970, smallmouth bass, ulewife (Alosa pseiidoharengus), fresh- water drum (Aplodinotus griinniens), and gizzard shad (Dorosoma cepedianiini ) in 1971. and wliite bass in 1971 and 1976. Sediments in Lake Erie were five to ten times more highly contaminated with '^DDT, dieldrin, and PCBs than were sediments from Lake Saint Clair. IDDT and dieldrin residues in fish tissues did not necessarily reflect this trend, hut PCBs were higher in fish from Lake Erie. Introduction DDT, dieldrin, and PCBs have been identified in fish from Lake Erie and Lake Saint Clair. Reinert reported residues of -DDT in 14 species caught in 1967-68 that ranged from 0.25 ppm in spottail shiner {Notropis hitdsoniiis) to 1.89 ppm in white bass (Morone chry- sops) (11). Dieldrin was not detected in nine species: ma.ximum dieldrin levels found in alewife (Alosa psciido- ^ Partial funding for 1975-76 sampling and analysis provided by the International Joint Commission under Task Force D of the Pollution f I om Land Use Activities Group. -Provincial Pesticide Residue Testing Laboratory, Ontario Ministry of Agriculture and Food, c/o University of Guelph, Guelph. Ontario NIG 2W1. ■'Fisheries Branch, Ontario Ministry of Natuial Resources, Queen's Park, Toronto, Ontario. ^Fisheries Research Station, Ontario Ministry of Natural Resources, Wheatley, Ontario. harengiis) were 0.15 ppm. Reinke et al. found similar residues in six species caught in 1970 (13). The highest residues of i;DDT were 0.56 ppm in alewife. Carr et al. reported on si.x species caught in 1970-71 (2). Coho salmon {Oncorhynchus kisutch) contained the highest mean residues of -DDT and dieldrin, 0.90 ppm and 0.07 ppm, respectively: channel catfish (Ictalurus piinc- tatus) had the highest mean PCB residues: 4.4 ppm. Kelso and Frank found that -DDT and dieldrin residues varied with time of catch in three species from the eastern basin of Lake Erie (7). Residues were generally low; higher residue levels were associated with fish hav- ing a higher fat content. Watersheds on the Canadian side of Lakes Erie and Saint Clair drain the most intensive agricultural belt in Ontario (Figure 1). Before restrictions on the use of aldrin, dieldrin, and heptachlor in 1969 and 2DDT in 1970-71, this area accounted for 90 percent of organo- chlorine insecticides used in Ontario. Miles and Harris (9, 10) and Frank et al. (3, 4) reported that DDT and dieldrin were deposited in Lake Erie by creeks draining areas of intensive pesticide use. Frank et al. found that fish caught in the streams and creeks had residues of -DDT and dieldrin that were one order of magnitude higher than those caught in the adjoining waters of Lake Erie (4). The present study was initiated in 1968 to determine organochlorine residues in fish before legislative restric- tion of the use of these materials. After use of the materials was restricted, monitoring of fish tissue was continued to determine the impact of these actions. At the same time, PCBs were identified in fish in both lakes, and monitoring for these contaminants was in- cluded to determine whether the voluntary restrictions on their use since 1971 were reflected in residue levels in fish tissue. Methods and Materials Twenty-eight species of fish were caught by gill net or trap net between 1968 and 1976 in Lakes Saint Clair and Erie (Table 1). Most were obtained from the field Vol. 12, No. 2, September 1978 69 LAKE ST CLAIR ® MrrCMtlL BAY B&SSETT CHAr#€L ^ nCIOLAY CRCCK O WESTERN BASIN CENTRAL BASIN © EASTERN BASIN ® KINGSVILLE © WHEATLEY © ERIEAU PORT STANLEY @ PORT BURWELL ® PORT MAiTLAND LONG POINT BAY FElCe ISLAND t HCjURF I. A/(//' <'f /.(/^(■\ Eric I.anglois ct al. was used to isolate organochlorines and PCBs (cS). Florisil (60-100 mesh), activated commer- cially at 650 C, was reheated at 135-C for at least 24 70 Pesticides Monitoring Journal hours; after the adsorbent cooled, it was equihbrated with 5 weight percent water. A maximum of 1 g fat from the fish extracts was thoroughly mixed with 25 g of conditioned Florisil; this was placed on top of a second 25-g portion of conditioned Florisil in a 25-mm ID cleanLip column. The column was eluted with 300 ml 1:4 (v/v) mixture of dichloromethane-hexane. The eluate was evaporated to dryness with rotary vacuum, and the residue was dissolved in 5 ml acetone. PCBs were separated from organochlorine insecticides and HCB on a charcoal column as described by Holdri- net (6). Charcoal (Fisher No. 5-690, 50-200 mesh) was washed with acetone, filtered by suction, dried, and stored at 135'C. Columns (9-mm ID) were prepared by sandwiching a 7.5-cm layer of charcoal between 1.3-cm layers of sand and prcwashing with a 1 :3 (v/v) mixture of acetone-diethyl ether, The acetone solution from the Florisil cleanup was quantitatively transferred to the charcoal column and eluted successively with 180 mi of 1:3 (v/v) mi.xture of acetone-diethyl ether and 80 ml benzene; the organochlorine insecticides were contained in the first eluate, and PCBs were in the second eluate. Eluates were concentrated to dryness by rotary vacuum and dissolved in measured amoLints of hexane. Extracts were analyzed on a Tracor Model 550 gas chromatograph with the following instrument parameters and operating conditions: Detector: '■■'Ni election-capture Column: glass. 15 cm x 0.64 cm OD packed with a mixure of 4 percent SE-.TO and 6 percent QF-1 on 80-l()ll-mesh Cliromosorb W Temperature: 180"C Carrier gas: nitrogen flowing at 60 ml/minute Injection volume: 5 /j 1 equivalent to 1 ng fat Residue identity was confirmed on random samples by thin-layer chromatography (TLC); appropriate areas of the chromatogram were removed, redissolved, and re-examined by gas-liquid chromatography (GLC). This confirmation was essential for the positive identification of '-DDT, 91 percent; dieldrin, 89 percent; r/.s-chlordane, 92 percent; fra/;.s-chlordane, 90 percent; and PCBs, 85-90 percent. The data do not include corrections for recovery. Quantitation limits, below which values were designated as either trace or not detected, were set at 0.005 ppm in fat for all or- ganochlorine insecticides and 0.05 ppm in fat for PCBs. PCB estimations were based on comparison with Vol. 12, No. 2, September 1978 standard mixtures of Aioclors 1254 and 1260 and were quantitated by comptirison of the sum of peak heights of peaks VII, VIII, and X according to the Reynolds ntmibering system (14). The ratio of Aroclor 1254 to Aroclor 1260 in ihe standard mixttire varied from 5:1 to 4:1. Analysis began in 1968 when the known main con- taminants in fish were p,p'-DDJ and its analogs and dieldrin and heptachlor epoxide; PCB values before 1970 were estimated. With the introduction of a column frac- tionation technique in 1970 for the separation of PCBs from organochlorine insecticides, the measurement of PCB residues became more precise. Analysis for hexa- chlorobenzene (HCB) was included in the procedure in 1973 but was subsequently discontinued because of the low levels and incidence of HCB found in the samples. Analysis and confirmation for cis- and Irans- chlordanc was refined in 1975, and the analyses for mire\ and oyychlordane were introduced in 1976. Results LAKE SAINT CLAIR ^DDT — None of the 18 species caught in Lake .Saint Clair contained metin residues of iJDDT that exceeded the 5 ppm action level established by both the Canadian and United .States governments. Longnose gar (Lepisos- tciis osseiis) caught in 1971 had the highest mean residue of 1.19 ppm ;tnd was the only species with a mean residfie above 1.0 ppm (Table 2). Eight of 12 longnose gar caught otT Tremblay Creek contained -DDT residues of 1.10-2.35 ppm. Individual fish from three other species contained residues that exceeded 1.0 ppm. In 1971, two of eight carp (Cyprinus caipio) from Mitchell Bay contained 1,19 ppm and 1,26 ppm -DDT, Four of 12 mooneye (Hiodoii tergisits) caught in 1970 off Tremblay Creek had 1,12-2.38 ppm 2DDT. Three of six smallmotith bass (Micropicrus dolomieui) caught in 1975 had :;:DDT residues of 1.02-1,15 ppm. Eight of the 18 species from Lake Saint Clair were caught in 1968-71. In seven of the species, residues of i:DDT showed a decline by 1971 (Tables 2, 3). Only quillback {Carpiodes cyprinus) showed no apparent change. In all years, however, residues of -DDT were below 0,5 ppm, Smallmouth bass, freshwater drum (A plodinotiis griin- n'wns), and walleye {Stizostedion vitrcum vitreitin) were the only three species caught in 1968-71 and again in 1975-76, In smallmouth bass, mean -DDT residues were higher in 1976 (0,76 ppm) than in 1968 (0,42 ppm); however, the mean weight of fish was 853 g as opposed to 453 g (Table 2). When residues of similar weight classes were compared, the residue declined slightly between the two periods (Table 3). A mean 71 TABLE 2. OifHiiioililuiiiif nxitliies in Iti jisli ipccUw caiis^hl in Canadian waters of Lake Saint Clair, I96S-76 Mean and Range Puree, ppm- ■\'i:ar No. oi ANALYSE! Weiuhi. 1 G Fat, % Mean CONIENI AND RanCiF of CONlAMlNAN is in nan Species DDE TDE DDT :;ddt DlELDRIN PCBs .-1 iniiiluc Bow I'm 1971 10 I.K.7 955-2050 0.2 0.1-0.4 <0.01 <0.01-0.0I <0.0I <0.01 0.01 <0.01-0.02 <0.01 <0.1 CaliistoniUlae Quillbuck 197(1 6 1.119 4.2 0.03 0.03 0.02 0.08 0.01 0.3 .300-1775 1.6-7.6 0.01-0.04 0.01-0.06 0.01-0.03 0.03-0.13 <0.01 0.02 0.2-0.4 1971 9 1244 2.1 0.03 0.03 0.02 0.08 <0.01 0.2 350-1935 1.1-4.5 <0.01-0.07 <0.0I 0.08 <0.01-0.06 0.02-0.17 <0.1-0.3 Rcdhorsc 1970 8 928 2.6 0.07 0.03 0.03 0.13 0.01 0.7 695 1235 0.3-5.8 <0.0 1-0.25 <0.01-0.11 <0.0I-0.13 <0.01-0.49 <0.0l-0.04 <0. 1-2.6 1971 8 698 0.7 0.01 0.01 ses perliirmed on single fish in most cases; in sonic cases composite markeil clrop \v;is iiotciJ for -DDT between 1968 and 1971, hut there;il"ter the iJecline was small (Tahles 2, 3). Dicldrin — Mean residues in all speeies were less than 0.10 ppm. In addition, 12 species had mean residues at or below 0.01 ppm dieldrin. The highest mean resi- due of 0.09 ppm was present in smallmouth bass caught in 1975 (Table 2). By weight class, smallmouth bass exhibited an increase in dieldrin residues between 1968 and 1976 (Table 3). Only three other species, carp, nioone_\e. and walleye, had individual fish with residues ot 0.10-0. 1.*^ ppm dieldrin (Table 2). Dieldrin residues in walleye peaked in 1971 ;ind declined by 1976 (Table 3). Freshwater drum, the only other species caught in the earh and late years, showed no change in dieldrin residues (Tables 2, 3). PCB,s— Only one fish trom Lake Saint Clair, a 435-g mooneye, exceeded the 5.0 ppm tolerance level for PCB residues in fish tissues set by the Food and Drug Ad- ministration, U.S. Department of Health, Education, and Welfare. However, several species and individual fish e.xceeded the 2.0 ppm Health and Welfare Canada tolerance level (Table 2). Smallmouth bass caught in 197.S and channel catfish caught in 1971 had mean residues of 2.1 ppm and 2.3 ppm PCBs, respectively (Table 2). In 1970, one of six largemouth bass (Mic- ropterus salmoidcs), four of 12 mooneye, and one of samples were analyzed, and the number of fish is in parentheses. eight redhorse (Moxostoma sp.) contained 2.1-7.2 ppm PCBs. In 1^)71, three of 1 1 longnose gar, and four of six channel catfish caught in Tremblay Creek and in Mitchell Bay, respectively, had residues of 2.0-4.0 ppm PCBs. In 1975, PCB levels in four of six smallmouth bass ranged from 2.2 to 3.1 ppm. PCB residues increased in smallmouth bass between 1968 and 1975. However, freshwater drum and walleye showed little change even by weight class (Tables 2, 3). HCB — Forty-eight fish of 17 species caught in 1970-71 and analyzed in 1973 had detectable HCB residues below 0.1 ppm. Redhorse mullet had the highest mean residue, 0.024 ppm, and the highest residue in a single fish, 0.08 ppm. Carp, channel catfish, and yellow perch (Perca fhivesci'iis) had the second highest residues of 0.013 ppni HCB (Table 4). Chlordiinc ami hcplacldor epoxide — The same 48 fish caught in 1970-71 were anal\zed for cis- and trans- chlordane and hcptachlor epoxide. Interfering com- pounds prevented confirmation of chlordane below 0.05 ppm. Smallmouth bass caught in 1975 contained low levels of chlordane but these could not be satisfactorily separated from interfering compounds. By 1976, both chlordane and hcptachlor epoxide were identified at low levels in freshwater drum and walleye (Table 5). TABLE 4. He. aclitorohenzcne residues in 17 sp •cies of fisli (-fS fisli) caiisihl in Lake Saini Clair. 1970-71 Yl AR No. OF Fish Avi.RAt.i: Wiiicm, G HCB, PPM Fish Sfecies Mean Range I.OCAIION Largemouth bass 1970- 71 ■> 683 0.005 0.002-0.008 Mitchell Bay Rock bass 1971 3 2211 0.008 0.002-0.013 Tremblay Creek Bluegill 1971 6 1711 0.002 <0.00 1-0.004 Mitchell Bay Bowfin 1971 1 163(1 0.008 0.005-0.015 Mitchell Bay Brown bullhead 1971 3 412 (l.(K)3 0.002-0.1)03 Mitchell Bav Carp 1971 2 2890 0.013 0.006-0.020 Mitchell Bav Channel catfish 1971 2 1910 0,013 (1.005-0.020 Trcmblav Creek. Milchell Bay Black crappic 1971 3 243 0.(1112 (1.001-0.003 Mitchell Bay Freshwater drum 1971 3 623 0.0116 11.(102-0.008 St. Lukes Bav i.ongnosc gar 1970 1 1195 0.007 Tremblay Creek Mooneye 1970 2 158 0.009 Tremblay Creek Yellow perch 1971 2 55 0.013 0.007-0.019 Mitchell Bav Pumpkinsccd 1971 5 123 0.001 <0.00 1-0.002 Mitchell Bay Quillback 1970- -71 4 1670 0.008 0.005 0.010 Mitchell Bav Redhorse mullet 1970- -71 4 670 0.024 0.002-0.080 Bassctt Channel. Mitchell Bav White sucker 1970 3 1185 0.004 tl.003-0.006 Bassetl Channel W;,lle>c 1971 1 120 0.002 Mitchell Bay 74 Pesticides Monitoring Journal TABLE 5. Chlordanc and heptachtor epoxide residues in fish species caiiuht in Lukes Saint Clair and Erie, 1972-76 Lake Saint Clair Lake Erie Central basin Eastern basin Fjsh Species Freshwater drum Walleye Rainbow trout ' While bass Yellow perch Coho salmon Emerald shiner Rainbow smelt Year 1976 1976 1974 1972 1976 1972 1975 1976 1976 1976 1975 1976 Mean Mean Content of Residues in No. OF Weight, G Fat, Fish Tissues, ppm FlSHl % Chlordane- Heptachlor Epoxide 10 259 9 1726 5 642 11 156 7 118 10 133 15 60 15 121 6 2198 4(12) 5.6 5 74 10 20 1.7 0.8 4.4 5.9 3.6 3.2 2.1 1.6 11.5 5.6 8.9 5.1 O.UII ND-0.080 0.008 ND-0.028 ND 0.023 0.010-0.050 0.010 0.008-0.011 0.011 <0.00l-0.020 0.007 0.002-0.016 0.007 <0.00I-0.0I4 0.037 0.011-0.045 0.038 0.011-0.050 0.015 0.004-0.021 0.046 0.022-0.134 0.003 ND-0.0I3 0.004 ND-0.013 0.006 ND-0.033 ND 0.004 0.002-0.007 ND 0.001 ND-0.006 0.003 <0 .00 1 -0.007 0.007 0.002-0.010 0.012 0.006-0.016 0.006 0.001-0,009 0.015 0.009-0.033 ■See footnote 1, Table 3. -NOTE: Chlordane present as c/i- and /r«;ij-isomers in all species except while bass and yellow perch cauyht in 1972. Then, only rii-chlordane was confirmed. •Three rainbow Irout caught in Silver Creek also conlaincd endosulfan with mean residue ot 0.025 ppm (0.007-0.050 ppm). NOTE: ND = not detected. Other organochlorines — No endrin or metho.xychlor was detecteiJ in fish caught in Lake Saint Clair. Samples were analyzed for mirex in 1975-76, but no residues were detected in smallmouth bass, freshwater drum, or wall- eye caught in those years. LAKE ERIE 'ZDDT — No mean residues of -DDT for any species caught in Lake Erie in 1968-76 exceeded the 5.0 ppm United States and Canadian tolerance levels. Three coho salmon caught in 1970 in the central basin con- tained levels of 8.23, 7.67, and 7.61 ppm i:DDT. and the whole catch of 1 I fish averaged 2.80 ppm (Table 6). These three fish were the largest, weighing 1,963, 2,276, and 2,640 g, respectively, Three coho salmon caught in 1971 from the same basin and weighing an average of 806 g contained only 1.76 ppm -DDT. SmallmoLith bass caught in 1971 from the eastern basin was the only other species with mean residues above 1.0 ppm; mean residues were 1.2 ppm -DDT. Smallmouth bass caught in 1968 from the same basin averaged 0.83 ppm; however, two of 16 fish had 1.53 ppm and 4.28 ppm -DDT. White bass and walleye had individual fish with residues above 1 .0 ppm. Five species were caught in all three basins during the same year, and one of these, coho salmon, was caught in three basins over two years (Tables 3, 6, 7). Emer- ald shiner {Notropis atherinoides) and yellow perch, which are localized species, contained residues of -DDT that were not significantly different among the three basins. In migrating species of white bass, freshwater drum, coho salmon, and rainbow smelt (Osmerus mor- dax), -DDT residues were similar for catches in the three basins. Where differences occurred, the higher residues correlated with fish size rather than with basin. The highest residues of -DDT from the central, eastern, and western basins, respectively, were freshwater drum caught in 1971 and 1975 and coho salmon caught in 1975. In all three cases, the individual fish were 1.5-4 times heavier than members of the same species from the other basins, and a correlation was evident between increasing weight and increasing i;DDT residue; these differences virtually disappear when similar weight classes are compared among the basins (Tables 3. 6, 7). Si\ species were divided into weight classes to deter- mine the extent of decline in -DDT residues between 1968 and 1976 (Tables 3, 7). In the eastern basin, smallmouth bass, which were caught in four separate years, offered the best example. -DDT mean residues for the species peaked in 1971 and declined thereafter (Table 6); when compared by weight class, however, species showed a decline in -DDT from 1968 to 1976 (Table 3). Declining residues of 2DDT in the eastern basin were evident in rock bass (Amhioplites nipestris), white bass, and yellow perch but not in rainbow smelt or freshwater drum (Tables 3. 6). In the central basin, 2DDT residues in coho salmon peaked in 1971 and declined thereafter. Residues also declined in freshwater drum and rainbow smelt but not Vol. 12, No. 2, September 1978 75 TABLE 6. Orfionochlorinc residues in 19 fish species canf;lil in Canadiun waters uj Lake Erie (I96H-76) and sevre.vatcd into western, central, and eastern basins Mean and Rance Fish Tissue, Fish Species Year No. OF Basin Analyses' Weigh). c Fat. Mean Content and i Range of Coniaminapjis in PPM DDE TDE DDT i;DDT Dieldrin PCBs Centriithiduf Larticmouth basH 1975 East 12 409 3.9 0.13 0.04 ;ill 1968 East 4 209 0.5 <0.01 <0.01 <0.0I 0.02 <0.01 <0.1 97-341 1)4-0.5 <().() 1-0.03 <0.0I-0.()1 ' 1.5 mm ID glass, packed with a .1:1 mixture of 4 percent SF-96 and 8 per- cent QF-I on U)0-120-mesh Chromosorb W AW/DMCS up[>ro\imalelv 1700 theoretical plates for p.p'- DDT Resolution: Tcmpci atures: Carrier ga.s: column I85°C injector 225°C detector 220°C niIrot;en flowing at 25 ml/minute The quantity of organochlorines in the samples was esti- mated by comparing peak heights of aliquots of purified extracts with peak heights of a known quantity of a standard solution. The results were not corrected for recovery. For the PCBs, a commercially available mix- ture, Clophen A50, was used as a reference. X2 Pesticides Monitoring Journal TABLE 2. OrganoMorinc residues in organisms from Parishan Lake, Kupor and Slia/ipour Rivers — 1974 Species Parishan Lake Barhus sp. Coot, Fulica atra Kupor River Barbiis sp. Shahpour River Varichorhinus sp. Barbia sp. Fat, Fresh Weight, ng/g DDE 0.4 7 0.4 7 0.3 3 2.4 37 0,8 1425 0.4 1161 0.1 251 2.5 3030 0.5 250 TDE ND ND ND ND ND 261 30 118 18 Fat Weight, mg/ko DDT V DDT DDE TDE ND 7 1.7 ND 7 1.8 ND 3 1.2 ND 37 1.6 180 1605 174.0 241 1662 72.9 39 320 482.3 910 4058 121.2 30 298 50.8 ND ND ND ND ND 16.4 57.6 4.7 3.7 DDT 2 DDT ND 1.7 ND 1.8 ND 1.2 ND 1.6 22.0 196.0 15.1 104.4 74.9 614.8 36.4 162.3 6.1 60.6 NOTE: ND = not delected. Results Only small amounts of /),/;'-DDE were detected in fish from Parishan Lake and in a coot which was foimd dead (Table 2). Fish obtained from the Shahpour and Kupor Rivers contained appreciable amounts of DDT and its metabolites DDE and TDE (Table 2). The Shahpour and Kupor Rivers flow through malaria-infected areas, and DDT is used for indoor spraying. In fish and fish eggs from two reservoirs supplying Teh- ran with potable water, various amounts of DDT were detected (Tables 3, 4). The levels in cyprinide fish (Varichorhinus nikoiskii) from the Latian reservoir far exceeded those found in fish from the Karadj reservoir. The main metabolite accumulated was /).p'-DDE. In samples from the Latian reservoir, the levels of DDT compoimds in rainbow trout (Saliiio gairdneri) were sim- ilar to those found in V. nikolskii. The Varichorhinus species has a shorter food chain than the Salnio species, resulting in a deviation from the usual pattern of bio- magnification of persistent compounds. Low levels of DDT were found in pike (Esox iucius) collected from the Bandar Pahlavi Mordab (Table 5). Again, the principal metabolite found was p,p'-DDE. The presence of only small proportions of p.p'-DDT suggests that the accumulation occurred over consider- able time, and that the input is not recent. In May 1974, more than 100 samples of sturgeon and their eggs were collected from two species (Accipencer TABLE 3. Or^anochlorine residues in fish and fish eggs from the Latian Dam, 1974 Fat. Fresh Weight, ng/g Fat Weight, mg/kg Species DDE TDE DDT 2 DDT DDE TDE DDT 2 DDT Salmo gairdneri 0.7 13 -) 13 28 1.6 0.3 1.6 3.2 0.2 650 ND ND 650 88 ND ND 88 1.4 97 ND ND 97 41 ND ND 41 1.0 340 ND ND 340 24 ND ND 24 2.4 75 ND ND 75 7.9 ND ND 7.9 Varichorhinus nikolskii 1.9 178 81 8 267 9.5 4.3 0.4 14.2 2.2 245 17 ND 262 11 0.8 ND 11.8 0.7 92 10 ND 102 10.6 1.2 ND 11.8 1.7 129 ND 10 139 7.6 0 0.6 8.2 1.4 77 ND ND 77 5.7 ND ND 5.7 Alhitrnoides hipanlattir 0.8 185 19 ND 204 24.2 2.5 ND 26.7 0.5 410 26 ND 436 262.7 16.4 ND 279.1 Coregontts sp. 0.8 13 2 13 28 1.6 0.3 1.6 3.5 Eggs from 5. gairdneri^ 1.6 235 21 ND 256 14.3 1.3 ND 15.6 NOTE: ND— not detected. 'Pooled sample from six indiv iduals TABLE 4. Organochlorine residues in cyprinide, Varichorhinus nikolskii, from Karadi Reservoir, 1974 Fat, Fresh Weight, ng /G Fat Weight, mg/kg % DDE TDE DDT 2 DDT DDE TDE DDT 2 DDT 0 3 11 3 ND 14 4.7 1.1 ND 5.8 0.6 23 ND ND 23 3.8 ND ND 3.8 0 6 n ND ND 11 1.7 ND ND 1.7 0 2 g ND ND 8 3.7 ND ND 3.7 0.9 22 ND ND 22 2.4 ND ND 2.4 NOTE; ND=not delected. Vol. 12, No. 2, September 1978 83 TABLE 5. Organochlorine leshliic.s in pike, Esox lucius, from Bandar Palilavi Monlab, 1974 Age, Fat. % Fresh Weight, nc/g Fat Weight, mg/kg Years DDE TDE DDT SDDT DDE TDE DDT SDDT 3+ 0.7 3 ND ND 3 0.4 ND ND 0.4 3 + I.I 6 ND ND 6 0.6 ND ND 0.6 3 + 0.6 5 ND ND 5 1.2 ND ND 1.2 3-r 0.7 17 ND ND 17 2.3 ND ND 2.3 3+ 0.6 3 ND ND 3 0.6 ND ND 0.6 3+ 0.5 9 ND ND 9 2.0 ND ND 2.0 3 + 0.7 5 ND ND 5 0.7 ND ND 0.7 3 + 0.5 8 ND ND 8 1.3 ND ND 1.3 3+ 0.5 2 ND ND 2 0.4 ND ND 0.4 3+ 0.4 4 ND ND 4 0.9 ND ND 0.9 NOTE: ND=not detected. TABLE 6. Ori;anochtorine residues in sliiriieon, Accipcnser stelliitiis, from Miankaleli and Tazre Alnid at llie Caspian Sea. 1974 Weight, KG Fat. Fresh Weight, ng/g Fat Weight. mg/kg Sample Lindane DDE TDE DDT :SDDT Lindane DDE TDE DDT SDDT Muscle 9.5 2.6 4 14 7 21 0.2 0.5 0.3 0.8 Eggs 17.5 13 67 16 8 91 0.1 0.4 0.1 0.1 0.6 Muscle 9.0 3.0 2 16 4 4 24 0.1 0.5 0.1 0.1 0.7 Eggs 17.3 ND 84 31 18 133 ND 0.5 0.2 0.1 0.8 Muscle 7.0 6.6 ND 276 46 149 471 ND 4.2 0.7 2,3 7.2 Eggs 16.1 23 494 484 224 1202 0.2 3.1 3.0 1.4 7.5 Muscle 8.0 4.8 7 96 19 44 159 0.2 2.0 0.4 0.9 3.3 Eggs 19.4 26 471 54 141 666 0.2 2.4 0.3 0.7 3.4 Muscle 8.5 2.0 ND 25 7 10 42 ND 1.2 0.4 0.5 2.1 Eggs 16.6 15 193 37 55 285 0.2 1.2 0.2 0.3 1.7 Muscle 10.5 3.1 4 208 97 126 431 0.2 6.7 3.1 4.1 13.9 Eggs 16.6 17 996 125 662 1783 0.1 6.0 0.8 4,0 10.8 Muscle 9.5 4.1 5 27 14 10 51 0.1 0.7 0.3 0.3 1.3 Eggs 16.9 17 79 38 27 144 0.1 0.5 0.2 U.2 0.9 Muscle 8.0 5.0 6 26 19 11 56 0.1 0.5 0.4 0.2 1.1 Eggs 19.6 23 79 44 34 157 0.2 0.4 U.2 0.2 0.8 Muscle 9.0 6.0 7 92 19 46 157 0.2 1.5 0.3 0.8 2.6 Eggs 14.3 13 204 38 77 319 U.l 1.4 0.3 0.5 2.2 Muscle 8.5 2.5 ND 55 12 20 87 ND T T 0.5 0.8 3.5 Eggs 14.0 16 300 48 114 462 0.2 2.1 0.3 0.8 3.2 NOTE: ND = not detected. guldensiadtl and A. xtellatus) from three diflferent places along Ihe Iranian coast of the Caspian .Sea (Figure 1). From these, 20 samples o{ A. steUatiis of similar size and weight were analyzed (Table 6). Fat content in the muscle was 2. ()-(>. 6 percent; corresponding range for the eggs was 12.0-19.6 percent. Calculated on the extract- able lipid fraction, the average levels of DDT in muscle and egg were 3.7 ppm and 3.2 ppm, respectively. BHC and lindane were detected, but no PCBs were found. No significant dilTercnces in the distribution of DDT and its metabolites in egg and muscle were revealed (Table 7). The range of DDT found in muscles of four species of sturgeon sampled at Babolsar in March 1974 was 1.0- 13.1 ppm (Table 8). For A. Mellatiis. the mean level of DDT was 4.7 ppm. The only samples in which PCBs were detected came from Tehran. .Sediment from ihe drainage system along Ihe streets contained appreciable amounts of DDT and PCBs (Table 9). TABLE 7. Distrilnition of DDT and its metabolites in inusele and egi^s of sturgeon, Accipenser stellatus — 1974 Sample Muscle Mc;in Hubs % DDE Mc.in 72 58 61 57 48 54 45 58 63 58 80 82 41 71 71 56 56 50 64 66 64 TDE 38 14 10 12 19 22 23 36 12 14 20 20 25 40 9 12 7 22 25 14 9 16 % DDT 14 32 27 24 30 23 19 30 23 22 13 19 20 17 37 22 25 22 25 20 84 Pesticides Monitoking Journ.\l TABLE 8. Oi ganocMorinc residues in sturgeon from Balyol sar at the Caspian Sea 797-^ Fat, % Fresh Weight, ng/g Fat Weight, mg/kg Species Lindane DDE TDE DDT 2 DDT Lindane DDE TDE DDT 2 DDT Accipenser 2.6 1 95 11 56 162 0.1 3.5 0.4 2.1 6.0 guldenstadti 1.7 ND 41 ND 15 56 ND 2.5 ND 0.9 3.4 1.5 2 18 ND 7 25 0.1 1.3 ND 0.9 1.8 0.5 1 51 1 19 71 0.1 1.1) ND 0.4 1.4 2,4 1 37 5 21 63 0.1 1.5 0.2 0.9 2.6 2.0 1 23 ND 1 24 0.1 1.1 ND 0.1 l.I 3.7 1 24 3 22 49 0.1 0.6 0.1 0.6 1.2 2.7 16 220 ND 142 362 0,5 8.0 ND 5.1 13.1 4.8 ND 106 10 85 201 ND 2.2 0.2 1.7 4.1 A. stellatus 1.0 ND 12 ND 7 19 ND 2.2 ND n.7 1.9 1.2 ND 84 3.6 51 139 ND 6.7 0.3 4.1 11.1 4.6 ND 239 ND 119 368 ND 4.9 ND 2.5 7.7 3.7 ND 310 40 24U 59 ND 3.9 0.5 3.(1 7.4 5.7 9 141 2') 155 318 1.1 2.5 0.4 2.7 5.6 5.0 ND 64 32 71 167 ND 1.2 11.7 1.3 3.2 2.9 ND 23 ND 18 41 ND 0.8 ND 0.6 1.4 1U.4 ND 242 ND 84 326 ND 2.3 ND 0.8 3.1 0.5 ND 15 ND 3 18 ND 2.7 ND 0.6 3.3 1.4 ND 56 ND 31 87 ND 3.9 ND 2.1 6.0 A. nudiventris 2.9 1 27 2 8 37 U.l 0.9 0.1 (1.3 1.3 12.3 76 12 45 133 0.6 0.1 0.4 1.0 2.7 5 28 5 18 56 0.2 1.1 0.2 0.7 2.0 Huso huso 0.6 26 ND 9 35 4.0 ND 1.3 5.4 NOTE: ND^not detected. TABLE 9. Orgaiioehlorine residues in sediment from street drainage systems in Tehran, 1974 Wei Weight, ng/c Street SDDT PCB Karim Kahn Zand Fisherabad ShahAbbas 85 112 35 138 155 ND NOTE: ND^not detected. Discussion Fish are exposed to pesticide residues not only in the water but in food and sediments. Some fish continue to accumulate residues over a period of years. Therefore, the levels in the fish may reflect their integrated history of exposure and can be used to assess the degree of pesticide contamination in a freshwater ecosystem. Food can he a significant source of residues if the prey species has had a greater exposure in its physical envi- ronment than has its predator. However, biomagnifica- tion of persistent residties does not depend simply on position in the food chain but is basically determined by the rate at which the residue is taken up and eliminated. Although of limited statistical significance, the results from the Latian reservoir show that despite a lower trophic position the Varichorhintts species acctmuilated about the same amount of DDT as did the Saliiio species. DDT and its metabolites were the principal organo- chlorine residues detected. Aldrin or dieldrin was not found, and PCBs occurred in significant quantities only in samples collected in Tehran. Very high levels of DDT were found in fish from the Kupor and Shahpour Rivers in southern Iran. The pro- portions of the DDT not metabolized, 12 percent in Kupor River samples and 16 percent in Shahpour River samples, indicate that the input of DDT to the rivers is of recent origin and/or is still occurring. DDT probably originates from the mosquito-spraying operations in these areas. Only the indoors are sprayed. The results of this study, however, s(.iggest a more direct contamination. Inter- views with villagers indicate that, at several places, the spraying equipment was cleaned in the rivers after spray- ing was completed. Very low levels of residues were found in organisms from the Parishan Lake. The levels are comparable to those found in areas subjected only to airborne contam- ination (14). However, due to the limited number of samples processed from Parishan Lake and the Kupor and Shahpour Rivers, the results are only tentative. The distribution within these areas requires further studies. However, the high levels found in the Kupor and Shah- pour Rivers may adversely afl'ect reproduction of certain fish species. Comparison of DDT levels in cyprinide fish from the Latian and Karadj reservoirs shows that the Latian reservoir is more e.xposed to pesticide contamination than is the Karadj reservoir. Pike collected from Bandar Pahlavi Mordab show re- markably low levels of DDT in the muscles. The pike is a predatory fish and usually accumulates persistent sub- stances readily. DDT has been used in the area for agriculture and in vector control programs. However, due to rimolT, the amount of clay and soil particles in the water is extremely high. So, most DDT probably Vol. 12, No. 2, September 1978 85 enters the lake attaehed to these partielcs, settles to the bottom, and is not directly incorporated in the pelagic food chain. The amounts of DDT found in the muscle and eggs of sturgeon from the Caspian Sea were similar to those re- ported by Higgins (3) but higher than those found by Hashemy-Tonkabony and Asadi Langaroodi (2). The magnitude and pattern of accimiulation of DDT in sturgeon muscle and eggs is closely related to the fat content. When calculated on a fat-weight basis, the amount accumulated in muscle and eggs of individual fish is not significantly different. Thus, the accumulation of DDT and its metabolites in muscle and eggs of the sturgeon seems to be of a similar magnitude. It is well known that even if the DDT accumulated by fish does not harm the individual, it might be disastrous for the population. This is because DDT may, even at low levels, interfere with the reproduction of certain species 16). Present levels of DDT found in the sturgeon eggs may be a threat to the sturgeon population. How- ever, different species respond differently to the influence of accumulated compounds. Lack of experimental infor- mation on the sensitivity of sturgeon to organochlorine pesticide residues make it impossible to evaluate the present threat. The occurrence of PCBs in various components of the global ecosystem is well documented (4. 5. 7. 10, 11). In Europe, and especially in industrialized areas, PCBs are frequently found in the biota and in airborne fallout 115. 16). In Iran, however, there is not yet any sign of a wide- spread contamination by PCBs as indicated by the ab- sence of these compounds in the organisms analyzed. PCBs have only been found in samples collected in Tehran, presumably originating from local runoff. Strict regulation of the PCBs and PCB-containing products might prevent their accumulation in food chains and reduce their impact on the environment. Acknowledgment Authors thank Eskandar Firouz, Director of Department of the Environment, for valuable comments on the manuscript and for permission to publish the results of the investigation. Thanks are also due to M. Taghi Farvar who initiated the study and to Kenneth and Sarah Kimball and Jack Boetcher who participated in various phases of the field work. LITERATURE CITED (/) Hcillcr. H. L.. cl (tl. 1945. The chemical composition of technical DDT. J. Am. Chem. Soc. 67(9): 1591- 1602. (2) Hashemy-Tonkabony, S. £., and F. Asadi Lonf;aroodi. 1976. Detection and determination of chlorinated pes- ticide residues in Caspian Sea fish by gas-liquid chro- matography. Environ. Res. 12(3) :275-280. (3) Higgins, R. P. 1973. Survey of pesticide residues and heavy metals in Caspian Sea biota from Bandar- Pahlavie, Iran. Mimeo. 1 1 pp.. Office of Environ- mental Sciences, Smithsonian Institution. Washington, DC (4) Holdcn. A. V. 1970. Source of polychlorinated bi- phenyl contamination in the marine environment. Nature 228(5277) : 1220-1221. (5) Jensen, S., A. G. Johnels, M. Ols.<;on, and G. Otterlind. 1969. DDT and PCB in marine animals from Swedish waters. Nature 224(5216) :247-25(l. (6) Johnson, D. W . 196S. Pesticides and fishes — a review of selected literature. Trans. Am. Fish. Soc. 97(4): 398-424. (7) Koeinan, J. H., M. C. Ten Noever Dc Braiiw, R. H. De Vos. 1969. Chlorinated biphenyls in fish, mussels, and birds from the River Rhine and the Netherlands coastal area. Nature 221 (5 186) : 1 126-1 128. (S) Kone, F. 1976. Global input and trends of chemical residues in the biosphere. Environ. Qual. Safety 5:183-196. (9) Monsanto Companx. 1960. Monsanto Co. Tech. Bull. No. PL-306, 50 pp! (/O) Rischionf;h, R. W., L. dc Lappe. 1972. Accumulation of polychlorinated biphenyls in ecosystems. Environ. Health Perspectives 1. (//) Rischrou^h, R. W., P. Ricchc. D. B. Pcakall, S. G. Herman, and M. N. Kirven. 196S. Polychlorinated bi- phenyls in the global ecosystem. Nature 220(5172): 1098-1102. (12) Sddcri;ren, A. 1973. A simplified cleanup technique for organochlorine residues at the microliter level. Bull. Environ. Contam. To,xicol. 10(2 ): I 16-119. (/.?) Sdder.vren, A. 1972. A simplified electron-capture de- tector. J. Chromatogr. 71 (3 ):532-533. (14) Siklergrcn. A. 1973. Transport, distribution, and deg- radation of organochlorine residues in a south Swedish lake ecosystem. Vatten 2:90-108. (/.'') Sode/^ren, A. 1972. Chlorinated hydrocarbon residues in airborne fallout. Nature 236(5347) :395-397. (/6) Sodeiiiien. A. 1975. Monitoring DDT and PCBs in airborne fallout. Environ. Qual. Safety Suppl. 3: 803-810. (17) IViirsler. C. F. 1969. Chlorinated hydrocarbon insecti- cides and world ecosystem. Biol. Conserv. I: 123-129. 86 Pesticides Monitoring Journal Chlorinated Hydrocarbon Pesticide Residues in Pacific Oysters (Crassostrea gigas) from Tasmania, Australia — 1973 Colin Edward Sumner* ABSTRACT Pacific oysters (Crassostrea gigas Tliiinherg) from 19 sites in Tasmania were surveyed for pesticide residues. All samples were analyzed for dieldrin and DDT, anil five samples were analyzed for hexaclilorobenzene (HCB) and lindane. Only DDT was found in all samples. Dieldrin levels were high in oysters from the Taniar River, hut were highest (0.39 mg/kg wet weight) in samples from Riiffin's Bay. In contrast, other residue levels were low. Distribution of pesticides in Tamar River samples differed: dieldrin cotdd he correlated with in- dustrial uses upstream and DDT could be correlated with low-level widespread agricultural use. Introduction Pacific oysters (Crassostrea gigas Thunherg). imported from Japan for cultivation trials, successfully reproduced themselves and colonized estuarine areas in the Tamar River, northern Tasmania (75, 16, 17). They represent the only commercial breeding stocks of Pacific oysters in Australia, and an oyster industry has evolved using annual spatfalls. Stick and shell cultch are set in Jan- uary and later relaid on growing areas around the state. Oyster spat from the river are also sold to growers in South Australia and are being used in cultivation trials in Tongan saltwater lagoons (P. Dinamani, Fisheries Research Division, New Zealand. 1977. Personal com- munication). Wild oysters abound on the shores of the Tamar River within easy access of the general public. In contrast, oyster farms are located on intertidal mud/ sand flats leased from the state for private use by individuals and companies. In February 1973, dieldrin and DDT residues in Tamar River oysters were surveyed to assess the risk of spatfall failure resulting from pesticide accumulation by adult oysters (3,7,9). The results indicated that significant levels of pesticides were present in oyster tissues, and a complete survey of major oyster beds in the Tamar River and other oyster-growing areas was commissioned ' Present address: Tasmanian Fisheries Development Aiittiority. P.O. Box 619F, Hobart. Tasmania, Australia, 7001. to investigate more fully the risk of spatfall failure and to establish pesticide levels in oysters available to the general public. Sampling and Analytical Methods Oysters were collected from 14 sites in the Tamar River: four oyster farms and ten natural reefs. Samples were also taken from five farms in other areas of the state (Fig. 1). Tamar sampling sites were identical to those chosen for a heavy metal survey (/). Samples of 12 oysters were considered representative of the local popu- lation (2). Ages of cultivated oysters were noted and, when available, year classes were sampled independently. All samples were routinely screened for dieldrin and -DDT residues. Five samples were analyzed also for he.xachlorobenzene (HCB) and lindane. DDT here in- ckides -DDT resdues and /7,/;'-TDE and /'.p'-DDE. .Analyses were performed at the Public Health Service Analysts Laboratory, Hobart, Tasmania. Shucked undrained oyster meats were stored at — I8°C, in mason jars. Before analysis, they were homogenized in an electric blender. Oyster meats were combined with a desiccant, anhydrous sodium sulfate (1:3, wet weight), and alternately blended and chilled until smooth flowing. Standard procedures were followed for cleaning high- moisture nonfatty foods (18). Aliquots were extracted with acetonitrile and were diluted with water before hexane partitioning. The hexane extract was back- washed with distilled water and filtered through a Florisil column. The column was packed with activated magnesium silicate and topped with 1 cm of anhydrous sodium sulfate. Residues were eluted from the column with 6 percent and 15 percent ethyl ether in petroleum ether. The 6 percent eluate was used directly to determine DDT residues, HCB, and lindane. The 15 percent eluate was concentrated and subjected to additional cleanup through a new Florisil column. Samples eluted from the Florisil columns were identified and quantitated by using a Varian Model 1400 gas Vol. 12, No. 2, September 1978 87 TAMAR RIVER i_V '^i^'' A , Tamar River B , Boomer Bay C. Tata nna Bay D. Ralph's Bay E. Simmon 's Bay F. Gardiner's B ay FICiURE 1. Oyster sampling sites, Tcisiuania, Australia with map of Tamar River area — 1973 (A: Tamar R.: B. Boomer Bay: C. Taruniia Bay: D. Ralph's Bay: E. Simmons Bay: F. Gardners Bay) chromatograph equipped with an electron-capture de- tector. Instrument parameters and operating conditions follow. Columns: Pyrcx. 5-ft X Vj-inch diameler, packed with a mixture of 3 percent UC-200 and 5 percent QF-1 on 80-100-mesh Gas-Chrom Q Temperatures: detector 200*C injector 210°C oven 185°C Carrier gas: nitrogen flowing at 40 ml/minute Thin-layer chromatography was used to check results obtained by gas chromatography and to check for possi- ble interference from the presence of polychlorinated biphcnyls (PCBs). Samples fortified with 1 Mg of each compound produced average recoveries of 88 p>ercent -DDT, 93 percent HCB and lindane, and 90 percent dieldrin. All data reported are corrected for recovery. The lower limit of quantitation was 10 ppb (10 ^ag/kg); values less than this but for positively identified peaks were recorded as trace. Results Residue levels of dieldrin, -DDT, HCB. and lindane in whole oyster meats are presented in Table 1. Dieldrin was detected in all but three samples. Elevated levels in oysters from the Tamar River were reflected in a high of 0.39 Mg/g in the Ruflins Bay sample. SDDT residues were positively identified from all samples but were of an order of magnitude lower than dieldrin levels, ranging from trace to 0.06 /ig/g. Traces of HCB were found only in the Gardners Bay oysters, and traces TABLE 1. Pesticide levels in Pacific oysters (Crassostrea gigas), Tasmania, Australia Sampling Station Samplin(, Date AGE, "\EAR No. Bllked Residues, mg kg. Whole Oyster Dieldrin ISDDT HCB Lindane TAMAR RIVER 1 Rosevears March 1973 — 18 0.20 0.03 — — 2 Swan Bay March 1973 — 12 0.10 0.02 — — 3 Gravelly Beach March 1973 — 15 0.21 0.01 — — 4 Supply Riveri February 1973 2 17 0.20 0.02 — — March 1973 2 15 0.09 0.01 — — 5 Millwood Jetty March 1973 — 22 0.10 0.02 — — 6 Devoit March 1973 — 12 0.10 0.02 — — 7 Craigburn March 1973 — 22 0.19 0.01 — — 8 Devils Elbow March 1973 — 20 0.10 0.01 — — 9 Redwood Bay February 1973 — 16 0.19 0.03 — — March 1973 — 12 0.09 0.01 — — 10 Ruflins Bay > February 1973 2 13 0.39 0.01 — — .March 1973 3 22 0.27 0.06 — — 11 East Arm' February 1973 1 34 0.10 0.02 — — 2 15 0.09 0.02 — — 3 19 0.19 0.01 — — March 1973 2 19 0.08 0.01 — — 3 13 0.20 0.01 — — 12 Middle Island- February 1973 3 16 0.11 0.03 — — Flats March 1973 2 21 0.09 0.02 — — 3 19 0.10 0.01 — — 13 West Arm March 1973 — 14 0.119 0.01 — — 14 Br>ants Bay March 1973 — 14 0.08 0.01 — — Boiittifr Bay^ August 1973 1.5 15 ND T ND T Tiiranna Bay^ July 1973 1.5 15 T T ND T Ritlptn Bay i January 1972 2 24 ND T — — Sinnnons Bay ' August 1973 K5 15 ND 0.01 ND T Gardners Bay^ July 1973 1.5 15 T 0.06 r T NOTE: — = nol analyzed. ND = not detected, T=<0.01 mg/kg. ' Oyster Tarms. 88 Pesticides Monitoring Journal of lindane were identified in samples from three of the leased farms. The limited sampling of oysters of different ages from growing areas in the Tamar River suggests few differ- ences in pesticide concentrations among the groups; this agrees with Butler's observations (2). Tamar River samples taken at increasing distances downriver from Launceston showed diflferences in pesti- cide concentrations in oyster fats (Fig. 2). Dieldrin levels were inversely correlated with distance from Launceston (/■ = 0.900; P = 0.001), whereas DDT levels showed a more general spread suggestive of wide- scale low-level use of the pesticide (r = 0.490; 0.05 ) Sumner, C. E. 1974. Oysters and Tasmania, Part 2. Tasmania Fish. Res. 8(2): 1-12. (16) Thomas. J. M. 1952. The acclimatization and growth of the Pacific oyster (Gryphaea i:if;as) in Australia. Aust. J. Marine Freshwater Res. 3( I ):64-73. (/7) Thomson. J. M. 1959. The naturalization of the Pacific oyster in Australia. Aust. J. Marine Fresh- water Res. 10(2): 144-149. (/iV) U.S. DepartinenI of Health. Education, and Welfare. Food and Drui; Ailministration. 1971. Pesticide Ana- lytical Manual, Vol. 1. Section 212 13a(l). 90 Pesticides Monitoring Journal FOOD AND FEED DDT Residues in Butter and Infant Formula in India, 1977 ' G. S. Dhaliwal- and R. L. Kalia = ABSTRACT Samples of commercicd brands of biilter and infant formula from ilifferenl parts of India were examined for DDT residues. All 18 samples of butter representing nine brands were con- taminated. Levels of DDT residues ranged from 0.42 to 11.36 ppm and exceeded the Food and Agriculture Orga- nization/World Health Organization practical residue linul of 1 .25 ppm in 90 percent of the samples. Alt four brands of infant formula contained DDT residues above the prac- tical residue Until. Most DDT residues were in the form of p.p'-TDE in both commodities. Tliis contamination of milk with excessive amounts of DDT residues seems to be wide- spread in India. Introduction The proportions of DDT and its metabolites present in cows' milk indicate possible sources of these residues (5). Different routes of animal exposure result in secretion of DDT in different forms (//). Animal uptake by aspiration or intravenous injection results in secretions of DDT; ingestion leads to secretions in the form of DDT metabolites. Limited information is available in India on the nature of DDT residues in bovine milk. Milk samples from Delhi contained only residues of p.p'-DDT (I). On the other hand, most DDT residues in milk from Ludhiana were in the form of p.p'-lDE (2). Because milk is an important food commodity, particularly for children, it is necessary to know the extent and sources of its con- tamination with DDT. Samples of commercial brands of butter and infant formula from different parts of India were analyzed for DDT residues. These commodi- ties were chosen because of their availabilitv. 'Study financed in part by the Agricuitiiial Research Service, U.S. Department of Agricuhiire, under PL 4St) project "Studies on pesti- cides residues and monitoring of pesticidal pollution (IN-ARS-65)," -Department of Entomology. Punjab Agricultural University. Ludhiana- 141004, Punjab. India. Materials and Methods BUTTER Different commercial brands of butter manufactured in Punjab, Haryana, Delhi, Rajasthan. and Gujarat were purchased from the local market in lOO-g packages February and March 1977. Three butter samples weighing 100 g each were also purchased during the same period from local dairies situated in different parts of Ludhiana city. Laboratory extractions were made within 2 days. The method described by Faubert Maunder at al. (4) was modified slightly and used to extract and isolate DDT residues. The butter was warmed at about 50°C to separate the fat which was decanted through dry filter paper. A 5-g sample of the clarified fat was dissolved in 10 ml of hexane and transferred quantitatively to a 12.'5-ml separatory funnel by using additional small por- tions of hexane totaling 15 ml. The hexane extract was partitioned three times into hexane-saturated dimethyl- formamide. using 10 ml of solvent each time. The dimethylformamide fraction was backwashed with 10 ml of dimethylformamide-saturated hexane, diluted with 250 ml of water and 50 ml of sodium chloride-saturated aqueous solution, and extracted twice with 100 ml of hexane. The combined herane extracts were concen- trated to about 5-10 ml for subsequent column cleanup. Silica gel, 60-200 mesh, was thoroughly washed with acetone and methanol and activated 1 hour at 130°C. It was packed in a 50-cm X 2-cm glass column to a height of 10 cm between la>ers of anhydrous sodium sulfate. The column was prewashed with 100 ml of hexane. The sample extract in hexane was added to the column and eluted with 150 ml of 50 percent benzene in hexane. The eluate was concentrated to 1-10 ml and was analyzed by thin-layer and gas-liquid chromatog- raphy. Thin-layer chromatography was done by the method of Thompson et al. (7) on AgNO.-incorporated, alumina- VoL. 12, No. 2, September 1978 91 G-coated glass plates. /;-Hexane was used as the devel- oping solvent. The Rf values were; p./ADDF. 0.65: pp-DDE, 0.88; p.p'-TDE, 0.35: o.p-DDT, 0.77: o.p- TDE. 0.42: n-BHC. 0.52: /i-BHC. 0.1 : y-BHC, 0.32: and 8-BHC, 0.1. GLC determinations were made by injecting 1-10 ^i\ of the sample solution into a Model 7624 Packard gas chromatograph. Two columns were used: (A) was the working column and (B) was used for confirmation. Instrument parameters and operating conditions follow: Deleclor: Columns: Temperature Carrier gas: Flow rate: m ID. packed 1 80-1 no-mesh Tritium electron-affinity (A) Pyrex. 102 cm long x 0.4 with 5 percent DC-200 Gas-Chtom Q (B) Pyrex 1.S4 m long X 0.4 cm ID. packed w'ith 2 percent DECS on 80-IOO-mesh Gas- Chrom Q : Column 190'C Detector 200°C Inlet 210°C Nitrogen 70 ml/ minute for Column A 100 ml/ minute for Column B Retention times, in minutes, are listed below: Column A Column B /),p-DDE p.p-TDE p.p-DDT o.p'-DDT o.p'-TDE ,.-BHC -,-BHC /i-BHC 2.5 3 2.5 2 1 1.10 1 3.5 10 8 5 6.5 1.5 2 5.5 On column .A, the half-scale deflection was obtained with 0.5 ng of /7,p'-DDE, 0.8 ng of /;,//-TDE, and 1.0 ng of /7,p'-DDT. Quantitative estimations were made by comparing peak heights of the unknown with the standards treated similarly. Recoveries of DDT and its metabolites at the fortification levels of 0.5 ppm were 80-90 percent. Results were expressed as such and were not corrected for recovery. The limit of detection of p,p'-DDT in butter was 0.01 ppm. The nature of DDT residues was confirmed by a micro- alkali dehydrohalogenation procedure in the Manual of Analytical Methods for Analysis of Pesticide Residues in Human and Einironmculal Samples {10) . INFANT rORMLLA Four brands of infant formula manufactured in Punjab, Bombay, and fiujarat were purchased from a local market in 500-g packages February-April 1977. Ten g of infant formula was weighed and diluted to 80 ml with distilled water. Each sample was blended with 160 ml of acetone and 160 ml of he.\anc in a vortex beaker for 3 minutes. The extract was ccntrifuged at 3000 rpm for 10 minutes. The hcxane layer was removed by 92 pipet, concentrated to about 25 ml, and partitioned inlo^ dimethvlformamide three times, using 15 ml of solvent' each time. The combined dimethvlformamide fractions were cleaned and analyzed by the procedures described for butter. Results ui\d Discussion DDT residues in butter occurred mainly in the form of p.p'-DDT. p,p'-DDE. and p.p'-JDE. Small amounts of o.p'-DDT and o.p'-TDE were also detected. Some sam- ples had BHC residues in the form of a-, /i-, and 7- isomers. Only traces of BHC were found. The maxi- mum residue, 1 ppm BHC, was found in a sample of butter from Gujarat. Levels of DDT residues in eighteen samples of butter representing six commercial and three local brands are given in Table 1. All but one brand of butter contained DDT residues higher than the practical residue limit of 1 25 ppm established by the United Nations Food and Agriculture Organization (FAO)/World Health Organi- zation (WHO) (9). The level of DDT residues varied from 0.42 to 1 1.36 ppm with an average of 4.77 ppm. In a study at Uttar Pradesh Agricultural University, Pantnager, India (S), two of five butter samples were contaminated with DDT at an average level of 0.4 ± 0 14 ppm. The highest level of DDT detected was 0.5 ppm. Agnihotri et al. (/) reported that seven of eight samples of butter collected from Delhi contained DDT residues higher than the practical residue limit. The concentration of residues varied from 1.1 to 8.0 ppm with an average level of 3.8 ppm. The present study shows that most of the commercial brands of butter manufactured in Punjab, Haryana, Delhi, Rajasthan, and Gujarat contained DDT residues higher than the practical residue limit, and suggests widespread con- tamination in India of milk with high levels of DDT residues. TABI F 1 . Residues of DDT and its metabolites in euinnuTcial Initter samples, India. 1977 Sample Number Orioin Residues , PPM Bui IIR DDT DDE TDE 2 DDT Brand 1 Gujarat 1.88 2.54 1.62 1.48 1.44 1.44 8.00 6.53 6.35 11.36 10.51 9.41 Biand II Haryana 1.16 1.18 0.50 0.74 0.73 0.30 3.74 3.51 1.36 5.64 5.42 2.16 Brand 111 I'unj. h 0.75 0.73 0.63 0.58 0.42 0.41 3.54 3.25 2.53 4.87 4.40 3.57 Brand IV RajaMh.ui 0.75 0.68 0.70 0.73 0.49 0.42 3.73 2.63 2.50 5.21 3.80 3.62 Brand V Brand VI Delhi Gujarat 0.35 0.02 0.02 0.25 0.17 0.19 1.55 0.3.1 0.21 2.15 0.52 0.42 Locale 1 Locale II Locale Ml 1 udliiana Ludhiana Ludhiana 0.81 0.70 0.57 0.58 0.42 0.38 4.47 2.84 2.16 5.86 3.96 3.11 Pesticides Monitoring Journ.\l TDE is the predominant metabolite detected in all brands of butter (Table 1). Milk collected recently from Ludhiana and surrounding areas showed similar results (2). Since TDE is not being used in India for crop protection or mosquito control, then TDE residues must arise as a result of metabolism of DDT. However, milk and butter samples from Delhi did not show resi- dues of any metabolite. The residues were detected as DDT only (/). The other two studies carried out in India on the DDT contamination of milk and milk products did not consider the metabolites (6.8). The high level of TDE found in butter samples suggests that cattle ingest DDT mainly through contaminated feed. Witt et al. found a 1 : 1 relation between levels of DDT residues in cattle feed and the concentration of DDT secreted in bovine milkfat (12). If this relationship were true in the present study, DDT residues in cattle feed would be expected to vary between 0.42 and 1 1.36 ppm, averaging 4.77 ppm. The sources of such high DDT contamination of cattle feed must be determined particularly because the use of DDT for plant protection is limited in India. DDT is used mainly for malaria control; indoor residual spraying on the walls and roofs is carried out at the rate of 1 g/m^. Dhaliwal and Kalra suggested that the indoor spraying might contaminate stored feed, and thereby contribute partly toward the ingestion of DDT by cattle (2). However, the con- tribution of this and other sources of contamination of milk needs further investigation. All four popular brands of infant formula contained DDT residues above the tolerance level of 1 .25 ppm, usually in the form of TDE (Table 2). The concentra- tion of DDT varied from 1.52 to 2.72 ppm, averaging 1.90 ppm. Apparently, no other study has been carried out in India on the DDT contamination of commercial infant formula. The present study shows that even the spray drying process in the manufacture of infant for- mula, does not reduce residues of DDT to below the FAO/WHO tolerance level. This corresponds with the observation of Engst et al. {3). The average level of DDT residues found in infant for- mula is 1.90 ppm. The consumption of this milk by a three-month-old child weighing approximately 5 kg at TABLE 2. RcsUUics nj DDT and its metcihoUtcs in conunercial inftinl formula .samples, India. 1977 Infant Origin Fat Content, % Resi DUES ON Fat Basis PPM Formula DDT DDE TDE SDDT Brand I Punjab 19 0.6.1 0..13 1.76 2.72 Brand I] Bombay 19 0.40 0.25 1.04 1.69 Brand III Gujarat 18 0.26 0.36 1 03 1,65 Brand IV Bombay 18 0.33 0.17 1.(12 .1.52 the normal feeding rate of 135 g/day would result in a daily intake of 47 ;u,g of DDT. This value is about twice the acceptable daily intake of 0.005 mg/kg of baby weight (25 ^g for an infant weighing 5 kg) estab- lished for DDT by the Joint Pesticides Committee of FAO and WHO (9). LITERATURE CITED (/) Agnihotri. N. P., R. S. Dcwan. H. K. Jain, and S. Y. Pandey. 1974. Residues of insecticides in food com- modities from Delhi — II. High-fat-conlent food ma- terials. Indian J. Entomol. .16( 3 ) ;203-2O8. (2) Dhaliwal. G. S.. and R. L. Kalra. 1977. DDT res- idues in milk samples from Ludhiana and surrounding areas. Indian J. Ecol. 4( 1 ) : I 3-22. (.?) Eng.st. R.. L. Pruhl, and E. Jarmatz. 1969. Effect of food processing on insecticide residues. II. Behaviour of chlorinated insecticides during industrial production of dried milk. Nahrung 1 3(6 ) :47 1-475. (4) Funhcrt Maunder. J., H. Sgan. E. W . Codly, E. W. Hammond. J. Roluirn, and J. Thompson. 1964. Clean- up of inimal fats and dairy products for the analysis of chlorinated pesticide residues. Analyst 89(1056): 168-174. (5) Haxes. W. ]. 1975. Toxicology of pesticides. Williams and Wilkins, Baltimore. MD. 5Sf) pp. (6) Luk.slin)inurayana. W. and P. Krishna Mcnon. 1975. Screening of Hyderabad market samples of foodstuffs for organochlorine insecticide residues. Indian J. Plant Protect. 3(1):4-19. (7) Thomp.son, R. H.. E. G. Hill, and F. B. Flshwick. 1970. Pesticide residues in Great Britain. XIII. Organo- chlorine residues in cereals, pulses, and nuts. Pestic. Sci. 1:93-98. (S) Tripathi. H. C. 1966. Organochlorine insecticide resi- dues in agricultural and animal products in Terai area. M.Sc. thesis, Uttar Pradesh Agricultural University, Pantnagar, India, 120 pp. (9) United Nations. Food and Agricidlnre Oriianizution/ World Health Organization. 1973. Pesticide Residues in Food. Report of the 1972 Joint Meeting of the FAO Working Party of Experts on Pesticide Residues and the WHO Expert Committee on Pesticide Residues. World Health Organization Tech. Rep. Ser., No. 525; FAO Agricultural Studies No. 90, 47 pp. (10) U.S. Environmental Protection A.vency. 1974. Manual of Analytical Methods for the Analysis of Pesticide Residues in Human and Environmental Samples. Pre- pared by Environmental Toxicology Division, Health Effects Research Laboratory, Research Triangle Park. N.C. Section XII D, pp. 1-7. (//) Witt. J. M., F. M. Whilin.i;. W. H. Brown, and J. W. Stall. 1966a. Contamination of milk from different routes of animal exposure to DDT. J. Dairy Sci. 49: 370-380. (12) Witt, J. A/., F. M. Whiting, and W. H. Brown. 1966b. In Organic Pesticides in the Environment. Advances in Chemistry Series. No. 60, American Chemical So- ciety, Washington, DC. 99 pp. Vol. 12, No. 2, September 1978 93 GENERAL Organocliloriiw Pesticides and Polychloiinated Biphenyls on Sediments from a Subarctic Salt Marsh, James Bay, Canada — -1976 W. A. Glooschenko ' and R. C. J. Sampson ^ ABSTRACT Sediment suniples were eollecled from a suhaietic sail marsh on James Bay, Ontario in May 1976. Of 15 ori>ano- chlorine compounds analyzed, trace amounts mainly of p.p'-DDE and polychlorinated biplienyls (PCBs) were de- tected, luit could not he quantitated. llUnxlllCtioil Organochlorine pesticides and polychlorinated biphenyls (PCBs) have been detected in subarctic and arctic ma- rine food chains. PCBs and -DDT have been found in polar bears, seals, and fish in the Canadian arctic (/) and in fish in a landlocked lake in northwestern Que- bec (5). The authors wished to determine levels of these organochlorine compounds in sediments of a subarctic wetland since this part of the ecosystem would be the ultimate sink of many of the compounds. Sediment samples were collected in May 1976 from a subarctic salt marsh at North Point, Ontario (51°29'N, 80°27'W), on the western shore of James Bay, approxi- mately 27 km northeast of Moosonee at the southern end of James Bay. A sample was collected in Moosonee from a drainage ditch to check the possibility of local sources of contamination. Methods and Materkds Sediment samples were collected by hand with a stainless steel trowel from the top 5 cm of five salt marsh sites, two freshwater creek sediments, and a drainage ditch in the Moosonee settlement. Samples were placed in alumi- num cans which had been carefully cleaned with inter- ference-free solvents and were frozen until analysis within two months of collection. 'Geology Seclion. Process Rcscarth Division. Can.ida Centre for Inland Walcrs. I' (). Box 5()5I). Burlinglon. Omano. Canada I 7R 4A6. -Waicr Qualiiy Branch (Uniario Region). Inland Walcrs Dircciorale. P.O. Box 5050, Burlington, Ontario, Canada I 7R 4A6. Thawed wet-sediment samples (10 g) were extracted by using an ultrasonic probe. Each sample was extracted three times with 75 ml of acetonitrile for 2 minutes each time and filtered through Celite and sodium sulfate. The combined filtrate and washings were partitioned into petroleum ether, washed with water, dried with sodium sulfate, and evaporated with a rotary evapwrator to 1 ml, using isooctane as a keeper. Recovery was 80-100 percent (2). The concentrate was analyzed by high-pressure liquid chromatography. Four fractions were collected, evap- orated to 1 ml, and analyzed by computerized gas chromatography (GC) with automatic sampling. Identi- fication was based on quantitative reproducibility (±20 percent) on four columns of varying polarity with a 2 percent retention time variability window. Instrument parameters and operating conditions follow. Delectois: linearized ''-Ni electron-capture Cohimns: (1) 2 m x 3.5 mm I.D.. pyrex, packed witti mixture of 1.5 percent OV-17 and 1.95 percent QF-I on llX)-i:0-mesh Gas-Chrom Q (2) 1.86 m X 4 mm I.D.. packed with mixline of 4 percent OV-101 and 6 percent OV-210 or QF-1 on 80-100-mesli Gas-Chrom Q (.1) 1.86 X 4 mm l.O., packed with J percent OV- 101 on 811-10()-mcsh Chromosorb W-HP (4) 2 m X 3.5 mm I.D., packed with 3 percent OV-225 on 100-1 20-mesh Gas-Chrom Q Icmpciatures: column 200° C injector 225° C detector 325° C Carrier gases: mixture of 5 percent methane and 95 percent argon flowing at 50-75 ml/ minute Quantitation limits are given in Table I. Detection limits for the pesticides analyzed are approximately one- tenth the quantitation limit. Authors were unable to confirm identities of residues by mass spectrometry because of the low levels of compounds. 94 Pesticides Monitoring Journal TABLE 1. Distrihulion of organochtoriiws in sediments from North Point salt marsh complex Quantitation Limit. MC/G Sample Site Salt Marsh Creek Beds MOOSONEE Compound 1 2 3 4 5 1 2 1 0.001 Residues, ;iC 'G DRY WEIGHT Lindane < 0.001 ND ND ND ND ND ND < 0.001 Heptachlor 0.001 ND ND ND ND ND ND ND ND Aldrin 0.001 ND ND ND ND ND ND ND ND Heplachlor epoxid : 0.001 ND ND ND ND ND ND ND ND ;i.;>'-DDE 0.001 < 0.001 < 0.001 ND < 0.001 < 0.001 < 0.001 < 0.001 < O.OOI Dieldrin 0.001 ND ND ND ND ND ND ND ND p.;>-DDT o.ooi ND ND ND ND < 0.001 ND ND ND o.p'-DDT 0.001 ND ND ND ND ND ND ND ND Endrin 0.001 ND ND ND < 0.001 ND ND ND ND ft-Chlordane 0.005 ND ND ND ND ND ND ND ND -,-Chlordane 0.005 ND ND ND ND ND ND ND ND rv-EndosuIfan 0.01 ND ND ND ND ND ND ND ND /3-Endosulfan 0.01 ND ND ND ND ND ND < 0.01 ND p-p'-Melhoxychlor 0.05 ND ND ND ND ND ND ND < 0.05 Total PCBs 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < O.I < 0.1 < 0.1 < 0.1 Results and Discussion Results are in Table I. Of the 15 organochlorine com- pounds, none could be quantitated. However, p.p'-DDE and PCBs were detected in nearly all the samples. Traces of lindane, p,/?'-DDT, endrin /i-endosulfan, and /^.p'-methoxychlor were noted. No river entering James Bay drains regions of agricul- ture, nor is there intensive recreational use of the area, a source of pesticide input in southern Ontario (2^). Therefore, it appears that traces of organochlorine compounds have been transported to the area by air. LITERATURE CITED '1) Bowes, G. W., and C. J. Jonkel. J975. Presence and distribution of polychlorinated biphenyls (PCBs) in arctic and subarctic marine food chains. J. Fish. Res. Board Can. 32(11) :21I 1-2123. (2) Glooschenko, W. A.. W. M. J. Sirachan. and R. C. J. Sampson. 1976. Distribution of pesticides and poly- chlorinated biphenyls in water, sediments, and seston of the Upper Great Lakes — 1974. Pestic. Monit. J. 10(2):61-67. (3) Miles, J. R. W.. and C. R. Harris. I97J. Organochlorine insecticide residues in streams draining agricultural, urban-agricultural, and resort areas of Ontario, Can- ada—1971. Pestic. Monit. J. 6(4):363-368. (4) Frank, R., A. E. Armstrong. R. G. Boelens, H. E. Braiin, and C. W. Douglas. 1974. Organochlorine insecticide residues in sediments and fish tissues, On- tario, Canada. Pestic, Monit. J. 7(3/4): 165-180. (5) Risebrough, R. W., and D. D. Bergcr. 1971. Evidence for aerial fall-out of polychlorinated biphenyls (PCBs) in the eastern Canadian Arctic, Manuscript Rept. No. 23, Pesticide Section, Canadian Wildlife Service. Vol. 12, No. 2, September 1978 95 APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN AROCLOR 124: ARCKLOR 1:54 AROCLOR 126(1 AZINPHOSMETHYL BENZENE HEXACHLORIDE (BHC) BROMACIL CARBOPHENOTHrON CHLORDANE DDE DDT DACTHAL (DCPA) DEF DEM ETON DIA/INON Din DRIN DIURON ENDOSL'LFAN ENDRIN ETHION HEPTACHLOR LINDANE MALATMION METHOX^ ( 111 OR MIREX PAKATHION PHORATE PCBs TDE TOXAPHENE TRiri IRALIN Hcxachloriihexahydro-p. cfu/c-dimethanonaphthalene 0,O,O',0'-Tctraclhyl .S..V'-methyIene bisphosphorodithioate Heptachlorotetrahydro-4,7-meihaniiindenc and related compounds Gphosphate of diethyl niercaptosiiccinate 2,2-Ris{/j-methox\phcnyl)-l.l.t-Irichlori>ethane SS*"^ and related compounds 12% Dodecachlort)Octahydro-l,3-mcthailo-I//-cycIobulalcd)pcntalene O.O-Diethyl 0-/;-nitropheny! phosphorothioate O.O-Dielhyl .V-| (elhylthio ) methyl | phosphorodithioale Polychlorinatcd biphenlys. mixtures of chlorinated biphcinl compounds havinji various percentages of chlorine Dicllloiodiphcnyldiclllorocthane Technical chlorinated camphcne 61-69% chlorine M.<.,M-'rrinuoro-2,6-din it ro-.V,,\'-iJi propyl /i-toluidine 96 Pesticides Monitoring Journal Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators associated with pesticide monitoring, research, and other programs concerned with pesticides in the environ- ment. Other subscribers work in agriculture, chemical manufacturing, food processing, medicine, public health, and conservation. Articles are grouped under seven headings. Five follow the basic 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. Monitoring is defined here as the repeated sampling and analysis of environmental components to obtain reliable estimates of levels of pesticide residues and related compounds in these components and the changes in these levels with time. It can include the recording of residues at a given time and place, or the comparison of residues in different geographic areas. The Journal will publish results of such investigations and data on levels of pesticide residues in all portions of the environment in sufficient detail to permit interpretations and con- clusions by author and reader alike. Such investigations should be specifically designed and planned for moni- toring purposes. The Journal does not generally publish original research investigations on subjects such as pesticide analytical methods, pesticide metabolism, or field trials (studies in which pesticides are experimen- tally applied to a plot or field and pesticide residue de- pletion rates and movement within the treated plot or field are observed). Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and references. Pesticides ordinarily should be identi- fied by common or generic names approved by national or international scientific societies. Trade names are acceptable for compounds which have no common names. Structural chemical formulas should be used when appropriate. Accuracy, reliability, and limitations of sampling and analytical methods employed must be described thoroughly, indicating procedures and con- trols used, such as recovery experiments at appropriate levels, confirmatory tests, and application of internal standards and interlaboratory checks. The procedure employed should be described in detail. If reference is made to procedures in another paper, crucial points or modifications should be noted. Sensitivity of the method and limits of detection should be given, particularly when very low levels of pesticide residues are being reported. Specific note should be made regarding cor- rection of data for percent recoveries. 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Requests for microfilm and correspondence on editorial matters should be addressed to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U.S. Environmental Protection Agency Washington, D.C. 20460 For questions concerning GPO subscriptions and back issues write: Superintendent of Documents U.S. Government Printing Office Washington, D.C. 20402 98 Pesticides Monitoring Journal The Pesticides Monitoring Journal is published quarterly under the auspices of the Federal Working Group on Pest Management (responsible to the Councii on Enviftua- 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 Api- culture; Commerce; Defense; the Interior; Health, Education^ and Welfare; Stat«; Transportation; and Labor; and the Environmental Protection Agency. The Monitoring Panel consists of representatives of the Agricultura) Research Service, Animal and Plant Health Inspection Service, Fxtension Service, Forest Service, Department of Defense. Fish and Wildlife Service, tieojogical Survey, Food and Drug Administration, Environmental Protection Agency, National Manoe Fiisbeirtej Service., National Science Foundation, and Tentjessee Valley Authority. The Pesticides Monitoring Journal j« puibilrshed by the TechnicaJ Service* Division, Office of Pesticide Programs, V.S, Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies represented on the Monitoring Panel which participate iiii operation of the nattonail 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 witfe State and community monitoring programs, universities, hospitals, and nongovermneatal 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, genei.al information, trade names, and commercial sources in the Pesticides Monitofing Jmtrmd does nsA 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, Chmrman Robert L. Williamson, Animal and Plant Health Inspection Servkf Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Gerald E. Walsh, Environmental Protection A,gency G. Bruce Wiersma, Environmental Protection Agency William H. Stickel, Fish and Wildlife Service Milton S. Schechter, Agricultural Research Service Herman R, Feltz^ Geological Survey Address correspondence to: Paul Fuschini (WH-569) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agei»ey Washington, DC. 20460 Editor Martha Finaa CONTENTS Volume 12 December 1978 Number Page FISH, WILDLIFE, AND ESTUARIES Pesticide residues in estuuiine mollitsks. 1977 versus 1972 — Natioiud Pesticide Monitoring Program 99 Philip A. Butler, Charles D. Kennedy, and Roy L. Schutzmann Chlorinated insecticide and PCB residues in fish and mussels of east coastal waters of the middle and north Adriatic Sea. 1974-75 ^ 1 0: Mhiden Picer, Nena Picer, and Marijan Ahel Organochlorinc residues and reproduction in the little hro)\n bat. Laurel, Maryland — June 1976 1 13 Donald R. Clark, Jr.. and Alex Krynitsky SOILS Pesticide residue levels in soils and crops, 1 97 1 — National Soils Monitoring Program (III) 1 17 Ann E. Carey, Jeanne A. Gowen, Han Tai, William G. Mitchell, and G. Bruce Wiersma Pesticide application and cropping data from 37 states. 1971 — National Soils Monitoring Program 137 Ann E. Carey, Jeanne A. Gowen, and G. Bruce Wiersma WATER Organochlorines, cliolineslerase iidiibitors, and aromatic amines in Dutch water samples, September 1969-Deceinber 1975 149 Ronald C. C. Wcgman and Peter A. Greve BRIEF Organochlorine pesticide levels in Ottawa drinking water, 1976 163 David T. Williams, Frank M. Benoit, Edward E. McNeil, and Rein Otson APPI NDIX 164 Infortiiul'nnt lor Contributors . . ^ 165 FISH, WILDLIFE, AND ESTUARIES Pesticide Residues in Estuarine MoUusks, 1977 versus 1972- National Pesticide Monitoring Program Philip A. Butler,' Charles D. Kennedy," and Roy L. Schiitzmann" ABSTRACT Bivalve moUusks were monitorecl for residues of 20 organo- chlorine and organopliosphale pesticides and polychtorinated biphenyls in spring 1977 in 87 of the 181 estuaries routinely monitored on a monthly basis during 1965-72. DDT, the only pesticide delected in 1977, occurred at low levels in one estuary eacli on the Atlantic and Pacific coasts. Introduction In 1965 the U.S. Bureau of Commercial Fisheries ini- tiated a program to monitor shellfish populations for organochlorines. In cooperation with local laboratories, about ISO permanent monitoring stations in 15 coastal states were sampled for any one of 10 species of mol- lusks monthly. The eastern oyster, Crassostrea virginica. was the principal species collected on the Atlantic coast, and C. gigas was the species usually monitored on the Pacific coast. The program continued until 1972, but not all areas were monitored for the entire period. About 8,100 samples containing 15 pooled individuals were analyzed. DDT was found in almost all samples. Dieldrin was the next most commonly detected pesti- cide; residues of endrin, mirex, toxaphene, and poly- chlorinated biphenyls (PCBs) were detected occasion- ally. By 1972, there was a clearly defined trend toward fewer and smaller residues of DDT and its metabo- lites (/). Early in 1977, the U.S. Environmental Protection Agency monitored mollusks at some of the same sites to determine further trends in pollution levels after the 5-7-year lapse. 1 Ecological Monitoring Branch, Technical Services Division, U.S. Environmental Protection Agency. Gulf Breeze, FL .12561. - Ecological Monitoring Branch. Pesticides Monitoring Laboratory, U.S. Environmental Protection Agency, National Soil Testing Labo- ratory Station. MS 39529. Materials and Methods The original cooperating laboratories agreed to collect the new samples. About half the former stations where pesticides had been found consistently a decade ago were monitored again. Single collections of 30 bivalves at each site were made just before or during early stages of the spawning cycle so that tissue lipid levels presumably would approach the maximum. There were 178 samples; replicate collections were made at 89 stations in 87 estuaries. Depending on the availability, seven species of mollusks were used in- cluding the freshwater Asiatic clam, Corbicula manilen- sis: eastern oyster, Crassostrea virginica: Pacific oyster, C. gigas: Atlantic ribbed mussel, Geulcensia demissa; northern quahog, Mercenaria mercenaria: soft-shell clam, Mya arenaria: and blue mussel, Mytilus edidis. Oysters were sampled in 63 estuaries, mussels in 14, and clams in 10 estuaries. However, clams are the least satisfactory as biomonitors (2). Two samples of 15 bivalves each were collected at each station. They were shucked but were not drained, and were homogenized in an electric blender. A single aliquot of about 50 g from each pooled sample was preserved with 50 ml reagent grade methanol and mailed in a methylpentene vial to the EPA Pesticides Monitor- ing Laboratory in Bay St. Louis, Mississippi, for analysis. Analytical procedures, detailed elsewhere (3), pjcr- mitted the detection of 20 organochlorine and organo- phosphate pesticides and PCBs (Table I ). In the 1965- 72 program, samples were screened routinely for only 1 1 of the more persistent organochlorine pesticides. Results and Discussion The salient feature of the 1977 monitoring data was the absence of detectable pesticide residues in 85 of the 87 Vol. 12, No. 3, December 1978 99 TABIE [, Cotnpouneh delected hy ehemUal procedures usfd in monitoring moUtisks OWMNOCmiORrNES 0»G*NOimOSPH«TES Aldrin A-zinpho-^methyr GWordijBie Carbophenothion 2DOT DEF Dleidrin ncmeton EndosiiU'iiii. rMaiinffin Heptachlor Ethion Lindane Vtalathion Merhovychtor Pararhion Mirex PhoFare PCB>i Toxaphene ■Ti:ifli«»arm NOfE: Liwer detection liniif is fO MH/ks for all compounds cvcepi endo'iulfati. -^ MS/I^P; mcthoxythlor and eihion, 30 /it; kp; mirev., PCBs, iiixaphene. carbophenothion, and DEF, 50 estuaries sampled and the complete absence of PCBs. On the Atlantic coast, oysters from two adjacent New Jersey reefs, and owe reef on the Delaware side of upper Dteissware Baiy contained DDE. Average residue in the m ssOT^ks- was 3-3 ±. 15 ^g/kg. Oysters from reefs efoscr to the mouth of the estuary did not contain de- tectablie residues. As recently as 1972, every monthly ovsteir sanfvpte on the New Jersey side of the Bay con- tained ahout three times as much DDT as did samples collected in 1977, as well as residites of dieldrin and PCBs. The fauna in Delaware Bay were presumably contaminated by the hundreds of tons of DDT sprayed a«riallv between 1950 and 1966 to control New Jersey marsh mosquitoes (4). On the Pacific coast, bivalves in only one of the 14 estbwries monitored in California and Washington state Gonlained pesticide residues. Replicate samples of blue muss«ls from Muga Lagoon, about 35 miles north of Los Angeles, contained DDT and its metabolites, TDE and DDE, at the average level of 122 Mg/kg. A decade earlier, monthly samples of mussels from this station contained i:DDT residues of 500-1.800 Mg/kg. as well as traces of dieldrin and endrin. The reliability of these isolated data in documenting the virtual disappearance of pesticide pollution from estua- rine water is dependent on knowledge gained from the earlier program of the seasonal aspects of waterborne pesticide pollution. Monthly samples in that study showed that pesticide residues in intermittently polluted areas were typically present in the spring, and, if con- tinuously present, were usually larger in the spring, presumably the result of increased river runoff. The decline in pollution is emphasized by comparison of the present data with pesticide residue levels and in- cidence in bivalves from the same estuaries during the final 12 months of the earlier program (Table 2). This table shows the number of stations monitored in each state in 1977 but does not repeat the 1977 residue data. Since filter-feeding bivalves purge themselves of organic residues within a few weeks in the absence of continuing pollution (2), the 1977 data show essentially the dis- appearance of pesticides from the water mass. However, there is evidence that persistent pesticides have not disappeared entirely from most of these estuarine eco- systems. During 1972-76, yearling lish of several species were monitored in many of the same estuaries from which bivalves were collected in 1977 (i). Samples consisted of 25 whole fish captured twice yearly. In 1976, 68 samples or 36 percent of the 190 samples analyzed contained DDT residues at levels up to 2,500 Mg/kg; 22 percent of the samples also contained PCBs. TABLE 2. Summary of pesticiilc rcaidues in estuarine moUusks durinfi the final 12 montlis of the 1965-72 program in those estuaries re-monitored in 1977 % OF Arith. Other FiM*L i: No. OF No. OF Samples Mean of Residues Species $[*TP. Months Stations Samples WITH DDT DDT, MS/ kg Detected > Monitored - Alabama 1968-69 2 10 100 102 D 2 California 1971-72 14 68 96 81 D.E.P 1,3,4,7 Dclijware J968-69 5 58 74 44 D 2,4,5 Florida 1968-69 6 61 85 308 D 2 Gesre^a 1971-71 5 60 20 14 D,T,P 2 Maine 1969-70 5 36 14 29 — 6,8 Maryland 1969-70 A 11 64 25 D 2 MissrsAtppi 1971-72 .1 30 63 31 — 2 New Jersey 1971-72 .1 IS 100 74 D.P 2 New York 1971-72 6 67 88 40 D 2,5,7 North Carolina 1971-72 9 88 35 46 D 2 South Carolina 1968-69 7 83 37 24 D.M 2 Tc)ta» 1971-72 6 56 73 72 D.E.T.P 2 Virpinia 1971-72 6 24 96 36 D.P 2 Wathin^lon Male 1967-68 6 72 18 20 — 3 ' D=dieldrin, E — endrin. M = mire«. P = PCB,T=Ioxaphene. ' I. Cnrlticula manllensis, Asiatic clam; 2. Crassoslren viminica, eastern oyster; 3. C. gigas. Pacific oyster; 4, Geut_v fish (Gibius sp.) collected in four areas located in eastern coastal waters of the middle and north Adriatic Sea. Most samples were collected in early sprint; and lale summer of 1974 and 1975. The compounds p.p'-DDT, p.p'-DDE. p.p'-TDE, and PCBs were detected n)Ost frequently. In about 60 percent of the samples dieldrin was al.w detected. of chlorinated hydrocarbons in terrestrial, freshwater, and marine ecosystems (4, //, 19). The most delicate and endangered parts of world oceans are scmiclosed formations such as the Mediterranean Sea and the Adriatic Sea. The Adriatic Sea is shallow and small, and its northernmost extension, the Gulf of Trieste, lies virtually in the heart of Middle Europe; hence it is among the most jeopardized marine eco- systems in the world (18). Average wet-weif;ht concentrations of ^DDT and PCBs in mii.Ksels from the four areas sampled were: Istrian coast, 65 and 76 pph: Rijeka Bay. 5S and 75 pph: Zadar, 36 and I2S pph: l.osinj Island. 167 and 133 pph. Average concen- trations in fish sinnples were: Istrian coast, 124 and 144 pph; Rijeka Bay. 37 and S2 pph: l.osinj Island. 166 and 157 pph. Dieldrin concentrations were in the low pph range. Althongli major Italian rivers di.Kcharge chlorinated hydro- carhons into the north Adriatic, sampling of biota from Istrian coastal waters indicates no significant effect on the pollution level. llo»ever, waste waters from small coastal settlements evidently do contribute significantly to chlori- nated hydrocarbon contamination of that ocean. Marine samples from l.osinj Island had high chlorinated hydrocarhrt(;d in purl by Sclf-Maiui^-umcnt Coninmniiy ,p'-TDE, and dieldrin. A Hewlett-Packard 7620 model gas chromatograph (GC) equipped with "^jvij electron-capture detector was used. Operating parameters for GC analysis were; Columns: Tc-tnpcralurcs: Carrier gas: Flow rale: (A) 1.8-m-by-4-mni glass packed with 1.5 per- cent SP-225() + 1.95 percent SP-2401 on 100/120 mesh Supelcon AW-DMCS (B) I.5-tn-by-4-mm glass packed with 4 per- cent SE-.TO + 6 percent OV-210 on 100/120 mesh Gas-Chrom Q Injector 240°C Column 210°C Detector 250°C 5 percent methane in argon .^0 ml/ minute Organochlorine compounds were quantitated by compar- ing peak areas in sample and standard chromatograms. PCBs were determined by using a standard solution of Aroclor 1254. Experiments comparing aldrin and mirex as internal standards showed mirex to be superior. Mirex was used as an internal standard throughout the analyses because it is rather easily separttted from PCBs on a GC column. Its loss was used as a measure of recovery in this study; in fact, recovery of chlorinated hydrocarbons varied between 68 and 87 percent. For the confirmatory test samples with higher contents of DDT were hydrolyzed by KOH (10). Sensitivity of DDT and its metabolites is 1 ppb wet weight and for PCBs it is 10 ppb. In some samples low concenlralions of dieldrin were fotiiul hut the data are not reported in this paper. The niethot.1 of organochlorine determination was inter- calibrated within the International Intercalibration Pro- gram on Chlorinated Hydrocarbons in Marine Materials funded by the United Nations Environmental Program (UNEP). Results obtained in the Centre for Marine Research were relatively close to the mean values after excluding disproportionately high residues according to criteria of Chauvenet (5, 14). Results and Discussion Concentrations of chlorinated hydrocarbons in mussels and fish from coastal waters of the eastern Adriatic are presented in Table 1. Distribution frequencies of -DDT and PCBs in mussel" and fish samples are presented in Figure 2. The level of organochlorine concentrations varied widely, which is not unreasonable considering the unusual pollution pattern and hydrography of the Adriatic Sea and the complexity of the biotic samples analyzed. Figures 3 and 4 present arithmetic means and ranges of DDT and its metabolites, dieldrin, and PCBs in mussels, goby fishes, and several species of benthic fishes. Although 14 species of benthic fishes were analyzed in the present investigation, results are pre- sented only for those species which had three or more valid samples analyzed. Except for gobies, fish species are presented by decreasing order of summed pesticide and PCB concentrations. Comparing these two de- creasing orders shows that the position of fish species differs according to whether the concentrations of pollut- ants are presented as wet weight or as extracted organic matter. But both figures indicate that fish species living in similar environments and eating similar food have similar concentrations of pollutants. Most specimens of goby fishes were caught in highly polkited coastal waters, especially semiclosed harbors polluted with industrial and domestic wastes, but con- centrations of chlorinated hydrocarbons in these fishes are not significantly higher than in other commercial fishes such as mullet, annular gilthead, and black tail sea bream. However, these differences become signifi- cant when concentrations of pollutants are compared as extracted organic matter (Figure 4). Stations for monitoring chlorinated hydrocarbon pollu- lioii of eastern coastal waters of the north and the middle Adriatic Sea are located in four dilfercnt areas. The Istrian coastal area belongs to the northern region o( the Adriatic Sea; Rijeka, Zadar, and Losinj areas be- long to the so-called Region of Islands (IS). The northern region of the Adriatic is predominantly alfected by river waters from northern Italy which create the most severe pollution problem in the whole Adriatic. Intensive urban, tourist, agricullural. and industrial de- velopment in both coastal areas contributes to the prob- lem. 1 he Region of Islands inekides water surrounding nearly 1000 islands along the eastern Adriatic coast and scmiseparated waters between islands and main- 104 PnsTiciDr.s Monitoring Journal TABLE 1. Chlorinated hydiocwboii concentrations in fish and mussels of east coastal waters of middle and north Adriatic Sea, 1974-75 Sampling p.p-DDT P.p' -DDE P-P' ■TDE DlELDRlN PCBs Station EOM. wet EOM, WET EOM. WET EOM. WET EOM. WET EOM, No. Species' Date r^ WEIGHT PPM WEIGHT PPM WEIGHT PPM WEIGHT PPM WEIGHT PPM ISTRIAN COAST 1 M.G. March 1974 1.63 ND ND ND ND ND ND ND ND ND ND 1 M.G. March 1974 1.25 ND ND ND ND ND ND ND ND ND ND 2 M.G. March 1974 2.79 ND ND 8 1.40 ND ND ND ND 2 M.G. Sept. 1974 0.71 29 4.10 21 3.00 26 3.60 ND NO 85 11.97 2 M.G. Sepl. 1974 n.37 13 3.50 13 3.40 14 3.80 1 0.32 34 9.20 2 M.G. March 1974 2.94 ND ND ND ND ND ND ND ND ND ND 2 G. Sepl. 1974 (1.84 16 1.90 15 1.80 13 1.60 2 0.24 ND ND 3 M.G. March 1974 1.16 23 1.94 18 1.51 10 1.81 3 0.26 ND ND 3 M.G. March 1974 2.53 41 1.65 15 0.60 13 0.53 25 0.98 3 M.G. March 1974 8.03 45 0.56 39 0.48 17 0.21 115 1.43 3 M.G. Sepl. 1974 0.62 15 2.41 19 3.05 20 3.22 4 0.58 ND ND 3 M.G. Sept. 1974 0.62 34 5,48 29 4.68 38 5.13 9 1,45 168 27.10 3 M.G. Sept. 1974 1,37 27 1.93 49 3.28 28 2.12 4 0,25 85 6.20 4 M.G. Oct. 1972 3.79 105 2.78 30 0.80 53 1.40 367 9.68 4 M.G. March 1973 1.52 35 2.30 65 4.30 44 2.90 256 16.80 5 M G. Oct. 1972 2.26 ND ND 1 0.05 ND ND 4 0.16 5 M.G. March 1973 1.22 ND ND ND ND ND ND ND ND 5 M.G. Oct. 1975 0.41 2 0.44 1 0.16 1 0.16 ND ND ND ND D.A. Sept. 1974 4.05 130 3.21 80 1.98 40 0.99 13 0,31 195 4.80 O.M. Sept. 1974 1.30 45 3.53 27 2.07 29 2 22 4 0.34 45 3.50 B.B. Sept. 1974 2.75 133 4.85 43 1.87 30 1.09 — — 422 15.35 P.E. Sept. 1974 0.91 9 0.99 14 1.54 5 0.48 1 0.12 45 4.90 M.A. Oct. 1973 1.57 24 1.5 29 1.84 !5 0.95 ND ND ND ND O.M. Sept. 1974 2.76 60 2.17 35 1.30 18 0.65 4 0.15 80 2.90 P.E. Sept. 1974 2.59 4 0,15 16 0.62 13 0.50 ■) 0.08 ND ND M.B. Sepl. 1974 2.64 30 1.13 20 0.76 14 0.53 6 0.24 ND ND M.A. Sept. 1974 3.67 64 1.95 48 1.31 76 2.07 15 0.40 520 14.20 RIJEKA AREA 1 M.G. March 1974 0.52 ND ND ND ND ND ND — — ND ND 1 M.G. March 1974 0.80 15 1.85 7 0.87 ND ND — — 8 0.94 1 M.G. Sept. 1974 0.68 5 0.74 4 0.53 4 0.53 ND ND 11 1.60 1 M.G. Sept. 1974 1.25 12 0.95 5 0.40 13 1.02 ND ND 192 14.20 1 G. Sept. 1974 0,89 X 0.84 9 0.96 3 0.35 1 0.07 27 3.10 1 M.G. March 1974 2,20 131 6,05 49 2.22 32 1.45 ND ND 23 1.03 2 M.G. March 1974 0.74 7 1.25 5 0.65 10 1.28 0.3 0.09 ND ND 2 M.G. March 1974 1.20 83 6.90 21 1.77 10 0.79 ND ND 75 6.20 2 M.G. March 1974 1 .05 28 2.52 9 0.90 7 0.65 ND ND 8 0.84 2 M.G. March 1974 1.35 15 1.10 8 0.51 7 0.54 — — 9 0.65 2 M.G. March 1974 1.20 63 5.20 28 2.30 38 3.15 — — 128 9.80 2 M.G. Sept. 1974 0.74 8 1.02 4 0.47 12 1.57 ND ND 168 22.50 2 M.G. Sept. 1974 0.82 7 0.85 2 0.25 8 1.02 ND ND 75 9.10 2 M.G. Sept. 1974 0.63 23 3.65 4 0.55 22 3.42 ND ND 83 13.20 -) M.G. Sept. 1974 0.56 42 7.50 5 0.80 48 8.60 ND ND 77 13.70 -t M.G, Sept. 1974 0.58 22 3.80 8 1.29 35 6.20 ND ND 164 28.20 3 M.G. March 1974 1.70 23 1.32 5 0.28 11 0.54 3 0.18 63 3.70 3 M.G. Sept. 1974 0.56 13 2.20 6 1.03 9 1.60 2 0.29 64 11.40 3 G. Sept. 1974 1.06 8 0.72 5 0.43 9 0.85 1 0.12 168 15.90 4 M.G. March 1973 1.10 49 4.50 17 1.54 6 0.52 — — 234 21.40 4 M.G. Oct. 1975 0.24 ■> 0.79 1 0.42 1 0.59 ND ND 26 10.60 5 G. Oct. 1975 3.29 49 1.48 86 2.60 14 0.44 ND ND 159 4.90 D.A. Sept. 1974 2.03 4 0.17 2 0.10 2 0.10 1 0.05 15 0.76 M.A. Oct. 1975 4.15 35 0.85 32 0.78 28 0.67 8 0.20 355 8.60 B.B. Oct. 1975 14.13 30 0.21 29 0.20 10 0.07 10 0.07 174 1.20 M.B. Sept. 1974 1.95 ND ND 9 0.46 10 0.52 ND ND 115 5.85 P.E. Sept. 1974 0.53 4 0.72 6 1.10 1 0.15 — — 4 0.71 M.Mer. Sept. 1974 0.32 14 4.40 14 4.40 2 0.77 — — 8 2.35 M.Mer. Oct. 1975 1.75 20 1.11 8 0.47 8 0.47 ND ND 98 5.57 G.M. Oct. 1975 0.92 ND ND ND ND ND ND ND ND 25 2.70 MB. Oct. 1975 2.52 ND ND ND ND ND ND ND ND 53 2.08 P.D. Sept. 1974 1.20 11 0.92 22 1.84 5 0.35 1 0.13 28 2.30 L.C. Sept. 1974 0.66 12 1.82 19 2.80 7 1.14 2 0.24 20 3.00 ZADAR AREA 1 M.G. March 1974 3.20 14 0.42 9 0.28 ND ND — — ND ND 1 MG. March 1974 2.60 17 0.64 9 0.33 ND ND — — ND ND 1 M.Ci. Sept. 1974 0.93 13 0.13 1 0.07 19 2.04 1 0.07 ND ND 1 M.G. Sept. 1974 0.87 33 3.80 3 0.32 ND ND 2 0.26 80 9.20 1 G. March 1974 1.69 ND ND ND ND ND ND — — ND ND 1 G. Sept. 1974 1.17 8 0.68 6 0.51 7 0.60 -> 0.14 ND ND 2 M.G. March 1974 1.10 7 0.59 7 0.59 ND ND — — ND ND 2 M.G. March 1974 1.40 n 0.81 4 0.28 5 0.43 ND ND ND ND 2 M.G. March 1974 1.70 63 3.70 28 1.52 11 0.62 — — 200 11.60 2 M.G. March 1974 1.76 37 2.25 14 0.78 23 1.32 ND ND 345 19.50 2 M.G. March 1974 1.07 33 3.10 10 0.97 20 1.87 4 0.37 390 36.50 {Continued next page) Vol. 12, No. 3, December 1978 105 TABLE 1 (cont'd.). Chloriiwreil hydiocurhon coiiceiiliiitions in fish unci ntnssels of east coastal waters of middle and north Adriatic Sea, 1974-75 Station No. Species' M.C. M.G. M.G. M.G. M.G. G. G. M.G. M.G. M.G. M.G. M.G. M.G. M.G. G. G. O. M.G. M.G. M.G. M.G. M.G. G. G. M.A. D.A. D.A. O.M. O.M. B.B. M.B. P.E. B.S. B.S. S.S. M.Ma. Sampling Date Sepl. Sept. Sept. Sept. Sept. 1974 1974 1974 1974 1974 March 1974 Sept. 1974 March March March Sept. Sept. Sept. Oct. March March Sept. March March .Sept. Sept. Oct. March Sept. Oct. Sepl. Oct. Sepl. Oct. Sept. Oct. Ocl. Sept. Oct. Oct. Oct. 1974 1974 1974 1974 1974 1974 1975 1974 1974 1974 1974 1974 1974 1974 1975 1974 1974 1975 1974 1975 1974 1975 1974 1975 1975 1974 1975 1975 1975 EOM. 0.49 0.72 071 1.66 (1.76 0.70 1.60 1.58 1.60 1,60 0.78 0.73 0.57 0.84 1.41 1.30 0.73 1.40 2.20 1.13 1.20 0.52 1.60 1.48 9.41 15.40 1.57 3.11 1.65 2.00 8.61 0.6(1 1.68 2.00 3.78 1.31 p.p'-DDT p.p'-DDE p.p'-TDE WET weight 5 6 18 7 6 43 17 375 46 138 8 25 8 33 «(l 78 44 119 128 27 13 30 94 17 172 215 7 82 25 43 42 17 8 ND 15 90 EOM, PPM WET WEIGHT EOM. PPM 1.02 0.76 2.55 0.42 0.79 6.07 1.06 LOSINJ 23.80 2.90 8.60 0.98 3.42 1.32 3.86 6,4(1 6.00 6.(14 8,50 5,80 2.38 1.08 5.80 5.61 1.15 1.83 1.39 0.44 3.65 1.50 2.12 0.49 0.88 0.65 ND 0,36 6.90 2 4 18 6 7 113 14 0.45 0.50 2.55 0.34 0,92 16,07 0.85 ISLAND 25 61 5 7 5 16 45 30 68 44 39 27 9 24 20 59 107 158 3 70 15 38 85 16 7 ND 21 62 5.50 1.56 3.85 0.50 0.95 0.79 1.88 3.20 2.30 9.32 3.13 1.76 2.38 0.71 4.62 1.20 3.95 1.14 1.03 0.18 2.25 0.91 1.87 0.99 2.63 0.39 ND 0.50 4.75 WET W1;I0H1 3 5 24 14 7 68 2 134 44 75 8 46 22 33 98 83 870 38 41 159 78 27 19 250 130 120 1 50 10 14 37 6 8 ND ND 30 EOM. PPM 0.65 0.69 3.38 0.80 0,92 9.64 0.10 8,50 2.70 4.70 0.98 6.30 3.80 3.86 6.91 6.40 119.00 2.73 1.85 14.10 6,50 5.20 1.13 17.00 1.38 0.78 0.07 1.60 0.61 0.69 0.43 1.00 0.45 ND ND 2.30 DlELDRlN PCBs WET WEIGHT EOM. PPM ND ND 1 1 ND 2 3 ND ND ND ND ND 4 3 ND ND ND ND ND 13 1 7 ND 5 ND 5 ND 4 ND ND 0.20 0,07 ND 0.29 0.16 0.43 ND ND ND ND ND 0.31 0.40 ND ND ND ND ND 0.08 0.07 0.22 ND 0.06 ND 0.27 ND 0,1(1 0,13 WET EOM. WEIGHT PPM II 36 326 336 36 148 11 200 138 ND 120 222 157 94 ND 43 152 ND 112 130 202 220 724 112 295 360 14 624 90 151 128 54 ND ND 102 40 2.30 5 00 46.00 22.20 4.80 21.10 0.68 12.70 8.60 ND 15.40 .30.40 27.50 1 1 .20 ND 3.30 20.80 ND 5.40 11.30 16.90 42.30 45.10 7.60 3.12 2.34 0.86 20.00 5.50 7.50 1.50 9.00 ND ND 2.40 3.05 = Ciihlus (several Note- ND = not detectable; — = not measured; EOM = extracted organic matter. , •Names of species in Latin. English, and Croatoserbian; M.G. = Mytllm K„IU>rr„nnch,li>>. Mediterranean mussel, Dagnia;0. species). Goby. Glavoc; D.A. = Dipl.ulm ann„lans L., Annular Billhead, Spar; O.M. -- OI,h.l., melanma L, Saddled hre,,m Usat,, B_B L.ps h„„nst.. Bo.ue. Bukva; P.E, -- r.,..lU,. cryllninu. L„ Pandora, Rumcnac; M.A, =- Mu.il .unans nssu Oo\dcn f--'>' •^"»^'- S*-°^t^ zlalac; M.B. .. M„Ls hurhan.s. Red mullet. Barhun: MMer. .. MvrUun,. nurlucm L.. Hake, Osl.c; CM. = Gc,d„s ,m-rla„m L.. Whil ng. Mol- L.C. ^ Lcp,J,„mla..,,lc,„e Lae.. unknown. Cucn, B.S. -. fl»-vv ,sc,;,.« 1... Saupe, Salpa; S.S. = Scnm,„s scnlm L.. Panned comber, Pirka. M.Ma. .= Muena maem, L., Caockarel, Modrak; T.D. =- Tracluims Jraca L.. Greater weever. Pauk bijelac. laniJ. Sparsely populated karstic islands and mountains, with modest agriculture and almost no industry, con- stitute the hinterland of these waters. But also in this region are several pollution nuclei: the Bay of Rijeka and nearby towns of Bakar. Zadar, and Sibcnik; the Bay of Kastela and the neighboring town of Split. Chlorinated hydrocarbon pollutants of marine environ- ments can originate from such land-based sources as direct industrial discharges, sewage, and rubbish. But indirect discharges of these pollutants, especially as agri- cultural runoff of pesticides and farm wastes into rivers, also contribute signiticanlly to their concentration in marine environments (4. 7. 16). These direct and in- direct discharges are the most common sources of local pollution. Air is an important secondary source of chlorinated hydrocarbon pollution (/); wet and dry lalloul contributes to the regional or even global pollu- tion of the marine environment. Concentrations of i:DDT, dieldrin, and PCBs in mussels, goby lishes, and other benthic fishes according to their sampling areas are presented in Figures 5-7. Stationary species of mussels and goby fishes, which are indicators of local pollution, were often sampled near the source of waste discharges. Other benthic fishes indicate broader areas of pollution. Data in the figures show differences in arithmetic means of residues in mussels, goby fishes, and benthic fishes between the areas inves- tigated. Since concentrations vary considerably, -DDT and PCB residues in mussels and benthic fishes were analyzed in order to find whether arithmetic means diller significantly among the areas investigated (Table 2). Mussels from the Losinj area had significantly higher concentrations of i:DDT than had those from any other area investigated. Significantly higher PCB concentrations were found in the l.osinj area than along the Istrian coast and Bay of Rijeka, but PCB residues were lower than were DDT concentrations. In fish 106 Pesticides Monitoring Journal 2i 22 20 181- 16 LU 12 a 10 UJ d: b LL. 6 2 0 12' U 10 LU 8 3 C3 6 LU a: t. LL 2 MUSSEL I 1 IDDT V77A PCB 34d Iz IJT} k ^ m , M^^T] . n , -H M I I '/| ^^^ i-^i M i^^ K. r/) K^ v^ i:\ i , ^ , K/^ i^^ ^^ r^ // I , ^ 20 iO 60 80 100 m UO 160 180 200 220 240 260 280 300 320 340 360 380 400 4^0 550 650 FISH PT^ ^ ^ 41^ -P- -m- V/^ (TT^^ 100 120 140 160 180 200 220 240 260 280 300 320 340 360 400 500 600 700 CONCENTRATIONS, ppb wet weight FIGURE 2, Distrihiilioii frcquciKtes of ZDDT and PCBs in nui.sseh and fish from cost coastal waters of middle and north Adriatic Sea samples, the only concentrations that differed signifi- cantly by area were -DDT concentrations in samples from Rijeka Bay versus those from the Losinj area and in samples from the Istrian coast versus those from the Rijeka area. PCB concentrations did not differ sig- nificantly. Table 3 shows significant differences in arithmetic means of i:DDT and PCB concentrations in fish and mussel samples from the same area. No major difference between -DDT and PCB concentrations is indicated in mussels and benthic fishes from the same area. Sig- nificant difference appears only in -DDT concentrations in fish from the Istrian coastal area. The ratio of PCB and pesticide concentrations fre- quently is used for identifying chlorinated hydrocarbon pollution of marine areas. If this ratio is higher than 1, the source of pollution is more likely industrial than agricultural. The ratios of PCB and -DDT concentra- tions in samples investigated during the present moni- toring program are given in Figure 8. Only in the Rijeka area is this ratio significantly higher than 1 for all the indicator organisms investigated. To determine main sources of chlorinated hydrocarbon pollution in eastern Adriatic coastal waters, correlation between ^DDT and PCB concentrations in mussel and fish samples was investigated (Figure 9). Statistical results of the analysis are presented in Table 4 as Pearson's correlation coefficients. Significant correlation between concentrations of -DDT and PCBs existed only in mussels from the Istrian coastal area and fish from the Rijeka area. This suggests two possibilities: ditTercnt sources of DDT and PCB residues in the areas investigated, or different uptake and loss pathways of -DDT and PCBs for mussels and fish. Several papers have been published on investigations of chlorinated hydrocarbons in Adriatic biota and sedi- VoL. 12, No. 3, December 1978 107 10' « i i a to z o < z bJ u z o u :io o X o ~nx ° Xx Q 0. a M G. MA D.A 0 M B B SPECIES SAMPLED (See Table I footnote.) MB PE. FIGURE 3. Coitccntriilions (wel weiglil) of ':i:DDT. dichlrin, and PCBs in niii\sels and fish from east coastal waters of middle and north Adriatic Sea a E o I' O O oo. a 10 E Ol a. V) z o < o o 1 - UJ O z o o 01 £ M G IS ^ o X 0 M SB MA SPECIES SAMPLED (See Table I footnote.) DA, PE MB. MCillRF -4. Concenlrutions (extracted i>ri;anic matter) of ZDDT. dieldrin. and l'( lis in masscls and fish from east coastal waters of middle and north Adriatic Sen 108 Pesticides Monitoring Journal 10^ '« Q. lo- co 10 UJ U z o u I- Q- o WW EOM ISTRA Q U 1-1- 7 WW E OM RIJEKA y o o B: EH WW E.OM ZADAR W W'E OM. LOSINJ 10' to 10 y < I- z UJ u o E o 'c (7 O O ' U 4) E a. Q. 0.1 FIGURE 5. Comparison of "ZDDT. diclclriii. and PCB concentrations in mussels from cast coastal n'aters of middle and north Adriatic Sea FIGURE 6. 10' •lO' Ji a. a Z o Q O in o 0. x-J ;io < ui U z o o m o a. Q _j UJ a a: Q Q X X JZL I- m o u o a. Q Q OQ §s a o 10' 10 (A Z o I- < o E u 'c a tt) Ld a z t; o * lO E Ql Q. 01 W W I E O.M W.wIe.O.M. W.wI E O.M WW E O.M ISTRA RIJEKA ZADAR LOSINJ Comparison of '^DDT. dieldrin, and PCB concentrations in .i;ohy fishes from cast coastal waters of middle and north Adriatic Sea Vol. 12, No. 3, December 1978 109 . i 10^- f- »- .0- mo Q. u y^ . a. 0) c 2 ^ 1- CO ^ ^ J m ►- 1 o •- a. i^ 1— 1 »— Q Q 1 t— Q O 7 1 qCD 7 X D 3 Q. f— Ol g X 7 7 » Z y 7 — m» to q: y y r z o z 3 o UJ n JJ < Q Z UJ Q D en 10 - q: — •7 1— z ^ o UJ z Q — Q UJ Q -J 7 _) L) X UJ Q UJ Q z 7 o u X I 1 \N.\ /v. E c .M ^^ V V. E .0 M WW lE.QM ISTRA RIJEKA LOSINJ V o • F CO 10 2 o O c n h- m < u cc o 1- z -T3 UJ () u O 1 z O X U tt E o. a FIGURE 7. Compornon of -DDT, (/icUliiii, and I'CB concentrations in hvnihic fishes from east coastal waters of niithllc and north Adriatic Sea TABLE 2. Results of Student's t-test for :iDDT and PCB concentrations in mussels and fish from same areas of middle and north Adriatic Sea, 1974-75 SlGNIHt ANI DtFKtRENCn OF Arithmi tic Means 2 DDT PCBs CUMPARFI) ARKAS Mussels Fishes Mussels Fishes Islrian coasi— Rijcka None 0.01 None None Islrian coasi — Zudar (1.1 NC None NC Islrian coast — Losinj Isl ind 0.1 None 0.1 None Rijcka — Zadar 0.1 NC 0.1 NC Rijcka— Losinj Island 0.01 0.05 0.1 None Zudar — Losinj Island 0.01 NC None NC Noie; NC = nol calculated. TABLE y. Rcsidls of Student's t-test for i;/)D 7 and PCB concentrations in mussels and fish from same areas of middle and north Adriatic Sea, 1974-75 SlGNIFICANl DtFFFRENtl OF ARI1HME1IC Means ARE* i;Di)T I'CBs Islrian coasl Rijeka Losinj Island n.o5 None None None None None merits (.?. /5, / ^ SMjIfiKA AS'tA « i s * IK- Hi o 131 W* I ^ jU. W ,.)L^ rfflil PC©i(pipwi| ^J ZAOAS Agf A C a. 11^ fi5 ll ,(,,gt wiim mm ^1 >>)K iL 9 « «> » \ ;< 95! L fCBipipmi m (^ tiMdie mid tu^th Adfi, 3, I>&cBMi8e«; %^% jy TABLE 4. Pearson's coefficient of concldlion lu'twccn -DDT and PCS concentrations in mussels and fisli from coastal waters of middle and north Adriatic Sea. 1974-75 Area Mussels Fish Istrian coast Rijeka Zadar Losinj Island 0.927 0.205 0.712 -0.069 0.740 0.815 NC 0.578 Note: NC^not calculated. possibly because the first station waters had been con- taminated with waste waters and the second station had not. Evidently urban waste waters even from small settlements contribute significantly to the contamination of Adriatic coastal waters bv chlorinated hydrocarbon pollutants. LITERATURE CITED (/) Bidleinan. T. P.. and C. E. Ohiey. 1974. Chlorinated hydrocarbons in the Sargasso Sea atmosphere and surface water. Science 1S3(4I24): 516-518. (2) Cope. O. B. 1971. Interactions between pesticides and wildlife. Ann. R. Ent. 61(3 ) :325-332. ( .' ) Crisetif,'. (!.. P. Cortcsi. and E. Carpene. 1973. Resi- dties of chlorinated pesticides and polyehlorinated biphenyls in gonads of Adriatic clupei form fishes. La Niiova Vet. 46(3 ): 144-149. (4) Elder. D. t97f>. PCB's in N.W. Mediterranean coastal waters. Mar. Polkit. Bull. 7(2):63-64. (5) Elder. D. 1976. Inlercalibralion of organochlorine compound measurements in marine environmental samples. Progress report No. I, pp. 1-25. (6) Goldlwri,'. E. D. 1976. Health of the oceans. Pages 168-169 in The Health of the Oceans. The Unesco Press, Paris. (7) Hansen. D. J., and A. J. Wilson. Jr. 1970. Significance of DDT residues from the esluary near Pensacola, Fla. Pestic. Monit. J. 4l2):51-56. (8) Hayes, W. ]., Jr. 1969. Pesticides and human toxicity. Ann. N.Y. Acad. Sci. 16()( 1 ) :4(K54. (9) Holdeti. A. v.. and K. Marsden. 1969. Single-stage clean-up of animal tissue extracts for organochlorine residue analysis. J. Chromatogr. 40(1 ) :48 1-492. Ud) Jensen. .V., /.. Reidteri;. and R. Vaz. 1975. Methods for analysis of DDT and PCB in environmental samples using chromatographic methods. FAO Fisht Tech. Pap. 137:229-236. (//) hUinson. T. O. 1972. Chlorinated hydrocarbon resi- dues in marine animals of Southern California. Bull. Environ. Contam. Toxicol. 7(4) ;223-228. (12) Peakall. D. B., and J. L. Lincer. 1970. Polyehlorinated biphenyls, another long-life widespread chemical in the environment. Bio Science 20( 17 ) :958-964. (li) Picer, A/., and M. Ahel. 1978. Separation of PCB's from DDT and its analogues on a miniature silica gel column. J. Chromatogr. 150( I) : 1 19-127. (14) Picer. N.. M. Picer, and M. Aliel. 1976. Discussion of international intercalibration results of organochlorine compound measurements in marine environmental samples. Proc. Second Yugoslav Symposium Standard- ization. October 1976, G2, pp. 1-9. (15) Revclante, N.. and M. Gilmartin. 1975. DDT, related compounds, and PCB in tissues of 19 species of Northern Adriatic commercial fishes. Invest. Pesq. 39(2):491-507. (16) Schmidt, T. T.. R. W. Risehrough. and F. Cress. 1971. Input of polyehlorinated biphenyls into California coastal waters from urban sewage outfalls. Bull. Environ. Contam. Toxicol. 6(4):235-242. (17) Snyder. D. E.. and R. E. Reinert. 1971. Rapid separa- tion of polyehlorinated biphenyls from DDT and its analogues on silica gel. Bull. Environ. Contam. Toxi- col. 6(5):385-390. (18) Slim, J., A. Avein. J. C encelj, M. Dorer, S. Comiscck, S. Kveder, A. Malej, D. Meischner. I. Nozina. J. Paid, and P. Tusnik. 1974. Pollution problems of the Adri- atic Sea, an interdisciplinary approach. Rev. Int. Oceanogr. Med. 35-36:21-77. (19) Ten Berge.W. F.. and M. Hillehrand. 1974. Organo- chorine compounds in several marine organisms from the North Sea and Dutch Wadden Sea. Neth. J. Sea Res. S(4):36I-368. (20) Viviani. R.. C. Crisetif. V. Pelmzzi. and P. Cortcsi. 1973. Residues of chlorinated pesticides and poly- ehlorinated biphenyls in Adriatic clupei form fishes. Coll. Int. Oceanogr. Med. Messina 5:607-621. (21 I I'iviani. R.. G. Crisetig. P. Cortcsi. and E. Carpene. 1974. Residues of polyehlorinated biphenyls and chlorinated pesticides in fishes and birds of the Po Estuary. Rev. Int. Oceanogr. Med. 35-36:79-89. (22) Woodwcl. G. M.. P. P. CraiK, and H. A. John.son. 1971. DDT in the biosphere: where does it go? Science 174(40141:1101-1107. 112 Pesticioes Monitoring Journal Organochlorine Residues and Reproduction in the Little Brown Bat, Laurel, Maryland — June 1976 Donald R. Clark, Jr., and Alex Krynitsky^ ABSTRACT Twelve of 43 pregnant Utile brown hats (Myotis lucifugus) collected at Montpelier Barn. Laurel. Maryland, gave birth to dead young. Eleven of tliese 12 dead neonates were ab- normally snuill. Most of the stillbirths were attributable to unknown reproductive difficulties associated with first preg- nancies, but four may have been due to high concentrations of polychlorinated biphenyls (PCB) in the newborn. Residues of the PCB. DDE. and oxyclilordane crossed the placenta at similar rates. Moore, Inc., Fort Washington, Pennsylvania) and the occlusal tip width of the upper canine (canine tip width, CTW) was measured with an ocular micrometer in a 30 X dissecting microscope. This measurement is an indicator of relative age (/). Pregnant bats were fed mealworms, larvae of the beetle Tenehrio molitor. samples of which had been found free of organochlorine residues. Introduction A study of wild-caught, pregnant big brown bats {Eptesicus fiiscus) suggested that Aroclor 1260. a poly- chlorinated biphenyl (PCB), caused young to be still- born (3). However, experimental elevation of Aroclor 1260 levels produced no additional stillbirths (2). The results indicated only that both stillbirths and high levels of Aroclor 1260 were characteristic of young adult female big brown bats. The present study was undertaken after dead neonate little brown bats (Myotis lucifugus) were observed at Laurel, Maryland, roosts. Authors wished to determine whether high organochlorine residues are associated with stillbirths of little brown bats and, if so, whether this association resembles that found in big brown bats. Materials and Methods On June 3, 1976, 45 pregnant little brown bats were collected in Montpelier Barn at the Montpelier Mansion State Historical Site, Laurel, Prince Georges County, Maryland. Bats were confined individually at Patuxent Wildlife Research Center in stainless steel wire mesh cages, 18 cm X 22 cm X 37 cm, equipped with rodent watering bottles. Laboratory temperature averaged 28. 2X. Subdued sunlight entered two draped windows. Before being caged, the bats were anesthetized indi- vidually with the inhalant anesthetic Metofane (Pittman- • Fish and Wildlife Service. U.S. Department of the Interior. Patuxent Wildlife Research Center, Laurel, MD 20811. Parturition began June 3, and the last young was born June 13. All pregnancies prodticed single young. After parturition, each female and her young were killed by freezing. Two females never gave birth: one died of unknown causes June 8, and the other was frozen June 8 because she apparently was not pregnant although a small embryo (0.564 g) was found during dissection. ANALYTICAL PROCEDURES Adults were prepared for analysis as carcasses; young were analyzed whole, except for removal of the gastro- intestinal tract, according to procedures described pre- viously (2). Gastrointestinal tracts were left in several small fetuses (0.9 g or less) where removal would have been diflicult. Samples were ground with anhydrous sodium sulfate. The dried mixture was extracted with hexane in a paper extraction thimble on a Soxhiet extractor for about 7 hours. The extract was cleaned by Florisil column chromatography, and the cluate containing the pesticides and PCB was fractionated by Silicar column chroma- tography (5). The fractions were analyzed with a Hewlett-Packard Model 5753 gas-liquid chromatograph equipped with a '"'Ni detector, automatic sampler, and computing integrator. Instrument parameters and oper- ating conditions follow: Column: glass. 1.83 m. packed with a mixture of 1.5 per- cent OV-17 and 1.95 percent QF-1 Temperatures: column aOCC. detector 300»C. injection port 250°C Carrier gas: 5 percent methane in argon flowing at 60 ml/ minute; purge flow, 40 ml/minute Vol. 12, No. 3, December 1978 113 ^ete anafyztfcf Hot p. (/-DDE, p-y-TDE, />.//- DDT., rfiefiirin;. endrin, fteptiielivteT efxn-ide. mirex, oxy- sIlfcTctene, r(A'-chl(ird.ii>e. tram^nonnch\0f, ch-nonacMor, hevvKhfiorobenrzenc (HCB), to^'xaphcne, asnd PCB*, The PTB that Was peeovercd re^«fflfbfcd Arocfor \2fiO in alt C<»S€S. Resewsife'* from spiked maHard dwck (Anm platyrhyii- e/jwvV Jisswss rafiged from* 80 W \04 percetif. R«»«due dat» «rers not adjiPited on the ha*i» of these rccovcTies. The foweT liftwf of sensitivity was 0, { ppm. Residues in f© peteeTrt »{ the sample* were confirmed on an LKB Model 9000 g»s-liqi«id chromatograph-mass spcclrom- eiet G»peTated as descfibed previously (-^>. Samples for onw a*{tri{ antf fwe yoimg were tost during analysis. Kescrfts are given as ppm wet weight. GewnTetriHs msaffis- are given for ^esid^^es because the daf thart the smallest liveborn bat (1.072 g). T>te twelfth dead neonate weighed 1.541 g, Si.\ of the 12 dead young were partly eaten by their mothers: one 5 32 ' < r & , O" z 1 -b1« m 0 • hve born ysun; • stillbor n young O^^il/born young. 0 6 12 18 24 PCB ppm *»t w«,ghi + 0.1 IN NEWBORN BAT FIGURE 1. Helaiionship of weight as a percent of tiiliill female Hcivhl to Aroclor 1260 concentration amonii 41 neonatal little hrown hats (Sample includes all neonates except two whose extracts were lost during chemical analysis, ) young was missing its wing tips; a second, one wing and one foot; and a third, both wings and both feet. Only the head and the vertebral column of the fourth re- mained, and only heads remained of the other two. Total weights of the six young were estimated from the remaining portions. Estimations for the latter three young were based on a head-length-to-body-weight re- lationship derived from the undersized dead young that were recovered intact. The incompleteness of these six specimens probably did not seriously bias the results of the chemical analyses 'except perhaps for the latter three, which may actually have contained higher con- centrations of chemicals than were estimated because most of the young bats' fat. and. therefore, residues, was in the body portions eaten by the mother. Never- theless, residues of the PCB for these three bats (6.1, 12. and 25 ppm) exceeded the mean (Table 1) and in- cluded the maximum. Wimsatt (6) observed several times that a majority of a group of females of Myotis liicifugiis in advanced preg- nancy aborted their fetuses, usually stillborn, within a few hours of removal from a colony. He attributed this result to handling or confinement. In the present study, dead young tended to be more common among later births, but beyond this tendency there was no clear pattern. When all 43 births were divided into four groups of 11. 11. 11, and 1 0 according to chronological order, the incidences of dead young were 9.1, 18.2, 54.5. and 30,0 percent, respectively. So. the possible roles of handling and confinement in stillbirths were not clarified by the present study. TABLE 1. Principal or^anochlorinc residues in adult female Utile brown hats and llieir younf;, Laurel, Aiaryland — Jane 1976 Residues. PPM Wet Weight Adults Young Chemical (n = 44) (" = 43) PCB (Aroclor 1260) Geomelric mean 11.38 4.16' 95 ri CI 9.68-13.38 3,08-5,61 Range 3.6-24 ND-25 DDE Geometric mean 1.65 0,50 = 95% CI 1,50-1.82 0,36-0,69 Range 0.72-3.4 ND-2,2 DDT Geometric mean 0.08'' 4 95% CI 0.05-0.13 Range ND-1.0 Oxychlordane Geometric mean 0.45 = 4 95%i CI 0.33-0.60 Range ND-1 6 t3ieldrin Geometric mean 0.13" 4 95% CI 0,08-0,19 Range ND-0,94 — NOTE: CI — confidence interval; ND — not delected. ' Residue was not delected in 1 sample. -Residue was not detected in 2 samples. 'Residue was not detecled in !2 samples. ' Residue was not detected in 20 or more samples. Residue was not detected in 7 samples. 114 Pesticides Monitoring Journal GENERAL LEVELS OF RESIDUES Except for the PCB, levels of organochlorines in females and their young were generally low (Table 1) and similar to those found in big brown bats from Mont- pelier Barn (3). Levels of the PCB in adult little brown bats were 5.8 times greater than those found in the June 1974 collections of big brown bats; the amounts in new- born little brown bats were 3.5 times greater than those in newborn big brown bats (i). Eighteen pregnant big brown bats that had been dosed with Aroclor 1260 (2) contained 1.8 times the concen- tration found in little brown bats in the present study when their carcasses were analyzed after parturition. The young of big brown bats contained a mean residue of 4.38 ppm, similar to the mean residue of 4.16 ppm found in neonates in the present study. PLACENTAL TRANSFER OF RESIDUES Amounts in micrograms of the PCB, DDE, and oxy- chlordane in yoimg were computed as percentages of the amounts in adults, using the 29 females whose live- born young appeared to be full-term. The results were 13.2 ± 1.3 percent, 14.3 ± 1.5 percent, and 8.6 ± 1.7 percent, respectively. Paired I tests showed that the average percentage for oxychlordane was significantly less than that of either of the other chemicals. However, 1 3 of the values for oxychlordane in newborns were zero (not detected), and when zero values were elimi- nated (;i = 16) the respective averages became 15.6 ± 1.9 percent, 17.0 ± 2.2 percent, and 15.5 ± 1.6 per- cent and there were no significant differences. Elimi- nation of zeros was probably justified for this compar- ison because the small absolute amounts of oxychlordane made their detection less likely. These percentages resembled those for both control and dosed big brown bats when Aroclor 1260 was fed experimentally (2), but they were lower than one of two percentages for Aroclor 1260 and higher than both percentages for DDE found earlier in big brown bats that had not been dosed (3). RESIDUES AND DEAD YOUNG Dead young averaged more than twice as much PCB (mean = 6.68 ppm, ii = 12) as did live young (mean = 3.04 ppm, n = 29), but the difference was not significant at the 95 percent level (t = 1.91, 01 > P > 0.05). Levels of DDE and oxychlordane were almost identical in dead and live young. Possible effects of the PCB on weight of the young were calculated by correlating the ppm PCB in the young with the weight of the young expressed as a percentage of adult female weight; the result (Fig. 1) was significant ( ;• = -0.47,0.01 > p> 0.001). When the six data points based on estimated weights were eliminated, the relationship remained significant {r — Vol. 12, No. 3, December 1978 —0.46. 0.01 > p > 0.001 ). Although this relationship suggests that the PCB may have caused some neonates to be small, the plotted data in Figure 1 also indicate that neonates may at the same time be small and con- tain little PCB. A similar analysis for DDE produced no significant correlations. To determine whether weight of the young was related to residues in adult females, a correlation was made between weight of the young as a percentage of adult female weight, and ppm of the PCB. DDE, DDT, oxychlordane, and dieldrin in adult females. No sig- nificant relationships were found. Also, females that produced dead young did not contain residues signifi- cantly higher than those of females that produced live young. RESIDUES IN FEMALES COMPARED WITH RESIDUES IN YOUNG The relationships between total micrograms of the PCB, DDE, and oxychlordane in adult females and in their newborii young were tested using all 29 pairs of females and young in which the neonates were entire and of normal size. Micrograms of residues in the young were dependent in a positive, linear fashion on the amount in the adult female: PCB r = 0.74, p < 0.001; DDE r = 0.60. p < 0.001; oxychlordane /• = 0.48, 0.01 > p > 0.001. Similar relationships were found in other bat species {3, 4). RESIDUES COMPARED WITH DAYS IN CAPTIVITY Micrograms of residues of the PCB, DDE, DDT, oxy- chlordane, dieldrin, and »-fl/j.s-nonachlor in carcasses of adult females were compared to days in captivity for all 44 females in which residues were measured. Only oxychlordane declined significantly, from an average 2.6 Mg to 1.0 Mg. The 1 1 -day interval was probably too short to produce any major declines such as that for PCBs found earlier in big brown bats confined for 43 days (3). RESIDUES COMPARED WITH AGE OF FEMALE No correlations were found between age estimated by CTW and residues (total Mg in females plus young, n =44) of the PCB, DDE, DDT, oxychlordane, diel- drin, and /coHj-nonachlor, whereas PCB residues de- clined significantly with age in big brown bats (2, 3). CAUSE OF STILLBIRTHS Aroclor 1260 did not cause stillbirths in big brown bats, but high PCB levels and stillbirths were associated be- cause both occurred more often in younger parent female bats (2. 3). In the present study, CTW and PCB con- centrations were not correlated. Furthermore, when CTW for females with dead young (mean = 0.1 169 ± 0.0213 mm, n = 12) was compared with CTW for females with live young (mean = 0.1217 ± 0.0130 mm, 115 It = 31). the dilTcrcncc was highly significant among big hrown hatsr {2). Nevertheless, there appears to be an association between age and incidence of stillbirths. Among the neonates represented in Figure 1, there were .seven small dead bats, less than 16 percent of the female parent's weight that had PCB concentrations equal to or less than 7 ppm. Five of the seven female parents of these bats showed no wear on their canines and were probably yearlings producing their first off- spring. Among the 30 neonates that were heavier than 16 percent of the female's weight (Fig. 1). only nine showed no canine wear. The difference between these ratios is significant (.v'-' = 4.14. 0.05 > p > 0.01). Threfore, unknown reproductive difficulties associated with first pregnancies probably accounted for most of the young that were born dead. Beyond these, however, there remain the four dead young with the largest amounts of the PCB (12, 13, 18, and 25 ppm); none of their female parents was a yearling. Therefore, high levels of the PCB may have caused four young bats to be born dead, hut feeding studies with captive bats are needed to confirm this conclusion. Acknowledgment Authors thank J. Dowdy, G. Chasko, and W. Kramer for assisting in the capture and maintenance of live bats and for preparing the sample extracts for analysis; J. Carpenter for demonstrating the technique for in- ducing anesthesia; G. Perrygo and H. B. Robey of the Maryland National Park and Planning Commission for providing access to Montpelier Barn; and E. Dustman and A. Federighi for reviewing the manuscript. LITERATURE CITED (/) Clirist'uin, J. J. 1956. The natural history of a summer aggregation of the big brown bat, Epicsicus juscits jiiscii.s. Am. Midi. Nat. 55(n:66-95. (2) Clark. D. li.. Jr. 1978. Uptake of dietary PCB by preg- nant big brown bats (Ephsiciis jusciis) and their fetuses. Bull. Environ. Contam. To.xicol. 19(6) :707- 714. (.?) Clark. D. R. Jr.. and T. G. Lamont. 1976. Organo- chlorine residues and reproduction in the big brown bat. J. Wildl. Manage. 40(2) :249-254. (4) Clark. D. R.. Jr.. C. O. Martin, and D. M. Swineford. 1975. Organochlorine insecticide residues in the free- tailed bat (Tadarida brasiliciusis) at Bracken Cave, Texas. J. Mammal. 56(2 ) :429-443. (5) Cromurlie. E., W. L. Rciclicl. L. A'. Locke. A. A. Beli.slc. T. E. Kai.Kcr, T. G. Lamonl. B. M. Mulhcrn. R. M. Proiily, and D. M. Swineford. 1975. Residues of organochlorine pesticides and polychlorinated biphenyls and autopsy data for bald eagles, 1971-72. Pestic. Monit. J. 9( 1): 11-14. (6 1 Wimsatt. W. W. I960. An analysis of parturition in chiroptera. including new observations on Myotis I. Iucitiiga.t. J. Mammal. 41(2) : 183-200. 116 PESTiciL)i;s MoNiToRiNc; Journal SOILS Pesticide Residue Levels in Soils and Crops, 1971 — National Soils Monitoring Program (III) Ann E. Carey,' Jeanne A. Gowen,' Han Tai,' William G. Mitchell,' and G. Bruce Wiersma ' ABSTRACT Data from the 197 1 National Soils Monitorinti Profiram are siiiumaiizecl. Composite samples of soil and mature crops were scheduled for collection from 1,533 4-hectare sites in 37 states. Analyses were performed on 1,486 soil samples for organochlorines, organophosphates, PCBs, and elemen- tal arsenic; samples were analyzed for atrazinc only when pesticide application data indicated current-year use. Orjiano- chlorine pesticides were detected in 45 percent of the soil samples in the following order of frequency: dieldrin. ^DDT, aldrin, chlordane. and heptachlor epoxide. Most pesticide levels ranged from 0.01 to 0.25 ppm. Crop samples were collected from 729 sites, and all were analyzed for organo- chlorines. Crop samples were analyzed for organophosphates and atrazine only when pesticide application data indicated current-year use. Organochlorines were detected in 42 percent of the crop samples analyzed, organophosphates in 13 percent, and atrazinc in I percent. Introdiiclion The National Soils Monitoring Program is an integral part of the National Pesticide Monitoring Program (NPMP). The NPMP was initiated at the recommen- dation of the President's Science Advisory Committee in 1963 to determine levels and trends of pesticides and their degradation products in the environment (4). The Committee recommended that appropriate federal agen- cies "develop a continuing network to monitor residue levels in air, water, soil, man, wildlife and fish" (/). The U.S. Department of Agriculture (USDA) began monitoring agricultural soils in 1964. After a series of ^Ecological Monitoring Branch. Benefits and Field Studies Division. Oflice of Pesticide Programs. U.S. Environmental Protection Agency. TS-768, Washington. DC 20460. -Extension Agent. Colorado State Extension Service. Golden, CO. ^Ecological Monitoring Branch. Benefits and Field Studies Division. Office of Pesticide Programs. U.S. Environmental Protection Agency, Pesticides Monitoring Laboratory. Bay St. Louis. MS. * Chief, Pollutant Pathways Branch, Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Las Vegas. NV. short-term monitoring projects (5-7), a nationwide agricultural soil monitoring program was designed (9) and tested (!0). The USDA initiated widespread moni- toring in 1968 (//) and 1969 (3). The National Soils Monitoring Program was transferred to the U.S. Environmental Protection Agency (EPA), when EPA was created in 1970. The present report sum- marizes soil and crop pesticide concentration data col- lected in 1971 (fiscal year 1972) at 1.486 sampling sites in 37 states. Data were not collected from some larger western states because of budgetary limitations and because either those states have little widespread agriculture or they grow wheat and other small grains which require fewer pesticides than do nongrain crops. Sampling Procedures Site selection criteria and statistical design for the pres- ent study have been described by Wiersma et al. (9). During late summer and fall 1971, 1,486 sites in 37 states were sampled (Fig. 1). At each 4-hectare (10- acre) site, a composite soil sample and a composite mature crop sample were collected according to pro- cedures described in the U.S. EPA Sample Collection Manual {8). Information on cropping practices and a history of pesticide application for the current cropping season were obtained in interviews with landowners or operators. These data have been summarized and pub- lished separately (2). A nalytical Procedures ORGANOCHLORINES AND ORGANOPHOSPHATES Sample Preparation. Soil — A 300-g subsample was taken from a thoroughly mixed field sample. The sub- sample was moistened with SO ml water and extracted with 600 ml 3:1 hexane-isopropanol by concentric rotation for 4 hours. The isopropanol was removed by Vol. 12, No. 3, December 1978 117 FIGURE I . Slates wliere aaricidlural soils and crops were sampled for the 197 1 National Soils Monitoring Program, U.S. Environmental Proleetion Agency three distilled water washes, and the hexane extract was dried with anhydrous sodium sulfate. The sample ex- tract was stored at low temperature for subsequent gas-liquid chromatographic analysis. Sample Preparation. Crops — For samples containing less than 2 percent fat, e.g., alfalfa, bur clover, corn- stalks, cotton stalks, green bolls, miscellaneous hay, a 100-g sample of the crop was blended with 25 ml dis- tilled water for 3 minutes in SOO ml acetonitrile. An aliquot of the sample extract, representing 10 g of the original sample, was decanted into a 500-ml Eriemcyer flask. The sample extract was concentrated under a three-ball Snyder column to approximately 10 ml; 100 ml hexane was added, and the hexane-acctonitrile azeotrope was again concentrated to 10 ml. This process was carried out three times to remove the aceto- nitrile. The hexane extract was dried with anhydrous sodium sulfate, the volume was adjusted to 50 ml, and the extract was stored at low temperature until par- titioning. For crop samples containing more than 2 percent fat, e.g., corn kernels, cottonseed, soybeans, a lOO-g sample was prcwashed with 100 ml isopropanol and then with 100 ml hexane. Both prcwashes were discarded. The prewashes were used to remove surface residues which may have contaminated the grain during removal of shells, husks, or pods, thus assuring that residues de- tected were actually contained in the grain. The sample was dried, dry blended, added to 100 ml isopropanol, and blended again. After .300 ml hexane was added, the isopropanol was removed by two washes with satu- rated aqueous NaCl solution and one wash with dis- tilled water. The water-alcohol layers were discarded; the hexane layer was concentrated, adjusted to 50 ml, and held at low temperature until partitioning. After extraction, crop samples were partitioned with hexane-acetonitrile as follows: 50 ml of the hexane sample extract, representing 10 g, was shaken with 100 ml acetonitrile in a 500-ml separatory funnel. The bottom acetonitrile layer was set aside. Another 100 ml acetonitrile was added to the hexane extract and the separation step described above was repeated twice; the hexane was discarded and the three acetonitrile layers were combined. The .^00-ml acetonitrile extract, which contained essentially all the pesticides from the original hexane extract, was backwashed with 25 ml acctonitrile- saturated hexane. and the hexane layer was discarded. The acetonitrile sample extract was concentrated to ap- proximately 10 ml under a three-hall .Snyder column, and 100 nil hexane was added. This process was car- ried out three times to remove the acetonitrile. The 118 Pesticides Monitoring Journal hexane extract was adjusted to 7.5 ml and stored at low temperature for subsequent Florisil column cleanup and fractionation. A separate aliquot of the extract not subjected to Florisil cleanup was reserved for analysis for organo- phosphates by flame photometric detection. Florisil Cleanup — An extract equivalent to 5 g original crop sample was fractionated through a 1 5-g Florisil column by use of 100 ml 10 percent methylene chloride in hexane and 100 ml methylene chloride for fractions one and two, respectively. Methylene chloride was removed by concentration of each extract to low volume under a three-ball Snyder column, addition of 100 ml hexane. and concentration again to low volume. After two additions of hexane, the methylene chloride was essentially removed. Each extract volume was adjusted to 2.5 ml for separate injection on the gas-liquid chromatograph. Gas-Liquid Chromatoiiraphy — Gas chromatographs were equipped with tritium foil electron-affinity detec- tors for organochlorines and thermionic or flame photo- metric detectors for organophosphates. A multiple- column system with polar and nonpolar columns was used to identify compounds. Instrument parameters and operating conditions follow: Gas chromaiiigi aphs: Columns: Carrier biases: Temperatures; Hewlell Packard 40:a Hcwleil Packard 40:b Tracor MT-22(1 iilasH. 6 mm OD x 4 mm ID. 183 cm loni;. packed with 9 percent QF-I on 100-1 2t>-me.sh Gas- Chrom Q .■< percent DC-:(1I1 on 100-1 :o-mesh Gas- Chrom Q a mixitire of 1.5 percent OV-17 and 1 ,r'-Dm o.p'-DDE /i,/i'-DDE «,p'-TDE P.n'-TDE Dieldrin Endosulfan 1 1 ) Endosulfan (II ) Endosulfan sulfate Endrjn Heptachlor Heptachlor epoxide Uodrin Lindane (-,-BHC) Meihoxychlor Ovex PCBs PCNs Propachlor Toxaphene ORGANOPHOSPHATES DEF Diazinon Eihion Malathion Parathion. elhyl Paralhion. methyl Phorale Triihion OTHER HALOGENS Trifluralin NOTE: Althougi; trifluralin is a dinitroaniline compound, it is detected in the methodoloj^y used in the present study, and appears in Tables 1-7 under the Oryanochlorines heading. percent. Values from crops ranged from 70 to 100 percent, and varied with amount and type of pesticide and type of crop involved. Residues in both crop and soil samples were corrected for recovery. Soil samples were also corrected to a dry-weight basis. ATRAZINE A 50-g subsample was taken from a thoroughly mixed field sample. The subsample was extracted with 25 ml water and 300 ml methanol by concentric rotation for 4 hours. The sample extract was then decanted into a 1 -liter separatory funnel and 200 ml water was added. The extract was partitioned with 150 ml Freon 113 three times. The Freon 113 fractions were com- bined and concentrated to incipient dryness. The ex- tract was dissolved in hexane and adjusted to 5 ml for injection into a gas-liquid chromatograph equipped with a thermionic flame detector with a rubidium sulfate coating on a helix coil. Instrument parameters and operating conditions follow: Column: glass. 18.1 cm long « 6 mm OD ^ 4 mm ID. packed with ^ percent Versamid 900 on 100- 120-mesh Gas-Chrom Q Cairier gas: helium Detector fuel gases: oxygen flowing at 20(1-300 ml minute; hydro- gen flowing at 20-3(1 ml minute Teinperattires: detector 200"C injection port 240*C column 240''C Confirmatory analyses were performed on a DC-200 column at I80'C and a Coulson detector in the reduc- tive mode at the following temperatures: pyrolysis tube, 850°C; transfer line, 220°C; and block, 220°C. Re- covery was 90-110 percent with a minimum detection level of 0.01 ppm. Vol. 12. No. 3, December 1978 119 ARSENIC Arsenic was determined by atomic absorption spectro- photometrv. The soil sample was extracted with 9.6N HCI and arsenic was reduced to As ' ■' with SnCl,. As + -' was partitioned from the acid to benzene, and then further partitioned from benzene into water for the absorption measurement. A Perkin-Elmer Model 303 spectrophotometer was used, and absorbance was measured with an arsenic cathode lamp at 1972 A with argon as an aspirant to an air-hydrogen flame. Minimum detection limit was 0.1 ppm, and recovery averaged 70 percent. Results from all analyses were corrected for recovery and are expressed as ppm dry weight. Results and Discussion Tables presented in this report can be divided into two groups: those showing concentrations of pesticides in soil samples by all sites and states, and those showing concentrations of pesticides in mature agricultural crops. Most tables list the number of analyses, the number of times a compound was detected, the percent occurrence of the compound, the arithmetic mean, the estimated geometric mean, and the minimum and maximum posi- tive concentrations detected. The estimated geometric mean is routinely presented in the tables as an alternative to the arithmetic mean as a measure of central tendency for the data evaluation. Pesticide residue data frequently contain a large number of zero values, resulting either from the absence of pesticides or their presence at levels below the analytical sensitivity. Such data are seldom distributed normally, as shown by tests for skewness and kurtosis, but often approximate a log-normal distribution. After repeated tests for significant kurtosis and/or skewness, the log(A' + 0.01) transformation was used to determine the logarithmic means. The antilogs of these figures minus 0.01 were taken to estimate the geometric mean in the untransformed dimension. The estimated geo- metric mean was calculated only for those compounds with more than one positive detection. COMPOUND CONCENTRATIONS IN CROPLAND SOIL All Sites — A total of 1,486 soil samples were received from 1,533 sites in 37 states, resulting in a 97 percent design completion. Results of analyses for organochlo- rines, organophosphates, triazines, and elemental arsenic are presented in Table 2. The most frequently detected pesticide was dieldrin, found in 27 percent of all samples analyzed. Next were -DDT, aldrin, chlordane, and TABLE 2. Compoiiiul conccnlrutions in cruplaiul soils for all sample sites in 37 slates, 1971 (FY 1972} National Soils Monitoring Program No. OF % OF Residues. PPM Dry Weight Estimated Extremes of Positive Detections Positive Detections Arithmetic Mean Geometric Meani Detected Values Compound MiN Max. ORGANOCHLORINES. 1 4S6 SAMPLES AJdrin 144 9.7 0.02 0.002 0.01 1.88 Chlordane 119 8.0 U.06 0.003 0.01 6.98 op'-DDE 21 1.4 <0.01 <0.00l 0.01 0.34 ;>.P'-DDE .1.14 22.5 0.11 0.007 0.01 54.98 o.p'-DDT 198 13.3 0(17 0.004 0,01 32.75 p.p'-DDT 305 20.5 0 17 0.010 0.01 245.18 ".p'-TDE 10 0.7 1)111 <0.001 0.02 16.79 P.P'-TDE I 16 7 8 0 115 0.002 0111 38.46 i; DD I .15(1 24.0 0.61 0.013 0.01 388.16 Dieldrin 40K 27.5 0.05 0.009 0 in 9.83 Endosulfan ( I ) 2 0.1 <0.01 <0.00l 0.05 0.23 Endosulfan (11) .1 0.2 <0.01 <0.001 0.07 1.24 Endosulfan sulfate .1 0.2 <0.0 1 <0.001 O.K. 2.07 Endrin 14 0.9 <0.0I 10.00-ppm category. By State — Pesticide concentrations in soils of specific states or state groups are presented in Table 5. Because some of the smaller eastern states had very few sites, those with similar geographic locations and/ or agri- cultural characteristics were combined to obtain more representative data. State groups used were: Mid- Atlantic: Delaware, Maryland, New Jersey; New Eng- land: Connecticut, Maine, Massachusetts, New Hamp- shire, Rhode Island, Vermont; Virginia and West Virginia. Comparisons of the percent occurrence of aldrin, diel- drin heptachlor epoxide, i:DDT, chlordane, and arsenic TABLE 3. Occurrence of organochlorine. orgaiwphosphate and Iriazine residues in cropland soil. /)>■ Stale, 197 1~ National Soils Monitoring Program Organochlorines Orcanophosphates Triazinesi No. OF '"c of No. of ^r OF No. OF % of No. OF Positive Positive No. of Positive Positive No. of Positive Positive State Analyses Detections Detections Analyses Detections Detections Analyses Detections Detections Alabama 23 20 87 11 0 — 1 0 — Arkansas 46 34 74 33 1 3 1 0 — California 64 49 77 48 2 4 — — — Florida 18 9 50 15 2 13 — — — Georgia 30 3 10 15 0 — — — — Idaho 33 8 24 25 0 — — — — Illinois 142 102 72 93 3 3 23 20 87 Indiana 58 28 48 38 0 — 11 7 64 Iowa 152 108 71 104 0 — 54 44 81 Kentucky 31 1 10 31 0 — 6 5 83 Louisiana 26 20 77 12 0 — — — — Michigan 55 22 40 50 0 — 11 10 91 Mid-Atlantic 18 7 39 18 -> 11 2 1 50 Mississippi .11 31 100 15 3 20 — — — Missouri «(l '31 39 67 0 — 20 13 65 Nebraska 106 32 30 99 2 2 21 17 81 New England 20 8 40 19 1 5 1 0 — New York .18 12 32 35 0 — 6 6 100 North Carolina 11 27 87 7 0 — — — — Ohio 57 13 23 49 0 — 10 5 50 Oklahoma 64 7 11 58 0 — 1 1 100 Oregon 38 14 37 18 0 — — — — Pennsylvania 36 8 22 35 0 — 5 2 40 South Carolina 17 17 100 3 0 — ■ — — — South Dakota 106 7 7 101 1) — 3 3 100 Tennessee 27 12 44 16 0 — 1 0 — Virginia/West Virgin ia 27 12 44 25 0 — — — — Washington State 45 11 24 37 0 — — — — Wisconsin 67 7 10 64 0 — 36 18 50 TOTAL 1486 662 45 1141 16 • 213 152 71 1 Samples analyzed only when application records indicated atrazine use during the current growing season. TABLE 4. Percent incidence of selected pesticides in cropland soil from all sampling sites in 37 states, 1971 — National Soils Monitoring Program Concentration, Heptachlor PPM Dry Wt i:DDTi Aldrin DiELDRIN Chlordane Heptachlor Epoxide Toxaphene Trifluralin Not Detected 76.0 90.3 72.5 92.0 95.1 93.1 93.8 96.5 0.01-0.25 11.2 7.9 22.3 3.4 4.4 6.7 0.1 0.26-1.00 6.3 1,3 4.8 3.1 0.4 0.2 1.1 0.2 1.01-5.00 5.1 0.5 0.3 1.4 0.1 — 3.4 0.1 5.01-10.00 0.7 — O.I 0.1 — — 1.0 — > 10.00 0.6 . — — TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 '2DDT = o.p'-DDT -I- p.p-DDT + o.r'-DDE + p,p'-DDE + o.p'-TDE + p.p-TDE. Vol. 12, No. 3, December 1978 121 TABLE 5. Compound concenlralioiis in cropland soil, by state, 1971 — National Soils Monitoring Program Residues, ppm Dry Weight Compound No. OF Positive Detections "i OF Positive Detections ARITHMEnr Mean Concent R*i ION Geometric Mean Concentration! Extremes op Detected Values MiN. Max. ALABAMA, 23 SITES Ornanochlorincs. 23 samples Chlordane 1 p.p-DDE 18 o./j-DDT 10 p.p-DDT 16 2 DDT 18 Dicldrin 4 Endrin 1 Heptaclilor 1 Toxaphcne 5 Oreanophosphates. II samples: no residues delected Triazines. I sample: no residues detected Heavy Metals. 23 samples Arsenic 23 4.4 78.3 43.S 69.6 78.3 17.4 4.4 4.4 21.7 100.0 0.02 11.10 0.(15 0.26 0.41 <0.0I 0.02 <0.0I 0.76 2.84 0.044 l).lli4 0.065 0.106 0.0112 0.022 1.855 0.45 0.01 0.0 1 0.0 1 O.OI 0.0 1 0.42 0.07 0.18 0.39 0.33 0.38 1.39 2.07 0.02 6.78 8.13 ARKANSAS, 46 SITES Organochlorines. 46 samples Aldrin i<.;/-DDE p./i-DDE o.it-DUT /i.;)-DDT p,/y-TDE 2 DDT Dieldrin Endrin Toxaphene Trifluralin Organophosphaies, 33 samples Diazinon Triazines I sample: no residues detected Heavy Metals, 46 samples Arsenic 46 26 14 28 15 28 15 1 9 I 4.4 2.2 56.5 30.4 60.9 32.6 60.9 32.6 2.2 19.6 4.4 3.0 100.0 <0.0I <0.0I 0.10 11.117 (1..14 (1.07 (1.57 (1.02 <0.0I 0.50 <0.0I <0.(1I <0.00I 0.028 0.099 0.054 0.012 0.079 0.009 0.017 <(l.(10l 6.448 O.OI 0.03 0.01 O.OI 0.02 0.01 0.03 0.02 0.10 0.47 0.05 0.02 0.65 0.02 0.94 0.95 4.82 1.03 7.14 0.18 6.67 0.06 24.74 Organochlorines. 64 samples Chlordane ().;i'-DDE p./>'-DDE <'./i'-DDT /'.//-DDT ",//-TDE P./Z-TDE i;ddt Dieldrin Endosulfan II Endosulfan sulfate Heptachlor Heptaclilor epoxide Ovex Toxaphcne Trifluralin Organophosphaies. 48 samples Eihion Parathion. ethyl Heavy Metals. 54 samples Arsenic 4 45 30 39 2 10 47 3 1 1 1 I I 13 3 54 CALIFORNIA, 64 SITES 1.6 6.3 70.3 46.9 60.9 3.1 15.6 73.4 4.7 1.6 1.6 1.6 1.6 1.6 20.3 4.7 2.1 2.1 100.0 0.04 (1,01 (1.15 0.09 0.33 <(1.01 0.02 0.61 (1,01 <0.0I O.OI <0.0I <0.0I 0.02 (1.61 0.03 <0.0I <0.0I 5.26 0.(K)l 0.050 0.024 0.064 0.001 0.004 0.123 0.(101 0.020 0.002 3.802 2.45 0.02 0.01 0.02 0.01 0.01 0.02 0.01 0.09 0.18 0.39 0.02 0.07 1.13 0.73 0.10 0.24 0.17 0.72 0.34 0.87 0.71 2.53 0.20 0.93 3.88 0.19 8.30 1.29 19.14 Orjjanochlorines, 18 samples Aldrin 3 Chlordane 1 /)./7'-DDE 6 o.f/-DDT 3 />./>-DDT 6 />./)'-TDE 3 rDDT 7 Dicldrin 4 Endrin 2 Toxaphene 1 Organophosphaies. 15 samples Ethion 1 Parathion. ethyl 1 Heavy Metals, 18 samples Arsenic 16 FLORIDA. 18 SITES 16.7 5.6 33.3 16.7 33.3 16.7 38.9 22.2 11.1 5.6 6.7 6.7 88.9 (1.(11 0 (II (1.(14 0.(13 0.111 (1.(11 0.19 (1.15 0.06 0.13 <0.11l O.OI 1.49 0.003 O.OI I 0,006 0.015 0.004 0.025 0.014 (1.0114 0,575 0.01 0.10 0.02 0.02 0.04 0.03 0.02 0.19 0.02 2.35 0.06 0.19 0.12 0.11 0.42 0.33 1.14 0.09 1.89 1.70 1.00 (Continued next page) 122 Pesticides Monitoring Journal TABLE 5 (cont'd.). Compotind conceiuralioiis in cropland soil. I>y .state. l971~Natiomd Sods Moniloiinf; Pio.mant Residues, ppm Dry Weight Compound No. OF Positive Detections Positive Detections Arithmetic Mean Concentration Geometric Mean CONCENTRAllONl GEORGIA. .1(1 SITES Organochlorines. ."^0 samples Chlordane o.()'-DDE ;!,()'-DDE o.p-DDT ;).P'-DDT o./J-TDE /1.//-TDE i:DDT DIeldrin Heptachlor epoxide Toxaphene Trifliiralin Organophosphaies, 15 samples: Heavy Melals. 3(1 samples Arsenic 1 25 14 22 I 11 25 7 2 9 1 no residues detected 3(1 lIKfl 3.3 83.3 46.7 73.3 3.3 36.7 83.3 23.3 6.7 30.0 3.3 100.0 0.02 <0.0I 0.14 0.07 0.35 <0.01 0.03 0.59 0.04 <0.01 1.25 0.01 1.64 0.003 0.062 0.019 0.093 (1.010 0.172 0.007 0.001 0.046 IDAHO, 33 SITES Extremes of Detected Values Max. (1.14 (1.02 0(11 (1,(11 0.(11 (1.(13 (1.(12 0.01 0.01 0.01 1.06 0.21 0.20 0.21 0.83 0.63 2.70 0.26 4.42 0.45 0.04 10,20 6.99 Oryanochlorines, 33 samples ;i./>-DDE 9 o,;)'-DDT 4 p. (/-DDT 8 />.()'-TDE 1 i:DDT 9 Dieldrin 4 Toxaphenc 1 Trifliiralin 2 Organophosphaies. 25 samples; no resitlues detected Heavy Metals, 31 samples Arsenic 31 27.3 12.1 24.2 3.0 27.3 12.1 3.0 6.1 100.0 0.03 0.01 0.13 <0,0I O.IS <0.01 0.15 <0.01 0.008 (1.002 0.009 0.013 0.002 1.785 (1.(12 (1,02 (1.(11 0.08 (1,(14 (1.01 4.96 (1.06 0,30 0.41 0,27 3,23 3,99 0.03 0.07 4.99 ILLINOIS. 142 SITES Organochlorincs. 142 samples Aldrin Chlordane ,.,,/-DDE ,..;)'-DDT i;DDT Dieldrin Heplachlor Hep(achlor epoxide Propachlor TritUiralin Organophosphaies. 93 samples Diazinon Malathion Phoraie Triazines. 2.1 samples Atrazine Heavy Melals. 141 samples Arsenic 54 46 2 4 5 96 39 45 2 7 1 1 1 38.0 31,7 1.4 2.8 3.5 66.9 27.5 31.7 1.4 4,9 1,1 1.1 1.1 87.0 (1.06 0.47 <0.01 <0.01 <0.0I 0.14 0.04 0.02 .;/-DDT 4 I'.r'-rOE 2 i:DDT 6 Dieldrin 22 Endosiillan 1 Endostillan II 1 EndosnU.in suHaie 1 Heplachlor 5 Heplachlor epoxide 5 Isodrin 1 Trilliiralin 3 Organophosphaies. .IS samples: 1 ria/ines. 1 I samples Alra/ine 7 Heavy Melals. 5« samples Arsenic 58 24,1 10.3 1.7 10.3 3.5 6.9 3.5 10.3 37.9 1,7 1.7 1.7 8.6 X.ft 1,7 S.2 > resKlnes detected 6.1.6 1(10.0 0.08 0.12 <(1.0 1 0.01 <0.01 0.01 0.01 0.03 0.1(1 <0.01 <0.01 <(1.01 (1.01 (1.01 <(l.lll <0.01 0.05 4.66 0.009 0.0(16 (1.002 (1.001 0.002 0.00 1 0.004 0,019 0,002 (1.002 0.02(1 3,478 0,01 11114 0,(11 0,04 0.01 0,01 (1.0 I (1,01 0,111 0.02 0.05 0.19 ll.OK (1,01 0,16 (1,02 0,02 o,ii: 0,02 0,06 0,(14 0,01 0,05 0.07 0,16 11,01 0,01 Olll 0.03 0.01 0.42 1.83 6.98 0.06 O.IO 0.16 0,75 1.37 0.34 0,15 0,92 28.22 1.64 4.10 0,25 0,08 0.56 0,27 0.89 0.85 0.20 0.43 0,13 0.27 15.93 (Continued next pai^e) Vol. 12, No. 3. December 1978 123 TABLE 5 (cont'd.). Compound concentrations in cropland soil, by slate, 1971 — National Soils Monitoring Program Residues, ppm Dry Weight Compound No. OF Positive Detections % OF Positive Detections Arithmetic Mean Concentration Geometric Mean Concentration ^ Extremes of Detected Values MiN. Max. IOWA. 152 SITES Organochlorines. 152 samples Aldrin Chlordane ().p'-DDE P.p'-DDE o.p'-DDT P.p-DDT p.p-TDE i;DDT Dieldrin Heptachlor Hepiachlor epoxide Isodrin Toxaphcne Trilluralin Organophospliates. 104 samples; rriazincs. 54 samples Atrazine Heavy Metals. 152 samples Arsenic I 28.3 13.2 0.7 11.2 3.3 12.5 2.0 14.5 63.8 8.6 11.8 1.3 0.7 9.87 no residues detected 81.5 99.3 n.i)4 0.06 <().0I 11.01 ,p'-TDE SDDT Dieidrin Heptachlor epoxide Organophosphates, 18 samples Diazinon Parathion, elhyl Triazines, 2 samples Atrazine Heavy Metals. 18 samples Arsenic MID-ATLANTIC-. 18 SITES S.6 5.6 5.6 16.7 5.6 11. 1 5.6 16.7 27.8 11.1 5.6 5.6 50.0 100.0 <0.01 <0.01 <0.01 0.04 0.01 0.04 0.01 (1.10 no; 0.01 <().01 <0.01 0.0.1 3.8-1 0.005 0.004 0.007 0.007 0.001 Extremes of Detected Values MiN. 0.05 0.06 0.03 0.04 0.16 0.08 0.11 0.04 0.03 0.01 0.03 0.05 0.07 0.43 Max. 0.61 0.71 1.62 0.09 18.01 MISSISSIPPI. 31 SITES Organochlorines, 31 samples P,P'-DDE 30 (-.p-DDT 26 p,p'-DDT 30 P,P'-TDE 11 2 DDT 30 Dieidrin 6 Endrin 2 Toxaphene 22 Trifluralin 9 Organophosphates, 15 samples DEF 3 Heavy Metals. 31 samples Arsenic 31 96.8 83.9 96.8 35.5 96.8 19.4 6.5 71.0 29.0 20.0 lOO.O 0.29 0.41 1,98 0.08 2.68 0.01 0.02 3.82 0.1)1 0.08 9.65 0.152 0.203 0.61 1 0.015 0.922 0.003 0.002 0.579 0.006 0.010 7.726 0.01 0.01 0.01 0.02 0.02 0.01 0.02 0.46 0.02 0.15 1.26 1.73 16.07 1.16 19.97 0.10 0.64 21.00 0.15 0.66 20.15 Organochlorines, 80 samples Aldrin 7 Chlordane 5 o.p'-DDE 1 p.p-DDE 4 o.p'-DDT 1 /i.p'-DDT 5 i;DDT 7 Dieidrin 25 Heptachlor 4 Heptachlor epoxide 6 Propachlor 1 Trifluralin 3 Organophosphates, 67 samples: Triazines, 20 samples Atrazine i.i Heavy Metals. 80 samples Arsenic 80 MISSOURI, 80 SITES ) residues delected 8.8 6.3 1.3 5.0 1.3 6.3 8.8 31.3 5.0 7.5 1.3 3,8 65.0 100.0 0 (13 0.03 <0.0I <(>.01 <0.01 0,01 0.02 0.07 6 0.05 0.0.1 0.05 0.02 0.09 O.IH 0.04 0.0,1 0.14 060 0.44 0.22 0.90 0.92 2.16 3.26 69.10 NEW YORK. 18 SITES Orpanochlorines. ?8 samples Chlordane 2 o.p'-DDE 1 p.p'-DDE 1 1 o.p'-DDT 7 P.p'-DDT 10 ...P-TDE 2 P.p'-TDE 5 i DDT 1 1 Dieldrin 4 Heptachlor epoxide 1 Trifliiralin 1 5.3 2.6 29.0 18.4 26.3 5.3 13.2 29.0 10.5 2.6 2.6 Organophosphaies. ,15 samples: no residues detected Triazines. 6 samples Alrazine 6 lOO.O Heavy Metals. .18 samples Arsenic .18 100.0 0.01 v slate 1971 . National Soils Monitoring Program, U.S. Environmental Protection Agency 130 Pesticides Monitoring Journal X < IITTTTTTTI < 2x 1/2 '^< KS3^ ^ |.:;.: .,; Xi < 1/2 X FIGURE 6. Percent occurrence of chlordane residue detections in cropland soil, by stale, 1971, National Soils Monitoring Program, U.S. Environmental Protection Agency FIGURE 7. Percent occurrence of elemental arsenic detections in cropland soil, by slate. 1971. National Soils Monitoring Program, U.S. Environmental Protection Agency Vol. 12. No. 3, December 1978 131 Illinois showed the highest percent occurrence of aldrin, dieldrin. chlortlane. and heptachlor epoxide (Fig. 2-4, 6). Ihc compounds are soil insecticides or their degra- dation products used in corn production. -DDT resi- dues were concentrated in the southeastern states and California (Fig. 5). Generally, Oklahoma, Oregon, Penns\lvania, and Wisconsin had pesticide levels below the all-sites average detection frequency. COMPOUND CONCENTRATIONS IN CROPS Crop samples were collected from 729 sites, or 48 per- cent of the scheduled 1,533 sites. Samples were col- lected only from those sites where crops were mature and/or ready for harvest. All crop samples were analyzed for organochlorines. In addition, samples were analyzed for organophosphates and atrazine when pesti- cide application records indicated their use during the current growing season. Thus, the organophosphate and atrazine concentration data could result in higher oc- currence frequencies than might occur if all samples had been analyzed. Table 6 gives the occurrence of pesticide residues in the crop materials sampled. For all crops, 42 percent of the samples analyzed contained detectable concen-- trations of organochlorines, I 3 percent contained detect- able concentrations of organophosphates, and only 1 percent contained detectable concentrations of atrazine. In general, crops with known patterns of heavy pesticide application, or animal feed crops (alfalfa, hay, field corn, soybeans) grown in rotation with these crops, had the highest frequencies of detectable pesticides. Table 7 presents the compound concentrations detected in each crop sampled. -DDT occurred most frequently in all crops analyzed, with the exception of cornstalks, in which dieldrin residues predominated. The high fre- quency of occurrence of -DDT is probably the result of prior, widespread use of DDT. Acknowledgments It is not possible to list by name all persons who con- tributed to this study. The authors are especially grate- ful to the staff of the Pesticides Monitoring Laboratory, Bay St. Louis, Mississippi, who received, processed and analyzed the samples for compound residues, and to the inspectors of the Animal and Plant Health Inspection Service, USDA, who collected the samples. TABLE 6. Occurrence of pesticide residues in standing agricidtural crops. 1971 — National Soils Monitoring Program ORGANOrHLORINES Organophosphates Triazines No. OF % OF No. OF % OF No. OF % OF No. OF Positive Positive No. OF Positive Positive No. OF Positive Positive Crop Analyses Detections Detections Analyses Detections C ETECTIONS Analyses Detections Detections Alfalfa/bur clover 61 33 54 17 2 12 — — . — Beans, dry 5 0 0 4 0 0 — — ' — Clover 4 2 50 1 0 0 — — — Corn, field (kernels) 304 40 13 46 1 2 1 1 100 Cornstalks 286 164 57 125 1 1 73 0 0 Cotton 28 15 54 26 8 31 — — — Cottonseed 19 12 63 18 5 28 — — — Cotton stalks 44 40 91 35 27 77 — — — Cowpeas 1 0 0 — — — — — — Grass hay 11 6 55 3 0 0 — — — Milo 2 1 50 — — — — — — Mint 1 1 100 -^ — — — — — Mixed hay 51 26 51 17 1 6 — — — Oats 1 0 0 — — — — — — Oats, straw 4 4 100 2 0 0 — — — Pasture 18 10 56 3 0 0 — — — Peanuts 8 2 25 1 0 0 — — — Pecans 1 0 0 — — — — — — Rice 2 2 100 — — — — — — Rice straw 1 1 100 — — — — — — Sorghum (grain) 18 6 33 3 0 0 2 0 0 Sorghum stalks 2.1 14 61 4 0 0 2 0 0 Soybeans 177 69 39 45 0 0 9 0 0 Soybean hay 8 8 100 — — — — — — Sweet sorghum 1 0 0 — Timothy I 0 0 — — — — — Tobacco 2 2 100 — — — — — Wheat 1 0 0 — — — — — Wheat straw 1 0 0 — — — — — — TOTAL 1,084 458 42 350 45 13 87 1 1 132 Pesticides Monitoring Journal TABLE 7. Compound concenlralions in standing agricidlural crops, 1971 — National Soils Monitoring Program Residues, ppm Dry Weight Compound No. OF Positive Detections % OF Positive Detections Arithmetic Mean Estimated Geometric Mean ' Detected Values MiN. Max. Organochlorines, 61 samples Chlordane P,p'-DDE o,p-DDT p,p -DDT P,p'-TDE 2 DDT Dieldrin Toxaphene Organophosphales. 17 sample Parathion. elhyl Parathion, methyl ALFALFA/BUR CLOVER 2 20 15 27 1 28 11 3.3 32.8 24.6 44.3 1.6 45.9 18.0 1.6 11.8 0.01 0.01 0.01 0.04 <0.01 0.06 <0.01 0.01 2.32 0.27 0.001 0.005 0.004 0.014 0.018 0.002 0.17 0.01 0.01 0.01 0.01 0.01 0.01 0.38 3.20 4.57 0.42 0.09 0.14 0.66 0.88 O.OS 36.20 BEANS. DRY (All Varieties) Organochlorines, 5 samples: no residues detected Organophosphales, 4 samples: no residues detected CLOVER (Trifolium sp.) Organochlorines, 4 samples P.p'-DDT 1 ZDDT 1 Dieldrin 1 25.0 25.0 25.0 <0.01 <0.01 <0.0I Organophosphales, I sample: no residues detected 0.02 0.02 0.01 FIELD CORN (Kernels) Organochlorines, 304 samples Chlordane P.p-DDE o.p'-DDT p.p-DDT ^DDT Dieldrin Heptachlor Heptachlor epoxide Organophosphales. 46 samples Parathion, methyl Triazines. 99 samples Atrazine 3 2 2 3 38 1.0 0.7 0.3 0.7 1.0 12.5 0.3 0.3 2.2 1,0 <0.01 <0.01 <0.01 n'.nnp p.p'-DDE ).P-DDT 36.8 31.6 0.06 0,28 0.010 0.019 0.05 0.01 0.01 0.01 0.01 0.01 0.01 0.06 0.01 0.01 0.07 0.36 0.01 0.21 0.01 0.03 0.02 0.09 0.06 0.18 0.08 0.49 0.18 0.01 0.02 1.26 0.06 0.16 0.55 0.10 0.78 0.17 0.03 0.51 2.83 1.86 6.87 22.99 31.72 28.89 0.62 0.53 0.82 3.32 (Continued next page) Vol. 12, No. 3, December 1978 133 TABLE 7 (cont'd.). Compound concentrations in standing agricultural crops, 1971 — National Soils Monitoring Program Residues, ppm Dry Weight Compound No. OF Positive Positive % OF Positive Detections Arithmetic Mean Estimated Geometric Mean> Detected Values MiN. Max. P.P'-DDT 2 DDT Toxaphcne Organophosphates. DEF 8 samples 47.4 47.4 26.3 27.8 0.87 1.21 1.12 0.07 0.040 0.053 0.031 0.01-1 0.03 0.04 0.55 0.10 14.09 18.23 13.54 0.63 COTTON STALKS Organochlorines, 44 samples Chlordane 1 o.p'-DDE 1 p.p'-DDE 34 o,p'-DDT 34 P.P'-DDT 40 p.p-TDE 17 2 DDT 40 Dieldrin 4 Endrin 1 Endrin ketone 1 Heptachlor epoxide 1 Toxaphene 31 Organophospliates. 35 samples DEF 17 Parathion. ethyl 5 Parathion, methyl 21 2.3 2.3 77.3 77.3 90.9 38.6 90.9 8.9 2.3 2.3 2.3 70.5 48.6 14.3 60.0 0.01 <0.Q1 0.30 1.48 7.67 0.83 9.15 <0.01 0.14 0.01 <0.01 10.21 2.01 0.23 0.30 0.062 0.153 0.691 0.032 0.916 0.001 0.628 0.085 0.006 0.068 0.40 0.10 0.01 0.01 0.02 0.01 0.04 0.01 6.26 0.37 0.01 0.15 0.11 0.04 0.04 4.06 28.10 114.63 17.78 160.51 0.08 150.00 37.13 7.32 1.53 COWPEAS Organochlorines, 1 sample: no residues detected GRASS HAY Organochlorines, 1 1 samples Chlordane P.p'-DDE o.p'-DDT P.P'-DDT 2 DDT Dieldrin Toxaphene Organophosphates. 3 samples: 5 4 5 5 2 2 no residues detected 9.1 45.4 36.4 45.4 45.4 18.2 18.2 0.0 1 0.02 0.03 0.08 0.13 <-n.oi 0.21 0.007 0.008 0.015 0.021 0.002 0.012 0.19 0.01 0.01 0.02 0.03 0,01 0.26 0.12 0.32 0.73 1. 17 0.02 2.00 MILO Organochlorines, 2 samples Dieldrin 50.0 0.05 0.11 MINT Organochlorines, 1 sample P,p'-DDE o,p'-DDT P,p'-DDT 2 DDT Organochlorines, 51 samples Chlordane 4 P.p'-DDE 12 o.p'-DDT 8 P.P'-DDT 17 P.p'-TDE 1 2DDT 17 Dieldrin 15 Toxaphene 6 Organophosphates. 17 samples DEF 1 Parathion. methyl 1 100.0 0.05 — 100.0 0.01 — 100.0 0.15 — 100.0 0,21 — MIXED HAY 7.8 0.07 0.004 23.5 0.01 0.003 15.7 0.03 0.003 33.3 0.26 0.011 2.0 <0.0I — 33.3 0.31 0.012 29.4 0.01 0.004 11.8 0.36 0.007 5.9 <0.0I 5.9 <0.01 Organochlorines, 4 samples Chlordane 1 25.0 P.p'-DDE 2 50.0 o.p'-DDT 2 50.0 p.p'-DDT 3 75.0 2 DDT 3 75.0 Dieldrin 2 50.0 Organophosphates 2 samples: no residues detected 0.01 <0.01 <0.01 0.02 0.03 0.01 0.004 0.004 0.019 0.026 0.009 0.05 0.01 0.15 0.21 0.25 0.01 0.01 0.01 0.01 0.02 0.01 0.16 0.06 0.02 0.03 0.01 0.01 0.02 0.04 0.01 1.68 0.48 1.23 12.24 13.95 0.05 15.73 OATS Organochlorines, 1 sample: no residues detected OAT HAY/STRAW 0.04 0.06 0.05 (Continued next page) 134 Pesticides Monitoring Journal TABLE 7 (cont'd. ) . Compound concentrations in standing agricultural crops, 1971 — National Soils Monitoring Program Residues, ppm Dry Weight Compound No. OF Positive DETECnONS % OF Positive Detections Arithmetic Mean Estimated Geometric Mean' Detected Values MlN. Max. PASTURE Organochlorines. 18 samples Chlordane 3 16.7 p.p'-DDE 3 16.7 o.p'-DDT 2 11.1 p.p-DDT 6 33.3 D.p'-TDE 1 5.6 p.p'-TDE 1 5.6 2 DDT 6 33.3 Dieldrin 6 33J Endrin 1 5.6 Heptachlor epoxide I 5.6 Toxaphene 1 5.6 Organophosphates. 3 samples: no residues detected 0.05 <0.01 <0.01 0.01 <0.01 <0.01 0.04 <0.01 <0.0I <0.01 0.01 0.009 0.001 0.001 0.005 0.008 0.006 0.37 0.01 0.02 0.01 0.45 0.07 0.01 0.02 O.Ol 0.01 0.23 0.63 0.02 0.03 0.08 0.63 COS PEANUTS Organochlorines, 8 samples Dieldrin 2 Organophosphates. 1 sample: no residues detected 0.01 0.004 0.03 PECANS Organochlorines, 1 sample: no residues detected Organochlorines, 2 sample p.p'-DDE o.p'-DDT p.p'-DDT 2 DDT Heptachlor RICE 100.0 50.0 100.0 100.0 50.0 0.02 0.03 0.15 0.20 <0.01 0.018 0.096 0.126 0.01 0.06 0.03 0.04 0.01 0.03 0.27 0.36 Organochlorines, 1 sample p.p'-DDE o.p'-DDT p.p'-DDT 2 DDT Toxaphene RICE STRAW 100.0 100.0 100.0 100.0 1 00.0 0.04 0.11 0.12 U.27 0.52 0.04 0.11 0.12 0.27 0.52 SORGHUM Organochlorines, 18 samples Chlordane 3 p.p'-DDE 2 o.p'-DDT 1 P.p'-DDT 3 p.p'-TDE 1 2 DDT 3 Dieldrin 4 Endrin 1 Heptachlor epoxide 1 Toxaphene 1 Organophosphates, 3 samples: no residues detected Triazines, 2 samples: no residues detected 16,7 0.03 11.1 0.01 5.6 0.02 16.7 0.06 5.6 <0.01 16.7 0.04 22.2 0.02 5.6 <0.0I 5.6 <0.01 5.6 0.05 SORGHUM STALKS Organochlorines, 23 samples Chlordane 4 p.p'-DDE 6 o.p'-DDT 10 p.p'-DDT 15 P.p'-TDE 4 2 DDT 16 Dieldrin 6 Endrin 1 Endrin ketone 1 Heptachlor 1 Heptachlor epoxide 2 Toxaphene 4 Organophosphates. 4 samples: no residues detected Triazines, 2 samples: no residues detected 17.4 0.08 26.1 0.01 43.5 0.03 65.2 0.09 17.4 <0.01 69.6 0.13 26.1 0.05 4.3 0.03 4.3 0.01 4.3 ( 2 ) :22.1-2:7. (//I Wiersma. C H , II. lai. and P. E. Sand. 1972. Pesti- cide residue levels in soils. FY-1969 — Naliontil Soils Moniloiing Program. Peslic. Monil. J. 6( .1 ) : 194-22X. 136 PESTIC IDE MONITOKING JOURNAL Pesticide Application and Cropping Data from 37 States, 1971 — National Soils Monitoring Program Ann E. Carey.' Jeanne A. Gowen,- and G. Bruce Wiersma '^ ABSTRACT This report summarizes pesticide application and cropping data collected in 1971 from l,47S agricultural sampling sites in 37 states as pari of the National Soils Monitoring Program. Pesticide application data arc summarized by all sites, state, and crop. Tables generally give the number of reporting sites, the number of times a compound was ap- plied, the percent occurrence, and the arithmetic mean total application rate. Pesticides applied most frequently to sampling sites were atrazine. 2,4-D, caplan, and malatliion. Pesticides were most frequently applied to field corn and cotton, least fre- quently to alfalfu/hur clover and mixed hay. Introduction In 1963, the report of the President's Science Advisory Committee recommended that appropriate federal agen- cies "develop a continuing network to monitor residue levels in air, water, soil, man, wildlife and fish" (7). As a result of this recommendation, the National Pesti- cide Monitoring Program (NPMP) was established to determine levels and trends of pesticides and their degra- dation products in the environment (3). Federal re- sponsibility for monitoring pesticides was officially man- dated in Section 20 of the amended Federal Insecticide, Fungicide and Rodenticide Act of 1972 (PL 92-516). The National Soils Monitoring Program is an integral part of the NPMP, monitoring agricultural soils and raw agricultural crops. It was initiated in 1968 by the U.S. Department of Agriculture and is administered by the U.S. Environmental Protection Agency. The present report summarizes pesticide application and cropping data collected in 1971 from 1,473 sampling sites in 37 states. Composite soil and crop samples were also col- lected from these sites for pesticide residue analyses, the results of which are published separately (2). 'Ecological Monitiiriny Branch. Benefits and Field Studies Division. Office of Pesticide Prii^rams. U.S. Environmental Protection A^icncy. TS-768. Washinsiton. DC 2II46I1. -Extension Ayent. Colorado State Extension Service. Golden. CO. ■'Chief. Pollutant Pathways Branch. Environmental Monitoring and Support Laboratory. U.S. Environmental Protection Ayency, Las Vegas, NV. Sampling The site selection criteria and statistical design of the National Soils Monitoring Program have been de- scribed (4). In 1971, 1,533 sites in 37 states were scheduled for sampling (Fig. 1). At each 4-hectare (lO-acre) site, landowners or operators supplied infor- mation on the crops grown and the kinds and amounts of pesticides applied during 1971. Results and Discussion COMPOUNDS APPLIED TO CROPLAND Pesticide use data were received from 1 ,473 or 96 per- cent of the scheduled 1,533 sites. Of these, 784 or 53 percent of the sites had one or more pesticides applied during 1972. Tables summarizing the application data show the number and percent of sites with reported pesticide application and the average rate of total pesti- cide application for each site, expressed both in pounds per acre and kilograms per hectare. Table 1 gives the frequency of pesticide use on sample sites in various states and state groups. Because some of the smaller eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to obtain more represen- tative data. Slates were grouped as follows: Mid-At- lantic: Delaware, Maryland, New Jersey; New England: Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, Vermont; and Virginia and West Virginia. Among the individual states and state groups, frequency of pesticide use ranged from 23 percent in Pennsylvania to 77 percent in Mississippi. ALL SITES Applications of 132 compounds were recorded for all reporting sites. The compounds included 50 herbicides, including defoliants, 48 insecticides and/or acaricides, 28 fungicides, 4 nematocides, I soil fumigant, and 1 growth retardant (Table 2). The most frequently ap- plied compounds were atrazine, 2,4-D. captan, and malathion. which were reported from 14, 10, 9, and 8 percent of the reporting sites, respectively. Vol. 12, No. 3, December 1978 137 26-591 FIGURE 1. Slates scheduled for sampling, 1971, National Soils Monitoring Program TABLE I. Occurrence of pesticide applications by 1971 — National Soils Monitoring Program state, State Total Pesticides OR No. OF Sites Pesticides Applied Not Applied State No. OF No. OF Group^ Reporting Sites Tv Sites % Alabama 22 9 41 13 59 Arkansas 45 24 53 21 47 California 61 29 48 32 52 Florida 18 8 44 10 56 Georgia 29 19 66 10 34 Idaho 33 11 33 22 67 Illinois 142 100 70 42 30 Indiana 74 50 68 24 32 Iowa 152 103 68 49 32 Kentucky 28 11 39 17 61 Louisiana 25 17 68 8 32 Michigan 54 25 46 29 54 Mid-Ailantic 16 7 44 9 56 Mississippi 31 24 77 7 23 Missouri 79 37 46 42 54 Nebraska 106 65 61 41 39 New England 21 6 29 15 71 New York 36 17 47 19 53 N. Carolina 30 18 60 12 40 Ohio 57 31 54 26 46 Oklahoma 60 22 37 38 63 Oregon 37 13 35 24 65 Pennsylvania 35 S 23 27 77 S. Carolina 15 8 53 7 47 S. Dakoia 106 51 48 55 52 Tennessee 24 11 46 13 54 Virginia and W.Virginia 25 8 32 17 68 Washington state 45 22 49 23 51 Wisconsin 67 30 45 37 55 Total 1473 784 53 689 47 'Some smaller eastern stales which had few sites but similar geographic locations and /or agricultural characteristics were combined to obtain more represenlalive dala. including: Mid-Allanlic Mates: Oelawarc. Maryland. New Jersey; New Hngland stales: Connecticut. Mamc. Massachusetts, New Hampshire. Rhode Island. Vermont; and Virginia and West Virginia. BY STATE Table 3 presents the application data by state or state grouping. Because of the number of states sampled, it is not feasible to discuss in detail the pesticide data from each state. However, the pesticide application in- formation from each state reflects both the crops grown and the intensity of agricultural land use in the state. In Figure 2, the frequency of reported pesticide appli- cations in each state is designated as follows: low, states where less than 25 percent of the sites reported pesticide applications; medium, states where 25-59 percent of the sites reported applications: and, high, where over 60 percent of the sites in a state reported pesticide appli- cations. BY CROP Table 4 lists crops grown on sample sites in 1972 as well as the pesticide application status for each crop. Appli- cation data for selected major crops are presented in Table 5. Pesticide use varied widely among these crops. Table 6 shows the pesticide applications in 1971 selected major crops, by state. for Acknowledgment It is not possible to list by name all the persons who contributed to this study. However, the authors are especially grateful to the inspectors from the Plant Pro- tection and Quaranline Programs, Animal and Plant Health Inspection Service. U.,S. Department of Agri- culture, who collected the data. 138 Pesticides Monitoring Journal TABLE 2. Compounds applied to 1.473 cropland sites, 1971— National Soils Monitoring Program Average Total Trade Pesticides Applied Application Trade Pesticides Applied Average Total Application Compound Name, If Noted No. OF Sites % OF Sites LB./ Acre KG/ Hectare Compound Name, If Noted No. OF Sites % OF Sites LB./ Acre KG/ Hectare Alachlor Lasso Aldrin Arsenic pentoxide Atrazine AAtrex 65 45 2 214 4.4 3.0 0.1 14.1 1.58 1.15 0.50 1.78 1.77 1.29 0.56 1.99 Isodrin Lead arsenate Lindane 0.1 0.2 0.1 0.01 7.07 0.02 0.01 7.91 0.02 Azinphosmethy! Guthion 6 0.4 0.60 0.67 Linuron Lorox 23 1.6 0.89 1.00 Bacillus Londax 0.1 0.50 0.56 thuringiensis B.T. 1 0.1 0.11 0.12 Malathion 111 7.5 0.16 0.18 Barban Carbyne 1 0.1 0.25 0.28 Maleic hydrazide : MH 0.2 3.00 3.36 Benefin Balan 3 0.2 1.11 1.24 Mancozeb Dilhane M-45 2 0.1 12.40 13.89 BHC 3 0.2 0.02 0.02 Maneb 3 0.2 2.34 2.62 Bordeaux mixture 1 0.1 1.25 1.40 MCPA MCP 5 0.3 0.70 0.78 Bromacil Hyvar 3 0.2 0.62 0.70 Mercury 2 0.1 0.06 0.06 Butylate Sutan 18 1.2 1.74 1.95 Metham Vapam 1 0.1 2.16 2.42 Bux 17 1.1 1.26 1.41 Methomyl Lannate 1 0.1 1.13 1.27 Captafol Difolatan 1 0.1 1.50 1.68 Methoxychlor 24 1.6 0.17 0.19 Captan 138 9.3 0.11 0.12 Methylmercury Carbaryl Sevin 18 1.2 2.12 2.37 acetate Ceresan L 6 0.4 0.01 0.01 Carbophenothion Trithion 1 0.1 3.20 3.58 Methylmercury Carbofuran Furadan 20 1.3 1.01 1.13 dicyandiamide Panogen 18 1.2 0.08 0.09 Chevron RE-5353 1 4 0.3 0.85 0.95 Methyl trithion 1 0.1 3,00 3.36 Chloramben Amiben 41 2.8 1.39 1.56 Mevinphos Phosdrin 2 0.1 0.75 0.84 Chlordane 1 0.1 2.50 2.80 Mirex 6 0.4 0.07 0.08 Chlorobenzilate Acaraben 2 0.1 1.38 1.55 Monocrotophos Azodrin 4 0.3 0.33 0.36 Chloroneb Demosan 9 0.6 0.02 0.02 Monuron Telvar 2 0.1 1.30 1.46 Chloropropham Chloro-lPC 1 0.1 2.50 2.80 MSMA 17 1.1 1.77 1.99 Chlorothalonil Bravo 1 0.1 3.00 3.36 Nabam 1 0.1 5.00 5.60 Copper carbonate Naptalam Alanap 4 0.3 1.94 2.17 (basic) 1 0.1 3.90 4.37 Nitralin Planavin 5 0.3 1.05 1.18 Copper hydroxide 1 0.1 1.08 1.21 Oil Spray Ovex 2 0.1 60.00 67.20 Copper oxide 1 0.1 1.70 1.90 1 0.1 0.50 0.56 Copper sulfate 3 0.2 13.97 15.65 Oxydemeton- Cypromid Clobber 1 0.1 0.75 0.84 melhyl Metasystox- R 2 0.1 0.50 0.56 2.4-D Decamine 145 9.8 0.87 0.97 Paraquat 4 0.3 0.86 0.97 Dalapon 2,4-DB Dowpon Butyrac 4 7 0.3 0.5 2.60 0.64 2.91 0.72 Parathion, ethyl Parathion, methyl PCNB Pebulate Penlachloro- phenol Phenylmercury 21 48 1.4 3.2 3.32 2.81 3.72 3.15 DCPA DDT DEF Demeton Diallate Dacthal Systox Avadex 1 33 9 2 1 0.1 2.2 0.6 0.1 0.1 3.75 3.83 1.03 1.56 0.12 4.20 4.29 1.16 1.75 0.13 Tillam PCP 2 1 2 0.1 0.1 0.1 3.51 0.12 3.02 3.93 0.13 3.38 Diazinon 15 1.0 0.75 0.84 actate PMA 2 0.1 0.01 0.01 Dicamba Banvel D 12 0.8 0.31 0.34 Phenylmercury Dichlofenthion Nemacide 1 0.1 6.00 6.72 urea 3 0.2 0.01 0.01 Dichloropropene Dichlorprop Dicofol Telone 2,4-DP Kelthane 3 1 1 0.2 0.1 0.1 28.00 3.00 1.00 31.36 3.36 1.12 Phorate Phosalone Phosphamidon Thimet Zolone Dimecron 21 1 2 1.4 0.1 O.I 1.71 4.00 0.27 1.91 4.48 0.30 Dieldrin Dinitrocresol 6 3 0.4 0.2 0.09 1.64 0.10 1.84 Prolate Prometryn Imidan Caparol 2 1 0.1 0.1 11.60 1.08 13.00 1.21 Diphenamid Enide 1 0.1 0.25 0.28 Propachlor Ramrod 44 3.0 1.64 1.83 Disulfoton Di-Syston 24 1.6 1.21 1.35 Propanil Stam 6 0.4 3.46 3.87 Diuron Karmex 9 0.6 1.56 1.75 Propargite Omite 2 0.1 2.58 2.88 DNBP Premerge 16 1.1 1.35 1.51 Pyrazon Pyramin 1 0.1 1.25 1.40 Dodine 2 0.1 0.83 0.93 Silvex 3 0.2 0.42 0.47 DSMA 11 0.7 2.00 2.24 Simazine Princep 9 0.6 4.00 4.48 Dyfonate 1 0.1 0.90 1.00 Sodium chlorate 5 0.3 1.74 1.95 EMTS Ceresan M 9 0.6 0.06 0.06 Solan 1 O.I 1.00 1.12 Endosulfan Thiodan 8 0.5 1.44 1.61 Sulfur 12 0.8 34.27 38.38 Endrin 3 0.2 2.20 2.46 2,4,5-T 2 0.1 0.30 0.34 EPTC Eptam 10 0.7 2.09 2.34 TCA 2 0.1 2.50 2.80 Ethoprop Mocap 1 0.1 1.00 1.12 TEPP 1 0.1 4.00 4.48 Ethylmercury Terbacil Sinbar 1 0.1 1.40 1.56 chloride Ceresan Red 8 0.5 0.03 0.03 Fensulfothion Dasanit 5 0.3 1.15 1.28 Terbutryn Igran I 0.1 1.75 1.96 Fentin hydroxide 1 0.1 2.25 2.52 Terrazole 1 0.1 0.15 0.16 Ferbam 2 0.1 2,59 2.90 Tetradifon TedionV-18 1 0.1 0.75 0.84 Fluometuron Cotoran 22 1.5 0.95 1.06 Thiram 13 0.9 0.01 0.01 Folex 5 0.3 1.05 1.18 Toxaphene 33 2.2 7.00 7.84 Folpet Phaltan 1 0.1 1.00 1.12 Trichlorfon Dylox 2 0.1 0.88 0.98 Furethrin 1 0.1 8.00 8.97 Trietazine 1 0.1 0.70 0.78 Heptachlor 8 0.5 1.27 1.42 Trifluralin Treflan 64 4.3 0.95 1.06 Hexachloro- Vernolate Vernam 2 0.1 2.25 2.52 benzene HCB 7 0.5 0.01 0.01 Zineb 1 0.1 7.50 8.40 Vol. 12, No. 3, December 1978 139 TABLE 3. Coinpoittuh applied to cropland sites by state, 197 1 — National Soils Monitoring Program Average Total Average Total Trade Name. Pesticides Applied No. OF % OF Application Trade _ Name. ESTiciDES Applied Application LB./ KG/ No. of Tc OF lb./ KG/ Compound If Noted Sites Sites Acre Hectare Compound If Noted Sites Sites Acre Hectare ALABAMA. 22 SITES Propargite Omite 1.6 0.15 0.16 Simazine Sodium chlorate Princep 4.9 1.6 8.00 5.00 8.96 Atrazine AAtrex 13.6 2.67 2.98 5.60 Benefin Balan 4.5 0.75 0.84 Sulfur 8.1 15.34 17.19 Buiylate Sutan 9.0 0.25 0.28 Tetradifon Tedion V-18 1.6 0.75 0.84 DDT 13.6 3.67 4.10 Toxaphene 1.6 0.40 0.44 Disulfoton Di-Syston 4.5 7.00 7.84 Trichlorfon Dylox 3.2 0.88 0.98 Dluron Karmex 4.5 0.34 0.38 Trifluralin Treflan 2 3.2 0.20 0.22 DSMA 4.5 1.50 1.68 EMTS Ceresan M 4.5 0.01 0.01 1.56 1.02 2.24 1.56 2.50 7.84 FLORIDA, 18 SITES Endrin Fluomeiuron MSMA Parathion. ethyl Parathion, methyl PCNB Toxaphene Trifluralin Cotoran 4.5 13.6 4.5 4.5 13.6 4.5 1.40 0.92 2.00 1.40 2.23 7.00 Atrazine Carbaryl Carbofuran Chlorobenzilate Copper carbonate AAtrex Sevin Furadan Acarabcn 11.1 5.5 5.5 11. 1 2.75 5.00 4.00 1.38 3.08 5.60 4.48 1.54 Treflan 13.6 4.5 4.55 0.50 5.09 0.56 (basic) 2.4-D Dalapon Endrin Dowpon 5.5 16.6 5.5 5.5 3.90 5.33 1.50 1.00 4,37 5.97 1.68 ARKANSAS. 45 SITES 1.12 EPTC Malathion Eptam 5.5 5.5 0.20 3.17 0.22 Aldrin 1 2.2 0.75 0.84 3.55 Atrazine AAtrex 1 2 2 0.75 0.84 Maneb 5.5 0.08 0.08 Captan 1 2^2 0.01 0.01 Oil Spray 5.5 70.00 78.45 Chloroneb Demosan -» 4.4 0.01 0.01 Sulfur 16.6 78.67 88.16 2,4-D 1 2.2 0.50 0.56 Zineb 5.5 7.50 8.40 :.4-DB DDT 1 2.2 1.50 1.68 .1 6.6 0.57 0.63 GEORGIA, 30 SITES Disulfoton DNBP DSMA EMTS Fluometuron Linuron Di-Syston Premerge Ceresan M Cotoran Lorox 1 5 3 5 2 2.2 11.1 4.4 6.6 11.1 4.4 0.25 0.94 1.20 0.15 0.84 0.50 0.28 1.05 1.34 0.16 0.92 0.56 Benefin Butylate Captan Carbaryl Chlorothalonil Copper oxide Balan Sutan Sevin Bravo 3.3 3.3 16.6 6.6 3.3 3.3 1.50 0.75 0.02 2.56 3.00 1.70 1.68 0.84 0.02 2.86 3.36 1.90 Methylmercury dicyandiamide Monuron MSMA Nitralin Panogen Telvar Planavin 3 1 5 3 6.6 -} 2 11.1 6.6 0.25 1.00 1.20 1.17 0.28 1. 12 1.34 1.30 Copper sulfate 2,4-D DDT DNBP 3.3 6.6 16.6 6.6 30.00 0.75 2.61 1.50 33.62 0.84 2.93 1.68 Parathion, ethyl Parathion, methyl Propanil Solan Stam 1 5 2 1 1 2 2 11.1 4.4 2.2 2.2 7.00 2.00 5.50 1.00 0.01 7.84 2.24 6.16 1.12 0.01 Ethylmercury chloride Folex Malathion Maleic hydrazide Ceresan Red 6.6 3.3 6.6 3.3 O.OI 1.50 O.OI 3.00 0.01 1.68 0.01 3.36 Toxaphene Trifluralin Treflan 3 9 6.6 20.0 1.00 1.11 1.12 1.24 Methoxychlor Methyl trithion Mirex Parathion, ethyl 6.6 3.3 6.6 10.0 0.02 3.00 0.04 7.88 0.02 3.36 0.04 CALIFORNIA. 6 SITES 9.52 Parathion, methyl Sulfur 16.6 6.6 3.45 25.00 3.86 Aldrin I 1.6 0.01 0.01 28.02 Azodrin 1 1.6 0.50 0.56 Thiram 10.0 0.01 0.01 Bacillus Toxaphene 13.3 4.00 4.48 thurinyiensis 1 1.6 0.11 0.12 Trifluralin Treflan 16.6 0.39 0.44 Captan 2.4-D 1 1.6 3.2 0.01 0.31 O.OI 0.34 Vernolate Vernam 3.3 2.50 2.80 2 DCPA Dacthal 1 2 1.6 3.2 3.75 0.08 4.20 0.08 IDAHO. 33 SITES Diazinon Captan 1 3.0 0.08 0.08 Dicofol Kelthane 1 1.6 1. 00 1.12 2,4-D 3 9.0 0.67 0.75 Diphenamid Enide 1 1.6 0.25 0.28 DDT 2 6.0 3.25 3.64 Diuron Karmex 1 1.6 2.40 2.68 Diallale Avadex 1 3.0 0.12 0.13 EPTC Ethylmercury Eptam 1 1.6 3.00 3.36 Ethylmercury chloride Ceresan Red 2 6.0 0.10 O.ll chloride Ceresan Red 1 1.6 0.0 1 0.01 Malathion I 3.0 1.00 1.12 Malaihion 4 6.5 1.71 1.91 PCP 1 3.0 0.03 0.03 MCPA MCP 2 3.2 1.25 1.40 Trifluralin Treflan 3.0 1. 00 1.12 Mercury I annate Phosdrin 2 3.2 1.6 1.6 0.06 1.13 1.00 0.06 1.26 Melhomyl Mevinphos ILLINOIS, 142 SITES 1.12 Oil Spray 1.6 50.00 56.04 Alachlor Lasso 15 10.5 1,93 2.16 Ovex 1.6 0.50 0.56 Aldrin Atrazine AAtrex 13 22 9.1 15.4 1.15 1.74 1.29 1.95 Oxydemcton- Butylate Sutan 3 2 1 1.47 1.64 methyl Metasyslox R I 1.6 U.50 0.56 Bux 2 1.4 1.40 1.56 Paraquat 3.2 0.22 0.25 Captan 59 41.5 0.01 O.OI Parathion. ethyl 6.5 2.08 2.32 Carbofuran Furadan 2 1.4 0.33 0.36 Parathion, methyl 3.2 1.38 1 54 Chloramben Amihcn IS 12.6 1.47 1.64 PCNB 1.6 0.01 O.OI 2,4-D 6 4.2 l.ll 1.24 Pcbulatc Tillam 1.6 0.12 0.13 Demeton .Syslox 1 0.7 0.12 0.13 Phenylmcrcury Fensulfothion Dasanit 1 0.7 0.90 1.00 acelale PMA I 1.6 0.0 1 O.OI Ferbam 1 0.7 2.00 2.24 {Continued next page) 140 Pesticides Monitoring Journal TABLE 3 (cont'd. ) . Compounds applied to cropland sites by state, 1971 — National Soils Monitoring Program Average Total AVERAG E Total Trade Name. Pesticides Applied Application Trade Name, Pesticides Applied No. OF % OF Application Compound No. OF % OF LB./ KG/ LB./ KG/ If Noted Sites Sites Acre Hectare Compound DDT If Noted Sites Sites 20.0 Acre 6.62 Hectare Heplachlor 4 2.8 1.75 1.96 7.41 Linuron Lorox 6 4.2 0.89 0.99 DEF 4.0 1.12 1.25 Malathion 52 36.6 0.01 0.01 Diuron Karmex 4,0 0.70 0.78 Methoxychlor 15 10.5 0.01 0.01 DSMA 20.0 2.24 2.51 MSMA 1 0.7 0.25 0.28 EMTS Ceresan M 4.0 0.01 0.01 Paraquat I 0.7 2.00 2.24 Fluometuron Cotoran 24.0 0.99 1.11 PCP 1 0.7 6.00 6.72 Linuron Lorox 4.0 0.50 0.56 Phorate Thimet 7 4.9 0.62 0.69 Methylmercury Propachlor Ramrod 18 12.6 1.22 1.36 dicyandiamide Panogen 12.0 0.08 0.08 Simazine Princep I 0.7 2.00 2.24 Monocrotophos Azodrin 12.0 0.27 0.29 Trifluralin Treflan 8 5.6 1.20 1.34 Monuron 4.0 1.60 1.79 2,4,5-T 1 0.7 0.25 0.28 MSMA Nitralin 8.0 1.46 1.63 Planavin 4.0 0.75 0.84 INDIANA. 76 SITES Paralhion. methyl Promelryn Caparol 28.0 8.0 3.56 1.08 3.99 Alachlor Lasso 9 11.8 1.56 1.74 1.21 Aldrin 9 11.8 1.35 1.51 Propanil Stam 16.0 2.44 2.73 Atrazine AAtrex 20 26.3 1.92 2,15 Silvex 4.0 0.50 0.56 Azinphosmethyl Guthion 1.3 0.22 0.24 Sodium chlorate 4.0 0.05 0.05 Butylale Sutan 1.3 1.00 1.12 TCA 4.0 4.00 4.48 Chloramben Amiben 9.2 1.44 1.61 Toxaphene 6 24.0 13.45 15.07 Captan Sevin 1.3 1.3 0.01 0.61 0.01 0.68 Trifluralin Treflan 2 8.0 0.63 0.70 Carbaryl Chlordane 1.3 1.3 2.50 1.08 2.80 1.21 MICHIGAN, 54 SITES Copper hydroxide Aldrin 1.8 2.00 2.24 Copper sulfate 1.3 1.42 1.59 Atrazine AAtrex 14 25 9 2.00 2.24 2,4-D 5.2 0.63 0.70 Captan 1 g 5.00 5.60 Diazinon 1.3 0.40 0.44 Carbaryl 1 8 1. 00 1.12 DNBP Premerge 1.3 2.25 2.52 2.4-D 1 8 1.00 1.12 Endosulfan 1.3 0.54 0.60 Demeton 1 8 3.00 3.36 EPTC Eptam 1.3 2.00 2.24 Endosulfan 1 8 6.00 6.72 Linuron Lorox 2.6 0.55 0.61 EPTC Epiam 5 5 1.67 1.86 Maneb 1.3 2.14 2.39 Fentin hydroxide I 8 2.25 2.52 Propachlor Ramrod 2.6 1.20 1.34 Isodrin 1 8 0.01 0.01 Silvex 1.3 0.25 0.28 Lead arsenate 1 8 16.00 17.93 Simazine Princep 3.9 2.00 2.24 Mancozeb Dithane M-45 1 1 8 12.00 13.44 Trifluralin Treflan 6.5 2.37 2.66 Parathion. ethyl -> 3 7 3.50 3.92 2,4.5-T 1.3 0.35 0.39 Phosalone Prolate Imidan 1 1 3 8 7 4.00 11.60 4.48 13.00 IOWA, 152 SITES Pyrazon Silvex TCA TEPP Pyramin 1 1 1 1 1 1 1 8 8 8 8 1.25 0.50 1.00 4.00 1.40 Alachlor Aldrin Atrazine Lasso AAtrex Sutan 15 10 39 7 9.8 6.5 25.6 4.6 0.93 0.83 1.39 2.46 1.04 0.93 1.56 2.75 0.56 1.12 4.48 Butylale MID-ATLANTIC,i 16 SITES Bux 5 3.9 0.82 0.92 Captan 1 0.6 0.01 0.0 1 Alachlor Lasso 1 6.2 2.00 2.24 Carbaryl Sevin 1 0.6 1.60 1.79 Atrazine AAtrex 4 25.0 0.94 1.05 Carbofuran Furadan 7 4.6 0.92 1.03 Butylate Sutan 2 12.5 1.63 1.82 Chloramben Amiben 12 7.8 1.10 1.23 Captan 2 12.5 0.0 1 0.01 2.4-D 19 12.5 0.54 0.61 Carbofuran Furadan 1 6.2 1. 00 1.12 DDT 2 1.3 1.00 1.12 2.4-D 1 6.2 0.50 0.56 Diazinon 6 3.9 0.54 0.61 Diazinon I 6.2 0.80 0.89 Dicamba Banvel D 3 1.9 0.75 0.84 Malathion 2 12.5 0.01 0.01 2.24 53.79 DNBP Dyfonate Premerge Mocap -> 1 1 1 1.3 0.6 0.6 0.6 0.44 0.90 1.00 1.02 0.49 1.00 1.12 1.14 Paralhion, ethyl Sulfur 1 I 6.2 6.2 2.00 48.00 Ethoprop Fensulfothion Lindane MISSISSIPPI, 31 SITES 1 0.6 0.02 0.02 Alachlor Lasso 1 3.2 0.75 0.84 Linuron Lorox 3 1.9 1.00 1.12 Captan 1 3.2 0.03 0.03 Phorate Thimet 6 3.9 0.93 1.04 Chloroneb Demosan 7 22.5 0.03 0.03 Propachlor Ramrod 14 8.5 1.50 1.68 DDT 8 25.8 3.81 4.27 Toxaphene 1 0.6 2.73 3.05 DEF 4 12.9 0.90 1.00 Trifluralin Treflan 14 9.2 0.69 0.77 Disulfoton Di-Syston 7 22.5 0.01 0.01 Diuron DNBP Karmex -) 6.4 2.75 3.08 KENTUCKY. 31 SITES 4 12.9 1.19 1.33 DSMA I 3.2 1.86 2.08 Atrazine AAtrex 2 6.4 1.02 1.14 Endrin 1 3.2 4.20 4.70 Dalapon Dowpon -> 6.4 1.05 1.17 Ethylmercury 2.4-D 1 3.2 0.05 0.05 chloride Ceresan Red 1 3.2 O.OI 0.01 2,4-DB Butyrac 1 3.2 0.80 0.89 Fluometuron Cotoran 5 16.1 0.76 0.85 Paraquat 1 3.2 1.00 1.12 Folex I inuron Lorox 3 9.6 3.2 0.75 1.00 0.84 1.12 LOUISIANA, 25 SITES 1_ IIIUIL"! Malathion Methylmercury 1 3.2 2.40 2.68 Alachlor Lasso 1 4.0 1.00 1.12 Aldrin 3 12.0 0.15 0.16 acetate Ceresan L 6 19.3 0.01 0.01 Azinphosmethyl 2.4-D Guthion 1 4 4.0 16.0 0.75 0.81 0.84 0.91 Mirex MSMA 4 7 12.9 22.5 0.08 2.48 0.09 2.77 1.12 3.77 2.4-DB Butyrac 1 4.0 1.95 2.18 Nitralin Planavin 1 3.2 1.00 Dalapon Dowpon 1 4.0 6.80 7.62 Parathion. methyl 13 41.9 3.36 (Continued next page) Vol. 12, No. 3, December 1978 141 TABLE 3 (cont'd. 1. Compounds applied to cropland sites hy state, 1971 — National Soils Monitoring Program Average Total Average Total Trade Name, Pesticides Applied No. OF % OF Application Trade Name, Pesticides Applied No. OF % OF Application LB./ KG/ LB./ KO/ Compound If Noted Sites Sites ACRE Hectare Compound Simazine If Noted Princep Sites 1 Sites 2.7 Acre 2.04 Hectare Sodium chlorate 2 6.4 1.07 1.20 2.28 Tcrraiolc 1 3.2 0.15 0.16 0.04 Sulfur 1 2.7 0.50 0.56 Thiram I 3.2 0.04 Toxaphenc Treflan 10 7 32.2 22.5 6.90 0.75 7.73 0.84 NORTH CAROLINA , 30 SITES Trifluralin Alachlor Atrazine Carbaryl 2,4-D DEF Lasso AAtrex Sevin 10.0 23.3 6.6 16.6 3.3 3.00 1.86 3.00 2.20 0.75 3.36 2.08 3.36 MISSOURI. 80 SITES Alachlor Aldrin Atrazine Chlorambcn Lasso 8.7 3.7 1.82 0.63 2.03 0.70 2.46 0.84 AAtrcx Amibcn 17 21.2 2.5 2.24 0.88 2.50 0.98 Dichlofenthion Dichloropropcne Nemacidc 3.3 3.3 6.(X) 67.00 6.72 75.09 2 4-D 2.5 0.50 0.56 Disulfoton Di-Syslun 6.6 0.90 1.00 2'.4-DB DSMA I iniiron Bulyrac 1.2 1.2 0.22 3.00 0.24 3.36 Fensulfothion Fluometuron Coloran 3.3 3,3 2.00 1.25 2.24 1.40 Lorox 2.5 0.88 0.98 Malathion 3.3 0.50 0.56 MSMA Naptalam Propachlor Trifluralin 1.2 1.65 1.84 Maleic hydrazide 6.6 3.00 3.36 Alanap 2.5 2.00 2.24 Naptalam Alanap 3,3 3.00 3.36 Ramrod 3.7 3.13 3.51 Toxaphene 3.3 0.09 0.10 Treflan 3.7 0.75 0.84 Trifluralin Treflan 6.6 1.00 1.12 NEBRASKA. lOS i SITES OHIO, 59 SITES Alachlor Lasso 2 1.9 1.50 1.68 Alachlor Lasso 5.0 0.92 1.02 Atrazine AAtrex 22 20.9 1.38 1.54 Aldrin 5.0 3.67 4.10 Biix 5 4.7 0.91 1.01 Atrazine AAtrex 13,5 2.01 2.25 Captan Carbaryl Carbofuran 31 29.5 0.01 0.01 Azinphosmethyl Ciuthion 1,6 1.00 1.12 Sevin Furadan 2 6 1.9 5.7 1.17 0.89 1.31 0.99 Bordeaux mixtures Captan 1.6 1.6 1.25 5.20 1.40 5.82 Chevron RE-5353 4 3.8 0.85 0.95 Carbaryl Sevin 3,3 1.13 1.26 2. 4-D 21 20.(1 1)72 0.81 Carbophenothion Trithion 1.6 3.20 3.58 n 1 T 7 i n n n 0.9 1.30 1.45 Chlorambcn Amiben 3.3 2.75 3.08 Dichloropropcne Dicldrin 0.9 1.9 17.00 n.oi 19.05 0.01 Chloropropham Cypromid CIPC Clobber 1.6 1.6 2.50 0.75 2.80 0.84 Disulfoton Di-SystOTt 0.9 1.00 1.12 2,4-D 12 20.3 0.50 0.56 EPTC Hplam 0.9 3.00 3.36 Dicamba Banvel D 8.4 0.20 0.22 Fensulfothion 0.9 0.61 0.68 Dodine 1.6 0.50 0.56 Heptachlor Londax 0.9 0.01 0.01 Fcrbam 1.6 3.17 3.55 0.9 0.50 0.56 Heptachlor 2 3,3 1.57 1.76 Malathion 26 24.7 0.03 0.03 Lead arsenate 1,6 1.20 1.34 Melhoxychlor Mcthylmcrcury dicyandiatnide Panogen 2 2 1.9 1,9 0.01 0.01 0.01 0.01 Linuron Melhoxychlor Parathion. ethyl Lorox 6,7 1,6 1.6 1.25 2.00 0.50 1.40 2.24 0.56 Parathion. ethyl 2 1.9 1.00 1.12 Phosphamidon Simazine Dimecron 1.6 0.03 2.(X) 0.03 Phorate Thimet Ramrod 5 4 4.7 3.8 0.87 2.59 0.97 2.90 1,6 2.24 Propachlor OKLAHOMA. 62 SITES Thiram 1 0.9 0.01 0.01 Alachlor Arsenic pentoxide Atrazine Lasso AAtrex . 1.6 3.2 1.6 5.00 0.50 13.00 5.60 0.56 NEW ENGLAND.i 18 SITES 2 1 Alachlor Lasso 1 5.5 2.00 2.24 14.57 Atrazine AAtrex 1 5.5 1.00 1.12 Captan 2 3.2 0.01 0.01 Azinphosmethyl Carbaryl Guthion Sevin 1 1 5.5 5.5 0.50 1.25 0.56 1.40 2.4-D Disulfoton 3 2 4.8 3.2 3.08 0.65 3.45 0.72 Dinitrocresol 5.5 0.75 0.84 FMTS Ceresan M 4 6.4 0.01 0.01 Endosulfan 1 5.5 0.75 0.84 F.thylmercury EPTC Eptam 1 5.5 4.00 4.48 chloride Ceresan Re d 1 1.6 0.01 0.01 Maneb 1 5.5 4.80 5.37 Furclhrin 1 1.6 8.00 8.96 Parathion. methyl 1 5.5 1.25 1.40 Mcthylmcrcury dicyandiamide Nabam Parathion, ethyl Parathion, methyl Panogen 2 I 3 5 3.2 1.6 4.8 8.0 0.01 5.00 3.17 0.50 0.01 NEW YORK. .17 SITES 5.60 3.54 0.56 Atrazine AAtrex 11 29.7 1.38 1.54 Azinphosmethyl Guthion 2 5.4 0.56 0.62 Phorate 1 1.6 15.00 16.81 Butylatc Suian 1 2.7 3.00 3.36 Thiram 3 4.8 0.01 0.01 Captan Carbaryl d 10.8 0.66 3.20 0.37 0.25 2.67 0.70 2.97 0.33 0.50 1.00 4.00 0.01 12.80 0.01 0.73 3.58 0.41 0.28 2.99 0.78 3.33 0.36 0.56 1.12 4.48 0.01 14.34 0.01 Sevin 2 3 2 1 Di-Syston 2 Premerye 2 1 1 Phallan 1 1 -> Diihane M-J5 1 1 5.4 8.1 5.4 2.7 5.4 5.4 2.7 2.7 2.7 2,7 5.4 2.7 2,7 OREGON, 37 SITES 2, 4-D Dicldrin Dinitrocresol Disulfoton DNBP Dodine Endosulfan Folpet Lead arsenate Malathion Mancozeb Mcthoxychlor Atrazine Bromacil Captafol 2,4-D Dicamba Dichlorprop Dichloropropcne Disulfoton Endosulfan EPTC Heptachlor llcxachloro- benzenc Linuron AAtrex Hyvar Difolatan Banvel D 2,4-DP Di-.Syston Thiodan Eptam 2.7 2.7 2.7 8.1 2,7 2.7 2.7 5.4 5.4 2.7 2.7 4.00 0.37 1.50 0.50 0.06 3.00 0.01 2.00 0.75 3.00 O.OI 4.48 0.41 1.68 0.56 0.06 3.36 0.01 2.24 0.84 3.36 0,01 Phosphamidon Propargitc Dimecron Omile 1 2.7 2.7 0.50 5.00 0.56 5.60 Lorox 2.7 2.7 0.01 0.75 0.01 0.84 (Continued next page) 142 Pesticides Monitoring Journal TABLE 3 (cont'd. ). Compounds applied to cropland sites hy state, 1971— National Soils Monitoring Program Average Total Average Total Trade Name. Pesticides No. OF Applied % OF Application Trade Name. Pesticides Applied No, OF % OF Application LB./ KG/ LB./ KG/ Compound If Noted Sites Sites Acre Hectare Compound If Noted Sites Sites Acre Hectare Malathton Melhylmercury 1 2.7 1 .00 1.12 TENNESSEE, 24 SITES dicyandiamidc Panoycn J 8.1 0.14 0.15 DEF I 4.1 1.50 1,68 Mevinphos Phosdrin 1 2.7 0.50 0.56 Disulfoton Di-Syston 3 12.5 3.00 3,36 Oxydemelon- Diuron Karmex 2 8.3 1.55 1,73 methyl Paralhion, ethyl Metasystox-R 1 2 2.7 5.4 0.50 3.25 0.56 3.64 DSMA Fluomctuion Folex Parathion, methyl Cotoran 1 1 2 1 1 1 1 4.1 8.3 4.1 4.1 4.1 4.1 2.00 1.50 1.50 1.50 1.50 6.00 2,24 1.68 1.68 PENNSYLVANIA, 35 SITES 1.68 1.68 6.72 Alachlor Lasso 2 5.5 0.88 0.98 Toxaphene Atrazine AAtrex 5 13.8 1.65 1.84 Trietazine I 4.1 0.70 0.78 Bulylate Sulan 1 2.7 1.20 1.34 Trifluralin 3 12.5 0.98 1.09 ?,4-D 2 5.5 0.50 1.00 1.00 0.56 1.12 1.12 Malaihion 1 1 2^7 2.7 VIRGINIA/WEST VIRGINIA,' 26 SITES Melhoxychlor Atrazine Captan Carbaryl Diazinon AAtrex Sevin 2 7.6 3.8 3.8 2.00 0.08 2.00 2.24 SOUTH CAROLINA . 15 SITES 0,08 2.24 0.44 Benefit! Balan 1 6.6 1.08 1.21 3^8 0.40 BHC 1 6.6 0.03 0.03 Diniirocresol 3.8 1.50 1.68 Carbaryl Scvin 2 13.3 2.25 2.52 Endosulfan 3.8 1.20 1,34 Copper sulfate 1 6.6 10.50 11.76 EPTC Eptam 3.8 0.70 0,78 2.4-DB 1 6.6 0.25 0.28 Mctham Vapam 3.8 2.16 2.42 DDT J 2I).0 8.94 9,24 Metlioxychlor 3.8 0.80 0.89 DEF 2 13.3 1.16 1.30 Vernolalc Vcrnam 3.8 2.00 2.24 ni«n1 fnt r»n Di-Syston Karmex Alanap 2 13.3 13.3 6.6 0.59 1.00 0.75 0.65 1.12 0.84 Diuron 2 1 WASHINGTON STATE, 45 SITES Naptalam Aldrin 1 2.2 0.43 0,48 Parathion, methyl 5 33.3 4.76 5.34 BHC 2 4.4 0.01 0,01 Thiram 1 6.6 0.01 0.01 Bromacil 2 4.4 0.75 0.84 Toxaphene 3 20.0 13.16 14.75 Captan 2 4.4 0.06 0.06 Trifluralin Treflan 2 13.3 1.00 1.12 2,4-D DDT Dicamba HCB Banvel D 13 1 1 6 28.8 2.2 2.2 13.3 1.32 0.75 0.13 O.OI 1.48 SOUTH DAKOTA, 106 SITES 0.84 0.14 Atrazine AAtrex 5 4.7 1.59 1.78 0.01 Barban Carbync 1 0.9 0.25 0.28 Melhylmercury Bux 3 2.8 0.70 0.78 dicyandiamidc 1 2.2 0.01 0.01 Captan 24 22.6 0.01 0.01 Parathion, ethyl 1 2.2 1.50 1.68 2,4-D 32 30.1 0.45 0.50 Phenylmercury Diazinon 3 2.8 1.64 1.83 acetate 1 2.2 0.01 O.OI Dicamba Banvcl D 2 1.8 0.12 0.13 Phenylmercury Dicldrin 2 1.8 0.01 0.01 urea 3 6.6 0,01 0.01 Ethylmercury Terbacil Sinbar 1 2.2 1.40 1.56 chloride Fensulfothion Cercsan Red 1 0.9 0.01 0.0 1 Terbutryn Igran 1 2.2 1.75 1.96 1 0.9 1.20 1.34 Malathion MCP 17 16.0 1.8 0.01 0.25 0.01 0.28 WISCONSIN, 66 SITES MCPA Alachlor Lasso 6.0 1.44 1.61 Methoxychlor 0.9 O.lll 0.01 Atrazine AAtrex 25 37.8 1.83 2.04 Melhylmercury Bux 1.5 7.00 7.84 dicyandiamidc Panogen 3.7 0.01 0.01 Carbofuran Furadan 4.5 0.90 1.01 Parathion, methyl 0.9 0.50 0.56 2,4-D 3.0 1.50 1.68 Phorate Thimet 0.9 0.60 0.67 2,4-DB Disulfoton Butyrac Di-Syston 1.5 1.5 0.50 2.00 0.56 2.24 Propachlor Ramrod 2.8 2.40 2.68 Entiosulfan Thiodan 1.5 1.00 1.12 Thiram 1.8 0.01 0.01 Linuron Lorox 1.5 1.00 1.12 Atrazine AAtrex 8.3 1.85 2.07 MCPA MCP 1.5 0.50 0.56 2,4-DB Butyrac 4.1 0.29 0.32 Phorate Thimet 1.5 6.00 6.72 DDT 4.1 3.00 3.36 Thiram 1.5 0.01 0.01 'See Table 1. Vol. 12, No. 3, December 1978 143 .... .... 0 C)C)C<5Qw:^^ $: aX<>VJ^\VS C310 m'.'."^' < « M - Kf^HW y A 5AAA III- LoOowO FIGURE 2. Percent of sites reporting pesticide applications, 1971 , National Soils Monitoring Program TABLE 4. Crop and pesticide application data for sampling sites, 1971 — National Soils Monitoring Program Pesticides Pesticides Pesticides Pesticides Pesticides Not Application Pesticides Not Application Total No. OF Applied Applied Unknown Total Applied Applied Unknown No. OF No. OF No. OF No. OF No. OF No. OF No. OF Crop Sites Sites % Sites 7c Sites 9r Crop Sites Sites % Sites % Sites % Corn, field 445 366 82 70 16 9 2 Saffiower 1 33 2 67 Soybeans 251 147 59 100 40 4 Almonds 2 100 Wheat 115 56 49 59 51 Blueberries 2 100 Hay, mixed 112 3 3 108 96 1 Cabbage 2 100 Alfalfa and/ or Figs ~i 100 bur clover 108 10 9 97 90 1 Peaches -> 100 Cotton 63 55 87 6 10 2 Timothy -> 100 Sorghum, sweet Tomatoes sorghum, milo 52 32 62 19 37 1 Apricots 1 100 Oats 47 16 34 30 64 1 Broccoli 1 100 Pasture 41 2 5 39 95 Carrots 1 100 Hay, grass 25 25 100 Cherries 1 100 Barley 16 4 25 12 75 Cowpeas 1 100 Peanuts 11 9 82 2 18 Cucumbers 1 100 Potatoes, white 11 9 82 .> 12 Flax 1 100 Clover y 1 11 8 89 Grapefruit 1 100 Rice 9 8 89 1 11 Lemons 1 100 Beans, diy 8 5 63 3 37 Lentils 1 100 Grapes 8 7 88 1 12 Lettuce 1 100 Apples 7 7 100 Mint 1 100 Oranges 7 5 71 2 29 Pecans 1 100 Sugarbeels 6 5 83 1 17 Plums prunes 1 100 Sugarcane 6 6 100 String beans 1 100 Peas 5 2 40 3 60 VVatermcItm 1 100 Rye 5 5 100 Other 11 3 27 8 73 Tobacco 5 4 80 1 20 Fallow sites 83 3 4 80 96 144 Pesticides Monitoring Journal TABLE 5. Compounds applied lo cropland sites by crop, 1971— National Soils Monitoring Program Pesticides Applied Average Total Application Compound No. OF Sites • OF Sites LB. /Acre ko/Hectare Reported Total Application Rate, kg Hectare MiN. Max. ALFALFA and BUR CLOVER. 106 SITES Carbaryl Diazinon EPTC Malathion Melhoxychlor Mevinphos Parathion, elhyl Trichlorfon 0.9 0.9 1.9 2.8 1.9 1.9 2.8 0.9 1.00 0.40 1.8S L13 0.90 1.50 2.50 0.75 1.12 0.45 2.07 1.27 1.01 1.68 2.80 0.84 0.78 1.12 0.90 1.12 0.56 1.12 0.45 3.36 1.57 1.12 2.24 6.72 0.84 COTTON, 61 SITES Aldrin Arsenic penloxide Azodrin Cacodylic acid Captan Chloroneb 2.4-D DDT DEF Dicofol Disulfoton Diuron DNBP DSMA EMTS Endrin Eliiylmercury chloride Fluometuron Folex Linuron Malathion MCPA Mercury Methyl trilhion Methylmerciiry acetate Methylmercury dicyandia Mirexi Monuron MSMA Nitralin Paraquat Parathion. ethyl Parathion, methyl PCNB Prometryn Sodium chlorate Terrazole Thiram Toxaphene Trifluralin 4 1 1 9 1 25 9 1 14 8 2 11 4 2 1 21 5 2 2 1 2 1 6 mide 2 2 15 1 1 5 36 4 1 3 27 21 1.6 3.3 6.6 1.6 1.6 14.8 1.6 41.0 14.8 1.6 23.0 13.1 3.3 18.0 6.6 3,3 1,6 34.4 8.2 3.3 3.3 1.6 3,3 1.6 9.8 3.3 1.6 3.3 24,6 1,6 1.6 8.2 59.0 3,3 3,3 6.6 1.6 4,9 44,3 34.4 0.01 0.50 0.33 0.01 0.01 0,01 0,44 4,28 1.03 1.00 1.31 1.45 1.62 2.00 0.04 2.80 0.01 0.96 1.05 0.63 1.55 0.50 0.06 i.OO 0.01 0.01 0.01 1.30 1.86 1.00 0.25 6.78 3.26 3.51 1.08 1.80 0.15 0.01 7.95 0.74 0.01 0.56 0.37 0.01 0.01 0.01 0.49 4.80 1.16 1.12 1,46 1.63 1.82 2.24 0.04 3.14 0.01 1.07 1.18 0.70 1.74 0.56 0.07 3.36 0.01 0.01 0.01 1.46 2.08 1.12 0.28 7.60 3.65 3.M3 1.21 2.02 0.17 0.01 8.91 0.83 0.01 0.56 0.06 0.01 0.01 0.01 0.49 0.09 0.67 1.12 0.01 0.38 1.12 0.24 O.Ul 1.57 0.01 0.56 0.84 0.56 0.78 0.56 0.01 3.36 0.01 0.01 0.01 1.12 0.75 1.12 0.28 0.84 0.06 0.01 0.18 0.06 0.17 0,01 0.1(1 0.28 0.56 0.56 0.01 13,45 1.68 7.85 5.04 2,52 4,48 0.11 4.71 2.24 1.68 0.84 2.69 0.12 0.01 0.01 1.79 5.60 21.02 11.21 7.85 2.24 5.60 0.01 40.35 1.24 FIELD CORN, 427 SITES Alachlor Aldrin Atrazine Butylate Bux Captan Carbaryl Carbofuran Chevron RE-5353 Chloramben Chlordane Cypromid 2,4-D Dalapon DDT Demeton Diazinon Dicamba Dieldrin DNBP Disulfoton Dyfonate EPTC Ethoprop 37 37 199 18 17 116 3 18 4 2 1 1 72 2 2 1 11 9 3 1 2 1 1 1 8.7 8.7 46.6 4.2 4,0 27,2 0.7 4.2 0.9 0,5 0,2 0,2 16,9 0.5 0.5 0.2 2.6 2.1 0.7 0.2 0,5 0.2 0,2 0,2 1.66 1.37 1.72 1.74 1.26 0.01 1.32 0.81 0.85 1.12 2.50 0.75 0.73 1.05 1.00 0.12 0.93 0.37 0.01 3.20 0,65 11.90 2.00 1,00 1.86 1.54 1.93 1.95 1.41 0.01 1.47 0.90 0.95 1.26 2.80 0.84 O.SI 1.18 1.12 0.13 1.05 0.42 0.01 3.59 0.73 1.01 2.24 1.12 0.28 0,11 0.16 0.28 0.5(1 0.01 0,84 0.28 0.78 0.28 2.80 0.84 0.06 1.18 1.12 0.13 0,01 0,13 0.01 3.59 0.56 1.01 2 24 1.12 6.72 5.60 4.48 3.36 7.85 0.01 1,79 2,58 1,12 2,24 3,36 1.18 1.12 2.80 1.12 0.01 0.90 {Continued next page) Vol, 12, No, 3, December 1978 145 TABLE 5 (cont'd.). Compotiiuh applied to cropland sites by crop, 1971 — National Soils Monitoring Program Pesticides Applied Average Total Application Reported Total Application Rate. kg/Hectare Compound No. of Sites > OF Sites LB. /Acre kg/Hectare MiN. Max. Elhylmerciiry chloride 1 Fciisulfolhion 4 Ferbam 1 Furethrin 1 Hcptachlor 6 Isodrin I Lindane 1 Linuron 2 Londax 1 Malatliion 96 Methoxychlor 20 Mirexi 1 MSMA 1 Paraquat I Paratiiion, ethyl 3 PCP 1 Phorate 20 Propachlor 38 Silvex 2 Simazine 5 2,4, 5-T 2 Thiram 1 Toxaphene 1 Alachlor Captan Carbaryl Chloramben Chloropropham Dalapon 2,4-DB DDT Dichloropropene DNBP Fluometiiron Linuron Mirex' MSMA Naptalam Nitralin Paraquat Parathion. methyl Propachlor Solan Thiram Toxaphene Trifluralin Vernolaie 27 3 5 38 1 1 6 2 10 1 16 1 1 3 4 I 3 1 1 2 38 3 0.2 0.9 0.2 0.2 1.4 0.2 0.2 0.5 0.2 22.5 4.7 n.2 0.2 0.2 0.7 0.2 4.7 8.9 0.5 1.2 0.5 0.2 0.2 0.01 0.93 2.00 8.00 1.67 0.01 0.02 0.52 0.50 0.01 0.01 D.OI 0.25 1.00 0.87 6.00 (1.81 1.42 0.38 2.C0 0.30 0.01 2.73 0.01 1.04 2.24 8.97 1.87 0.01 0.02 0.59 0.56 0.01 0.01 0.01 0.28 1.12 0.97 6.72 0.91 1.57 0.42 2.24 0.34 0.01 3.06 11.1 1.2 2.1 15.6 0.4 0.4 2.5 0.8 0.4 4.1 0.4 66 0.4 0.4 1.2 1.6 0.4 1.2 0.4 0.4 0.4 0.8 15.6 1.2 1.33 0,04 1.88 1.42 2.50 6.80 0.84 2.50 67.00 1.08 1.00 0.96 0.01 2.00 2.33 1.06 2.00 2.55 2.80 1.00 0.04 3.82 I. II 0.80 1.49 0.04 2.11 1.59 2.80 7.62 0.94 2.80 75.09 1.21 1.12 1.08 0.01 2.24 2.61 1.19 2.24 2.86 3.14 1.12 0.04 4.29 1.24 0.90 0.01 0.68 2.24 8.97 0.01 0.01 0.02 0.33 0.56 0.01 0.01 0.01 0.28 1.12 0.56 6,72 0.19 0.10 0.28 1.40 0.28 0.01 3.06 0.22 0.01 0.90 0.25 2.80 7.62 0.25 1.12 75.09 0.43 1.12 0.28 0.01 2.24 1.12 0.84 2.24 1.12 3.14 1.12 0.04 2.24 0.25 0.78 1.34 3.36 0.84 0.01 0.02 1.23 16.81 6.72 0.56 2.80 0.39 MIXED HAY, 111 SITES 2.4-D Mirexi 2 1 1.8 0.9 0.80 0.01 0.90 0.01 0.67 0.01 1.12 SOYBEANS, 243 SITES 6.16 0.08 4.30 4.48 2.19 4.48 2.52 2.24 3.36 1.68 5.77 6.33 5.60 1.01 WHEAT. 113 SITES Aldrin 1 Azinphosmethyl 1 Barban 1 BHC 2 Bromacil 2 Captan 1 2,4-D 28 Dicamba 3 Dichlorprop 1 Disulfoton 2 EMTS 4 Ethylmcrcury chloride 4 Hexachlorobenzene 6 Methylmercury dicyandiamide 9 Parathion, ethyl 1 Parathion, methyl 4 Phenylmercury acetate 3 Terbutryne 1 Thiram 2 0.9 0.9 0.9 1.8 1.8 0.9 24.8 2.7 0.9 1.8 3.5 3.5 5.3 8.0 0.9 3.5 2.7 0.9 0.01 0.22 0.25 0.02 0.56 0.25 0.83 0.11 3.00 0.36 0.01 0.06 0.02 0.01 8.00 0.50 0.01 1.75 O.OI 0.01 0.25 0.28 0.02 0.63 0.28 0.93 0.12 3.36 0.40 0.01 0.06 0.02 O.OI 8.97 0.56 0.01 1.96 0.01 0.01 0.25 0.28 0.01 0.41 0.28 0.13 0.07 3.00 0.40 0.01 0.01 0.01 0.01 8.97 0.56 0.01 1.96 0.01 0.02 0.84 4.48 0.15 0.40 0.01 0.11 0.03 0.01 0.56 0.01 0.01 'Aerially applied for conlrol of the imported fire ant. 146 Pesticides Monitoring Journal TABLE 6. Pesticide application information on selected crops, by state, for sampling sites. 1971- National Soils Monitoring Program Total Pesticides Pesticides Pesticides Total Pesticides Pesticides Pesticides State No. OF Sites Applied Not Applied Use Unknown No. OF Sites Appl ED Not Applied Use Unknown ALFALFA AND/OR BUR CLOVER COTTON Alabama 0 4 4 Arkansas 1 1 9 7 7 6 1 1 1 California 5 3 2 Georgia 0 5 5 Illinois 4 4 0 Indiana 1 1 0 Iowa 19 19 0 Louisiana 0 7 7 Michigan 7 1 6 0 Mississippi 0 13 12 1 Missouri 3 1 2 1 1 Nebraska 10 10 0 New England 2 2 0 New York 4 4 0 N. Carolina 0 1 1 Ohio 2 2 0 Oklahoma 2 1 1 5 2 2 1 Oregon 5 1 4 0 Pennsylvania 7 1 5 1 0 S. Carolina 0 5 4 1 S. Dakota 16 16 0 Tennessee (1 6 6 Va./W, Va. 2 2 0 Washington stale 2 2 C Wisconsin 16 16 0 FIELD CORN SOYBEANS Alabama 5 3 2 7 1 6 Arkansas 1 1 24 13 11 California 1 1 0 Florida 1 1 2 2 Georgia 1.1 5 g 3 2 1 Illinois 67 65 2 58 36 22 Indiana 34 31 2 1 21 17 3 1 Iowa 81 70 11 42 34 8 Kentucky 16 10 4 2 3 1 1 1 Louisiana 1 1 5 2 3 Michigan 21 14 7 1 1 Mid-Atlantic 9 5 2 2 1 1 Mississippi 1 1 14 9 5 Missouri 18 16 2 22 13 8 1 Nebraska 46 40 4 2 3 3 New England 3 2 1 0 New York 15 11 2 2 0 N. Carolina 13 9 4 8 5 3 Ohio 23 19 4 14 8 5 1 Oklahoma 3 2 1 2 1 1 Pennsylvania 8 5 3 1 1 S. Carolina 2 1 1 7 2 5 S. Dakota 27 26 1 1 1 Tennessee 5 2 3 9 2 7 Va./W, Va. 3 3 1 1 Washington stale 2 1 1 0 Wisconsin 24 23 1 0 WHEAT MIXED HAY Alabama 0 1 1 Arkansas 1 1 2 2 California 4 1 3 1 1 Florida 0 1 1 Idaho 13 5 8 0 Illinois 6 1 S 1 1 Indiana 5 1 4 2 2 Iowa 1 1 5 5 Kentucky 0 2 2 Michigan 1 1 9 1 8 Mid-Atlantic 0 1 1 Mississippi 0 1 1 Missouri 1 1 20 20 Nebraska 3 1 2 0 New England 0 5 5 New York 0 9 8 1 N. Carolina 0 1 1 Ohio 5 1 4 6 6 Oklahoma 34 13 21 0 Oregon 3 3 3 3 (Continued next page) Vol. 12, No. 3, December 1978 147 TABLE 6 (cont'd. ). Pesticide appliiulion injonnation on selccleil crops, />>■ slate, for sampliiif; sites, 1971 — National Soils Motiitorinii Program Total No. OF Sites Pesticides Applied Pesticides Not Applied Pesticides Use Knovvn Total No. OF Sites Pesticides Applied Pesticides Not Applied Pesticides Use Known Pennsvlvania 0 S. Dakota 20 IS 5 Va./W. Va. 0 Washington state 18 15 3 Wisconsin 0 13 8 5 1 15 12 8 5 15 LITERATURE CITED (/) Bennett. I. L. 1967. Foreword. Peslic. Monit, J. 1(1). (2) Carey, A. £., J. A. Gowen. H. Tai, W. G. Mitchell, ami G. B. Wiersnia. I97S. Pesticide residue levels in soils and crops, 1971 — National Soils Monitoring Program (III). Pestic. Monit. J. 12(3) : 117-136. (.?) Panel on Pesticide Monitorini;. 1971. Criteria for defin- ing pesticide levels to be considered an alert to poten- tial problems. Pestic. Monit. J. 5(1);36. (•/) Wiersnui, G. B., P. F. Sand, and E. L. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(l):63-66. 148 Pesticides Monitorinc; Journal WATER Organochlorines, ChoUnest erase Inhibitors, and Aromatic Amines in Dutch Water Samples, September 1969-December 1975 Ronald C. C. Wegnian and Peter A. Greve i ABSTRACT The Dutch aquatic ciivironnwitt was monitored jrom Sep- tember 1969 to December 1975 for organochlorine pesti- cides and their metabolites, cholinesterase inhibitors, and aromatic amines. The 1,492 samples analyzed included surface water, rainwater, groundwater, and drinking water. The higliest concentrations of he.xachlorobeiizene (HCB) and a- and fi-benzene he.xachloride (BHC) were found in the Rhine River and its tributaries. Concentrations of the compounds in the Dutch part of the Rhine River decreased downstream. Other organochlorine pesticides and their metabolites, heptachlor. hcptachlor epoxide, aldrin, dieldrin. endrin a- and ji-endosulfan. and ^DDT were detected occa- sionally, but only in low conct ntrations. Cholinesterase in- hibitors and aromatic amines were always present in the Rhine River ami its tributaries. Introduction Preliminary investigations before 1969 of organochlorine pesticides and related substances in the Dutch aquatic environment indicated the necessity of a long-term in- vestigation. Endosuifan levels found in the Rhine River later in 1968 (6) underlined the need for such an in- vestigation. Samples were taken from surface water, rainwater, groundwater, and drinking water prepared from surface water. Presently, about one third of the Dutch popu- lation is at least partly supplied with drinking water prepared from surface water. Sampling sites varied every year, except for a few fixed sites including the Maas and Rhine Rivers, so that after 7 years all parts of The Netherlands were investigated for at least I year. Special interest was paid to large agricultural areas such as the IJsselmeerpolders. 'Laboralory of Toxicology. National InsUluiu of Public Healih. Bili- hoven, The Netherlands. During the study, the number of sampling sites at drinking water stations was gradually decreased as the stations acquired equipment and expertise to analyze their own samples. Levels of organochlorine pesticides were determined because they are persistent and accumulate in the food chain. Analyses were performed for cholinesterase in- hibitors including phosphates, thiophosphates, dithio- phosphates, and carbamates (e.g., dichlorvos, parathion. malathion, carbaryl, respectively). From the herbicide group, urea compounds were chosen because of their great application rate. This group of compounds was determined as their aromatic amine moiety. During the present investigation, papers were published on endosuifan in the Rhine River (6), cholinesterase inhibitors in Dutch surface waters {S), pesticides in the Rhine River (9), aromatic amines and their derivatives in Dutch surface waters (10), and the fate of pesticides during drinking water preparation (7). In cooperation with the Federal Health Office in Berlin, the concentra- tions of cholinesterase inhibitors in the German and Dutch parts of the Rhine River were compared and the main source was determined (5). From these papers, only the primary results are repeated here. Metlwds and Materials The 1,492 samples were collected by means of a bail and were transported in acetone-washed bottles to the National Institute of Public Health, Bilthoven, The Netherlands. Surface water was taken from a depth of about 1 m. Locations of the 92 sampling sites are given in Figure 1. The methods mentioned in the present report include im- provements introduced during the study. They had no Vol. 12, No. 3, December 1978 149 NETHERLANDS 1-16 surface water for preparation of drinking water 17-20 groundwater and rainwater 21-24 coastal waters 25-3A IJsselmeer region 35-44 Maas River and tributaries 45-50 Rhine River and 51-92 waters tributaries f" ~\S^*^ other surface _~^ — -d-Q'^^ FIGURE 1. Snmplina silex for study of organochlorines, choliite.sterasc inhibitors, and aromatic amines in Dutch water samples significant influence on the results, except for the C„ compounds which could be determined separately only from May 1970. ORGANOCHLORINE COMPOUNDS Water samples of 1000 ml, including silt, were extracted successively with 200, 100, and 100 ml of petroleum ether (boiling range, 40°-60''C). The combined ex- tracts were dried over anhydrous sodium sulfate and concentrated to about 5 ml in a Kiidcrna-Danish evapo- rative concentrator. The last few milliliters of solvent were evaporated to exactly 1 ml by a gentle stream of nitrogen at room temperature. The concentrated ex- tract was added to a microcolumn containing 2.00 g basic alumina (W-200, activity Super I, Woelm). Be- fore use, the microcolumn was activated for 16 hours at 150°C, and then deactivated with 11 percent water (11 g water + 89 g ahmiina). The column was eluted with 5 ml of petroleum ether to produce Eluate A containing HCB, «- and 7-BHC, heptachlor epoxide (about 10 percent), /;,/;'-DDF., o,p'- DDI. TDE, /).//-DDT, telodrin, isodrin. aldrin, and heptachlor. The receiving tube was changed and a 150 Pesticides Monitoring Journal second elution was carried out with 10 ml of a 20:80 (v/v) mixture of ethyl ether-petroleum ether to pro- duce Eluate B containing /J-BHC. heptachlor epoxide (about 90 percent), dicldrin, and endrin. The eluates were concentrated to exactly 1 ml by a gentle stream of nitrogen at room temp>erature. To determine a- and fi-endosulfan, a microcolumn con- taining 2.00 g 60-200-mesh silica gel (Fisher S 661) activated for 2-3 hours at 140°C was used. The column was eluted first with 8 ml of a 80:20 (v/v) mixture of hexane-toluene and next with 8 ml of a 40:60 (v/v) mixture of hexane-toluene and 8 ml toluene; «- and /J-endosulfan were present in the second eluate. One-Ml portions of the concentrated eluates were injected into the gas chromatographs. Instrument parameters and operating conditions follow: (I ) Model 1800 Varian Aerot!raph Detector: Column: Temperatures: tritium electron-capture 180 cm X 0.3 cm ID Pyrcx. packed with a mixture of 5 percent OV-210 and 5 percent OV-17 (4+1) on 80-IO(l-mesh Cliromosorb W-HP injection port 205^0 oven 190°C detector 200°C nitrogen flowing at 40 ml/minute Carrier gas (2) Perkin-Elmer Model F 22 gas chromatograph Detector: Column: Temperatures: Carrier gas: "■'Ni electron-capture 40 m X 0..15 mm ID Pyrex capillary, coated with SE-30 (CiC grade) injection port 215''C oven 155°-225°C at 3°C/minutc with a linear temperature program- mer detector 250°C helium (lowing at 2-3 ml/minute; helium splitting gas flow of 0-60 ml/minute; nitrogen purge gas flow of 80 ml/minute The practical lower limit of detectability was 0.01 ppb. Recovery data, obtained by spiking river water samples with the pesticides and carrying them through the entire analytical procedure, were over 90 percent. Results arc not corrected for recovery. To confirm the identity of the pesticides, p-values or chemical conversions were used, such as the quantitative conversion of o.^'-DDT and p.p'-DDT to, respectively, o.p'-DDE and p,p'-DDE by treatment with MgO, the disappearance of dieldrin and endrin by treatment with concentrated sulfuric acid, and the peak shift for endosulfan under the influence of alkali (6). AROMATIC AMINES The sums of aromatic amines and their derivatives were determined colorimetrically (10). Concentrations are expressed as 3.4-dichloroaniline. The practical lower limit of detectability was 0.5 ppb. CHOLINESTERASE INHIBITORS Colorimetric determination of cholinesterase inhibitors was performed in a methylene chloride extract of the sample on an AutoAnalyzcr (^). The enzyme source was freeze-dried human plasma. Concentrations were calculated as paraoxon equivalents. The practical lower limit of detection was 0.2 ppb. Resutts The 20,000 data points collected in the monitoring pro- gram during 1969-75 are summarized in Tables 1-7. In view of the low frequency of occurrence and the low concentrations found, the concentrations of p-BHC, aldrin, heptachlor, heptachlor epoxide, endrin, TDE, o.p'-UDT. p.p'-DDE, and p.p'-DDT are not given in the tables. Unless stated otherwise, all extracts of water samples included silt. The Rhine River was studied in more detail than the other Dutch surface waters. Samples were taken weekly near Lobith at sampling site 45 (Fig. 1). The geo- graphical distribution of HCB, and o- and t-BHC in the Rhine River is illustrated in Figures 2-4 for the southern branch of the river, Rhine-Boven Merwede- Nieuwe Waterweg. Discussion The data in Tables 1-7 indicate that the highest con- centrations of pesticides and related substances are found in the Rhine River and its tributaries. The highest concentrations in the Maas River, compared below, are much lower. Residue, ppb Maas River 0.29 0.07 0.18 0.03 0.09 1.7 2.4 Levels in other waters were lower still or not detected. HCB and o- and 7-BHC were almost always present in the Rhine water samples. Median values in ppb varied during 1969-75 as follows: HCB, 0.06-0.14; a-BHC, 0.06-0.22; and 7-BHC, 0.04-0.13. Concentrations of the by-product. o-BHC, are higher than those of the commercial product, 7-BHC. This means cither that significant amounts of a-BHC-containing products, which have been banned for years, are still used along the Rhine or that industry, rather than agriculture, is the main source of pollution. Because the source of contamination is located across the German border, it was not possible to determine the exact source of the BHC discharge. BHC has had only limited use as a fungicide. Since July 1974, the concentrations of o- and 7-BHC in the Rhine have decreased considerably. Median values of a- and 7-BHC in 1974 were 0.22 ppb and 0.13 ppb, respectively; in 1975, 0.06 ppb and 0.04 ppb, respectively. The levels of o-BHC in the Rhine and its tributaries are considered harmful to the repro- duction of Daplinia magna (water flea) (i). PliSIIClDF Rhine River HCB 0.55 ..-BHC 0.60 -BHC 0.42 Dieldrin 0.06 I-ndosulfan 0.81 Cholinesterase inhibitors 56 Aromatic amines 10 Vol. 12, No. 3, December 1978 151 TABLE 1. Concentrations of BHC, dieUiiin. endosidjan, and cholincsterasc inhibitors in Dutch samples, 1969 Residues, ppb tt- AND P- Cholinesterase » -BHC DiELDRIN Endosulfan Inhibitors' TVPLS OI Water No. OF Samples Sampling Site No. Max Med Max Med Max Med Max Med Surface water for drinking water preparation Braakman 1 raw water 2 — — 0.01 — — — Berenplaai 2 raw water 4 0.16 0.06 0.01 — 0.03 — 3.02 1.03 Bcrenplaat 2 treated water 4 0.1)2 — 0.01 — — — 0.17 0.17 Drentse A 3 raw water 3 — — — — — — Locnerveense Plas 4 raw water 3 — — 0.01 0.01 — — Wantij 6 raw water 3 0.09 0.05 0.01 — 0.11 0.09 5.20 1.82 IJsselmeer, Andijk 7 raw water 4 — — 0.04 — 0.01 — IJsselmeer. Andijk 7 treated water 4 — — 0.04 — 0.0 1 — Surface water for infiltral ion Amsterdam-Rijnkanaal 8 raw water 2 0.112 0.01 — — 0.17 0.14 1.42 1.06 Amsterdam-Rijnkanaal 8 raw water - 1 — — — — 0.06 0.06 1.20 1.20 Lek 9 raw water t 0.03 0.02 — — 0.10 0.09 1.38 1.09 Lek 9 raw water - 1 — — — — — — 1.52 1.52 Enschede 10 raw water" 3 0.15 0.02 0.01 — — — 0.05 0.05 St. Jansteen 11 raw water 3 — — 0.02 0.01 — — St. Jansteen U treated water 1 0.01 0.01 0.03 0.03 0.03 0.03 Valkenburgse Watering 15 raw water 4 0.03 0.02 0.02 — 0.05 — 0.32 0.22 IJsselmeer region IJsselmeer. Staveren 25 surface water 1 0.03 0.03 — — — — IJsselmeer. Y-2 27 surface water 1 — — — — — — IJsselmeer. Steile Bank 28 surface water 1 0.02 0.02 — — — — Maas and tributaries Maas. Eijsden 35 surface water 7 0.08 0.02 — — 0.09 — 0.44 0.22 Roer 42 surface water 2 o.o; 0.01 0.01 — — — Niers 43 surface water 3 0,11 0.03 0.02 0.0! 0.13 0.06 0.19 0.18 Rhine and tributaries Rhine 45 surface water 17 0.24 0.18 0.04 — 0.81 0.24 10.67 2.46 Kromme Rijn 47 surface water 6 0.08 0.02 0.02 — 0.04 — 2.04 1.00 Other surface waters Ooslermoerse Vaart 57 surface water 4 0.01 — 0.02 — — — Boomawetering 76 surface water 8 0.09 — 0.02 0.01 0.01 — 0.57 0.42 Rijnbeek 82 surface water 4 — — 0.01 — — — 0.52 0.52 Lage Vaart. Colijn 85 surface water 12 0.05 — 0.06 0.01 0.09 — Hoge Vaart, Colijn 86 surface water 24 0.08 — 0.08 — 0.10 — Lage Vaart. Wortman 89 surface water 29 11.10 — 0.14 — 0.09 — Larser Vaart 90 surface water 13 — — 0.08 0.02 — — Wortmanvaart 92 surface water 12 — — 0.03 0.01 — — NOTE: /i-BHC. aldnn. hcptachlor. heptachlor epoxide, endrin. and ZDDT were detected occasionally in low concentrations; — = not detected. Unless stated otherwise, all water samples included silt. 'As paraoxon-equivalenis. -After rapid filtration. 'Before infiltration. 152 Pf.sticidis Moniidrinc. Journal TABLE 2. Concentrations of HCB, BHC, dieldrin. entlosulfan. and choUnc.sterase inhibitors in Dutch water samples, 1970 |M« . Residues, ppb ^' Hi „. and /i- Chomnesterase No. TVPES OF Water Sak PLE CB «■ BHC T- BHC DtEL DRIN Endosulfan Inhibitors^ Sampling Site s Max Med Max Med Max Med Max Med Max Med Max Med Surface water for drinking water preparation Braakman 1 raw water 2 0.02 — 0.02 0.01 0.02 0.01 0.02 0.01 0.03 Berenplaat 2 raw water 2 — — 0,17 0.12 0.09 0.07 0.03 _ 0.07 — 0.80 0.30 Drentse A 3 raw water 2 — — — — 0.02 0.01 0.02 0.18 0.06 Loenerveense Plas 4 raw water 1 — — — — — — 0.03 Oud-Beijerland 5 raw water 2 0.03 — 0.17 0.12 0.06 0.05 0.01 0.12 1.08 0.83 Oud-Beijerland 5 treated water 2 0.01 — 0.13 0.09 0.07 0.06 0.02 — 0.04 — 0.79 0.50 Wantij 6 raw water }. 0.08 0.05 0.18 0.15 0.12 0.11 0.04 2.00 0.63 Wantij 6 treated water 2 0.01 — 0.06 0.06 0.05 0.05 0.02 _ (1.03 — 0.45 0.20 IJsselmeer, Andijk 7 raw water 3 — — 0.02 0.02 0.02 0.01 0.01 0.07 0.27 0.06 IJsselmeer, Andijk 7 treated water 3 — — 0.02 0.01 0.02 0.01 0.02 — 0.05 — 0.17 0.07 Surface water for infiltration Amsterdam-Rijnkanaal 8 raw water 3 0.05 0.03 0.13 0.08 0.13 0.08 0.01 0.05 0.82 0.52 Amsterdam-Rijnkanaal 8 raw water - 3 0.03 0.02 0.15 0.10 0.18 0.11 0.01 0.01 0.04 _ 0.82 0.42 Lek 9 raw water 3 0.04 0.02 0.16 0.08 0.20 0.10 0.02 0.01 0.07 — 1.10 0.36 Lek 9 raw water - 3 0.03 0.02 0.17 0.10 0.20 0.11 0.01 — 0.05 — 1.05 0.40 Enschede 10 raw water-' 3 — — 0.50 0.32 0.05 0.02 0.02 0.02 0.05 — 0.07 0.06 Enschede 10 raw water - 3 — — 0.14 0.12 — 0.01 0.04 St. Jansteen 11 raw water 3 0.01 — 0.01 — O.OI 0.02 0.03 Valkenburgse Watering 15 raw water 6 — — — — — — 0.01 — 0.03 — 0.75 0.34 Groundwater Bilthoven 18 groundwater -> — — — — — - - — — — — — Coastal waters Waddenzee 22 surface water 3 — — 0.01 - 0.01 — 0.01 - 0.10 - 0.15 0.08 IJsselmeer region Usselmeer, Y-1 26 surface water 2 0.01 — 0.03 0.02 0.04 0.03 0.01 — 0.05 0.02 0.34 0.21 Kelelmeer. Y-14 31 surface water 1 o.ii: 0.02 0.23 0.23 0.13 0.13 — — 0.04 0.02 0.63 0.49 Usselmeer, Y-104 34 surface water 2 0.01 — 0.03 0.03 0.04 0.04 0.01 — 0.01 — 0.24 0.22 Maas and tributaries Maas, Eysden 35 surface water 8 0.04 — 0.03 — 0.06 0.02 0.01 — 0.03 — 0.50 0.22 Roer 42 surface water 5 0.02 — 0.02 0.01 0.05 0.04 0.01 — 0.03 — 0.12 0.06 Niers 43 surface water 6 0.01 — 0.06 o.o: 0.05 0.03 tl.Ol — 0.04 — 0.11 0.06 Rhine and tributaries Rhine 45 surface water 51 11.39 0.08 0.26 0.14 0.16 0.08 0.04 _ 0.40 0.03 4.01 0.72 Kromme Rijn 47 surface water 6 0.02 — 0.15 0.05 0.11 0.05 0.03 — 0.03 — 2.08 0.40 Other surface waters Ruilen A 52 surface water 5 0.01 — — — — — 0.01 — 0.02 — 0.10 0.05 Overijsselse Vecht 60 surface water 4 — — — — — — 0.01 — 0.03 — 0.09 — ditch. A.Paulowna 68 surface water 5 — — 0.01 — — — 0.02 0.01 — — 0.33 0.10 ditch, HiUegom 69 surface water 2 — — 0.0.1 0.02 0.01 — _ — — — 0.22 0.18 ditch, Hillegom 70 surface water 2 — — 0.04 0.02 0.01 — 0.04 0.04 — — 0.37 0.18 ditch, Hillegom 71 surface water 2 — — 0.01 — — — — — — — 0.34 0.17 ditch, Hoogeveen 72 surface water 2 — — — — — — 0.02 0.01 — — 0.32 0.22 Leidse Vaart, Lisse 73 surface water 2 — — — — 0.02 0.02 0.03 0.02 — — 0.26 0.16 ditch. Noordwijkerhout 74 surface water 2 0.01 — — — — — 0.08 0.06 — — 0.21 0.10 leidse Vaart, Dc Zilk 75 surface water t — _ 0.01 — 0.05 0.02 0.04 0.03 — — 0.22 0.16 Boomawetering 76 surface water 5 — 0.03 0.01 0.04 0.02 0.03 — 0,15 0.01 0.40 0.12 Rijnbeek 82 surface water 6 D.MI _ 0.02 — 0.03 0.01 0.01 — 0.05 0.03 0.53 0.10 Lage Vaart, Colijn 85 surface water 5 — — 0.02 0.01 0.02 0.01 0.02 0.01 0.02 — 0.23 0.06 Hoge Vaart, Colijn 86 surface water 5 tl.Ol — 0.06 0(>2 0.04 0.02 0.02 0.01 0.02 0.01 0.24 Lage Vaart, De Block van KufTeler 87 surface water 5 0.04 _ 0.02 0.01 0.03 0.02 0.03 0.01 0.04 — 0.1 1 0.05 ditch, N.O. polder 91 surface water 1 — _ _ — — — 0.07 0.07 0.07 0.07 0.14 0.14 Wortman 92 surface water 5 0.01 0.01 0.03 0.02 0.03 0.03 0.01 — 0.03 — 0.13 0.12 NOTE: See NOTE. Table 1. 'As paraoxon-equivalents. -After rapid tiltralion. 'Before intiltralion. Vol. 12, No. 3, December 1978 153 TABLE 3. Concvntralions of HCB, BHC, tlieUlrin. ciuiosiilfan, and cholinesterasc inhibitors in Dutch water samples, 1971 Residues, ppb Sampling She Types of No. Water No. OF Sam- ples HCB re-BHC -BHC DiELDRIN n- AND ff- CHOLINESTERASE Endosulfan Inhibitors' Max Med Max Mf.d Max Med Max Med Max Med Max Med Surface water for ilrinkinti water preparation IJsselmeer 7 raw water Surface water for infiUration Enschede 10 Enschede 10 Valkenburgsc Waterinp 15 Groundwater Bilihovcn 18 Haarlem l") Hillcgom 21) IJsselmeer region Ketelmecr, Y-14 .11 Kelelhaven 32 Maas and tributaries Maas. Eysden }5 Maas, Urmond 36 Maas. Maasbracht 37 Maas. Kessel 38 Rocr 42 Niers 43 Rhine and tributaries Rhine raw water - raw water'' raw water 12 0.01 5 — 5 — 6 0.01 groimdwater 1 groundwater 1 groundwater I surface water surface water surface water surface water surface water surface water surface water surface water Other surface waters Winschoterdiep 51 surface water 5 Bagniolenbeek 58 surface water I Regge 63 surface water 3 Twentekanaal, Almelo 64 surface water 3 Twentekanaal, bovenpand 65 surface water 3 Lage Vaart, Colijn 85 surface water 6 Hoge Vaart, Colijn 86 surface water 6 Lage Vaart, Wortman 89 surface water 6 11.13 0.15 0.38 0.02 0.06 0.06 0.20 0.03 11.02 0.03 0.01 0.02 0.03 0.02" 0.03 0.02 0.01 11.01 0.03 U.05 11.02 0.01 0.01 0.01 0.01 45 surface water 52 0.52 0.02 0.01 0.01 0.14 0.13 0.18 0.01 0.05 0.12 0.01 0.01 0,01 0.01 — 0.02 0.01 0,08 0.02 0.48 — 0.06 0.16 0.06 0.10 0.14 0.03 0.01 0.12 I). 1 3 0.02 0.03 0.34 0.03 0.06 0.01 11,01 O.OI 0.02 0.03 0.01 0.06 — 0.03 0.05 0.02 0.03 0.02 0.06 0.06 0.04 0.01 0.02 0.01 0,04 0.01 — 0.07 0.02 0.02 0,25 0.02 — — 0.01 0.01 0.01 0.01 — 0.02 0.13 0.10 0.211 0.01 — 0.04 0.01 0.02 0.01 0.02 O.OS 0.04 0,05 0.04 0.02 0.03 0.02 U.02 0,01 0.04 0.02 — — 0.03 0.20 1.18 0,08 0.40 0,40 0,19 1.26 0,33 0,25 0.08 0,08 OM 0.20 — 0,18 — 0.12 0,08 0.08 0,08 2.00 0.16 0.56 0.12 0.74 0.38 0.14 0.12 0,50 OM 0,40 0.09 -0,46 0.23 0.32 — NOTE: See NOTE. Table 1. 'As paraoxon-eqiiivalenls. -Before infiltration. ^After rapid filtration. 154 Pesticidrs M0NITOKIN6 Journal TABLE 4. Concentrations of HCB, BHC, dieUrin, endosulfan, and cholinesterase inhibitors in Dutch water samples, 1972 Residues, ppb Sampling Site No. No. OF Types of Sam- Water PLEs Max HCB tt-BHC V-BHC DiELDRIN o- AND P- Cholinesterase Endosulfan Inhibitors i Med Max Med Max Med Max Med Max Med Max Meo Surface water for drinking water preparation Usselmeer, Andijlc 7 raw water Surface water for infiltration Enschede 10 Enschede 10 Valkenburgse Watering 15 12 0.01 0.05 0.02 0.04 0.02 0.05 0.01 — raw water" 6 0.01 — 0.17 0.10 0.02 0.02 0.05 raw water ' 6 0.01 — 0.09 0.06 0.01 0.01 raw water 9 0.03 — 0.04 0.02 0.03 0.02 0.02 — 0.44 0.24 — 3.52 0.76 Rainwater Bilthoven 17 rainwater 8 0.01 — 0.50 0.02 0.06 0.02 0.01 Usselmeer region Usselmeer, Y-2 27 surface water 11 0.01 — 0.05 0.02 0.05 0.03 0.02 Usselmeer, Y-2 27 surface water^ 4 0.03 — 0.04 0.03 0.03 0.02 0.02 Usselmeer, Y-10 29 surface water 11 0.05 — 0.25 0.03 0.20 0.03 0.03 Usselmeer, Y-10 29 surface water s 4 0.02 0.01 0.24 0.06 0.20 0.05 0.02 Usselmeer, Y-12 30 surface water 11 0.20 0.01 0.20 0.07 0.20 0.05 0.02 Usselmeer, Y-12 30 surface water ^ 4 0.03 0.01 0.12 0.12 0.13 0.08 0.04 Ketelhaven 32 surface water 11 0.08 0.04 0.20 0.12 0.22 0.10 0.02 Ketelhaven 32 surface water ^ 4 0.04 — 0.16 0.09 0.19 0.14 0.02 Usselmeer, Y-20 33 surface water 11 0.06 0.01 0.08 0.02 0.08 0.03 0.03 Usselmeer, Y-20 33 surface water ^ 4 0.01 — 0.02 0.02 0.03 0.02 0.05 Maas and tributaries Maas, Eijsden 35 surface water 11 0.03 0.01 0.07 0.01 0.07 0.02 0.01 Maas, Grave 39 surface water 12 0.02 — 0.08 0.01 0.13 0.02 0.01 Maas, Keizersveer 41 surface water 12 0.01 0.06 0.01 0.18 0.02 0.02 Roer 42 surface water 12 0.01 _ 0.09 0.04 0.02 0.02 Niers 43 surface water 12 0.08 0.0 1 0.15 0.08 0.06 0.04 0.08 Dieze 44 surface water 10 0.05 — 0.06 0.01 0.07 0.03 0.02 Rhine and tributaries Rhine 45 surface water 52 0.37 0.13 0.57 0.16 0.28 0.11 0.02 Other surface waters Zuidlaardermeer 53 surface water 6 0.01 — 0.01 — 0.01 — 0.01 Lauwersmeer 54 surface water 6 0.03 — 0.01 — 0.01 — O.OI Van Starkenborghkanaal 55 surface water 6 0.03 — 0.02 — 0.02 0.01 0.01 Meppelerdiep 56 surface water 6 0.02 — 0.02 — 0.02 — 0.01 Regge. bovenloop 61 surface water 3 Regge, benedenloop 62 surface water 3 0.02 0.02 0.11 0.06 0.05 0.04 0.01 Twentekanaal, bovenpand 65 surface water 2 — — 0.44 0.22 0.02 0.01 0.01 Eem 66 surface water 6 0.01 — 0.08 0.05 0.06 0.04 0.01 Vecht 67 surface water 6 0.01 — 0.06 0.03 0.05 0.02 — Lage Vaart, Colljn 85 surface water 7 0.01 — 0.01 — 0.02 0.01 0.03 Hoge Vaart, Coliin 86 surface water 7 0.01 — 0.08 0.02 0.09 0.01 0.01 Lage Vaart, De Block van Kuffeler 87 surface water 7 0.03 — 0.01 — 0.02 — — Hoge Vaart, De Block van Kuffeler 88 surface water 7 0.01 — 0.03 0.01 0.04 0.02 0.01 Lage Vaart, Wortman 89 surface water 7 0.01 — 0.01 0.01 0.02 0.02 O.OI 0.02 0.02 — 0.01 O.OI 0.01 0.09 0.02 — 0.03 0.42 0.13 1.10 0.25 2.44 0.48 1.18 0.76 1.94 0.17 0.44 0.14 — 0.16 0.07 0.50 — 0.12 — 0.32 0.14 2.36 0.73 0.12 — — 0.22 0.07 O.U — 0.06 — 1.72 0.17 0.64 0.06 0.06 — 0.52 0.06 0.14 0.36 NOTE: See NOTE, Table 1. lAs paraoxon-equivalents. ^Before infiltration. 'After rapid filtration. Vol. 12, No. 3, December 1978 155 TABLE 5. Concentrations of HCB, BHC, dieldrin, endosulfan, and cholinesterase inhibitors in Dutch water samples, 1973- Residues, ppb Sampling She No. No. OF Types of Sam- Water PLES Max HCB rt-BHC 7-BHC Dieldrin ft- AND /J- Cholinesterase Endosulfan Inhibitors^ Med Max Med Max Med Max Med Max Med Max Med Surface water for drinking water preparation Usselmeer. Andijk 7 raw water 9 11. til — 0.10 0.03 0.08 0.03 — 0.01 — 1.10 0.12 Surface water for infiltration Enschede 10 raw water - 6 — - 0.09 0.04 — — — - — — 1.90 — Rainwater Bilthoven 17 rainwater 13 — — 0.03 0.01 0.05 0.02 0.02 — — — Coastal waters Bocht van Waium ->l surface water 3 — — 0.01 — 0.05 0.01 — — — — 0.06 — Weslerschelde. Schaar van Ouden Doel 23 surface water 13 11.03 0.01 0.10 0.01 0.12 0.04 0.01 — — — 0.68 0.32 Weslerschelde. Hansweert 24 surface water 13 11.07 — 0.03 — 0.14 0.03 0.01 — — — 0.60 0.08 Usselmeer region Usselmeer, Y-2 27 surface water 12 0.01 — 0.14 0.04 0.13 0.03 — — — — 2.64 0.20 Usselmeer, Y-10 29 surface water 13 U.Ol — 0.10 0.05 0.06 0.04 — — — — 1.65 0.50 Ketelhaven 32 surface water 11 0.08 0.02 0.23 0.10 0.19 0.09 — — 0.07 — 5.10 1.88 Maas and iributaries Maas, Eijsden 35 surface water 13 0.29 0.01 0.02 0.01 0.05 0.01 — — 0.01 — 1.65 0.06 Maas, Grave 39 surface water 12 0.03 0.01 0.19 0.02 0.12 0.02 — — — - 1.26 — Maas, Keizersveer 41 surface water 13 0.04 0.01 002 0.01 0.06 0.02 — — — — 1.62 0.06 Roer 42 surface water 1 — — Niers 43 surface water 1 — — Dieze 44 surface water 1 — — Rhine and tributaries Rhine 45 surface water 52 0.55 0.08 0.45 0.19 0.42 0.12 0.02 — 0.10 — 15.80 2.42 Boven Merwede 48 surface water 24 0.10 0.03 0.36 0.15 0.23 0.11 0,01 — 0.02 — 4.40 1.46 Nieuwe Waterweg 50 surface water 13 0.06 0.02 0.35 0.13 0.21 0.09 0,01 — 11.01 — 4.45 1.24 Other surface waters Twentekanaal, Almelo 64 surface water 5 — — 0.03 0.01 0.01 0.01 — — 0.01 — 0.60 — Twentekanaal, bovenpand Roosendaalse Vliet 81 surface water 1 0.01 — — — — — — — — — 0.18 0.06 Hoge Vaart. Colijn 86 surface water 6 0.01 — 0.09 — 0.07 — — — 0.01 — 1.16 0.25 Hoge Vaart, De Block van Kuffeler 88 surface water 6 0.01 — 0.02 — 0.01 — — — 0.01 — — — NOTE: See NOTE, Table 1. 'As paraoxon-eqiiivalents. -After rapid fiitralion. 156 PEsriciurs Moniiorinc Journal TABLE 6. Concentrations of HCB, BHC. dicldrin, cndosuljan. cholincsterase inhihitois, and aromatic amines in Dutch water sample, 1974 Residues, ppb Sampling Site Types of No. Water HCB --BHC DiELDRIN No. OF Sam- - PLES Max Med Max Med Max Med Max Med Max Med Max Med Max Med 7-BHC ft- AND P- ChOLINESTERASE AROMATIC Endosulfan Inhibitors^ Amines- Surface water for drinking water preparation Enschede 10 Isabella Wctering 12 Pielers v.d.Endevaart 13 canal near Valkenburg 14 Wijde A 16 Rainwater surface water ' 5 surface water 5 surface water 6 raw water 6 raw water 6 Bilthoven 17 rainwater 0.01 — 0.15 0.07 0.02 — 0.01 — 0.0.1 0.01 0.01 — 0.01 — 0.11 0.06 O.CS 0.04 0.22 0.07 0.09 0.05 0.01 0.08 0.02 0.10 0.04 — 1.32 1.54 0.05 0.26 1.0 1 8 0.5 Coastal waters Bocht van Watum 21 surface water 5 — — 0.01 0.01 0.05 0.01 IJsselmeer region IJsselmeer. Y-10 29 surface water 12 0.01 — 0.12 0.06 0.10 0.04 Ketelhaven 32 surface water U 0.09 0.04 0.57 0.14 0.26 0.07 Maas and tributaries Maas, Eijsden 35 surface water 12 0.05 0.01 0.02 0.01 0.04 0.02 Maas, Keizersveer 41 surface water 13 0.02 — 0.03 0.01 0.05 0.02 Rhine and tributaries Rhine 45 surface water 50 0.39 0.10 0.60 0.22 0.33 0.13 Boven Merwede 48 surface water 12 0.12 0.06 0.55 0.28 0.26 0,12 Hollandse IJssel 49 surface water 6 0.01 — 0.10 0.03 0.05 0.04 Nieuwe Waterweg 50 surface water 11 0.05 0.03 0.36 0.21 0.23 O.Il Other surface waters Twentekanaal. bovenpand 65 surface water 7 0.05 2.1 0.58 0.12 0.05 ditch. Ouddorp 78 surface water 6 0.01 — 0.01 — 0.01 — Gentse Vaart 79 surface water 6 0.01 _ 0.01 — 0.02 0.01 Roosendaalse Vliel 81 surface water 6 — — 0.01 — 0.02 0.01 Zwarle Water 1 83 surface water 6 — — 0.01 0.01 0.16 0.01 Zwarte Water II 84 surface water 6 — — 0.09 0.02 0.04 0.02 Hoge Vaart, Colijn 86 surface water 6 0.02 — 0.14 0.01 0.10 — Hoge Vaart. De Block van Kuffeler 88 surface water 6 0.01 — 0.02 0.01 0.03 — — 0.8 0.05 1.36 0.70 4.6 0.8 3.34 0.56 15 3.4 0.50 0.8 1.64 0.12 1.0 — 3.64 1.36 8.6 4.5 3.36 0.79 16 3.8 1.16 0.09 1.0 0.6 2.40 0.60 5.8 2.6 0.83 1.60 — 3.7 — 0.12 — 0.7 — 0.05 — — — 0.10 — 8.1 — — — 3.0 0.6 0.58 — 4.4 0.7 — — I.O NOTE: See NOTE. Table I. 'As paraoxon-equivalents. -As 3.4-dichloroaniline-equivalents. ■■'Before infiltration. TABLE 7. Concentrations of HCB, BHC, dicldrin, endosulfan, cholincsterase inhibitors, and aromatic amines in Dutch water samples, 1975 Sampling Site No. Types of Water Residues, ppb HCB ft-BHC 7-BHC DiELDRIN ft- and /?- cholinesterase aromatic Endosulfan Inhibitors' Amines^ No. of Sam- _ PLES Max Med Max Med Max Med Max Med Max Med Max Med Max Med Rainwater Bilthoven 17 rainwater 10 0.01 0.03 0.02 0.04 0.03 — Maas and tributaries Maas, Eijsden 35 Maas, Lith 40 Rhine and tributaries Rhine 45 IJssel 46 Boven Merwede 48 Nieuwe Walerweg 50 Other surface waters Overijsselse Vecht 59 Twentekanaal, Almelo 64 Twentekanaal, bovenpand 65 polder ditch 77 Cirole Kreck 80 Zwarle Water I 83 Zwarte Water II 84 surface water 13 surface water 13 surface water surface water surface water surface water surface water surface water surface water surface water surface water surface water surface water 0.02 0.02 0.21 0.06 0.10 0.02 0.01 0.08 0.06 0.03 0.03 O.OI 0.01 0.03 0.21 0.09 0.13 0.09 0.01 0.03 0.02 O.OI 0.07 0.02 0.06 0.14 0,04 0.03 0.06 0.03 0.05 0.07 0.03 0.04 0.09 0.03 0.06 0.04 0.04 0.02 1.40 0.47 0.04 0.04 0.02 — 0.01 — 0.02 0.01 0.02 O.OI 0.01 — 0.O2 O.OI 0.30 0.04 0.09 0.02 0.02 0.02 NOTE: See NOTE. Table 1. 'As paraoxon-equivalents. -As 3,4-dichloroaniline-equivalenls. 0.44 — 1.5 0.6 0.18 — 2.4 0.7 56.0 7.80 10 3.7 21.0 8.70 14 2.8 18.0 7.20 9.5 3.8 10.0 6.00 4.0 2.6 0.12 0.04 — 1.9 0.7 2.10 — 1.0 0.6 — — 0.5 — 0.34 — 0.7 1.4 6.8 — 0.14 — 2.3 Vol. 12, No. 3, December 1978 157 concentration (/jg/l) 05 Oi 03 02 1973 197i SITE SAMPLED Rhine (45) Boven Merwede (i8) Nieuwe Waterweg (50) 1975 J fmannj j aso nd j fmami j asond j fmamj j asond month FIGURE 2. Concentrations of HCB in the southern region of the Rhine River {sites 45, 48, and 50 in Fij>. I) High concentrations of a-BHC were also found in the Twentekanaal. The source of the contamination was a chemical plant which produces 7-BHC. The a-BHC, a worthless by-product of the synthesis of 7-BHC, was dumped beside the canal. Removal of the dumped material led to a gradual decrease of concentrations in the canal and in drinking water removed from canal water. Concentrations of HCB have also decreased, but grad- ually and less drastically (Figs. 2^). HCB is a low- polarity compound which is volatile with water and readily adsorbed by the solid particles which settle in fluvial transport. Concentrations of cholinestcrase inhibitors have grad- ually increased since 1972 and significantly in 1975. Concentrations of a- and P-endosulfan have decreased greatly following the first sensational wave in June-July 1969 (9) and a second, less important one in autumn of the same year. In Table 8, maximum and median or mean concentra- tions of a-BHC, 7-BHC, :i;BHC, dieldrin, 2DDT, and DDE from nine nations are summarized (/, 2, 4, 12- 23). Levels of a- and 7-BHC, i;BHC, dieldrin, 2DDT, and DDE in Dutch surface waters arc of the same order of magnitude as are the concentrations in other indus- trialized countries. Concentrations of aromatic amines are comparable in Dutch and German parts of the Rhine River (II). 158 Pesticides Monitoring Journal SITE SAMPLED Rhine (45) concentration (yug/l) 05 Boven Merwede (^8) Nieuwe Waterweg (50) FIGURE 3. Concentrations of a-BHC in the southern region of the Rhine River (sites 45, 48, and 50 in Fig. 1) Vol. 12, No. 3, December 1978 159 concentration (/jg/l 05- SITE SAMPLED Rhine (45) Boven Merwede (48) Nieuwe Waterweg (50) FIGURE 4. Concentrations of y-BHC in the southern region of the Rhine River (sites 45, 48, and 50 in Fig. J) 160 Pesticides Monitoring Journal TABLE 8. Concentrations of organochlorine pesticides in worldwide surface waters, 1968-75 No. OF Types of _ Sites Water Residues, PPB « -BHC 7 -BHC 2 BHC DiELDRIN DDT DC >E Med Literature Location Max Med Max Med Max Med Max Med Max Med Max References Brazil 9 surface water 4 <1 <1 <1 Lara and Barreto, 1972 (15) Canada 3 surface water — — 1 — 1 0.04 0.01 ■ 0.07 0.01' 0.01 — ' Miles and Harris, 1973 (76) Czechoslovakia 150 surface water 1971-72 0.52 0.81 0.60 UhnSh et al., 1974 (23) Federal Republic of Germany (FRG) 8 surface water 1970 1.90 0.10' 7.10 0.10' 0.04 I 0.25 1 Herzel, 1972 (72) 27 surface water 1971 2.40 0.07' 1.75 0.17' — 1 0.84 — I Herzel, 1972 (72) German Democratic Republic (GDR) 26 surface water 0.67 0.15 3.2 0.34 0.98 0.15 Engst and Knoll, 1973 (4) Japan 130 river water 1970-73 3.43 0.20 14.15 0.92 Suzuki et al., 1974 Hungary 4 Balaton Lake 1973 0.04 0.04' 0.01 — ' 1 . 1 (21) P4szlor et al., 1975 (18) the present report Netherlands 16 surface water 1969 0.24 1 0.14 1 0.20 _, 0.16 1 26 surface water 1970 0,50 0.03' 0.20 0.05' 0.08 — 0.11 — 1 1 17 surface water 1971 0.48 0.04' 0.34 0.03' 0.06 I 0.11 — 1 1 26 surface water 1972 0.57 0.04' 0.28 0.03' 0.08 1 0.17 — 1 0.15 1 21 surface water 1973 0.45 0.07 0.42 0.04' 0.02 — 0.11 — 0.01 . 17 surface water 1974 0.60 0.17 0.33 0.07 0.06 — 0.04 — 0.01 . 13 surface water 1975 1.40 0U3 0.14 0.03 0.02 — 0.03 — 0.01 United States of America 1 Utah Lake 1970-71 Mississippi River 1974 - - 1.3 0.01 - 4.1 Bradshaw et al., 1972 (1) Brodlmann, 1976 (2) 6 Iowa Rivers 1968 0.01 — 0.01 — 0.01 — Johnson and Morris, 1971 (13) 10 Iowa Rivers 1969 0.06 — 0.01 0.01 10 Iowa Rivers 1970 0.06 — 0.02 0.02 1 Des Moines River Iowa 1971 Iowa 1972 Iowa 1973 0.05 U.04 0.02 0.03 0.01 Kellog and Bulkley, 1976 (14) 10 Iowa rivers 1968 0.01 0.01 0.01 Morris et al.. 1972 (17) 10 Iowa rivers 1969 0.06 0.02 0.01 10 Iowa rivers 1970 0.06 0.02 0.02 10 Iowa rivers 1971 0.04 0.22 0.03 19 surface water 1974 0.07 3.92 Richard et al., 1975 (19) 20 rivers 1968 rivers 1969 rivers 1970 rivers 1971 0.07 0.04 0.16 0.05 0.03 0.02 0.02 0.01 0.46 0.05 0.09 0.09 O.IO 0.06 0.05 0.08 Schulze et al., 1973 (20) 4 streams 1969 0.33 — 2.50 0.01 0.71 — Truhlar and Reed, 1975 (22) 4 streams 1970 0.15 — 11.0 0.02 0.21 — 4 streams 1971 — — 0.12 — 0.05 — ' Mean value. LITERATURE CITED ( / ) Bradshaw, J. S., E. L. Lovcridge, K. P. Rippee, J. L. Peterson, D. A. White, J. R. Burton, and D. K. Fuhri- man. 1972. Seasonal variations in residues of chlori- nated hydrocarbon pesticides in the water of the Utah Lake drainage system — 1971) and 1971. Pestic. Monit. J. 6(3): 166-170. (2) Brodtmann, N. V., Jr. 1976. Continuous analysis of chlorinated hydrocarbon pesticides in the lower Mis- sissippi River. Bull. Environ. Contam. Toxicol. 15( 1 ): 33-39. U) Canton. //., P. A. Greve, W. SloofJ, and G. J. van Esch. 1975. Toxicity-, accumulation- and elimination studies of n-hexachlorocyclohexane (n-HCH) with fresh water organisms of different trophic levels. Water Res. 9( 12) : 1 163-1 169. (4) Engst, R.. and R. Knoll. 197?. Contamination of sur- face water, rain water, and drinking water with chlori- nated hydrocarbons. Die Nahrung 17(8) :837-851. (5 I Fritschi. G., P. A. Greve, H. KnssmanI, and R. C. C. Wegnian. 1978. Cholinesterase inhibitors in the Rhine river. Organic compounds in the environment. Deter- mination, significance, decrease. Erich Schmidt Press, Berlin, pp. 265-270. (6) Greve, P. A., and S. L. Wit. 1971. Endosulfan in the Rhine river. J. Water Pollut. Contr. Fed. 43(12): 2338-2348. (7) Greve, P. A. 1971. Toxic substances in water: Occur- rence and significance. H2O 4( 12):272-275. (5) Greve, P. A., J. Frendenthal, and S. L. Wit. 1972. Potentially hazardous substances in surface waters. Vol. 12, No. 3, December 1978 161 Part II. Cholinesterase inhibitors in Dutch surface water. Sci. Total Environ. l(3):253-265. (9) Grcve, P. A. 1972. Potentially hazardous substances in surface waters. Part I: Pesticides in the river Rhine. Sci. Total Environ. 1(2) : 173-180. {10) Greve, P. A., and R. C. C. Wegman. 1975. Determi- nation and significance of aromatic amines and their derivatives in Dutch surface waters. Schr. Reihe Ver. Wasser-, Boden-, und Lufthyg., Berlin-Dahlem 46(1): 59-80. (//) Hegazi, M. 1977. Analysis and fate of urea herbicides and their metabolites on bankfiltration, drinking water and soil passage. Thesis. Bonn. (12) Herzcl. F. 1972. Organochlorine insecticides in surface waters in Germany — 1970 and 1971. Pestic. Monit. J. 6(3):179-187. (li) Johnson, L. G., and R. L. Morris. 1971. Chlorinated hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J. 4(4):216-2I9. (14) Kellogg. R. L.. and R. V. Bulktey. 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. (15) Lara. W. H., and H. H. C. Barreto. 1972. Chlorinated pesticides in water. Rev. Inst. Adolfo Luti'. 32(1): 69-74. (16) Miles. J. R. W., and C. R. Harris. 1973. Organochlu rine insecticide residues in streams draining agricul- tural, urban-agricultural, and resort areas of Ontario, Canada— 1971. Pestic. Monit. J. 6(4) :363-368. (17) Morris, R. L., L. G. Johnson, and D. W. Ehert. 1972. Pesticides and heavy metals in the aquatic environ- ment. Health Lab. Sci. 9(2): 145-151, (18) Pdsztor, Z., J. E. Ponyi, A. Holld. and L. Gonezy. 1975. Investigations by gas chromatograph on the chlorinated hydrocarbon pollution in two areas of Lake Balaton. Annal. Biol. Tihany 42(2) : 191-202. (19) Richard, J. J., G. A. Junk, M. J. Avery, N. L. Nehring, J. S. Fritz, and H. J. Svec. 1975. Analysis of various Iowa waters for selected pesticides: atrazine, DDE, and dieldrin— 1974. Pestic. Monit. J. 9(3) : 1 17-123. (20) Schulze, J. A., D. B. Manigold, and F. L. Andrews. 1973. Pesticides in selected western streams — 1968-71. Pestic. Monit. J. 7(l):73-84. (21) Suzuki, M., Y. Yamalo, and T. Akiyama. 1974. BHC ( 1,2,3,4,5,6-hexachlorocyclohexane) residue concen- trations and their seasonal variation in aquatic envi- ronments in the Kitakyushi district, Japan 1970-1973. Water Res. 8(9) :643-649. (22) Truhtar, J. F., and L. A. Reed. 1975. Occurrence of pesticide residues in four streams draining different land-use areas in Pennsylvania, U.S. Geological Sur- vey, Water Resource Investigations 6-75. (23) Uhndk, J., M. Sackmauerovd, A. Szokolay, and O. Pal'Usovd. 1974. TTie use of an electron-capture detec- tor for the determination of pesticides in water. J Chrcmatogr. 91:545-547. 162 Pesticides Monitoring Journal BRIEF Organochlorine Pesticide Levels in Ottawa Drinking Water, 1976 David T. Williams, Frank M. Benoit, Edward E. McNeil, and Rein Otson' ABSTRACT Duplicate samples of Ottawa drinking ttaler were collectetl once a month dnrini; 1976 and analyzed for organochlorine pesticides. The samples were analyzed hy gas chromatog- raphy-mass spectrometry, and pesticides were identified hy comparing their retention times, coupled with selected ion monitoring, with those of known standards. The pesticides detected and their mean concentrations in parts per trillion were aldrin (0.9), heptachlor epoxide 13), heplachlor (0.6), n-BHC (6). y-BHC (3). endrin (4), dieldrin (I). o,p'-TDE (I). o,p' -DDT (3). and o,p'-DDE (0.2). Introduction Ottawa drinking water was monitored for organochlorine pesticides by a simple new method using Amberlite XAD-2 macroreticular resin for the analysis of potable water at the parts per trillion (ppt) level. Sampling and A nalysis In 1976, duplicate 200-liter samples per month, except July, of Ottawa drinking water was passed through Amberlite XAD-2 macroreticular resin during a 10-day period according to the procedure of McNeil et al. (/). The resin was eluted with 250 ml hexane, and the eluates were dried with sodium sulfate and concentrated to 1 ml. The concentrated hexane eluates were then analyzed with a Finnigan Model 4000 gas chromato- graph-mass spectrometer coupled to a Model 6000 Data System with the following instrument parameters and operating conditions: Column: 1.8 m X 2 mm ID glass, packed with 3 per- cent OV-17 on 8()-10n-mesh Chromosorb 750 Temperatvires: oven from 200°C (0.1 minute hold) to 250°C (hold) at 5°C/minute; injection port 225°C Carrier gas: helium flowing at 25 ml/minute The mass spectrometer, operating in the selected ion mode, was programmed to monitor four ions (m/q 66, 81, 100, 109) for the first 4 minutes and four other ions (m/q 67, 79, 235, 246) for 10 minutes more. Analyses were performed on a standard pesticide mixture, includ- ing the 10 pesticides detected under identical GC-MS conditions to permit identification and quantitation. The lower limit of detection was about 0.1 ppt of pesticide in the original 200-liter water sample. Results and Discussion Results of the pesticide analyses are presented in con- densed form in Table 1, including the relative retention time and specific ion monitored for each pesticide. There was no consistent seasonal trend for any of the 10 pesticides detected. The monthly pesticide values varied considerably with the mean as shown by the high standard deviations in Table 1. This is expected since the levels of many of the pesticides were close to the detection limit, and the use of selected ion monitoring, although more selective than simple gas chromatography, is still subject to interference, particularly at the trace levels found. Authors concluded that organochlorine pesticides de- tected in Ottawa drinking water exist as background levels which are consistently present in trace amounts in the environment. TABLE 1. Organochlorine pesticide residue levels in Ottawa drinking water, 1976 SElIiCTED Relative Range Mean Ion Retention MIN.-MAX.. It Pesticide Monitored Time PP1 Std Dev. Median ..-BHC 109 1.00 0.1-15 6±4 6 V-BHC 109 1.30 0.4-11 3±3 2 Heptachlor 100 1.63 0.1-1 0.6±0.3 0.7 Aldrin 66 1,97 0.1-6 0.9±1 0.5 Heptachlor epoxide 81 2.70 0.2-9 3±3 1 o.p'-DDE 246 3.72 0.1-0.5 0.2±0.2 0.2 Dieldrin 79 3.77 0.1-4 1±1 0.7 (),/)'-TDE 235 4.17 0,1-3 1±I O.g Endrin 67 4.35 1-7 4±4 4 o.p'-DDT 2.35 4.72 0.2-8 3±3 2 ' Bureau of Chemical Hazards, Environmental Health Directorate, Health and Welfare Canada, Ottawa, Ontario, Canada KIA OL2. LITERATURE CITED (/) McNeil, E. £,, R. Otson, W. F. Miles, and F. J. M. Rajahalee. 1977. Determination of chlorinated pesti- cides in potable water. J. Chromatogr. 132(2) :277-286. Vol. 12, No. 3, December 1978 163 APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN AROCLOR 1254 AROCLOR 1260 BHC (BENZENE HEXACHLORIDE) CARBARYL CHLORDANE DDE DDT DICHLORVOS DIELDRIN ENDOSULFAN ENDRIN HCB HEPTAC HIOR HEPTACHLOR EPOXIDE ISODRIN MALATIUON MIREX NONACHLOR PARATHION PCBs (POrVCHI ORINATED BIPHENYI S) TDE TELODRIN TOXAPHENE Not less than 95% of 1.2..1.4,lU,IO-hexachloro-1.4,4a.5.8.8a-hexahydro-l,4:5,8- dimeihanonaphthalene PCB. approximately 54'^r chlorine PCB. approximately 60% chlorine 1,2,-^.4.5,6-Hexachlorocyclohexane (mixlure of isomers) I-Naphlhyl N-methylcarbamate 1 .2.3.4,5.6,7,8,8-Ociachloro-2.3,3a.4.7,7a-hexahydro-4,7-methanoindene. The technical product is a mixture of several compounds including heptachlor, chlordene. and two isomeric forms of chlordane. Dichlorodiphenyl dichloro-ethylene (degradation product of DDT); p.p'-DDE: 1,1-Dichloro- 2.2-bis(/'-chlorophenyl ) ethylene; o.p'-DDE: l,l-Dichloro-2-(o-chIorophenyl)-2- (p-chlorophenyl) ethylene Main component (/?./^'-DDT) : -f:ic(7-5,8-dimeth3nonaphthalene 6,7.8.9.10. l0-Hexachloro-1.5.5a,6,9,9a-hexahydro-6.9-meihano-2.4J-benzodioxalhiepin 3-oxide Hexachloroepoxyoctahydro-e/irfo. crt^a-dimeihanonaphihalene Hexachlorobenzene l,4,5.6,7.8.8-Heptachloro-3a.4,7,7a-tetrahydro-4.7-e/jdo-methanoindene l,4,5.6.7,8,8-Heptachloro-2.3-epoxy-3a,4.7.7a-telrahydro-4.7-meihanoindanc Hexachlorohexahydro-c.v^j.p.tw-dimethanonaphthalene S-l 1 ,2-Bis(ethoxycarbonyl ) eihyll (>,(>-dimclhyI phosphorodilhioale l,la,2,2.3,3a.4.5,5.5a,5b,6-Dodecachlorooclahydro-1.3.4-mclheno-lH-cyclohula|cdlpcnlalene l.2,3.4.5,6.7.8-Nonachlor-^a.4.7.7a-te(rahydro-4,7-methanoindan (>.()-Oiclh\\ 0-/»-nilrophcn> 1 phosphoroihioiiie Mixtures of chlunn.iicd biphcnvl compounds having; various percentages ot chlorine 2.2-Bis(p-chlorophfnyl )-I , I -dichlorocihane (includinj; isomers anti dehydiochlorinalion products ) Ocuchlorohcxahydro-4.7-melhanoisobenzofuran Chlorinated camphenc (67 69'"; chlorine! Product is a mixiiire of poKchlor hicyclic iLTpencs wiih chloiuKiicd cainplicncs prcdoininaiitit: 164 Pf.str i»i:s Monitoring Journal Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretative information on pesticide monitoring. The publication is distributed principally to scientists, technicians, and administrators associated with pesticide monitoring, research, and other programs concerned with pesticides in the environ- ment. Other subscribers work in agriculture, chemical manufacturing, food processing, medicine, public health, and conservation. Articles are grouped under seven headings. Five follow the basic environmental components of the National Pesticide Monitoring Program: Pesticide Residues in People; Pesticide Residues in Wafer; Pesticide Residues in Soil; Pesticide Residues in Food and Feed; and Pesticide Residues in Fish, Wildlife, and Estuaries. The sixth is a general heading; the seventh encompasses briefs. Monitoring is defined here as the repeated sampling and analysis of environmental components to obtain reliable estimates of levels of pesticide residues and related compounds in these components and the changes in these levels with time. It can include the recording of residues at a given time and place, or the comparison of residues in different geographic areas. The Journal will publish results of such investigations and data on levels of pesticide residues in all portions of the environment in sufficient detail to permit interpretations and con- clusions by author and reader alike. Such investigations should be specifically designed and planned for moni- toring purposes. The Journal does not generally publish original research investigations on subjects such as pesticide analytical methods, pesticide metabolism, or field trials (studies in which pesticides are experimen- tally applied to a plot or field and pesticide residue de- pletion rates and movement within the treated plot or field are observed). Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and references. Pesticides ordinarily should be identi- fied by common or generic names approved by national or international scientific societies. Trade names are acceptable for compounds which have no common names. Structural chemical formulas should be used when appropriate. Accuracy, reliability, and limitations of sampling and analytical methods employed must be described thoroughly, indicating procedures and con- trols used, such as recovery experiments at appropriate levels, confirmatory tests, and application of internal standards and interlaboratory checks. The procedure employed should be described in detail. If reference is made to procedures in another paper, crucial points or modifications should be noted. Sensitivity of the method and limits of detection should be given, particularly when very low levels of pesticide residues are being reported. Specific note should be made regarding cor- rection of data for percent recoveries. Numerical data, plot dimensions, and instrument measurements should be reported in metric units. PREPARATION OF MANUSCRIPTS Prepare manuscripts in accord with the CBE Style Manual, third edition. 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Construct this piece as an entity separate from the paper itself; it is potential material for domestic and foreign secondary publications concerned with the topic of study. Choose language that is succinct but not detailed, summarizing reasons for and results of the study, and mentioning significant trends. Bear in mind the literature searcher and his/her need for key words in scanning abstracts. Forward original manuscript and three copies by first-class mail in flat form; do not fold or roll. Type manuscripts on S'/z-by-l 1-inch paper with generous margins on all sides, and end each page with a completed paragraph. Recycled paper is acceptable if it does not degrade the quality of reproduction. Double-space all copy, including tables and references, and number each page. Place tables, charts, and illustrations, properly titled, at the end of the article with notations in the text to show where they should be inserted. Treat original artwork as irreplaceable material. 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Do not list private com- munications among Literature Cited. Insert them parenthetically within the text, including author, date, and professional or university affiliation in- dicating author's area of expertise. The Journal welcomes brief papers reporting monitor- ing data of a preliminary nature or studies of limited scope. A section entitled Briefs will be included as necessary to provide space for short papers which pre- sent timely and informative data. These papers must be limited to two published pages (850 words) and should conform to the format for regular papers accepted by the Journal. Manuscripts require approval by the Editorial Advisory Board. When approved, the paper will be edited for clarity and style. Editors will make the minimum changes required to meet the needs of the general Journal audience, including international subscribers for whom English is a second language. Authors of accepted manuscripts will receive edited typescripts for approval before type is set. After publication, senior authors will receive 100 reprints. Manuscripts are received and reviewed with the under- standing that they have not been accepted previously for publication elsewhere. If a paper has been given or is intended for presentation at a meeting, or if a significant portion of its contents has been published or submitted for publication elsewhere, notations of such should be provided. Upon acceptance, the original manuscript and artwork become the property of the Pesticides Monitoring Journal. Every volume of the Journal is available on microfilm. Requests for microfilm and correspondence on editorial matters should be addressed to: Paul Fuschini (TS-757) Editorial Manager Pesticides Monitoring Journal U.S. Environmental Protection Agency Washington, D.C. 20460 For questions concerning GPO subscriptions and back issues write: Superintendent of Documents U.S. Government Printing Office Washington, D.C. 20402 166 Pesticides Monitoring Journal 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 Technical Services Division, Office of Pesticide Programs, U.S. Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies represented on the Monitoring Panel which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and articles. However, pertinent data in summarized form, together with discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institutions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Publication of scientific data, general information, trade names, and commercial sources in the Pesticides Monitoring Journal does not represent endorsement by any Federal agency. Manuscripts received for publication are reviewed by an Editorial Advisory Board established by the Monitoring Panel. Authors are given the benefit of review comments prior to publication. For further information on Journal scope and manuscript prepara- tion, see Information for Contributors at the back of this issue. Editorial Advisory Board members are: John R. Wessel, Food and 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: Paul Fuschini (TS-757) Editorial Manager Pesticides Monitoring Journal U. S. Environmental Protection Agency Washington, D.C. 20460 Editor Martha Finan CONTENTS Volume 12 March 1979 Number 4 Page FOOD AND FEED Acephate and mclhamidophos residue behavior in Florida citrus — 7976 167 Herbert N. Nigg, James A. Reinerl, and Glenn E. Fitzpatrick FISH, WILDLIFE, AND ESTUARIES Effects of organochlorine residues on eggshell thickness, reproduction, and population status of brown pelicans (Pelecanus occidentalis) in South Carolina and Florida, l969-76_ 172 Lawrence J. Blus. Thair G. Lamont, and Burkett S. Neely, Jr. Pesticide contamination of water rats in the Murrumbidgee irrigation areas. New South Wales, Australia, 1970-72 185 Penny Olsen and Harry Settle Organochlorine residues in harp seal (Phagophilus groenlandicus) tissues. Gulf of St. Lawrence, 1971 , 1973 189 K. T. Rosewell, D. C. G. Muir, and B. E. Baker Nationwide residues of organochlorine compounds in starlings (Sturnus vulgaris), 1976 193 Donald H. White SOILS Pesticide application and cropping data from 37 states, 1972 — National Soils Monitoring Program 198 Ann E. Carey and Jeanne A. Gowen Pesticide residue levels in soils and crops from 37 states, 1972 — National Soils Monitoring Program (IV) 209 Ann E. Carey, Jeanne A. Gowen. Han Tai, William G. Mitchell, and G. Bruce Wiersma Organochlorine pesticide residues in soils from six U.S. Air Force bases, 1975-76 230 Jerry T. Lang, Leopoldo L. Rodriguez, and James M. Livingston APPENDIX 234 ERRATA 235 ACKNOWLEDGMENTS 236 ANNUAL INDEX (Volume 12, June 1978-March 1979) Preface 237 Su bject Index . 238 Author Index 246 Information for Conlributom . 248 FOOD AND FEED Acephate and Methamidophos Residue Behavior in Florida Citrus, 1976 Herbert N. Nigg,= James A. Reinert," and George E. Fitzpatrick' ABSTRACT The half-life of acephate and its hydrolysate, methamido- phos, in the rind of Temple and Valencia oranges, and grapefruit, lemons, and tangerines was 10.3 days and 10.5 days, respectively. Half-lives of acephate and methamido- phos in citrus pulp were 15.0 days and 6.1 days, respectively, based on 7-, 14-, and 21-day data. Seven days after treat- ment, acephate and methamidophos reached maximum levels in rind and pulp. Acephate residue levels in rind were less than 3.0 ppm 14 days after treatment; acephate residues in pulp were less than 3.0 ppm throughout the experiment. Methamidophos residue levels averaged less than 0.25 ppm after 21 days. Introduction In 1937, the citrus blackfly, Aleurocanthus woghimi Ashby (Homoptera: Aleyrodidae), was eradicated from the Florida Keys by use of petroleum oil (7). Early in 1976, the citrus blackfly was again discovered in Fort Lauderdale, Florida, and surrounding Broward County (8). Infestations are currently found in Broward, Collier, Dade, Indian River, Martin, Okeechobee, Palm Beach, and Saint Lucie Counties (G. E. Fitzpatrick, University of Florida Institute of Food and Agricultural Sciences, October 1978: personal communication). After discovery of the infestations, an intensive state and federally sponsored eradication program was begun, but it was complicated by the urban nature of the citrus blackflv infestation. Based on chemical efficacy and citrus blackfly life-cycle data, three treatments of acephate at 3-week intervals were necessary for eradication {8). Treatments were applied to all Florida citrus owned by individual home- owners in the heavily urbanized area under an emer- ' Florida Agricultural Experiment Stations Journal Series No. 1148. Research supported by special funds from tlie Center for Environ- mental Programs, University of Florida. 21)14 McCarty Hall, Gaines- ville, FL 32611. -'University of Florida, Institute of Food and Agricultural Sciences, Agricultural Research and Education Center, P.O. Box 1088, Lake Alfred. FL 3.1850. 'University of Florida. Institute of Food and Agricultural Sciences, Agricultural Research Center, 3205 S.W. 70th Avenue, Fort Lauder- dale, FL 33314. gency exemption granted by the United States Environ- mental Protection Agency (EPA). The homeowner was advised by the Florida and U.S. Departments of Agri- culture to wait 7 days before consuming treated fruit. It was not known whether acephate and its environ- mental metabolite, methamidophos (Monitor), would reach their respective action levels of 3.0 ppm and 0.25 ppm in whole fruit within 7 days. In addition, acephate and methamidophos are systemic chemicals and might readily penetrate fruit rind into the edible pulp. The purpose of the present study was to monitor levels of acephate and methamidophos in common Florida citrus to determine half-lives and tolerances of these materials. Materials and Methods Each experimental unit consisted of one city block. Within each city block, a random 8-fruit sample was taken from 3-10 trees of Temple and Valencia oranges, and grapefruit, lemons, and tangerines on each sample date. Treatments were replicated four times in a completely random design including four unsprayed check blocks. Acephate at 0.6 g active ingredient (AI)/ liter (ca 38 liters/tree) was applied with a hydraulic sprayer at 29 kg/ cm- and with a mist blower at 2.4 g Al/liter (ca 0.8 liter/tree). The hydraulic sprayer was a standard, truck-mounted unit with two 100-m hoses and attached handheld sprayguns. The mist blower was a gasoline-driven backpack unit (KWH Whirlwind, Hol- land). Three separate treatments were applied at 3-week intervals. Dual samples of each variety were taken after the third application on days 1, 3, 5, and 7, and single samples of each variety were taken on days 14 and 21 by clipping the fruit into plastic bags. Each sample consisted of eight fruits. One set of the dual samples was washed in a weak soap solution of Ivory liquid to simulate homeowner washing. Samples were frozen at -20'C and transported frozen to the laboratory for analysis. Vol. 12, No. 4, March 1979 167 Samples were stored approximately one month at — lO'C prior to analysis. Valencia oranges were 0.8 mature when harvested; other varieties were completely mature. The method of I.cary (4) was modified for extraction and analyses of acephate and mcthamidophos. Fruits were thawed, the rind was removed from one half of each fruit, and the pulp was sliced into a Waring blender. The pulp was blended for ?• minutes, and a 10-g sub- sample was removed for analysis. The rind was diced, blended for 3 minutes, and a 10-g subsample was taken for analysis. Separate fruit knives were used for all operations, and between samples all equipment was washed thoroughly with hot soapy water, rinsed in tap water, deionized water, isopropanol, and again in deion- ized water. The 10-g sample of either rind or pulp was homogenized in 100 ml ethyl acetate and 15 g sodium sulfate for 5 minutes in a Sorvall blending cup in an ice bath. The blender cup top was loosened upon removal from the mixer, and particulate matter was allowed to settle for 1 minute. A 20-ml aliquot was evaporated to dryness under a nitrogen atmosphere at 40°C, and transferred to brown glass bottles over sodium sulfate in 10 ml methyl isobutyl ketone (MIBK) for gas chromatographic (GC) analysis. No further cleanup was performed on the extractions, and they were stored at — ZO^C until analysis. The elTect of storage on the hydrolysis of acephate to mcthamidophos was not determined. For acephate and mcthamidophos, GC was conducted on a Hewlett-Packard Model 57.^0A gas chromatograph equipped with dual nitrogen-phosphorus detectors. In- strument parameters and operating conditions follow: Column: jilass. M) inches long "'' In-inch ID. packed with 1 percent Reoplex 400 iin «0-KIO-mesh Gas- Chiom Q Temperatures. °C; detector 300 injecldr 2U) program 150-200 at K minute. 8-minute final hold. 45-second delav alter injection Carrier gas: helium llowing at 30 ml minute Compounds were quantified by comparing peak heights of standard materials chromatographed at the same at- tenuation. Unsprayed fruit extracts fortified with stand- ard acephate and mcthamidophos (Chevron Chemical Co., Richmond, Virginia) were linear at each GC at- tenuation setting. However, at the attenuation setting of 8, standard materials chromatographed in MIBK. alone produced a 10-20 percent lower response than in fortified fruit extracts. Fruit extracts alone were blank, apparently as a result of an unexpected synergistic efiect of some component in the fruit extract on the nitrogen- phosphorus detector response. Consequently, fruit ex- tracts fortified with acephate and mcthamidophos were used for quantification. Standards were chromato- graphed every fourth injection. All injections were 5 fd. All solvents were assessed for interferences by evapo- rating 100 ml of each solvent to 1 ml and chromato- graphing 5 mI. Recoveries of standard materials from fortified homo- genates were 7.^.1 percent mcthamidophos and 77.8 per- cent acephate at 1 ppm and 82.6 percent mcthami- dophos and 85.4 percent acephate at 5 ppm for both peel and pulp. There were no varietal differences in recovery of standard materials. Variations in recovery averaged 16.8 percent for mcthamidophos and 15.3 per- cent for acephate at 1 ppm and 4.6 percent for mcth- amidophos and 5.5 percent for acephate at 5 ppm. Low- est accurate level of detection for both standards was 0.01 ppm; lower levels are reported as trace. The data in Tables 1 and 2 are not corrected for recovery. No analyses were performed on either the formulated ace- phate or tank mixes. The equation for decay was: -/)/ ln(y ly ) = —bt Half-life, / , was calculated as t = In(0.5)/(— /)) (1) (2) (3) Residue levels were compared among varieties on indi- vidual sampling davs and among sampling davs for indi- vidual varieties with a t-test (/O). Degrees of freedom were 14 for da^s 1-7 and 6 for days 14 and 21 f^// = 2(« — 1)] (/O). Comparison of residue levels are significant at the 0.01 level. Results and Discussion There was no statistical difference between residues of acephate and mcthamidophos on or in washed and un- TABLF. 1. Acepliate residues in rind and pulp of Florida citrus, 1976 Day, Post Application 14 21 Residues (Mean ± Std Dev.), ppm Temple orange Rind 2.3 ± 0.7 Pulp 1.3 ±0.5 4.6 ± 1.6 0.8 ± tr 2.8 ±2.8 0.8 ±0.5 7.9 ± 5.8 2.6 ± 1.3 2.6 ± 1.8 1.6 ±0.8 2.0 ± 1.2 1.2 ±2.0 Grapefruit Rind 2.7 ±2.1 Pulp 0.3 ± 0.2 1.9± I.l 0.4 ± 0.3 2.3 ±2.1 0.4 ± 0.4 3.9 ±2.5 0.9 ± 0.6 1.4 ±0.2 0.5 ± Ir 1.9 ±0.8 0.3 ± 0.3 \';ilencia orange Rind 3.9 ±1.5 Pulp 1.1 ±0.7 3.1 ± 2.5 0.6 ±0.8 4.1 ± 2.8 1.4 ±0.5 4.2 ± 1.5 0.7 ±0.5 1.8 ± 1.2 0.8 ± 0.3 2.1 ± 1.3 1.0 ± 1.0 lemon Rind 3.8 ±2.2 Pulp 1,5 ±0.7 5.7 ±4.1 1.9 ± 1.0 2.9 ± 1.8 1.0 ±0.6 6.2 ± 2.9 2.4 ± 1.6 2.6 ± 1.8 1.3 ± 1.2 1.4± I.O 1.4 ±0.9 Tangerine Rind 3.8 ± 2.3 Pulp 0.7 ± 0.3 4.9 ± 3.8 2.0 ± 1.3 4.9 ±2.1 1.3 ± 1.1 4.9 ± 1.8 2.0 ± 0.7 2.1 ± 1.2 0.9 ±0.4 4.9 ± 4.6 1.0 ±0.6 NOTF. : tr = trace = <0.01 ppm. 168 Pesticides Monitoring Journal ACEPHATE IN FLORIDA CITRUS RIND DAYS POST APPLICATION ACEPHATE IN FLORIDA CITRUS PULP • • TEMPLE o o GRAPEFRUIT i 4 VALENCIA -i LEMON -♦TANGERINE 7 14 DAYS POST APPLICATION METHAMIDOPHOS IN FLORIDA CITRUS RIND • — • TEMPLE o — 0 GRAPEFRUIT A — t VALENCIA A — A LEMON » — » TANGERINE 3 5 7 a DAYS POST APPLICATION METHAMIDOPHOS IN FLORIDA CITRUS PULP A I 2 ppm • • TEMPLE o o GRAPEFRUIT 4 1 VALENCIA A A LEMON ♦ — ♦ TANGERINE 7 14 DAYS POST APPLICATION FIGURE 1. Acephate and methamidophos residue in rind and pulp of Florida citrus. Points for days 1, 3, 5, and 7 are averages of eight determinations. Days 14 and 21 are averages of four determinations. TABLE 2. Methamidophos residues in rind and pulp of Florida citrus, 1976 Day. Post Application 1 3 5 7 14 21 Residues (Mean ± Std Dev.), ppm Temple orange Rind 0.2 ±tr 0.3 ± 0.4 1.3 ± 1.1 1.0 ±0.5 0.2 ±0.1 0.4 ± 0.2 Pulp 0.1 ±lr 0.1 ±tr 0.2 ±0.2 tr 0.2 ±0.1 0.1 ±0.2 Grapefruit Rind 0.1 ±0.1 0.3 ± 0.2 0.6 ± 0.5 0.5 ± 0.3 0.2 ± 0.1 0.2 ± tr Pulp ND 0.1 ±0.1 0.1 ±0.2 0.2 ±0.3 0.6 ± tr 0.1 ±0.1 Valencia orange Rind 0.2 ±0.1 0.3 ± 0.3 1.3 ± 0.6 1.0 ±0.8 0.2 ±0.1 0.2 ±0.1 Pulp 0.1 ±0,2 0.1 ±0.1 0.4 ±0.1 tr 0.1 ± 0.1 0.1 ±0.1 Lemon Rind 0.1 ±0.1 0.2 ±0.2 0.5 ± 0.3 0.6 ± 0.6 0.2 ±0.1 0.1 ± 0.1 Pulp tr 0,1 ±0.1 0.3 ± 0.6 1.2 ± 1.8 0.1 ± 0.1 0.2 ±0.1 Tangerine Rind 0.2 ±0.2 0.5 ± 0.4 1.5 ± 1.2 1.5 ± 1.2 0.2 ±0.1 0.6 ± 0.4 Pulp tr 0.2 ±0.2 0.2 ±0.2 0.4 ±0.4 0.1 ± tr 0.1 ±0.1 NOTE: tr = trace = <0.01 ppm. ND not detected. washed fruit (days 1, 3, 5, 7), and data for washed and unwashed fruit were combined for statistical analy- ses. This result may be due to the method of handling samples (i). In the present study, frozen fruits were thawed before being peeled. Condensation on the fruits collected in the bottom of the bag; this condensate was Vol. 12, No. 4, March 1979 not added to the extract because only half of each fruit was peeled. The fruits were thus washed by condensa- tion prior to peeling. This accounts for the absence of statistical difference between washed and unwashed fruits. The data presented here can only properly be considered penetrated residues. Also, no residues of acephate or methamidophos were detected in fruit which had been misted. Only the results of the hydraulic ap- plication are reported here. Both acephate and methamidophos are systemic insec- ticides, and the data in Figure 1 indicate that at least acephate readily penetrates the rind of all citrus varie- ties. Because methamidophos can be produced from acephate by hydrolysis, internal methamidophos could have come from acephate. The peak of penetrated residues of both compounds oc- curs on days 5 and 7. Acephate residues in rind are significantly higher (0.01 ppm) on day 7 than on days 5 and 14 for Temple oranges, grapefruit, and lemons. For Valencia oranges and tangerines, day 14 residues are significantly lower than are day 7 residues, but due to the variability of the data, the peak of penetrated residues may have occurred on day 5 (Table !)• Had data been taken on day 9, higher methamidophos resi- 169 dues might have been found, indicating additional con- version of acephate. The data do show, however, that the residues are above the EPA action levels of 3.0 ppm acephate and 0.25 ppm mcthamidophos on day 7 (Tables 1,2; Fig. 1). The acephate-in-piilp pattern is similar to that in rind. Day 7 residues are significantly higher than are residues on days 5 or 14 in Temple oranges, grapefruit, lemons, and tangerines. For Valencia oranges, the peak of ace- phate in pulp may have occurred on day 5 when resi- dues of acephate were significantly higher than on days 3 or 7. Acephate in pulp was never above the action level of 3.0 ppm. The maximum level of acephate in pulp was 2.0 ppm in tangerines on day 14. Most pulp acephate residues averaged 1.0 ppm or less (Table 1). The pattern of methamidophos residues was similar to that of acephate (Table 2). For Temple orange, grape- fruit, Valencia orange, lemon, and tangerine rind, day 7 residues were significantly higher than were day 14 residues. However, methamidophos levels in rind were the same on days 5 and 7, so residues may have peaked on day 5. In pulp, no peak of methamidophos residues was apparent in Temple oranges, but statistically signifi- cant peaks occurred on day 7 in lemons and tangerines, on day 5 in Valencia oranges, and on day 14 in grape- fruit. The pattern of penetration of acephate and methami- dophos in both rind and pulp of these varieties was statistically significant and consistent. The peak pene- trated residues of acephate and methamidophos in rind and in pulp occurred on or before day 7 with decreas- ing residues thereafter. The statistical comparison of varieties in Table 3 indi- cates that by day 14 there are no differences in acephate residue levels in rind among varieties. Before day 14, no consistent pattern of residue levels is evident. The same comparison for acephate in pulp (Table 4) points to significantly lower residues in grapefruit pulp than in lemon and tangerine pulp. With this exception, there were no dillerences in acephate residues in piilp by TABLE 4. Statistical comparison of acephate residue levels in citrus pulp, 1976 Day, Post Application 1 3 5 7 14 21 Temple i)r;inge vs. grapefruit yes yes yes yes yes no Temple vs. Valencia oranges no no yes yes yes no Temple orange vs. lemon no yes no no no no Temple orange vs. tangerine yes yes yes yes yes no Cirapcfruit vs. Valencia orange yes no yes no yes no Grapefruit vs. lemon yes yes yes yes yes yes Grapelruit vs. tangerine yes yes yes yes yes yes Valencia orange vs. lemon no yes yes yes no no Valencia orange vs. tangerine yes yes no yes no no Lemon vs. tangerine yes no no no no no See NOTE, Table 3. day 21. Residues in Temple oranges were significantly higher than were residues in grapefruit until day 21 (Tables 1,4). By day 14 there were no significant differences in meth- amidophos levels in rind among varieties, yet dilTer- ences appear on day 21 (Table 5). There were no differences in methamidophos residues in pulp by tlay 21 (Table 6). There is a nonrandom source of variation in the com- parison of residue levels in citrus which has been noted in greenhouse tomato studies with acephate, surface area-to-weight ratios (5). Confounded with fruit size is varietal rind thickness. Valencia orange rind thickness has been reported as 4.0 mm (2). 4.1 mm (//), and 3.0 mm (9). Marsh grapefruit rind thickness has been noted as 5.5 mm (Jl) and 12.0 mm (9), Lemon rind thickness has been reported as 7.3 mm (11), 3.6 mm (7), and 5.0 mm (9). In addition to genetic differences in rind thickness, many climatic and cultural practices affect rind thick- ness (7, 2, 9, //). In the present experiment, thick grapefruit rind with a low surface area-to-weight ratio appears to account for low pesticide residues in grape- fruit. Future experiments to compare citrus variety dif- ferences in residue behavior should include rind thick- ness and surface area measurements to determine TABLE 3. Statistical comparison of aceplialc residue levels in citrus rind, 1976 TABLE 5. Statistical comparison of metliamidophos residue levels in citrus rind, 1976 Day. Post Applicat ION 1 3 5 7 14 21 Temple orange vs. grapefruit no yes no yes no no Temple vs. Valencia oranges yes yes no no no no Temple orange vs. lemon yes no no no no no Temple orange vs. tangerine yes no yes yes no no Grapefruit vs. Valencia orange yes yes yes no no no Grapefruit vs. lemon yes yes no yes no no Grapefruit vs. tangerine no yes yes no no no Valencia orange vs. lemon no yes no yes no no Valencia orange vs. tangerine no yes no no no ntj Lemon vs. tangerine no no yes yes no yes NOTE: Yes = means arc slaiisticnlly difTcrcnt at O.OI level; no means arc not statistically dilTcrcnt at U.Ul level {W). Day. Post Application 3 Temple orange vs. grapefruit yes no yes yes no yes Temple vs. Valencia oranges no no no no no yes Temple orange vs. lemon yes no yes yes no yes Temple orange vs. tangerine no no no yes no no Grapefruit vs. Valencia orange yes no yes yes no no Cirapefruit vs. lemon no no no no no yes Grapefruit vs. tangerine yes yes yes yes no yes Valencia orange vs. lemon yes no yes yes no no Valencia orange vs. tangerine no yes no no no yes Lemon vs. tangerine yes yes yes yes no yes See NOTE. Table 3. 170 Pesticides Monitoring Journai TABLE 6. Slalislical comparison of melhamidophos residue levels in citrus pulp, 1976 TABLE 7. Acepluitc and melhamidophos first-order disappearance in Florida citrus, 7-21-day data, 1976 Day, Post Applicat ION Slope (HALF-LIFE, DAYS) 1 3 5 7 14 21 r Temple orange vs. grapefruit yes no no yes yes no Metha- ACE- Metha- ACE- Metha- ACE- Temple vs. Valencia oranges no no yes no no no MIDOPHOS PHATE MIDOPHOS PHATE MIDOPHOS phate Temple orange vs. lemon yes no no yes no no Temple orange vs. tangerine yes yes no yes yes no Temple orange Grapefruit vs. Valencia orange yes no yes yes yes no Rind -0.07 -0.10 9.9 6.9 -0.57 = -0.94' Grapefruit vs. lemon yes no no yes yes no Pulp 0.32 -0.06 2.2 11.6 -0.79 = -0.98» Grapefiuit vs. tangerine yes yes no yes yes no Grapefruit Valencia orange vs. lemon yes Valencia orange vs. tangerine yes Lemon vs. tangerine no no yes yes no yes no yes yes yes no no no no no no Rind -0.07 Pulp -0.05 Valencia orange Rind -0.05 Pulp 0.32 -0.05 -0.08 -0.05 0.03 9.9 13.9 13.9 2.2 13.9 8.7 13.9 23.1 -0.86 = -0.38 -0.68 = 0.86 ••! -0.68 = -0.99' See NOTE, Table 3. -0.77 = 0.99 » whether any differences in residue levels cou d be due Lemon Rind -0.08 -0.11 8.7 6.3 -0.99-- -0.99' to fruit structure. Pulp Tangerine -0.13 -0.04 5.3 17.3 -0.69 = -0.81 = Penetration of both compounds into rind plicates data analyses. The overall data and pulp actually corn- show Rind Pulp Averages -0.07 -0.10 -0.05 9.9 6.9 13.9 -0.45 -0.87 = -0.79 = that the appearance of residue is due to penetration. Rind Pulp 10.5 6.1 10.3 15.0 The fit to a first-order dis anneara nee model is corre- spondingly poor, ranging from a low of r = 0.02 for acephate in Valencia pulp to a high of r ^ — 0.79 for acephate in lemon rind. However, when data from days 7 (ma.\imum concentration), 14, and 21 are used, disappearance is clearer (Fig. 1). There are still positive correlations for melhamidophos in Temple and Valencia orange pulp which reflect an appearance of the compound in the pulp, and the tan- gerine rind data for acephate do not fit a first-order model. Based on 7-, 14-, and 21 -day data the half-life averages are 10.5 days and 10.3 days for melhami- dophos and acephate, respectively, in fruit rind, and 6.1 days and 15.0 days for melhamidophos and ace- phate, respectively, in pulp (Table 7). The data presented for acephate and melhamidophos show that both compounds disappear under Florida conditions after reaching maximum penetrated residues on day 7. Acephate was below 3 ppm in rind 14 days after application and never reached 3 ppm in pulp. Pen- etrated residues of melhamidophos reached an average level of less than 0.25 ppm 21 days after application. LITERATURE CITED (/) Chace, E. A/.. C. P. Wilson, and C. G. Church. 1921. The composition of California lemons. U.S. Depart- ment of Agriculture Bulletin No. 993, 18 pp. (2) Cooper, W. C, A. Peynado, J. R. Furr, R. H. Hilge- man, C. A. Cahoon, and S. B. Boswell. 1963. Tree growth and fruil quality of Valencia oranges in rela- tion to climate. Proc. Amer. Soc. Hon. Sci. 82:180- 192. 'fVi = ln(0.5) /slope. = Significant at 5 percent level (6). 'Significant at 1 percent level or higher (6), (J) Gunther, F. A. 1969. Insecticide residues in Califor- nia citrus fruits and products. Residue Rev. 28:1-127. (■#) Leary, J. B. 1974. Gas-liquid chromatographic deter- mination of acephate and Ortho 9006 residues in crops. J. Assoc. Off, Anal. Chem. 57( 1) : 189-191. (5) Leidy, R. B.. T. J. Sheets, and K. A. Sorensen. 1978. Residues of acephate and melhamidophos in green- houses. L Amer. Soc. Hon. Sci. 103(3) :392-394. (6) Morrison, D. F. 1967. Multivariate Statistical Methods, p. 104. McGraw-Hill, New York, N.Y. (7) Newell. W., and A. C. Brown. 1939. Eradication of the citrus blackfly in Key West, Fla. J. Econ. Entomol. 32(5):680-682. (5) Reinert, J. A. 1976. Citrus blackfly control by foliar treatments of dooryard citrus. Proc. Fla. State Hort. Soc. 89:365-366. (9) Reuther, W., and D. Rios-Castano. 1969. Comparison of growth, maturation, and composition of citrus fruits in subtropical California and tropical Califor- nia. Proc. Isl Int. Citrus Symp. 1 :277-300. (10) Steel, R. G. D., and J. H. Torie. 1960. Principles and Procedures of Statistics, p. 76. McGraw-Hill, New York, N.Y. (//) Turrell, F. M.. S. P. Monselise, and S. W. Austin. 1964. Effect of climatic district and of location in tree on tenderness and other physical characteristics of citrus fruit. Bot. Gaz. 125(3) : 158-170. Vol. 12, No. 4, March 1979 171 FISH, WILDLIFE, AND ESTUARIES Effects of Organochlorine Residues on Eggshell Thickness, Reproduction, and Population Status of Brown Pelicans (Pelecanus occidentalis) in South Carolina and Florida, 1969—76 Lawrence J. Blus,' Thair G. Lamont," and Burkett S. Neely, Jr.' ABSTRACT Shells of brown pelican (Pelecanus occidentalis) eggs col- lected in South Carolina from 1969 through 1975 and in Florida during 1969, 1970, and 1974 were significantly thinner (P > 0.05) than eggshells collected before 1947. Thickness of South Carolina eggshells increased in 1975, and mean thickness of eggshells collected in Florida during 1974 was greater than that of eggshells collected during 1969 and 1970, primarily in Gulf Coast colonies. Residues of 13 organochlorines were found in eggs and tissues of pelicans found dead during 1974 and 1975, al- though residues in brains of these specimens were not high enough to cause death. Residues of organochlorines, except PCBs, declined through 1975. PCBs increased in eggs from Atlantic Coast colonies. Reproductive success and population status of brown peli- cans in South Carolina have improved markedly since authors began their studies in 1969. Good reproductive succes'i was reported in 3 of 5 years from 1973 through 1977. Introduction This is part of a series of papers on the effects of en- vironmental pollutants on the brown pelican (Pelecanus occidentalis). In previous papers, organochlorine resi- dues in brown pelicans have been related to eggshell thinning (6. 7), reproductive success (9), adult mor- tality (5, 10), population decline (4), and possible ex- tirpation of a population in Louisiana {8). The objective of the present study is to further explore effects of or- ganochlorines on brown pelicans, particularly the sig- 'Fish and Wildlik Service. US ncparlmcnt of the Interior. Patuxent Wildlife Research Center. Laurel. MD 20811. Present address: Pacific Northwest Field Station, 480 S.W. Airport Road. Corvallis. OR 973.10. ^Fish and Wildlife Service. U.S. Department of the Interior, Patuxent Wildlife Research Center. Laurel, MI) 20811. "Fish and Wildlife Service. U.S. Department of the Interior. Division of Wildlife Refuge, Washington, DC 20240. nificance of declining residues. Emphasis is placed on data gathered during 1974-76, but data from 1969 on- ward are used to show trends over 8 years. Procedures jar Sampling, Necropsy, and Field Study Most procedures have been described in previous papers (4, 10). Brief visits were made to brown pelican colo- nies in South Carolina in 1969, 1970, and 1976 and to Florida colonies in 1969, 1970, and 1974. The two brown pelican nesting colonies in South Carolina, Deveaux Bank and Marsh Island, Cape Remain Na- tional Wildlife Refuge (CRNWR), were studied in- tensively in the spring and summer each year from 1971 through 1975. Censuses were made of total nests and fledged young in both South Carolina colonies from 1969 through 1976. However, most accurate data were collected during 1971-75 when a number of visits were made to each colony during each nesting season. Addled and viable eggs in all stages of incubation were collected. One egg was usually taken from each nest selected for sampling. Eggs were weighed and measured, and their contents were placed in chemically cleaned glass bottles and frozen. Eggshells were thoroughly washed with tap water and allowed to dry. Shell thickness (shell plus shell membranes) was measured at three sites on the waist of the egg with a micrometer graduated in units of 0.01 mm. Nests with full clutches and nests from which one egg was collected were marked on Marsh Island to determine their success. Marked nests were checked for eggs or young on each visit to the colony; colonies were visited twice a week for up to 1 hour. Several dead pelicans and samples of fish regurgitated by pelicans were collected and fro/en. The pelicans were removed from the freezer several months later. 172 Pesticides Monitoring .Iournai thawed, and subsequently necropsied. Tissues for histo- logical study were fixed in 10 percent formalin, em- bedded in paraffin, sectioned, and stained. The entire brain was removed and placed in a chemically cleaned glass bottle, and the carcass, except for skin, feet, wings, liver, kidney, and gastrointestinal tract, was wrapped in foil and refrozen. Brains and carcasses were later ana- lyzed for organochlorine residues. A nalytical Procedures The contents of eggs collected during 1969-71 were homogenized. A 20-g portion was mixed with anhydrous sodium sulfate in a blender and extracted for 7 hours with hexane in a Soxhlet apparatus. The extract was cleaned by acetonitrile partitioning and was eluted on partly deactivated Florisil. For pesticide analyses, resi- dues in the cleaned extract were separated and removed in four fractions from a silica gel thin-layer plate (17). Each thin-layer fraction was analyzed by electron- capture gas chromatography (GC) on a column of 3 percent OV-1 or 3.8 percent UCW-98 on Chromosorb W-HP. 2DDT in fractions III or IV was confirmed on a column of 3 f)ercent XE-60 or 3 percent QF-1 Gas- Chrom Q. Polychlorinated biphenyls (PCBs) were identified and measured semiquantitatively by thin-layer chromatography (16). Average recoveries of organo- chlorine pesticides and their metabolites were 75-112 percent. Methodology was modified for eggs collected from 1972 to 1975 (11). The extract of the 10-g portion was cleaned on a Florisil column. Pesticides and PCBs were separated into three fractions on a Silicar column and analyzed by GC on a column packed with a mixture of 4 percent SE-30 and 6 percent QF-1. This methodology enabled authors to detect toxaphene, cw-chlordane, and/or /ra«i-nonachlor, and c;j-nonachlor. Until 1973, there was neither a c/.s-nonachlor standard for quantifi- cation nor a procedure to estimate toxaphene levels. Lipids were removed from the eggs collected during 1974-75 either by Florisil cleanup or by automated gel permeation chromatography. In 1974, r/5-chlordane and /ra;!i-nonachlor were separated and quantified by chang- ing the column packing to a mixture of 1.5 percent OV- 17 and 1.95 percent QF-1. Residues in about 10 percent of the samples were con- firmed by combined gas chromatography-mass spec- trometry (GC-MS). Average recoveries from spiked chicken eggs were 81-1 10 percent; residues are not cor- rected for recovery values. The lower limit of detection for pesticides or their metabolites was 0.01 Mg/g in fish and 0.10 Mg/g in other samples (0.01 Mg/g for hexa- chlorobenzene). The lower limit for PCBs was 0.05 Mg/g in fish and 0.50 Mg/g in other samples. Results REPRODUCTIVE SUCCESS AND POPULATION STATUS From 1969 through 1972 (10) and for previous years (3), reproductive success of South Carolina pelicans was below the recruitment standard of 1.2-1.5 fledged young per breeding female per year that is necessary to main- tain a stable population (14). Following a successful reproductive season in 1973, pelicans experienced poor success in 1974 and 1975, then had successful reproduc- tive seasons in 1976 (Table 1) and 1977 (Vivian Men- denhall. Fish and Wildlife Service, U.S. Department of the Interior, 1977: personal communication). Except in 1969, reproductive success was higher on Deveaux Bank than on Marsh Island (Table 1). How- ever, there was a significant positive correlation (r = 0.797. P < 0.05) between young fledged per nest in the two colonies over the 8 years considered in the present report. Thus reproductive success in one colony paralleled that in the other colony. Lower reproduction on Marsh Island was attributed to tidal flooding of nests each year, a rare occurrence on Deveaux Bank. Many of the pelicans with flooded nests laid a second clutch, but replacement clutches also were frequently laid in low areas that were eventually flooded. The size of the breeding population of brown pelicans in South Carolina slowly increased from 1969 through 1974 and then increased 41 percent from 1974 to 1975 as follows: 1,266 pairs in 1969; 1,670 pairs in 1974; 2,400 pairs in 1975; and 3,300 pairs in 1977. TABLE 1. Reproductive success of brown pelicans in South Carolina, 1969-76 No. OF Young No. OF Young Fledged Year Colony Nests Pledged per Nest 1969 Cape Remain 1016 900' 0.821 Deveaux Bank 250' 80 0.321 Both Colonies 1266 980 0.78 1970 Cape Remain 6J7 500' 0.78' Deveaux Bank 479 445 0.93 Both Colonies 1116 945 0.85 1971 Cape Remain 1094 949 0.87 Deveaux Bank 375 400 1.07 Both Colonies 1469 1349 0.92 1972 Cape Remain 763 514 0.67 lOeveaux Bank 652 456 0.70 Both Colonies 1415 970 0.69 1973 Cape Remain 836 1082 1.29 Deveaux Bank 810 1644 2.03 Both Colonies 1646 2726 1.66 1974 Cape Romain 920 825 0.90 Deveaux Bank 750 800 1.07 Both Colonies 1670 1625 0.97 1975 Cape Romain 900 500 0.56 Deveaux Bank 1500 1300 0.87 Both Colonies 2400 1800 0.75 1976 Cape Romain 1440 1399 0.97 Deveaux Bank 11001 1738' 1.58' Both Colonies 2540 3137 1.23 'Estimated numbers — all other figures are based on actual counts. Vol. 12, No. 4, March 1979 173 TABLE 2. Year Sex Probable causes of brown pelkan inorialily, South Carolina, 1974-75 Age Probable Cause of Mortality 1974 F 4 weeks F 6 weeks F 12 weeks 1975 sacrificed, had subcutaneous emphysema hemorrhafiic cnlcrilis in ctimbination with severe pecking injuries respiratory problems — apparent air saculitis sacrificed, bird was near death of diarrhea and excessive fluid in lungs, air sacs, and pericardium hemorrhagic enteritis hemorrhagic enteritis M M M 8 weeks adult adult MORTALITY Pelicans died of possible starvation and several diseases. Hemorrhagic enteritis caused the death of at least two of the si,\ adults found dead on Deveaux Bank April 9, 1975 (Table 2). These pelicans apparently had recently migrated to South Carolina. Many brown pelicans that breed in South Carolina winter on the Atlantic Coast of Florida where hemorrhagic enteritis was responsible for many deaths of the birds in 1972 {10, 20). In 1974, a 6-week-old pelican apparently died of hemorrhagic enteritis and severe pecking; the pecking probably occurred when the sick young was attacked by hostile young and adults. A 12-week-old pelican ap- parently died of respiratory problems including air sacu- litis. One of two young sacrificed in 1974 (Table 2) was near death, and the other had subcutaneous emphy- sema, a condition that is rarely fatal (13). Several hundred downy young were found dead on Deveaux Bank in 1974. Little regurgitated food was observed during visits to the colony compared to visits in other years, and except for the usual heavy mortality after hatching, the deaths involved young at least 4 weeks old, an age when food demand rapidly increases. EGGSHELL THICKNESS Mean eggshell thickness of brown pelican eggs col- lected in South Carolina (Table 3) was 10-17 percent less than the pre- 1947 mean of 0.557 mm (/). The sig- nificant increase {P < 0.05) in mean shell thickness in 1975, compared to the 6 preceding years, initiated an upward trend extending to 1977 (Vivian Mendenhall: personal communication). Overall eggshell thickness of pelican eggs in Florida increa.sed slightly from 1969-70 to 1974 (Table 3); it increased markedly in the Gulf Coast colonies and re- mained unchanged in the Atlantic Coast colonies (Tables 4, 5). Shell thickness of Gulf Coast pelican eggs collected in 1974 averaged just 2 percent less than the pre- 1947 mean, whereas Atlantic Coast eggs averaged 1 1 percent less. There were insufficient data to com- pare trends in shell thickness in Florida Bay colonies (Table 4). In addition to South Carolina and Florida, eggshell thickness of brown pelicans has been increasing in California (2) and Louisiana (5), RESIDUES IN EGGS PCB and DDE residues made up the bulk of the 13 organochlorines identified in eggs of brown pelicans (Tables 6-8). Residues in pelican eggs in 1974—75 followed the same pattern in each of the two South Carolina colonies: there was a similarity in mean resi- dues of each organochlorine in a given year, there was much individual variation in residues of each organo- chlorine, and there was a general decline in residues of most organochlorines (Table 9). These patterns and trends were also evident in samples collected from 1969 through 1973 {4, 10). Residues of DDE, DDT, and :^DDT declined steadily from 1969 through 1975, whereas TDE declined steadily to 1973 and then in- creased somewhat. Dieldrin declined until 1971 and then remained essentially stable through 1975. PCB residues were erratic and followed no definite trend. From 1969-70 to 1974 (Table 10), there were signifi- cant declines (P < 0.05) in DDE, TDE, DDT, and 2DDT in brown pelican eggs from four regions of the southeastern United States; dieldrin decreased signifi- cantly (P < 0.05) in South Carolina and along the At- TABLF. 3. Shell thickness of brown pelican ef>gs. 1969-75. compared to pre-1947 levels Eggshell Thickness. mm> Pre-1947 1969 1970 1971 1972 1973 1974 1975 SOUTH CAROLINA 0.557 i: A-' 0.012 (23) 0.46.1 ± D 0.0t)6 (49) 0.461 ± D 0.007 (38) 0.480 ± C 0.470 ± CD 0.005 (65) 0.005 (67) 0.463 ± D 0.003 (104) 0.469 ± CD 0.004 (116) 0.499 ± B 0.004 (95) FLORIDA 0.557 ± A 0.003 (169) 0.516 i: B 0.005 (89) 0.511 ± B 0.004 (144) 0.521 ± B 0.004 (122) < Mean ± standard error; sample size in parentheses. -A significant difference anions thickness means (/" < 0.05) is indicated for those means not sharing a common letter. Means were separated by multiple range tests (12. 15). MA Pesticides Monitoring Journai TABLE 4. Shell thickness of brown pelican eggs from Florida colonies, 1969-70, 1974 Eggshell THrcKNEss, mm> Colony 1969 1970 ATLANTIC COAST Port Orange 0.488 ± 0.012 (9) 0.497 ± 0.009 (9) 0.476 ± 0.013 (14) Crane Island — 0.491 rt 0.009 ( HI) — Cocoa Beach 0.497 ± 0.01 M 111) 0.482 ± 0.019 ( 101 0.499 ± 0.010 (15) Pelican Island 0.499 + 0.012(10) 0.498 ± 0.017 (9) 0.499: Fort Pierce 0.513 ± 0.012 (6) 0.504 ± 0.(X)9 (9) 0.508: ; 0.010 (14) : 0.011 (8) FLORIDA BAY Nest Key — 0.532 ± 0.012 (10) Buchanan Key 0.530 ±0.015 (31 0.545^0.013(10) Fanny Key — 0.523 ± 0.019 (7) Marquesas Key — 0.541 ±0.012 (10) 0.523 ±0.016 (9) GULF COAST 0.547 ±0.009 (15) Seahorse Key 0.530 ±0.015 (6) 0.531 ± 0.016 ( 10) Tarpon Key 0.509 ± 0.015 (8) 11.487 ± 0.015 ( 10) Cortez — 0.502 ±0.012 (10) Bird Key 0.559 ± 0.014 ( 10) 0.517 ± 0.014 ( 10) Matlacha Pass 0.522 ± 0.023 (9) 0.504 ± 0.019 ( 10) Hemp Island 0.516 ±0.012 (10) 0.519 ± 0.015 ( 10) 0.534: 0.549 : : 0.010 (15) 0.013 (15) 0.549 ± 0.012 (15) 'See footnote 1. Table 3. TABLE 5. Shell thickness of brown pelican eggs from the Gulf and Atlantic Coasts of Florida, 1969-70, 1974 Eggshell Thickness, MM' 1969 1970 1974 GULF COAST 0.528 ± AS - 0.007 (43) 0.510 ± A 0.006 (60) 0.545 ± B 0.006 (60) ATLANTIC COAST 0.498 ± A 0.006 (35) 0.494 ± A 0.006 (47) 0.494 ± A 0.006 (51) 'See footnote 1, Table 3. 'See footnote 2, Tabic 3. lantic Coast of Florida, remained stable in Florida Bay, and increased slightly on the Gulf Coast. In contrast, PCBs increased significantly (P < 0.05) in two areas and showed little change in the other two areas. The most striking change was on the Atlantic Coast of Florida where the PCB residues more than doubled from 1969-70 to 1974. The DDE: PCB ratio changed dra- matically in most areas. For example, the ratio was appro.\imately 1 : 1 on the Atlantic Coast of Florida in 1969-70 and 1:6 in 1974. DDT residues were rarely found in 1974 samples. The order of decreasing organo- chlorine contamination, by area, in pelican eggs during each sampling period was: South Carolina > Florida Atlantic Coast > Florida Gulf Coast > Florida Bay (Table 10). Eggs collected from the Gulf Coast and Florida Bay colonies in 1974 were essentially devoid of organochlorine residues. RESIDUES IN TISSUES Birds found dead were analyzed for organochlorine residues. Residues in tissues of four pre-fledgling peli- cans found dead in South Carolina in 1974 were as low as those reported previously in other young pelicans (4, 10). Six freshly dead adult pelicans were found on Deveaux Bank April 9, 1975. Residues in three male adults were much higher than in the young birds collected in 1974, but residues in their brains were below lethal levels (Table 11). RESIDUES IN FISH Breeding brown pelicans in South Carolina feed almost exclusively on young-of-the-year Atlantic menhaden (Breevoortia tyranniis) that hatch off the coast from October through April and migrate into the estuaries as larvae where they usually remain for 6-8 months (19). Residues of DDE in menhaden in 1974 and 1975 were much lower than those reported in 1973 {10); DDT and dieldrin were found in most 1973 samples but were not detected in 1974-75 samples (Table 12). PCB resi- dues averaged about the same in 1973 and 1974 but declined substantially in 1975. Discussion Because trips to Deveaux Bank were infrequent, it could not be established that starvation was responsible for the deaths of downy young in 1974. Both young that were necropsied exhibited signs of disease that may or may not have been related to starvation (Table 2). There were no apparent deaths of downy young on the CRNWR, about 65 km northeast of Deveaux Bank, although the pelicans there had poor reproductive suc- cess and, judging from regurgitated boluses, they preyed on a greater variety of fish than usual. Therefore, poor food supply was probably responsible for the deaths of downy young on Deveaux Bank. The authors previously suggested that migration of Atlantic menhaden complicate interpretation of biomag- nification of residues from fish to pelican eggs {10) because adult menhaden are exposed to varying levels of organochlorine residues during migration. However, authors have since determined that breeding pelicans in South Carolina feed almost exclusively on young-of- the-year menhaden that apparently accumulate nearly all their residues from local estuaries. The interpreta- tion of biomagnification is still complicated by the migratory behavior of the brown pelican that exposes it to several habitats with differing degrees of organo- chlorine pollution. Vol. 12, No. 4, March 1979 175 TABLE 6. Orgcinnchlorinc residues in brown pelican e,;',i?.v, Soulh Ciirolinii, 1974 Residues, juo/g fresh wet weight DDE TDE DDT DiELDRIN Hepta- cis- CHLOR OXYCHLOR- CHLOR- EPOXIDE MIREX DANE DANE trans- NONA- CHLOR cis- NONA- CHLOR HCB TOXAPHENE PCBs MARSH ISLAND 1.89 1.43 1.37 1.56 1.70 2.39 1.35 1.51 1.65 1.65 1.67 1.00 7.03 2.46 1.33 3.83 2.36 1.37 1.75 4.69 1.95 2.75 1.86 3.42 1.40 2.94 3.79 5.85 5.51 1.22 2.45 2.82 3.80 4.13 2.21 2.38 5.91 0.81 3.90 1.40 3.86 5.57 2.41 1.53 2.38 5.00 3.04 3.68 2.67 2.99 1.95 1.95 2.08 1.07 0.60 0.48 0.48 0.46 0.48 0.58 0.46 0.38 0.37 0.38 0.30 0.32 1.48 0.36 0.39 0.91 0.47 0.35 0.42 1.80 0.57 0.60 0.45 0.64 0.34 0.16 0.41 0.78 0.59 0.47 0.40 1.25 0.19 0.68 0.34 0.63 1.09 0.63 0.26 0.59 0.90 0.78 0.83 0.49 0.67 0.53 0.36 0.47 0.23 0.58 0.15 0.73 0.34 0.44 0.33 0.27 0.39 0.55 0.46 0.30 0.40 0.40 0.36 0.42 0.27 1.46 0.46 0.36 0.96 0.57 0.13 0.28 2.89 0.62 0.73 0.42 0.73 0.46 0.74 0.88 1.27 1.03 0.49 0.61 0.86 0.90 0.83 0.64 0.71 1.21 0.18 0.71 0.31 0.84 1.26 0.56 0.26 0.36 1.10 0.71 0.71 0.36 0.57 0.49 0.38 0.59 0.26 0.18 0.15 O.U 0.16 0.19 0.16 0.13 0.16 0.19 0.15 0.15 0.25 U.IO 0.13 0.11 0.10 0.14 0.10 0.32 0.20 O.U 0.16 0.10 0.15 0.13 — 0.41 0.63 0.35 0.14 0,21 0.16 0.15 0.16 — 0.31 0.34 0.22 0.21 0.24 0.18 0.12 0.15 — 0.11 0.14 — 0.61 U.71 0.63 0.19 0.17 0.15 0.19 0.19 0.25 0.16 0.10 0.10 0.21 0.11 0.22 0.17 0.13 — — — 0.15 0.22 0.17 0.31 0.36 0.33 0.30 0.35 0.38 0.25 0.13 0.17 0.15 0.14 0.20 0.27 0.24 0.24 0.22 0.17 0.19 0.18 0.17 0.16 0.23 0.14 0.13 0.16 0.40 0.42 0.45 0.15 0.11 O.U 0.23 0.19 0.11 0.22 0.24 0.17 0.44 0.39 0.31 0.24 0.22 0.15 0.11 0.16 — 0.10 — 0.10 0.45 0.47 0.45 0.28 0.28 0.18 0.27 0.32 0.17 0.16 0.16 0.14 0.22 0.30 0.15 0.14 0.12 0.22 0.16 0.20 0.12 0.25 0.23 0.16 0.11 0.15 — 0.27 5.60 0.12 4.15 0.18 5.25 0.11 6.87 1.88 7.57 0.12 7.98 — 4.34 0.21 8.30 0.22 4.19 0.19 7.02 0.18 6.90 0.15 5.40 0,83 18.09 0.15 13.80 0.21 9.21 0.38 13.88 0.29 11.80 0.20 7.66 0.17 17.00 — 13.00 — 6.49 — 10.50 — 5.69 — 1 1 .70 — 8.15 — 12.50 — 7.10 — 22.11 — 21.80 — 7.34 — 8.53 — 12.15 — 11.65 — 9.80 — 8.19 — 7.38 — 17.72 — 6.39 — 8.28 0.21 0.70 0.46 11.33 0.82 14.04 0.46 7.05 0,17 8.02 0.17 5.47 0.57 27.48 0.58 14.43 0.39 11.77 0.23 5.10 0.37 9.90 0.35 2.30 — 8.80 — 8.00 0.35 5.80 GM CL Range 2.35 0.41 2.04-2.70 0.34-0.51 0.81-7.03 ND-1.80 0.55 0.47-0.63 ND-0.73 0.17-2.89 ND-0.32 ND-0.20 0.17 0.14-0.20 ND-O.U ND-0.51 0.16 0.12 0.13-0.19 0.10-0.15 ND-0.71 ND-0.63 0.13 0.10-0.17 ND-0.10 ND-1.88 8.32 7.10- 9.76 0.70-27.48 DEVEAUX BANK 1.50 1.27 0.65 1.36 1.48 1.84 1.48 1.93 0.89 2.44 2.70 2.18 1.20 2.30 0.50 0.38 0.35 0.37 0.38 0.48 0.47 0.56 0.22 0.76 0.61 0.40 0.34 0.59 0.36 0.33 0.34 0.29 0.33 0,45 0.45 0.59 0.26 0.66 0.81 0.62 0.26 0.54 0.30 0.20 0.11 0.09 — 0.10 — — 0.14 0.13 0.09 0.09 0.21 0.09 — 0.18 — 0.22 0.12 — — 0.14 0.23 0.19 0.15 0.18 0.19 0.15 0.17 0.23 — _- 0.17 O.U 0.22 0.10 — 0.32 5.01 — 0.20 5.16 — 0.22 4.07 — 0.21 5.00 — — 1.90 — — 8.14 — — 7.53 — — 12.00 — — 4.24 _ — 11.07 - — 9.82 - — 12.16 - — 4.80 - — 7.58 (Continued next page) 176 Pesticides Monitoring Journal TABLE 6 (Cont'd.) Organochlorine residues in brown pelican eggs, South Carolina, 1974 Residues, ^o/g fresh wet weight TDE DDT DIELDRIN Hepta- CHLOR Epoxide MiREX en- OXYCHLOR- ChLOR- DANE DANE trans- NONA- CHLOR CIS- NONA- CHLOR HCB TOXAPHENE PCBs 1.40 0.34 2.50 — 3.53 0.95 2.29 0.37 2.42 0.59 2.99 0.69 1.70 0.46 1.72 0.37 1.60 0.31 2.19 0.50 1.65 0.43 2.08 0.45 2.02 0.52 1.15 0.42 1.43 0.42 2.87 0.48 2.11 0.37 1.36 0.21 1.37 0.31 0.74 0.23 0.78 0.16 0.76 0.21 1.41 0.22 2.35 0.10 0.80 0.27 2.18 0.39 2.05 0.37 2.16 0.96 1.84 0.48 4.51 0.95 3.04 0.84 3.76 0.73 3.11 0.62 1.98 0.45 2.12 0.31 1.96 0.51 1.92 0.62 2.33 0.44 3.32 0.59 4.62 0.92 4.94 1.22 3.59 0.76 3.67 0.37 2.98 0.69 1.59 0.38 4.48 0.96 2.30 0.80 GM 1.96 0.45 CL 1.74-2.21 0.40-0.52 0.18 0.36 — — 0.73 — — 0.95 — 0.13 0.56 — — 0.61 — — 0.83 — — 0.50 — — 0.39 — — 0.39 — — 0.59 0.26 — 0.43 — — 0.61 — — 0.47 — — 0.44 — — 0.42 — — 0.60 — — 0.55 — — 0.29 — — 0.60 — — 0.22 — — 0.32 — — 0.19 — — 0.27 — — 1.28 0.11 — 0.27 — — 0.44 — — 0.56 — — 0.86 — 0.10 0.39 — — 1.10 0.13 0.17 1.14 0.12 — 0.80 — — 0.53 — — 0.54 — — 0.33 — — 0.54 — — 0.67 0.11 — 0.61 — — 0.88 0.12 — 1.43 0.23 — 1.22 0.14 3.01 0.84 — 0.33 0.85 0.11 — 0.71 0.10 0.21 0.40 — — 0.85 0.10 0.25 0.96 D.I3 — 0.53 0.47-0.60 0.11 0.12 — _ — 5.37 — 0.13 _ — — 8.84 0.31 0.24 0.24 — — 16.76 0.12 0.16 0.14 — — 12.90 0.16 0.16 0.14 _ — 8.27 0.23 0.41 0.21 — — 17.00 0.21 0.26 0.18 — — 7.91 0.12 0.27 0.11 — — 9.58 0.15 0.19 0.13 — — 7.50 0.12 0.83 0.22 — — 12.71 0.16 0.19 0.11 — 0.17 4.74 0.20 0.28 0.19 — — 3.07 0.19 0.25 0.13 — — 7.18 0,21 0.24 0.14 — — 5.51 0.17 0.17 0.10 — — 8.02 0.24 0.29 0.22 — 0.24 6.47 0.16 0.15 0.16 — 0.76 5.70 0.18 0.23 0.14 — — 5.96 0.31 0.24 0.20 — — 1.32 0.11 0.10 0.10 — _ 0.62 _ — — — 0.95 0.10 — — — — 2.18 0.14 0.16 0.10 — — 3.17 0.45 0.25 0.23 — 0.24 2.20 0.14 0.13 0.13 — 0.39 5.35 0.18 0.15 0.14 — 0.41 6.04 0.16 0.12 0.13 — 0.41 2.68 0.18 0.19 — 0.49 4.91 0.29 0.14 0.24 — 0.31 6.54 0.41 0.32 0.33 — 0.74 9.90 0.41 0.30 0.25 — 0.48 14.18 0.33 0.27 0.29 — 0.57 15.48 0.29 0.31 0.20 — — 5.27 0.17 0.14 0.10 — 0.26 3.30 0.12 0.12 0.10 — 0.14 8.11 0.24 0.12 0.13 — 0.22 5.88 0.29 0.24 0.15 — — 5.80 0.15 0.18 0.14 — 0.21 7.70 0.20 0.21 0.19 — — 9.50 0.44 0.42 0.32 — — 19.40 0.45 0.40 0.35 0.02 0.73 21.40 0.26 0.33 0.23 0.02 0.41 12.40 0.22 0.22 0.18 0.02 — 12.60 0.30 0.25 0.20 0.01 0.16 11.50 0.22 0.14 0.13 0.01 0.18 8.80 0.36 0.34 0.25 0.02 0.49 14.30 0.50 0.21 0.37 0.04 0.41 24.80 0.17 0.18 0.13 0.14-0.19 0.16-0.21 0.11-0.15 0.11 6.59 0.09-0.14 5.48- 7.94 Range 0.65-4.94 ND-1.22 ND-0.20 0.19-1.43 ND-0.26 ND-3.01 ND-0.53 ND-0.50 ND-0.83 ND-0.37 ND-0.04 ND-0.76 0.62-24.80 MARSH ISLAND AND DEVEAUX BANK GM 2.13 0.44 0.54 0.17 0.17 0.13 0.12 7.36 CL 195-2 34 0 39-0 49 0 49-0 59 0.15-0.19 0.15-0.19 0.11-0.14 0.10-0.14 6.50-8.32 Range 0.65-7.01 ND-1.80 ND-0.73 0.17-2.89 ND-0.32 ND-3.01 ND-0.53 ND-0.61 ND-0.83 ND-0.63 ND-0.10 ND-1.88 •.62-27.48 ND or — = no residue detected. GM = geometric mean. CL = 95 percent confidence limits. 12, No. 4, March 1979 177 TABLE 7. Organochtorinc rcsiiliics in brown pelican c.ij.e.v, South Ciirolina, 1975 Residues, tto/a fresh wet weight DDE TDE DDT tranS' HEPTACHLOR OXY- CIS- NONA- DiELDRiN Epoxide MiRtx chlordane Chlordane chlor cis- NONA- CHLOR TOXAPHENE PCBs MARSH ISLAND 1.41 0.38 1.04 0.30 1.91 0.75 1.68 0.37 I.IS 0.27 1.84 0.33 1.00 0.35 1.61 0.53 3.10 0.69 1.53 0.26 1.20 0.33 1.10 0.18 1.22 0.31 2.59 0.49 1.64 0.41 1.20 0.34 0.81 0.19 1.44 0.59 1.09 0.34 1.42 0.50 1.03 0.34 1.10 0.34 0.75 0.30 0.65 0.21 0.96 0.31 0.88 0.21 1.61 0.57 1.73 0.64 1.13 0.34 1.50 0.37 1.91 0.58 1.34 0.38 1.57 0.54 1.64 0.47 1.12 0.41 0.70 0.34 1.57 0.41 0.36 0.10 0.87 0.29 1.76 0.62 1.15 0.45 0.70 0.20 0.95 — 1.71 0.39 1.85 0.60 2.76 0.74 1.65 0.57 0.89 0.37 1.72 0.67 0.95 0.21 1.80 0.38 1.08 0.42 2.51 0.58 2.36 0.65 1.58 0.43 1.60 0.18 2.00 0.81 1.59 0.58 0.13 0.50 0.22 0.58 0.44 0.34 0.36 0.32 0.50 0.72 0.36 0.35 0.23 0.31 0.66 0.48 0.27 0.22 0.38 0.27 0..14 0.27 0.24 0.16 0.17 0.26 0.22 0.38 0.45 0.34 0.37 0.53 0.30 0.51 0.55 0.32 0.22 0.51 0.10 0.23 0.41 0.34 0.19 0.23 0.43 0.53 0 76 0.42 0.28 0.92 0.26 0.40 0.28 0.71 0.67 0.49 0.50 0.50 0.40 0.10 0.10 0.10 0.14 0.11 0.10 0.27 0.38 0.10 0.13 0.13 — 0.15 0,38 5.02 0.11 0.13 — 0.28 3.01 0.29 0.27 0,24 0.27 4.35 0.15 0.14 0.10 0.32 3.95 0.15 0.13 0.11 0.24 4.64 0.33 0.23 0.29 0,57 7.40 0.17 0.19 0. 1 3 0,24 3.28 0.15 — 0,09 0.43 3,36 0.26 0.24 0,19 0,31 10.03 — O.IO — 0.48 3.10 0.17 0.18 0,11 0.48 4.50 — 0.13 — — 5.31 0.12 0.16 — 0.14 6.45 0.18 0.26 0.19 0,49 11.05 0.20 0.26 0,18 0,55 6.20 0.12 0.16 — 0.14 5.20 0.10 0.10 — 0.11 8.80 0.25 0.25 0,13 0.18 6.98 0.14 0.18 0,10 0.16 5.02 O.IS 0.25 0.13 0.15 6.31 0.19 0.15 0.11 0.21 5.95 — 0.15 . — 0.22 4,87 0.11 — — 0.16 7.06 O.IO 0.11 — 0.41 6.92 0.16 0.18 0,12 0.16 8.73 — — — 0.16 7.33 0.25 0.14 0.14 0.26 8.38 0.31 0.24 0.15 0.22 10.89 0.16 0.14 0.11 0,21 7.96 0.17 0.18 0.14 0,21 14.40 0.31 0.22 0,20 0,34 12.78 0.17 0.19 0.12 0.20 9,84 0.24 0.16 0,14 0.42 12.96 0.27 0.17 0 23 0.27 13.45 0.21 0.19 0,13 0.20 10.72 0.18 0.16 0,11 0.15 9.85 0.22 0.16 0,16 0.28 12.91 — — — — 5.23 0.13 0.14 — — 5.81 0.25 0.21 0.18 0.27 14.89 0.23 0.13 0.14 0,12 6.46 — — — — 4.70 0.14 0.10 0,14 0.11 11.53 0.19 0.15 0,19 0.21 12.32 0.25 0.14 0,20 0.37 14.53 0.31 0.29 0.31 0.27 13.91 0.26 0.18 0.18 0.21 9.67 0.15 — 0,11 0.23 7.57 0.67 0.35 0,40 0.40 12.93 0.16 0.98 0,16 0.14 12.31 0.17 0.16 0,18 0.29 17.99 0.17 0.15 0,11 0,14 6.57 0.39 0.23 0.33 0.33 20.08 0.28 0.19 0.19 0.31 10.81 0.21 0.12 0,13 0.27 7.43 — — — — 1.40 — — — , — 0.38 0.31 0.33 0.19 0.50 7.47 0.28 0.28 0.17 0.29 10.95 GM 1.30 0.36 CL 1.15-1,46 0.30-0.42 Range 0.18-3.10 ND-0.81 ND-0.13 0,35 0.31-0.40 ND-0.92 ND-0.11 ND-0.38 ND-0.13 0,16 0.15 0,14-0,19 0,13-0.18 ND-0.67 ND-0.98 0 12 0.21 0,10-0,14 0,18-0.25 ND-0.40 ND-0.57 DEVEAUX BANK 1.24 0.36 3 03 0.68 1.70 0.37 2.51 0.91 1.34 0.37 1.35 0.32 2.03 0.54 0.91 0.33 1.34 0.41 0.39 — 0.39 0.63 0.40 0.55 0.41 0.34 0.59 0.21 0.29 0.19 0.19 O.IO 0.12 0.22 1.77 0.15 0.11 0,15 0.54 1.84 0.15 0,17 0,12 0.22 3.49 0.25 0,17 0, 1 3 0.50 7.32 0.16 0,15 0.12 0.13 2.60 0,13 0,14 0,12 0.24 2.69 0.19 0.19 0.16 0.40 3.96 0.14 — _ 0.11 2.51 0.17 — 0.10 0.21 2.43 — 0.09 — — 1.70 (Continued next pa^e) 178 Pesticides Monitoring Journal TABLE 7 (cont'd.). Oraaiwchlorinc residues in brown pelican eggs. Soiilh Curoliiia, 1975 Residues, /IC/G FRESH 1 WET WEIGHT trans- cis- Heptachlor OXY- cis- NONA- NONA- DDE TDE DDT DiELDRIN Epoxide MiREX ( :hlordane Chlordane CHLOR CHLOR TOXAPHENE PCB 0.65 0.11 — 0.11 — — 0.13 0.13 0.11 0.07 0.09 6.82 — 0.29 — 0.34 — — — 0.17 0.24 0.16 0.22 3.92 0.10 0.80 — 0.64 — — — 0.29 0.29 0.18 0.31 4.20 1.02 0.26 — 0.28 — — — 0.14 0.19 0.11 3.07 1.62 0.45 — 0.40 — — — 0.16 0.20 0.14 0.38 3.60 0.88 0.31 — 0.21 — — — 0.17 — _ 0.18 1.54 3.69 0.10 — 0.97 — — — 0.59 — 0.35 0.35 5.93 1.00 0.34 — 0.27 — 0.10 — 0.12 — — 0.22 1.98 1.52 0.41 — 0.97 — 0.14 — 0.15 0.27 0.11 0.36 3.63 0.50 — — 0.11 — — — — — — 0.21 4.37 1.78 0.60 — 0,44 — — — 0.24 0.33 0.18 0.58 13.56 1.48 0.35 — 0.29 — — — 0.16 0.22 0.14 0.31 9.66 0.97 0.35 _ 0.3.1 — — — 0.17 0.19 0.10 0.20 5.55 1.99 0.52 — 0.39 — — — 0.18 0.24 0 14 0.37 7.88 1.19 0.30 — 0.35 — — — 0.13 0.18 0.11 0.40 10.81 1.02 0.42 — 0.35 0.10 — — 0.17 0.22 0.11 0.14 8.40 1.23 0.31 — 0.33 — — — 0.15 0.22 0.14 0.10 6.86 1.59 0.54 — 0.45 — — — 0.20 0.27 0.14 0.25 5.19 1.40 0.38 — 0.34 — — — 0.19 0.26 0.14 0.15 9.88 1.99 0.51 — 0.51 0.12 — — 0.19 0.27 0 16 0.12 9.86 2.48 0.72 — 0.46 0.10 — — 0.23 0.34 0.18 0.27 10.25 1.00 0.20 — 0.21 — — — 0.10 0.12 0.09 — 7.92 1.73 0.22 . 0.43 — — — 0.14 0.19 0.12 — 10.43 1.28 0.20 0.35 — — 0.10 0.2-1 0.16 0.09 — 7.22 0.76 0.23 0.20 — — — 0.10 0.13 — 0.23 7.93 2.09 0.38 0.53 0.10 — 0.13 0.26 0.28 0.13 0.26 10.03 3.04 0.58 0.40 0.14 — — 0.96 — 0.20 1.27 11.46 1.90 0.41 0.63 — — — 0.46 0.16 0.12 0.09 3.90 2.91 0.78 — 0.70 0.20 — — 0.24 — 0.20 1.02 6.06 3.62 1.38 — 1.04 0.50 — 0.10 0.61 0.68 0.22 0.38 6.11 1.86 0.44 — 0.46 0.14 — — 0.13 0.28 0.14 0.51 4.88 3.13 0.96 — 0.96 0.31 — — 0.36 0.53 0.31 0.67 10.10 2.22 0.38 — 0.68 0.21 — — 0.28 0.40 0.17 0.57 6.37 CM 1.29 0.38 0.38 0.18 0.16 0.12 0.23 5.07 CL 0.99- 1.67 0.31-0.47 0.31- 0.46 0.16-0.22 0.13-0.20 0.10-0.14 0.18-0.30 4.20- 6.1 Range ND- 3.69 ND- 1.38 ND ND- 1.04 ND-0.50 ND-0.19 ND-0.13 ND-0.96 ND-0.68 ND-0.35 ND-1.27 1.54-13.5 MARSH ISLAND AND DEVEAUX BANK GM 1.29 0.36 0.36 0.17 0.15 0.12 0.22 6.24 CL 1.14-1.47 0.32-0.41 0.32- 0.40 0.15-0.19 0.14-0.17 0.11-0.13 0.19-0.25 5.50- 7.01 Range ND- •3.69 ND- 1.38 ND-0.13 ND- ■1.04 ND-0.50 ND-0.38 ND-0.13 ND-0.96 ND-0.98 ND-0.40 ND-1.27 0.38-20.0! ND or — = no residues detected. GM = geometric mean. CL = 95 percent confidence limits. Vol. 12, No. 4, March 1979 179 Colony DDE TABLE 8. Organochloriiic rcsidms in brown pelican eggs, Florida, 1974 Residues, (ic/o fresh wet weight TDE PCBs Heptachlor Epoxide CIS- trans- cis- MiREX Chlordane Nonachlor Nonachlor Toxaphene DiELDRIN GULF COAST Cedar Key — 0.11 0.91 0.16 — 0.36 0.23 — 0.86 0.52 — 1.50 0.47 — 1.20 0.29 — 11.56 0.99 0.31 0.75 0.20 — 0.47 0.«4 0.18 1.40 0.42 — 0.65 0.24 — 0.69 — — 0.69 — 0.14 0.79 — _ 0.44 0.24 — 1.10 0.10 0.14 0.10 0.14 0.21 0.16 0.58 0.44 0.19 GM CL Range 0.29 0.16-0.43 ND-0.64 ND-0.31 0.80 0.62- 1. 00 0.36- 1.60 ND ND ND-0.14 ND-0.12 ND ND-0.58 Cortez 0.51 0.10 2.10 0.33 — 1.00 0.57 0.18 2.00 1.00 0.12 1.80 0.64 0.14 1.10 0.39 0.13 1.1(1 0.37 0.10 1.00 0.12 0.10 10.30 0.31 — 1.50 1.47 0.20 2.20 0.35 0.11 0.99 — 0.11 3.90 0.66 0.22 0.75 — 0.15 1.40 0.52 0.14 1.20 020 — 0.13 0.27 — 0.15 1.00 oin 0.13 — 0.15 0.19 — 0.33 0.23 0.18 0.14 0.17 0.10 0.15 0.11 — 0.17 — — 0.19 0.17 0.12 0.29 0.20 (1.10 0.23 0.19 0.11 0.18 0.14 0.19 0.12 0.15 0.15 0.11 0.38 0.23 0.18 0.10 0.19 0.17 0.20 GM CL Range Bird Key 0.45 0.28-0.65 ND-1.47 0.12 0.08-0.15 ND-0.22 1.74 I. II- 2.57 0.75-10.30 ND ND 0.15 — 0.60 0.29 — 0.41 0.26 O.IO 0.15 0.55 0.16 1.70 0.57 0.11 1.60 — 0.19 0.25 0.59 0.13 1.20 0.30 — 1.00 0.22 — 0.33 0.33 0.13 3.20 0.20 — 1.20 — — 1.20 0.31 0.14 2.80 0.22 — 1.50 0.12 — 0.51 0.19 0.14 0.14 0.06 0.08-0.20 0.04-0.26 0.02-0.10 ND-0.33 ND-1.00 ND-0.18 ND 0.60 — 0.15 0.16 0.10 — 0.17 0.22 0.13 — 0.19 — — — 0.10 — — — 0.10 — — — 0.10 — — 0.31 0.17 0.10 0.09 — — 0.16 0.12-0.20 ND-0.38 0.11 0.12 0.18 0.25 0.17 0.13 O.U 0.15 0.10 0.19 GM CL Range 0.27 0.18-0.37 ND-0.59 0.06 0.02-0.10 ND-0.19 1.02 0.63- 1.51 0.15- 2.80 ND ND-0.31 0.07 0.03-0.11 ND-0.19 ND-0.22 ND-0.13 ND-0.60 0.10 0.07-0.14 ND-0.25 Hemp Island 1.05 0.41 4.10 0.16 — 0.94 0.70 0.30 1.50 0.28 — 0.61 — — 0.25 0.52 — 1.10 0.58 — 0.60 0.16 _ 0.80 0.73 — 3..30 0.60 0.13 1.40 0.63 0.11 1.80 0.29 — 1.70 0.23 — 0.50 0.31 0.13 1.30 0.40 — 1.30 0.13 0.10 0.83 0.45 0.48 0.33 0.15 0.18 0.13 0.15 0.13 0.14 0.44 0.18 0.23 0.10 0.65 0.30 0.10 0.22 0.26 0.19 0.15 0.12 O.U 0.10 GM CL Range 0.42 0.29-0.58 ND-1.05 ND-0.41 1.24 0.82- 1.77 0.50-4.10 ND-0.13 ND-O.IO ND-0.83 ND-0.48 ND-0.44 ND-0.23 0.12 0.08-0.18 ND-0.65 (Continued next page) 180 Pi STRIDES Monitoring Journal TABLE 8 (Cont'd.). OrganocMorine residues in brown pelican egs-s, Florida, 1974 Residues, ^c/g fresh wet weight Colony DDE TDE PCBs Heptachlor cis- Epoxide MmEX Chlordane trans- NONACHLOR NONACHLOR TOXAPHENE DiELDRIN FLORIDA BAY Marquesas Key 0.13 0.64 0.23 0.11 0.42 0.44 1.05 0.25 0.42 0.14 0.41 1.29 1.60 0.83 1.06 0.12 Fort Pierce 1.61 0.31 10.90 0.91 0.12 4.66 1.47 0.34 8.89 1.16 0.31 6.63 0.60 0.19 3.98 1.15 0.22 7.79 2.15 0.65 12.92 1.19 0.38 10.47 0.12 0.10 0.14 0.21 0.21 0.22 0.18 0.11 0.14 0.11 0.13 0.11 0.12 0.20 0.16 0.20 0.14 0.10 0.14 GM CL Range 0.39 0.19-0.61 0.11-1.05 ND-0.14 0.47 0.08- 1. 00 NO- 1.60 NO ND ND ND ND ND-0.14 ND-0.14 Fanny Key 0.37 0.19 0.10 2.41 0.85 — — — — — — 0.12 ATLANTIC COAST 0.26 0.19 0.42 0.40 0.24 0.28 0.41 0.40 GM 1.24 0.31 7.79 CL 0.89-1.66 0.19-0.44 5.49-10.91 Range 0.60-2.15 0.12-0.65 3.98-12.92 ND-0.12 0.13 0.05-0.21 ND-0.22 ND-0.18 0.10 0.04-0.16 ND-0.20 ND-0.20 0.31 0.24-0.40 0.19-0.42 Cocoa Beach 0.67 0.14 2.98 1.81 0.45 7.80 1.39 0.29 6.10 1.13 0.32 4.77 0.72 0.13 2.40 0.44 0.19 5.16 0.74 0.18 5.43 0.85 0.23 3.00 1.73 0.40 5.58 1.72 0.40 8.35 1.20 0.27 4.76 1.20 0.28 7.77 3.40 0.78 9.22 0.94 0.29 3.38 0.49 0.17 2,83 — — — — 0.20 0.16 0.12 0.14 0.25 0.35 0.16 — 0.18 0.18 0.44 0.15 0.17 0.13 0.14 0.34 — — — — 0.14 — — — 0.21 0.27 0.16 0.13 0.15 — 0.25 0.13 — O.ll 0.10 0.41 0.30 0.15 0.23 0.21 0.70 — 0.13 — — 0.38 0.15 0.15 0.16 0.22 0.41 0.16 0.10 0.13 0.21 0.33 0.24 0.18 0.20 0.46 0.78 — — — 0.44 0.23 0.12 — 0.10 — 0.18 GM CL Range 1.13 0.82-1.51 0.44-1.81 0.29 0.21-0.38 0.13-0.78 4.94 3.89- 6.24 2.40- 9.22 ND ND 0.11 0.06-0.16 ND-0.30 0.07 0.03-0.11 ND-0.18 0.10 0.05-0.15 ND-0.23 0.15 0.07-0.24 ND-0.46 0.32 0.25-0.42 0.14-0.78 ican Island 0.99 0.25 2.48 1.33 0.25 5.77 1.25 0.28 4.18 1.01 0.16 3.07 0.72 0.21 4.67 1.11 0.35 6.36 1.40 0.46 7.25 1.77 0.62 9.73 1.03 0.49 9.06 1.40 0.60 9.52 1.40 0.35 9.24 0.49 — 2.71 1.72 0.50 9.26 0.66 0.13 1.98 — — — 0.22 0.15 0.19 0.12 0.20 — 0.33 0.15 — 0.13 0.14 0.23 — — — — 0.26 0.13 0.11 — — 0.23 0.13 0.16 — — 0.31 0.16 0.16 0.13 0.27 0.46 0.18 0.20 0.15 0.30 0.60 0.14 0.13 0.13 0.12 0.42 0.35 0.30 0.25 — 0.65 0.19 0.17 0.12 — 0.45 — — — — 0.13 0.15 0.17 0.14 0.11 0.48 — 0.12 — — 0.15 GM CL Range 1.13 0.92-1.37 0.49-1.77 0.32 0.22-0.43 ND-0.62 5.47 3.96- 7.45 1.98- 9.73 ND-0.11 ND 0.12 0.07-0.18 ND-0.35 0.11 0.06-0.17 ND-0.30 0.09 0.04-0.14 ND-0.25 ND-0.30 0.31 0.23-0.42 0.13-0.60 Port Orange 1.67 0.43 10.01 0.91 0.14 4.97 1.80 0.65 7.80 2.11 0.59 11.27 2.64 0.74 11.78 1.55 0.38 8.10 0.10 0.18 0.17 0.10 0.26 0.43 0.10 0.10 — — 0.46 0.24 0.21 0.14 0.23 0.54 0.18 0.22 0.13 0.33 0.47 0.53 0.34 0.26 0.29 0.62 0.17 0.16 0.11 0.24 0.38 (Continued next page) Vol. 12, No. 4, March 1979 181 TABLE 8 (Cont'd.). Orf^aiiochtorine residues in hrowii pelican enKS, Florida. 1974 Residues, iio/o fresh wet weight Colony DDE TDE PCBs Heptachlor Epoxide Mirex CIS- Chloroane trans- NONACHLOR NONACHl.OR Toxaphene Dibldrin 1.02 0.12 5.45 1.16 0.34 6.05 1.04 0.38 4.90 0.4S 0.10 4.17 1.51 0.45 8.42 1.00 0.37 8.30 1.94 0.46 7.43 1.34 0.22 9.70 0.24 0.47 0.31 0.15 0.33 0.12 0.28 0.11 0.12 0.31 — 0.13 0.30 — — .0.18 H.Il 0.23 0.42 — 0.41 0.83 0.33 1.53 0.46 — 0.18 0.28 GM CL Range 1.32 1.03-1.71 0.45-2.64 0.33 0.23-0.47 0.10-0.74 7.39 6.13- 8.91 4.27-11.78 ND-0.10 ND 0.14 0.08-0.23 ND-0.53 0.12 0.08-0.19 ND-0.34 0.09 0.06-0.13 ND-0.33 0.19 0.11-0.32 ND-1.53 0.40 0.32-0.50 0.18-0.83 NOTE: ND or — = no residue delected. GM — geometric mean. CL — 95 percent confidence limits. TABLE 9. T, ends for ori;anoi htorine residues in hrown pelican eHQs, 1969-75 Deveaux Bank ind Marsh Island, S nurh Carolina, Residues. iig/g ^RESH wet weight Sample Year Size DDE TDE DDT 2 DDT DiELDRIN PCBs 1969 15 5.45 'A = 1.65 A 0.45 A 7.81 A 1.16 A 6.11 AB (4.44^6.70) (1.. ^0-2. 10) (0.15-0.83) (6.48-9.40) (1.03-1.52) (5.00-7.45) 1970 13 3.58 B 0.79 B 0.55 A 5.27 B 0.82 B 5.25 AB (2.23-5.72) (0.53-1.20) (0.42-0.69) (3.49-7.77) (0.52-1.32) (3.92-7.04) 1971 65 2.48 C 0.48 C 0.17 B 3.20 D 0.46 C 6.49 A (2.27-2.71) (0.43-0.53) (0.13-0.21) (2.94-3.48) (0.40-0.52) (5.44-7.73) 1972 72 3.03 B 0.36 C 0.18 B 3.69 C 0.45 C 7.51 A (2.7l>-3.40) (11.31-0.42) (0.15-0.21) (3.31-4.12) (0.39-0.52) (6.68-8.46) 1973 104 2.09 D 0.19 D 0.17 B 2.56 E 0.45 C 4.75 B (1.91-2.29) (0.17-0.22) (0.15-0.20) (2.35-2.78) (0.41-0.50) (4.26-5.31) 1974 115 2.22 CD 0.49 C 0.02 C 2.72 E 0.58 C 7.63 A (2.03-2.43) (0.44-0.54) (0.01-0.04) (2.49-2.96) (0.53-0.64) (6.80-8.55) 1975 1(12 1.40 E 0.41 C (1.004 C 1.80 F 0.40 C 6,45 A (1.27-1.54) (0.37-0.46) (0.()ll2-().()07) (1.64-1.97) (0.36-0.43) (5.75-7.24) > Geometric mean; 95 percent confidence limits are in parentlieses. = See Footnote 2, Table 3. The factors iincierlying the large population increase were not evident. The excellent reproductive success in 1973 cannot account for the large population increase just 2 years later. It is possible that many South Caro- lina adults did not breed before 1975 because of insuf- ficient food. Many adult brown pelicans in Mexico and California apparently do not breed when the food supply is poor (2). The breeding population in .South Carolina showed only a slight increase in 1973 when pelicans had an excellent reproductive season and men- haden were apparently readily available. Thus it is doubtful that large numbers of adult pelicans in South Carolina failed to breed from 1969 to 1974. There is no evidence from banding studies that large numbers of pelicans migrated from natal areas in Florida to South Carolina to breed. Although the population increase was probably caused by a combination of factors, the most likely factor seems to be the decline in organo- chlorine residues that resulted in improved reproductive success and probable increased longevity after fledging. DDE is the organochlorine exerting most influence on reproductive success. However, little is known about adult mortality from organochlorines except that several TABLE 10. Organochlorine residue trends in brown pelican eggs from four regions, 1969-70, 1974 Mean residues, ;ig/g fresh wet weight Pollutant DDE TDE DDT >: DDT Dieldrin PCBs Region' SC AC FB GC SC AC FB GC SC AC FB GC SC AC FB GC SC AC FB GC SC AC FB GC 1969-70 1974 4.65 A = 2.22 B 2.32 B 1.21 C 1.04 C 0.37 D 1.48 C 0,36 D 1.29 A 0.49 C 0.91 B 0.32 D 0.18 E 0.03 E 0.55 C 0.07 E 0.49 A 0.02 C 0.43 A 0.01 C 0.07 C NDC 0.27 B NDC 6.52 A 2.72 C 3.68 B 1.52 D 1.25 D 0..39 E 2.27 C 0.42 E 1.09 A 0.58 B 0.51 B 0.36 C 0.06 D 0.04 D 0.11 D 0.13 D 5.77 B 7.63 A 2.68 C 6.12 AB 0,75 D 0.62 D 0.70 D 1.I8D 'SC = South Carolina, AC = Florida Atlantic Coast, FB = Florida Bay, and GC = Florida Gulf Coast. -See Footnote 2, Table 3. 182 Pesticides Monitoring Journal TABLE 11. Ori^anochlorine residues in tissues of brown pelicans found dead, South Carolina, 1974-75 Residues, iiG/a fresh wet weight Year Sex Tissue DDE TDE DDT Hepta- CHLOR Dieldrin Epoxide CIS- Chlor- dane trans- NONA- CHLOR as- NONA- CHLOR TOXA- PHENE Ml REX PCBs 1974 1975 F 4wk Carcass 0.14 — — — 0.25 Brain — — — — — — 0.25 K 6wk Carcass 0.16 — — — __ 1.44 Brain 0.52 — — 0.14 — 2.46 F 12 wk Carcass 0.46 0.16 — 0.13 — — — 1.27 Brain — — — — — — — — 0.74 M 8 wk Carcass 0.15 — — — — — — — 1.28 Brain 0.20 — ■ — — — — — 1.58 M AD Carcass 3.09 1.25 0.14 1.67 0.22 0.44 0.56 0.47 0.56 1.40 25.28 Brain 3.43 0.55 — 0.99 0.10 0.26 0.20 0.22 0.48 0.64 14.22 M AD Carcass 3.24 1.56 0.14 1.87 0.26 0.62 0.92 0.71 0.73 1.80 38.80 Brain 1.31 0.54 — 0.91 — — 0.19 0.23 0.54 0.87 12.83 M AD Brain 1.46 0.61 — 0.99 0.10 0.27 0.31 0.27 0.47 0.65 2.92 NOTE; — = no residues detected. AD = adult. TABLE 12. Organoclilorine residues in Atlantic menhaden refiurgitated by brown pelicans. South Carolina, 1974-75 Residues, /lO/o fresh wet weight Year DDE TDE Heptachlor Epoxide cts~ CIS- trans- Chlordanc Nonachlor Nonachlor Toxaphene PCBs 1974 0.01 0.04 0.01 0.06 0.04 0.01 0.02 0.01 0.23 0.19 0.02 0.36 0.22 GM CL 0.016 0.004-0.060 0.147 0.036-0.608 1975 0.03 0.04 0.01 0.03 0.02 0.06 0.03 0.06 0.01 0.01 0.02 0.03 0.01 — 0.02 0.03 0.01 0.01 0.03 0.03 0.02 0.02 0.01 0.01 0.01 — 0.06 0.03 — 0.02 0.03 — 0.02 0.09 — — 0.08 — — 0.02 0.01 — 0.10 — — 0.10 0.01 0.02 0.15 — 0.01 0.11 GM CL 0.014 0.009-0.022 0.020 0.010-0.039 0.050 0.024-0.107 NOTE: — = no residues detected. GM = geometric mean. CL = 95 percent confidence limit. pelicans have died of endrin and dieldrin poisoning. An increase in adult survival would have a marked effect on the breeding population and on the recruitment standard necessary to maintain a stable population. There are no data to support the theory of increased adult longevity, but it may be investigated in the future by analyzing banding data. The South Carolina brown pelican population formerly numbered about 6,000 breeding pairs (i, 10), and if the present rate of reproductive success continues, the population should reach 6,000 breeding pairs within the ne.xt 5 years. The pelican population in Florida has been essentially stable since aerial surveys of nesting colonies were initiated in 1968 (18. 21). Acknowledgments Authors thank A. Stana Federighi and Eugene H. Dust- man for critically editing the manuscript. Appreciation is expressed to Steve Joyner, Daniel Doshier, Fred Milton, Stewart Givens, George Garris, Julie Keahey, Brad Winkler, John Sheerer, Scott Osborne, George She- gogue, and others for assistance in the field. We are grateful to Gary Hensler, Jane Dowdy, Ann Potoski, and Robert Schwenk for statistical assistance, and to Louis N. Locke for necropsy reports. Vol. 12, No. 4, March 1979 183 LITERATURE CITED (/) Amierson. D. W.. ami J. J. HUkey. 1970. Oological data on egg and breeding characteristics of brown pelicans. Wilson Bull. 82(1): 14-28. (2) Anderson, D. W.. J. R. Jehl. Jr.. R. W. Ritehrough, L. A. Wooth, Jr.. L. R. DeWcese. and W. G. Ed);e- comh. 1975. Brown pelicans: improved reproduc- tion off the Southern California Coast. Science 180(4216) :806-808. (.?) Beckett. T. A., 111. 1966. Deveaux Bank— 1964 and 196.'!. Chat 30(4):93-100. (4) Blu.s. L. J.. A. A. Belhle. and R. M. Proiity. 1974. Relations of the brown pelican to certain environ- mental pollutants. Pestic. Monit. J. 7(3/4): 181-194. (5) Bins. L. J., E. Croniartie. L. McNease. and T. Joanen. In press. Brown pelican: Population status, repro- ductive success, and organochlorine residues in Louis- iana, 1971-1976. Bull. Environ. Contam. Toxicol. (6) Blus. L. J.. C. D. Gish, A. A. Belisle, and R. M. Prouty. 1972. Logarithmic relationship of DDE resi- dues to eggshell thinning. Nature 235(5338) :376-377. (7) Blus. L. J.. R. a. Heath. C. D. Gish. A. A. Belisle. and R. M. Prouty. 1971. Eggsell thinning in the brown pelican: implication of DDE. BioScience 21(24): 1213-1215. (8) Blut. L. J., T. Joanen. A. A. Belisle, and R. M. Prouty. 1975. The brown pelican and certain environmental pollutants in Louisiana. Bull. Environ. Contam. Toxicol. 13(6):646-655. (9) Bhds, L. J.. B. S. Neely. Jr.. A. A. Beli.sle. and R. M. Prouty. 1974. Organochlorine residues in brown peli- can eggs: relation to reproductive success. Environ. Pollut. 7(2):81-91. {10) Blus. L. J.. B. S. Neely. Jr.. T. G. LamonI, and B. Mulhern. 1977. Residues of organochlorines and heavy metals in tissues and eggs of brown pelicans, 1969-73. Pestic. Monit. J. 11(1) :4a-53. (//) Cromariie. E.. W. L. Reiehel. L. N. Locke. A. A. Belisle. T. E. Kai.ser. T. G. LamonI. B. M. Mulhern, R. M. Prouty, and D. M. Swineford. 1975. Residues of organochlorine pesticides and polychlorinated bi- phenyls and autopsy data for bald eagles, 1971-72. Pestic. Monit. J. 9(1): I 1-14. 1.12) Duncan. I). B. 1955. Multiple range and multiple F tests. Biometrics 1 1( 1 ): 1-42. (/.?) Gochfeld. M. 1974. Prevalence of subcutaneous em- physema in young terns, skimmers and gulls. Wildl. Dis. 10(1): 115-120. (/•/) Henny, C. J. 1972. An analysis of the population dynamics of selected avian species — with special refer- ence to changes during the modern pesticide era. Fish and Wildlife Service, U.S. Department of the Interior, Wildl. Res. Report No. 1, 99 pp. (/.')) Kramer. C. Y. 1956. Extensions of multiple range tests to group means with unequal numbers of replica- tions. Biometrics 12(2) :307-310. (/6) Mulhern. B. M.. E. Cromartie. W. L. Reiehel. and A. A. Belisle. 1971. Semiquantitative determination of polychlorinated biphenyls in tissue samples by thin layer chromatography. J. Assoc. Off. Anal. Chem. 54(3):548-550. {17) Mulhern, B. M.. W. L. Reiehel, L. N. Locke. T. G. LamonI, A. A. Belisle, E. Cromartie, G. E. Bagley, and R. M. Prouty. 1970. Organochlorine residues and autopsy data from bald eagles, 1966-68. Pestic. Monit. J. 4(3):141-I44. (IS) Neshitt, S. A.. M. J. Fomrty. and L. E. Williams. Jr. 1977. Nesting status of brown pelicans in Florida: 1971-76. Bird-Banding 48(2):138-144. {19) Reintjes. J. W . 1969. Synopsis of biological data on the Atlantic Menhaden (Brevoortia tyrannusj. Fish and Wildlife Service, U.S. Department of the Interior, FAO Fish. Synopsis No. 42. 29 pp. {20) White. F. H .. C. F. Simpson, and L. E. Williams, Jr. 1973. Isolation of Edwardsiella tarda from aquatic animal species and surface waters in Florida. J. Wildl. Dis. 9(3): 204-208. {21) Williams. L. E., Jr.. and L. Martin. 1970. Nesting populations of brown pelicans in Florida. Pages 154- 169, Proc. 24th Annual Conf. S. E. Assoc. Game Fish Comm. 184 Pesticides Monitoring Journal Pesticide Contamination of Water Rats in the Murrumbidgee Irrigation Areas, New South Wales, Australia, 1970-72 Penny Olsen ' and Harry Settle - ABSTRACT OrganocMorine pesticides were found in all samples of livers, kidneys, mammary glands, and fetuses of eastern water rats (Hydromys chrysogaster) collected in the Mur- rumbidgee irrigation areas of New South Wales in 1970 and 1972. DDE was the predominant residue. Livers contained 0.01-3.10 ppm ZDDT air-dried weight; kidneys, < 0.01-1.12 ppm; mammary glands, 0.14-23.75 ppm: and fetal liver, 0.28-0.66 ppm. Variations in residue levels are discussed in relation to the possible effects of environmental and physio- logical factors. Introduction Large amounts of water are used in the Murrumbidgee irrigation areas of New South Wales for flood irrigation of rice crops. Drainage water from these crops and from irrigated orchards, vineyards, and cereal and vegetable crops enters Mirrool Creek. A weir. Willow Dam, con- trols entry of the creek's water into a storage swamp or diverts it for further irrigation use. Several pesticides are used on area farms, although DDT predominates. About 1-4.5 kg/ ha. is used an- nually (2), largely to control the bloodworm (Chirono- miis sp.) which damages rice seedlings. Eastern water rats (Hydromys chrysogaster) , common in the irrigation area, were collected monthly from Mirrool Creek and Willow Dam as part of a study of the biology of the species. Little is known of pesticide contamination of Australian fauna (2). The present study is a preliminary examina- tion of the degree of exposure of water rats to pesticides. Materials and Metlwds SAMPLE COLLECTION Eastern water rats were live-trapped from Mirrool Creek at Willow Dam near Griffith, New South Wales, > Division of Wildlife Research. Commonwealih Scientific and Indus- trial Research Organization, P.O. Box 84, Lyneham, Australian Capital Territory, Australia, 2602. -Australian Government Analytical Laboratories, South Australia Regional Laboratory, 344 Tapleys Hill Road, Seaton, South Australia, Australia, 502.1. between January 1970 and January 1973, Livers, kid- neys, mammary glands, and fetuses were removed from the freshly killed rats and preserved in 10 percent formalin. A small number of samples taken during 1970 and 1972 were analyzed for pesticides as follows: in 1970, January (7), April (3), October (3), No- vember (4); in 1972, February (2), May (2), July (7), August (6). Sampling pattern is illustrated in Figure 1. ANALYSIS In the laboratory, samples were drained and air dried, cut into small pieces, mixed with sodium sulfate, and extracted with hexane in a Soxhlet thimble for 4 hours. Extraction for a longer period did not increase residue recovery. The hexane extracts were concentrated to about 10 ml and partitioned three times with 25 ml acetonitrile as a preliminary cleanup. The acetonitrile phase was passed into 300 ml 2 percent sodium sulfate and shaken with 100 ml hexane. The hexane layer was dried by passing it through anhydrous sodium sulfate and was concentrated to 5 ml. The concentrate was mixed with 20 g 2 percent deactivated Florisil, poured into a chromatographic column containing 20 g 2 per- cent deactivated Florisil, and eluted in three frac- tions (5, 6) as follows: Fraction A, eluted with 200 ml 20 percent methylene chloride-hexane, was analyzed for lindane, HCB, aldrin, heptachlor, heptachlor epoxide, DDE, TDE, DDT, and polychlorinated biphenyls (PCBs). Fraction B, eluted with 200 ml 20 percent methylene chloride-hexane, was analyzed for dieldrin, dursban, and trithion. Fraction C, eluted with 200 ml acetone, was analyzed for malathion, ethion, delnav, and diazinon. The eluates were concentrated to 1 ml. Fractions A and B were examined by injection into a Varian Model 2700 gas-liquid chromatograph fitted with a tritium electron-capture detector. Fraction C was injected into Vol. 12, No. 4, March 1979 185 E a Q. CD D ■g w 1-6f 1-4 $ 1-2 10 •8 S -6 FIGURE 1. 0 Rice crops drained ^^^^ Rice crops treated for bloodworm 1970 1972 M M O N D Month Mean organochlorinc conteii! of eastern water rat livers by month sampled, Miirriimbiclgee irrij;ation area. New South Wales, Australia, 1970-72 ( :DDT represented at least 94 percent of residues in each month. Number of samples analyzed each month was 7, 2, 3, 2, 7, 6, 3, 4, respectively.) a Tracer gas-liquid chroniatograph fitted with a phos- phorus-mode flame photometric detector (Table 1). Residues detected at 0.005 ppm and above were reported to the nearest 0.0 1 ppm. CONFIRMATION OF RESIDUES ANO RECOVERIES All samples having organochlorine residues greater than 0.1 ppm were spotted on a thin-layer chromatographic plate for confirmation. Blank analyses were carried out TABLE 1. Parameters jor gas-liquid chromatographic analyses for pesticides in eastern water rats, 1970-72 V*B1AN 2700 Tracor 550 Detector tritium FPD (P mode) Columns glass Va-inct) I.D.. 6 foot effective lengiti Column packing a mixture of 0.2Cc Vc^ OV-1 on DC-2110 :ind O.X":*, Gas Chrom Q QI--1 on Varaport 30 Tcmperatuics, °C column 200 220 inlet 221) 230 delcclor 220 170 Carrier pas flow (ml minute) nitrogen 30 60 hydrogen 50 air 100 at frequent intervals from the sodium sulfate/Soxhlet step. Replicate recoveries (Table 2) were carried out by adding known amounts of organochlorine and organo- phosphorus pesticides to sodium sulfate in the Soxhiet thimble and treating the recovery as in the sample procedure. Because a one-step cleanup was not sufficient, the aceto- nitrile-hexane partition method was used (6). This re- sults in low HCB recoveries; consequently HCB results were corrected for recovery as follows: HCB (reported) = HCB found in determination X (100/33) Results and Discussion Pesticide residues detected in the water rats are listed in Table 3. All samples contained organochlorines and an unidentified organophosphorus compound. There were no significant dilTcrenccs in residue levels between males and females. Mammary glands, because of their fatty composition, contained the highest levels, and residues tended to increase as parturition approached. Mammary TDE positively correlated with fetal weight 186 Pesticides Monitoring Journal TABLE 2. Results of replicate recoveries of organochlorines and organophosphates in eastern water rats, 1970-72 Amount ADDED, No. OF IV EAN % RECOVERY Pesticide liO REPLICATES ± STD DEV HCB 0.25 6 33.0 ± 4.49 DDE 0.25 4 76.5 ± 6.70 TDE 0.25 6 89.0 ± 8.61 DDT 0.25 only 2 recoveries measured (71% and 92%) Dieldrin 0.25 7 83.0 ± 6.36 Malathion 4 98.8 ± 8.93 Diazinon 5 75.4 ± 13.31 Delnav 4 85.8 zt 4.91 Dursban 6 86.7 ± 7.49 Ethior 5 84.6 ± 4.03 Trithion 5 86.2 ± 7.68 (P < 0.05). Liver TDE was correlated with mammary TDE (P < 0.001 ). Fetal residues tended to reflect ma- ternal liver residues and were positively correlated with fetal weight (P < 0.01). No significant differences in residues were found be- tween younger and older animals and breeding and non- breeding animals (Table 4). However, younger animals tended to carry lower levels than older animals. The nonbreeding female group was the only one which showed a positive correlation between age and residue level (P < 0.05). Breeding females had the highest liver pesticide loads, and nonbreeding females, mature and immature, had the lowest. Kidney residues were lower in breeders than in nonbreeders. Stomachs of pregnant females contained more food items, particularly insects, than did those of males or nonbreeding females (8). This suggests that breeders may have a greater opportunity for contamination through greater food consumption and may consume more dead and dying nontarget arthropods weakened by insecticides, as demonstrated by Stchn in small mammal scavengers (7). Lower liver residues in non- breeding females and increasing residues in mammary glands as parturition approached suggested a lowering of body burdens through mobilization of fat during pregnancy and lactation; this phenomenon is thought to occur in harbor porpoises (i) and Arctic ringed seals (1). Seasonal changes in residue levels may be related to irrigation and pesticide application practices in the area. Peak residues occurred in animals in April after water had been drained from the rice fields in March (Fig. 1). Because DDT has a low water solubility and deposits out of suspension to be adsorbed on organic matter, plants, and sediments (4), increased amounts may be available to water rat prey in the dry soil of drained rice fields and, particularly, through flushing of water with suspended clay, organic matter, and plant material into the creek. Up to 8 ppm DDT has been found in sediments of drainage channels adjacent to the rice bays, indicating considerable movement of the pesticide from the site of application (K. H. Bowmer. Division of Irrigation Research, 1974, personal communication). Fish and aquatic insects may also be flushed from the bays or may be stranded in drained fields, becoming easy prey. A smaller peak in residue levels in November coincides with the treatment of rice for bloodworm. Corresponding with the April peak residue levels, there was a seasonal decline in weight of the rats which may indicate a breakdown of body fats and consequent release of stored pesticides. Because trophic level is thought to be one factor in biomagnification of residues, TABLE 3. Pesticide residues in liver, kidney, mammary glands, and fetal liver samples from water rats, Murrumbidgee irrigation areas, New South Wales, Australia, 1970-72 Residues, ppm air-dried WT (± STD DEV.) No. (Range) Tissue Samples DDE TDE DDT Dieldrin HCB 2 DDT Females 17 0.40 -<- 0.14 0.09 + 0.05 0.01 0.01 ±0.01 0.03 ± 0.02 0.49 ±0.19 (2.10-0.01 > (0.85-ND) (0.()6-ND) (0.09-ND) (0.40-ND) (3.10-0.01) Kidneys 12 0.17-1- 0.03 0.03+0.01 ND ND 0.01 ±0.01 0.20 ± 0.03 (0.46-ND) (0.15-ND) (0.11-ND) (0.57-0.06) Mammary glands 6 5.07 ± 2.22 2.11 ± 1.68 0.64 ± 0.37 0.01 ± 0.01 ND 7.82 ± 3.86 (12.20-0.13) (10.40-ND) (2.23-ND) (0.05-ND) (23.75-0.14) Fetal liver 2 0.30 0.13 0.05 0.04 ND 0.47 (0.38-0.22) (0.23-0.02) (0.05-0.04) (0.05-0.02) (0,66-0.28) Males Livers 17 0.44-^0.10 0.05 + 0.02 ND 0.01 ND 0.49 ±0.11 (1.57-0.02) (0.22-ND) (0.04-ND) (0.04-ND) (0.08-ND) (1.61-0.02) Kidneys 13 0.31 ±0.06 0.02 ± 0.01 0.01 0.01 0.33 ± 0.07 (0.89-ND) (0.20-ND) ND (0.04-ND) (0.08-ND) (1.12-ND) NOTE; PCBs not detected in any sample; ND ^One liver with O.OI ppm malathion. <0.01 ppm. Vol. 12, No. 4, March 1979 187 TABLE 4. Differences in organoclilorinc residues in livers and kidneys of eastern water rats, MurrumlMdgce irrigation areas, New South Wales, Australia, 1970-72 Mean total residues, ppm wet wt Liver Kidney Females Est. age < 6 months Est. age ^ 6 months Nonbrceding Pregnant only Pregnant and lactating Males Est. age < 6 months Est. age ^ 6 months 0.39 (5) 0.64 (12) 0.40 (11) 0.83 (4) 0.67 (2) 0.33 (5) 0.56 (12) 0.10 (2) 0.26 (10) 0.24 (8) 0.18 (3) 0.06 ( 1 ) 0.36 (4) 0.33 (9) NOTE: Age of all animals was estimated by use of dry eye lens weights. Tests were scrotal in males 6 months or older and nonscrotal in those younger than 6 months. Number of animals used in samples is in parentheses. it is of interest that in the months of high residue levels, April-August, vertebrates were more important in the diet and insects were less important (8). Although stomach and rectal contents revealed food intake over a limited period, they may represent individual preference and reflect seasonal trends. Higher residues were found in those animals with fish, mammal, bird, and crus- tacean remains in their guts than in those with insects and spiders (P < 0.01). Mean liver residues and corre- sponding stomach contents were as follows: mammals (n = 3), 0.99 ppm; fish (n = 3), 1.29 ppm; birds (/I = 5), 1.04 ppm; crustaceans (n = 2), 1.89 ppm; spiders (« = 4), 0.33 ppm; and insects {n = 9), 0.51 ppm. There was no significant difference between residue levels in 1970 and 1972. HCB was found in 1970 sam- ples only. Dieldrin, found in 4 of 17 liver samples (0.01-0.03 ppm) in 1970, occurred in 7 of 17 samples in 1972 (0.01-0.09 ppm). DDT and dieldrin sales were unchanged during the study. However, in 1972, the organophosphate abate was used in more rice-growing areas for bloodworm treatment, and HCB was no longer recommended for use as a fungicide. Data from other studies on water rats are scarce. The Australian Academy of Science (2) reports in its ap- pendices that residues of 2DDT in a water rat in Vic- toria were: fat. 0.50; muscle, 0.23; kidney, 0.19 ppm wet weight. However, no biological information or lo- cality is given. Although DDT is no longer recommended for blood- worm control, the moderate degree of contamination found in water rats and the continuing use of poten- tially harmful pesticides in the area point to the need for a more detailed study on the fate and ecological effect of these substances, with particular emphasis on more sensitive species. A cknowledgments Authors thank the staff of the pesticide group, Australian Government Analytical Laboratories, South Australia, for preparation and analysis of samples; officers of the New South Wales Department of Agriculture at Griffith and Yanco for information on pesticide use; J. Duns- more for suggesting that the analyses be made; and K. H. Bowmer. H. J. Banks, and B. V. Fennessy for their comments on the manuscript. LITERATURE CITED (/) Addison, R. F., and T. G. Smith. 1974. Organochlorine residue levels in Arctic ringed seals: variation with age and sex. Oikos 25(3 ) :335-337. (2) Australian Academy of Science. 1972. The use of DDT in Australia. Reports of the Australian Academy of Science No. 14. (.?) Gaskin. D. £., M. Holdrinet, and R. Frank. 1971. Or- ganochlorine pesticide residues in harbour porpoises from the Bay of Fundy region. Nature (London) 233(5320) :499-500. (4) Muirhead-Thomson, R. C. 1971. Pesticides and Fresh- water Fauna. Academic Press. New York, NY, pp. 190-191. (5) Settle, H., and R. Swift. 1972. Simultaneous extraction of organophosphorus and organochlorine pesticide residues and subsequent clean-up for G.L.C. and T.L.C. determinations. Residue 1(4): 3-8. (6) Smyth, R. J. 1972. Detection of hexachlorobenzene residues in dairy products, meat fat, and eggs. J. Assoc. Off. Anal. Chem. 55(4) :806-808. (7) Stchn, R. A. 1976. Foraging response of small mammal scavengers to pesticide-killed arthropod prey. Amer. Midi. Nat. 95(1 ):253-256. (8) Woollard, P., W.J. M. Vestjcns, and L. Maclean. 1978. The ecology of the eastern v\ater rat. Hydromys chry- sogaster, at Griffith, N.S.W. Food and feeding habits. Aust. Wildl. Res. 5I(l):59-73. 188 Pesticides Monitoring Journal Organochlorine Residues in Harp Seal (Phagophilus groenlandicus) Tissues, Gulf of St. Lawrence, 1971, 1973' K. T. Rosewell, D. C. G. Muir, and B. E. Baker ABSTRACT Levels of p,p'-DDT, p,p'-TDE, p.p'-DDE. dieldrin. poly- chlorinated biphenyls (PCBs), and HCB were determined in certain tissues of 31 harp seals (Phagophilus groenlandicus) taken from the Gulf of St. Lawrence during 1971 and 1973. The seals ranged in age from less than two weeks to 18 years. Mean concentrations of PCBs and ZDDT in the vari- ous tissues were about the same. ZDDT levels were 1.64- 9.8S ppm in adult seal blubber and 1.08-3.73 ppm in seal pup blubber. Organochlorine levels in harp seal samples taken in 1973 were similar to those reported by other work- ers for samples collected in the Gulf of St. Lawrence during 1967-71. Introduction Seals occupy a top position in long food chains, and because they carry large quantities of subcutaneous fat which can store organochlorines, they have been used as indicators of pollution in the marine environment (/, 3, 5, 7, 8. II, 13). Organochlorine concentrations in seals collected in 1967 and 1968 in the Gulf of St. Lawrence indicated a degree of marine pollution similar to that in European coastal waters (10). In the present study, harp seals {Phagophilus groenlandicus) from the Gulf of St. Lawrence region were examined for organo- chlorines to determine whether 1967-68 marine pollu- tion levels still existed and to measure organochlorine residue levels in various tissues of adult and young harp seals. Materials and Methods SAMPLE COLLECTION Tissue samples were obtained from 1 1 harp seals (age 1-18 years) caught in the Gulf of St. Lawrence in 1971, and 20 harp seal pups caught in the same region in 1973. All samples were frozen immediately after collec- tion and transported to the laboratory where they were stored at — 20°C until analysis. Blubber, kidney, liver, muscle, spleen, brain, and gonad tissues were taken for analysis. ANALYTICAL METHODS Tissue samples obtained in 1971 were analyzed as de- scribed by Porter et al. (16) for their fat content in order to estimate how much tissue would contain the 1-3 g of fat required for organochlorine analysis. An appropriate weight of each sample was dried with sodium sulfate and then extracted with petroleum ether {16). The petroleum ether extracts were cleaned by acetonitrile-petroleum ether partitioning and Florisil column chromatography (17). The 6:94 (v/v) diethyl ether: petroleum ether eluate from the Florisil column was transferred to a 4:1 (by weight) silica-Celite col- umn (4) in order to separate PCBs from 2DDT. The 15 percent eluate from the Florisil column, which contained dieldrin residues, was subjected to further cleanup in which concentrated eluate was refluxed with 2:92 (v/v) methanolic KOH (17). Tissue samples from harp seal pups caught in 1973 were analyzed for fat content by the method of Holdrinet (12). An appropriate weight of each sample was mixed with sodium sulfate and sand and then extracted with hexane on a Soxhlet extractor. The hexane extracts were cleaned on a deactivated (2 percent) Florisil column (12, 15), and then were passed through a charcoal column (12) in order to separate PCBs and HCB from SDDT. Pesticides and PCBs were determined by (-'H) electron- capture gas chromatography under the following conditions: Chromatograph: Columns: Temperatures. °C: Chromatograph: Columns: Temperatures, "C: Varian Model 600D (1) glass, 1.08 m X 3 mm OD, packed with a mixture of 6 percent QF-1 and 4 percent SE-3() on Chromosorb W-HP (2) glass. 1.68 m V 3 mm OD, packed with 1 percent OV-1 on Chromosorb W-HP column ( 1 ) 195 column <2) 185 Varian Model 1400 glass. 1.83 m X 3 mm ID packed with: (Da mixture of 6 percent QF-1 and 4 percent SE-30 on Chromosorb W-HP (2)3 percent OV-225 on Chromosorb W-HP column (1) 215 column (2) 185 'Department of Agricultural Chemistry and Physics. Macdonald Col- lege of McGill University, Saint Anne-de-Bellevue, Quebec, Canada HOA ICO. Research was supported in part by the Quebec Agricultural Research Council and by a scholarship from the National Research Council. Known quantities of pesticides (p,p'-DDT, p,p'-TDE. p,p'-DDE, and dieldrin) and PCBs (Aroclors 1242 and Vol. 12, No. 4, March 1979 189 1260) were added to a sample of the sodium sulfate used to dehydrate the tissues. Extraction by the method of Porter et ai. (16) produced recoveries of 69-102 percent for organochjorine pesticides and 69-84 percent for PCBs. The following recoveries were obtained using the method of Holdrinet {12): p.p'-DDT, p.p'-TDE, and p.p'-DDE. 85-112 percent; dieldrin, 81-89 percent; PCBs (Aroclor 1254), 84-85 percent; HCB, 78-89 percent. Gas-liquid chromatography results were confirmed by use of two columns of different polarity, by thin layer chromatography, and by chemical derivatization. In all instances, the results were confirmed by at least two of the three procedures. Results and Discussion The fat content of seal tissues is shown in Tabic 1. Tables 2 and 3 show the results, not corrected for re- covery, of analyses of the various tissues for organo- chiorines. -DDT and PCBs were detected in all samples. Dieldrin was detected in all but five tissue samples analyzed. Forty of 42 tissue samples from harp seal pups contained HCB. Blubber contained the highest levels of organochlorines. The mean PCB and SDDT concentrations in various tissues were about the same. Mean HCB levels, determined only in seal pups, and mean dieldrin levels were similar in all tissues analyzed. Brain tissue contained more extractable lipid (8.3 per- cent) than did liver (3.5-4.0 percent), kidney (4.2 percent), muscle (2.6 percent), and spleen (2.8 per- cent). Mean levels of i:DDT and PCBs in the brain, however, were lower than in other ti.ssues. The results suggest that a brain barrier to PCB- and DDT-type compounds may exist in the harp seal as reported by Frank et al. (7). This may result from a difference be- tween the constitution of brain lipids and the lipids of depot fat. The authors suggest that a similar phenome- non may exist with dieldrin, but it was not observed in the present work. TABLE 1. Fat content of tissues oj harp seals. Gulf of St. Lawrence— 1971. 197 S Tissue Blubber (adulls) (pups) Liver (adulis) (pups) Kidney (adulls) Muscle (adults) Spleen (adulls) Brain (pups) Gonad (male pups) (female pups) No. Samples Analyzed Average Fat Content, % 5 7 82.5 86.2 2 3 3.5 4.0 3 4.2 2 2.6 2 2.8 3 8.3 1 1 1.7 7..1 Since the types of residues in tissues of the harp seal pups were similar to those in the same tissues of older seals, it is probable that the residues in the adult seals are passed along to the fetus as well as to nursing seal pups. Holden concluded that organochlorine residues in nursing gray seal pups were derived solely from the parent seals, since the pups were still being fed by the adult females at the time of capture (//). This conclu- sion is supported by the fact that organochlorines have been found in the milk of fur seals ( 2 ) and harp seals (6) . Organochlorine levels in harp seal pups in the present study are similar to those reported previously in harp seals taken from the Gulf of St. Lawrence (9, 10, 14). In the present study, blubber, liver, and brain tissues of young harp seals contained PCB levels similar to and dieldrin levels higher than those found by Frank et al. (7), i;DDT levels were slightly higher in the blubber and liver, but similar in brain tissue to those of pups studied by Frank et al. (7). In the present study, the blubber of adult harp seals contained slightly lower levels of -DDT and PCBs than did those reported by Addison et al. (/) and Frank et al. (7). Muscle tissue of adult seals contained higher levels of PCBs but similar levels of -DDT and dieldrin. Liver tissue had lower levels of -DDT but higher con- centrations of PCBs than did the corresponding tissue analyzed by the above authors (/, 7). Dieldrin concen- trations in tissues analyzed for the present study were similar to those reported previously (/. 7, 14). The ratio of 2DDT to PCBs (Table 4) was close to 1.0 in all tissues except the liver, muscle, and spleen of the adult seals. This may reflect heavy use of DDT for spraying forests in areas drained by rivers flowing di- rectly into the Gulf of St. Lawrence, as well as the high degree of urban industrial pollution which is the major source of PCBs in the environment. A cknowledgmen ts Authors thank D. E. Sergeant and the staff of the Fisheries Research Board of Canada for providing the 1971 samples and for assisting in the collection of the 1973 samples. LITERATURE CITED (/) Addison, R. F.. S. R. Kerr, J. Dale, and D. E. Serjeant. 1973. Variation in organochlorine residue levels with age in Gulf of St. Lawrence harp seals (I'liaaophitus aroenlandicus). J. Fish. Res. Board Can. 30(5): 595-600. (2) Anas, R. E.. and A. J. Wilson, Jr. 1970. Organo- chlorine pesticides in nursing fur seal pups. Pcstic. Monit. J. 4(3):114-116. (3) Anas. R. E. 1974. DDT plus PCBs in blubber of harbor seals. Pestic. Monit. J. 8(1): 12-14. 190 Pesticides Monitoring Journal TABLE 2. Organochlorine residues in tissues of adult harp seals. Gulf of St. Lawrence— -March 1971 Residues, ppm wet weiuht Seal Age. Number Sex years Tissue p,p'-DDE P.P-TDE P,p'-DDT 2 DDT DiELDRIN PCBs 1 M 11 blubber 0.680 0.359 1.096 2.135 0.320 2.05 Itidney 0.070 0.036 0.212 0.318 0.012 0.26 liver 0.105 0.043 0.291 0.439 0.006 1.45 muscle 0.138 0.039 0.102 0.279 0.005 0.47 spleen 0.039 0.016 0.076 0.131 <0,002 0.16 2 F 1 blubber 0.918 0.433 8.530 9.881 0.244 0.49 kidney 0.268 0.194 2.197 2.659 0.002 1.54 liver 0.147 0.088 0.079 0.314 0.004 0.65 muscle 0.048 0.017 0.063 0.128 0.002 1.10 spleen 0.358 0.292 0.759 1.409 0.004 2.57 3 M 3 blubber 2.056 0.683 2.684 5.423 0.011 2.45 kidney 0.145 0.060 0.206 0.411 0.005 0.86 liver 0.060 0.075 0.147 0.282 0.007 0.37 muscle 0.052 0.031 0.090 0.173 0.003 0.18 spleen 0.108 0.059 0.086 0.253 0.004 0.55 4 M 5 blubber 0.726 0.631 2.550 3.907 0.024 13.30 kidney 0.057 0.020 0.082 0.159 0.005 0.62 liver 0.086 0.116 0.106 0.308 0.009 0.76 muscle 0.089 0.018 0.097 0.204 0.002 0.34 J M 6 blubber 1.187 0.459 1.280 2.926 0.096 1.96 kidney 0.048 0.023 0.047 0.118 0.002 0.25 liver 0.039 0.071 0.036 0.146 <0.002 0.11 muscle 0.076 0.057 O.084 0.217 0.002 0.46 spleen 0.056 0.038 0.156 0.250 <0.002 0.17 6 M 6 blubber 0.835 0.316 1.501 2.652 0.012 3.51 kidney 0.097 0.041 0.039 0.177 0.004 0.45 liver 0.170 0.086 0.055 0.311 <0.002 0.48 muscle 0.094 0.040 0.106 0.240 0.005 0.32 spleen 0.112 0.062 0.103 0.277 0.009 0.30 7 M 2-3 blubber 0.610 0.287 1.551 2.448 0.124 3.46 kidney 0.034 0.016 0.042 0.092 <0.002 0.04 liver 0.052 0.030 0.087 0.169 0.016 0.82 spleen 0.051 0.021 0.059 0.131 0.002 0.07 8 M 1-2 blubber 1.063 0.732 3.391 5.186 0.010 1.53 kidney 0.074 0.036 0.070 0.180 0.006 0.19 liver 0.077 0.114 0.057 0.248 0.002 0.36 muscle 0.091 0.087 0.130 0.308 0.003 0.77 spleen 0.094 0.095 0.152 0.341 0.007 0.30 9 M 13 blubber 0.556 0.354 0.731 1.641 0.022 1.20 kidney 0.071 0.022 0.128 0.221 0.005 0.18 liver 0.217 0.149 0.455 0.821 0.018 0.36 muscle 0.098 0.038 0.068 0.204 0.004 0.07 spleen 0.075 0.023 0.091 0.189 0.010 0.33 10 M 13 blubber 1.849 0.770 2.300 4.919 0.022 2.77 kidney 0.125 0.077 0.366 0.568 0.008 0.20 liver 0.347 0.215 0.121 0.683 0.026 0.64 muscle 0.060 0.033 0.112 0.205 0.008 0.06 spleen 0.049 0.023 0.047 0.119 0.003 0.09 11 M 18 blubber 1.108 0.680 1.326 3.114 0.01 1 2.83 kidney 0.061 0.047 0.064 0.172 0.005 0.31 muscle 0.066 0.054 0.200 0.320 0.009 0.41 spleen 0.043 0.161 0.090 0.294 0.016 0.07 NOTE: Detection limit = 0.002 ppm. (4) Armour, ]. A., ami ]. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Assoc. Off. Anal. Chem. 53(4) ;761- 768. (5) Bowes. G. W., and C. J. Jonkel. 1975. Presence and distribution of polychlorinated biphenyls (PCB) in arctic and subarctic marine food chains. J. Fish. Res. Board Can. 32(11 ):21 11-2123. (6) Cook. H. W.. and B. E. Baker. 1969. Seal milk. I. Harp seal (Phaaophilus groentandicus) milk: Compo- sition and pesticide residue content. Can. J. Zool. 47(6): 1129-1132. (7) Frank. R., K. Ronald, and H. E. Braun. 1973. Or- ganochlorine residues in harp seals (Phagophilus groenlandicus) caught in eastern Canadian waters. J. Fish. Res. Board Can. 30(8) : 1053-1063. (S) Gaskin. D. £.. R. Frank, M. Holdrinct, K. Ishida, C. J. Walton, and M. Smith. 1973. Mercury. DDT and PCB in harbour seals (Phoca viiulina) from the Bay of Fundy and Gulf of Maine. J. Fish. Res. Board Can. 30(3):47I^75. (9) Holden, A. V., and K. Marsden. 1967. Organochlo- rine pesticides in seals and porpoises. Nature 216 (5122): 1274-1276. Vol. 12, No. 4, March 1979 191 TABLE 3. Organochlorine residues in tissues of harp seal pups, Gulf of St. Lawrence — March 1973 > Seal Number Tissue p.p'-DDT P.p'-TDE P.P-DDE 2DDT DiELDRIN HCB PCBs 1 blubber liver brain 0.833 0.041 0.026 0.132 0.007 0.003 2.019 0.096 0.021 2.984 0.144 0.050 0.087 0.005 0.006 0.054 0.003 0.002 1.812 0.116 0.097 2 blubber liver brain 0.602 0.027 0.028 0.119 0.004 0.003 1.044 0.025 0.010 1.765 0.056 0.041 O.ISO 0.007 0.010 0.130 0.007 0.005 1.869 0.063 0.022 3 blubber liver brain 0.830 0.031 0.034 0.209 0.008 0.006 1.314 0.037 0.014 2.353 0.076 0.054 0.117 0.007 0.008 0.061 0.003 <0.002 2.984 0.116 0.037 4 blubber liver brain 0.460 0.038 0.022 0.079 0.006 0.003 0.690 0.036 0.011 1.229 0.080 0.036 0.092 0.006 0.006 0.109 0.007 0.004 1.392 0.112 0.029 5 blubber liver brain 0.599 0.032 0.007 0.100 0.004 0.002 0.787 0.019 0.007 1.486 0.055 0.016 0.075 0.004 0.004 0.106 0.005 0.003 1.601 0.043 0.019 6 blubber liver brain 0.811 0.023 0.015 0.096 0.004 0.002 1.206 0.024 0.010 2.113 0.051 0.027 0.103 0.004 0.006 0.114 0.005 0.003 1.476 0.039 0.017 7 blubber liver brain 0.750 0.023 0.023 0.129 0.005 0.004 1.713 0.040 0.017 2.592 0.068 0.044 0.082 0.003 0.005 0.062 0.003 0.002 2.908 0.071 0.039 8 blubber liver brain 0.670 0.031 0.019 0.144 0.008 0.003 1.294 0.060 0.016 2.108 0.099 0.038 0.096 0.009 0.009 0.034 0.004 0.002 2.623 0.145 0.033 9 blubber liver brain 0.729 0.021 0.034 0.115 0.006 0.005 1.294 0.041 0.014 2.138 0.068 0.053 0.096 0.004 0.007 0.055 0.003 <0.002 2.664 0.099 0.041 10 blubber liver brain 0.660 0.037 0.006 0.086 0.007 0.003 1.079 0.056 0.007 1.825 0.100 0.016 0.095 0.007 0.005 0.085 0.006 0.002 1.810 0.115 0.022 11 blubber 0.578 0.117 1.137 1.832 0.088 0.121 2.020 12 blubber 0.536 0.086 0.757 1.379 0.075 0.065 2.268 13 blubber gonad 0.468 0.023 0.053 0.003 0.562 0.012 1.083 0.038 0.076 0.002 0.083 0.002 1.150 0.045 14 blubber gonad 0.634 0.079 0.132 0.014 1.327 0.116 2.093 0.209 0.093 0.008 0.119 0.011 2.225 0.211 15 blubber 0.735 0.152 0.994 1.881 0.104 0.067 2.074 16 blubber 0.760 0.159 1.362 2.821 0.144 0.097 2.416 17 blubber 0.460 0.071 0.830 1.361 0.073 0.068 1.926 18 blubber 1.188 0.404 2.138 3.730 0.179 0.042 6.226 19 blubber 0.475 0.100 0.708 1.283 0.087 0.050 2.313 20 blubber 0.626 0.070 0.875 1.571 0.074 0.028 1.512 NOTE: Deteclion limit ^ Age of pups <2 weeks. 0.002 ppm. DDT/DDE i:DDT/PCB 2.32 1.24 0.58 0.86 1.10 0.62 0.70 0.92 3.30 1.04 1.30 0.54 1.65 0.74 1.62 1.03 TABLE 4. Ratios of DDT to DDE and ^DDT to PCBs in harp seal tissues, Gulf of St. Lawrence — 1971-1973 Tissue Blubber (adults) (pups) Liver (adults) (pups) Kidney (adults) Muscle (adults) Spleen (adults) Brain (pups) NOTE; Ratios calculated from mean concentrations of each residue. (10) lloUicn. A. V. 1969. Organochlorine residues in seals. Report No. E. 22, Fisheries Improvement Committee, International Council for Exploration of the Sea, 7 pp. (//) Holdcn, A. V. 1970. Monitoring organochlorine con- lamination of the marine environment by analysis of residues in seals. Report presented to the FAO Con- ference on Marine Polltilion, Rome, 15 pp. (12) Holdrinet, M. V. H. 1974. Determination and confir- mation of hcxachlorobenzene in fatty samples in the presence of other residual halogenated hydiocarbon pesticides and polychlorinated biphenyls. J. Assoc. Off. Anal. Chem. 57(3 ) :580-584. (13) Jensen, S., A. G. Johnels, M. Olsson. and G. Otter- lind. 1969. DDT and PCB in marine animals from Swedish waters. Nature 224(5216) :247-250. (14) Jones, D., K. Ronald, D. M. Lavinnc. R. Frank, M. Holdrinet, and J. F. Uthe. 1976. Organochlorine and mercury residues in the harp seal ( Phai;ophilus groen- landicus). Sci. Total Environ. 5:181-195. (15) Langlois, B. E., A. R. Stemp, and B. J. Liska. 1964. Analysis of animal food products for chlorinated insec- ticide residues. I. Column clean-up of samples for electron capture gas chromatographic analysis. J. Milk Food Technol. 27( 7 ) :2()2-204. (16) Porter, M. L., S. J. V. Yoiini;. and J. A. Burke. 1971. A method for the analysis of fish, animal and poultry tissue for chlorinated pesticide residue analysis. J. Assoc. Off. Anal. Chem. 53(6) : 1300-1303. (17) We.s-.Kcl, J. R., H. C. Barry. J. A. Burke, J. Cummings, and J. R. McDowell. 1975. Pesticide analytical man- ual. Vol. I. Food and Drug Administration, U.S. Department of Health, Education, and Welfare, Wash- ington, DC. 192 Pesticides Monitoring Journal Nationwide Residues of Organochlorine Compounds in Starlings (Sturnus vulgaris), 7976 Donald H. White ' ABSTRACT Organochlorine pesticide and PCB residues in starlings from 126 sites within the contiguous 48 states were monitored during fall 1976. The average nationwide level of DDE and PCBs has increased significantly since 1974, but the number of sites reporting PCB residues has decreased fivefold. Diel- drin residues have remained unchanged since 1974. Highest DDE levels occurred in samples from parts of Arizona, Arkansas, California, Louisiana, and New Mexico. Introduction The Fish and Wildlife Service, U.S. Department of the Interior, began nationwide monitoring of organochlorine residues in starlings (Sturnus vulgaris) in 1967-68 as part of the National Pesticides Monitoring Program. Residue data from the original collections were to serve as a baseline against which future residue levels might be compared. Initially, organochlorine compounds were to be monitored at 2-year intervals. However, in 1976, starling collections were scheduled at 3-year intervals to coincide with waterfowl wing collections which also are monitored nationwide for organochlorine residues. Star- lings were selected because their range is the continental United States, they are considered expendable, and their omnivorous feeding habits should reflect residues from a wide range of food sources (7). The present report presents results of the 1976 starling collections including residue levels from each collection site, a comparison of nationwide averages of DDE, dieldrin, and polychlorin- ated biphenyls (PCBs) in the four collection periods since 1970, and the distribution of DDE, dieldrin, and PCBs by frequency of occurrence at collection sites. Collection Methods Sampling design and collection procedures have been reported previously (1-3). The sample area lies within the continental United States and consists of 40 blocks of 5° latitude and longitude. In the initial 1967-68 study, 139 collection sites were randomly selected within these blocks and were to be used for starling collections thereafter. During September-December 1976, samples were obtained from 126 of the sites. Table 1 lists col- ipish and Wildlife Service, U.S. Department of the Interior. Patuxent Wildlife Research Center, Gulf Coast Field Station. P.O. Box 2506, Victoria, TX 77901. lection sites for 1976 by state and county; Figure 1 shows their actual locations within sampling blocks. Starling samples consist of pools of 10 birds taken by trapping or shooting, although some samples may be smaller; those samples with fewer than 10 birds are identified in Table 1. Each pool is wrapped in alumi- num foil, placed in a polyethylene bag, frozen as soon as possible, and shipped to Raltech Scientific Services, Inc., Madison, Wisconsin, for chemical analysis. A total of 227 pools were analyzed for organochlorine residues. A nalytical Procedures The feet, beaks, wing tips, and skins were removed from birds in each composite sample and the sample was weighed and ground in a food grinder. Twenty grams of the homogenate was ground with 150 g anhydrous sodium sulfate and allowed to air dry overnight in a hood. The dried sample was placed in a 43 mm X 123 mm Whatman extraction thimble and extracted for 8 hours on a Soxhlet apparatus with 150 ml ethyl ether and 150 ml petroleum ether. The resulting solution was concentrated to near dryness on a steam bath, and the remaining solvent was removed with nitrogen at room temperature. The residue was transferred to a 25-mI volumetric flask with 93:1 toluene-ethyl acetate solution and diluted to volume. Five ml of the extract was placed on an Auto-Prep Model 1001 gel permeation chromatograph, standard- ized for chlorinated insecticides and PCBs, with the following operating conditions: Packing: 80 g Bio-Beads (SX-3), 200^00 mesh Column: 600 mm x 25 mm ID Solvent: 3:1 toluene-ethyl acetate solution Flow rate: 5.5 ml/minute Dump time: 30 minutes Collect time: 14 minutes Wash time: 4 minutes The resulting solution was concentrated on a flash evaporator to approximately 5 ml in the presence of 5 ml isooctane and diluted to 25 ml with petroleum ether. A 4-/^1 sample was injected into a gas chro- matograph equipped with an electron-capture detector. If PCBs were not detected, the results were quantified. Vol. 12, No. 4, March 1979 193 TABLE 1. OrganocMorine residues in starlinns, continental United States, 1976 Residues, PPM WET WEIGHT Heptachlor Chlordane State County 1 Site DDE DDT DiELDRIN PCBS2 Epoxide HCB Isomers Alabama Marion 3-H-l 0.28 ND 0.14 ND 0.05 ND 0.04 Calhoun 4-H-3 0.31 ND 0.01 0.85 0.04 ND 0.04 Arizona Navajo 3-C-3 0.13 ND ND ND ND ND ND Yavapai 3-C-4 0.27 ND 0.03 ND 0.01 ND ND Maricopa 4-C-l 5.00 ND 0.01 ND 0.01 ND ND Graham (3) 4-C-2 3.41 ND 0.01 ND ND ND ND Arkansas Yell 3-G-2 0.31 ND ND 0.35 0.13 ND 0.06 Lonoke 3-G-3 11.10 ND 0.09 0.15 0.17 ND 0.06 California Colusa (9) 2-A-l 0.39 ND 0.02 ND ND ND ND Shasta 2-A-2 0.16 ND 0.01 ND ND ND ND Modoc 2-A-3 0.13 ND 0.01 ND 0.01 ND ND Ventura 3-A-l 1.26 ND 0.04 ND ND ND ND Monterey (9) 3-A-3 2.20 0.02 0.08 0.39 ND ND 0.01 Kern 3-B^ 3.14 ND 0.03 ND ND ND ND Imperial 4-B-l 7.41 ND 0.02 ND ND ND ND Los Angeles 4-B-2 1.37 ND 0.04 ND ND ND ND Colorado Weld 2-D-4 1.36 ND 0.06 ND 0.01 ND ND Montrose 3-D-l 0.26 ND ND ND ND ND ND Crowley 3-D-2 0.15 ND ND ND 0.01 ND ND Connecticut New London 2-K-2 0.54 ND 0.03 0.39 0.09 ND 0.17 Florida Bay 4-H-l 0.23 0.04 0.09 0.28 0.04 ND 0.07 Madison 4-1-3 0.90 ND 0.11 ND 0.07 ND 0.18 Highlands 5-1-2 0.67 ND 0.01 ND ND ND ND Georgia Upson 4-H-4 1.03 ND 0.16 0.44 0.30 ND 0.20 Wayne 4-1-2 0.35 0.03 0.11 0.26 0.03 ND 0.13 Idaho Nez Perce 1-B-l 0.16 ND ND ND ND 0.01 0.01 Owyhee 2-B-l 1.15 ND 0.03 ND 0.01 ND ND Franklin 2-C-3 1.12 ND 0.05 ND 0.02 ND ND Minidoka 2-C^ 2.06 ND U.06 0.16 0.01 ND ND Illinois Stephenson 2-G-l 0.49 ND 0.17 0.21 0.06 ND 0.05 Adams 2-G-3 0.04 ND 0.22 ND 0.36 0.56 0.09 Kane 2-H-2 0.65 ND 0.12 ND 0.04 ND 0.01 Indiana Henry 2-H-3 0.02 ND 0.03 ND 0.03 0.03 0.01 Iowa Fremont 2-F-3 0.05 ND 0.23 ND 0.12 ND 0.04 Jasper (8) 2-G-2 0.08 ND 0.28 ND 0.17 0.01 0.06 Marshall (9) 2-G-4 0.09 ND 0.07 ND 0.11 ND 0.O2 Kansas Rawlins 2-E-l 0.29 ND 0.02 0.15 ND ND ND Phillips (7) 2-E-2 0.05 ND 0.02 ND ND 0.03 ND Kearny (9) 3-E-l 0.03 ND 0.02 ND 0.01 ND 0.03 Nemaha 2-F.^ 0.07 ND 0.16 ND 0.04 0.01 0.02 Marion 3-F-2 0.04 ND 0.06 ND 0.03 0.06 0.02 Kentucky Ohio 3-H-2 0.15 ND 0.04 ND 0.02 ND 0.03 Hopkins (9) 3-H^ 1.04 ND 0.04 ND 0.02 ND 0.11 Louisiana Jefferson 4-G-3 0.93 ND 0.04 0.42 0.08 0.02 0.10 Rapides 4-G^ 10.70 ND 0.04 0.63 0.03 ND 0.01 Maine Penobscot l-K-2 0.13 0.06 0.01 0.24 0.01 ND 0.01 Michigan Chippewa 1-H 1 0.03 ND 0.03 ND ND ND ND Grand Traverse 1 H-2 0.47 ND 0.02 ND ND ND ND Kent 2-H-l 0.17 ND ND 0.11 ND ND ND Ingham 2-H^ 0.51 ND 0.02 ND 0.03 ND 0.01 Minnesota Aitkin 1-G-l 0.05 ND ND ND ND ND ND Renville l-F-2 0.04 ND 0.03 ND ND ND ND Mississippi Leake 4-G-l 0.42 ND 0.18 ND 0.26 ND 0.09 Harrison 4-G-2 0.67 0.04 0.24 ND 0.11 ND 0.07 Jackson 4-H-2 1.43 ND 0.07 ND 0.04 ND 0.03 Missouri Butler (7) 3-G-l 0.12 ND 0.06 0.11 0.03 0.23 ND Bollinger 3-G-4 0.06 ND 0.02 ND ND ND ND Montana Meagher (9) l-C-1 0.03 ND ND 0.14 ND ND ND Missoula 1-C^ 0.06 0.04 O.lll ND 0.02 0.02 ND Richland (6) 1-D 1 0.01 ND ND ND ND ND ND Yellowstone l-D-4 ND ND ND ND ND ND ND Nebraska Keith (7) 2-E-3 0.04 ND 0.02 ND ND ND ND Brown 2-E^ 0.04 ND 0.02 ND 0.03 ND ND Lancaster (6) 2-F-l 0.25 0.07 ND 0.14 0.05 0.01 0.04 Clay 2-F-2 0.10 ND 0.07 ND ND ND ND Nevada White Pine 2-B-3 0.07 0.04 ND ND ND ND ND Humboldt 2 B^ 0.53 ND (1.02 ND 0.02 ND 0.04 Nye 3 B 2 0.17 ND 0.04 ND ND ND ND Clark 3-B-3 0.20 0.04 0.06 0.32 O.lfl ND 0.21 New Mexico Bernalillo 3D 3 0.60 ND ND ND ND ND ND Santa Fe 3 D-4 2.20 ND 0.03 ND ND ND ND Luna 4-D-l 0.63 ND ND ND ND ND ND Otero 4-D-2 1.71 ND 0.02 ND ND ND ND Chaves 4-D-3 12.40 ND 0.03 ND 0.03 ND 0.01 Quay 3-E-2 0.15 ND ND ND 0.01 ND ND (Continued next page) 194 Pesticides Monitoring Journal TABLE 1 (Cont'd.). Organochlorine residues in Starlings, continental United States, 1976 Residues, PPM WET weight Heptachlor Chlordane State County' Site DDE DDT DiELORIN PCBs = Epoxide HCB ISOMEIS New York Jefferson (5) 2-J-4 0.09 ND ND ND 0.03 ND 0.04 Rensselaer (8) 2-K-l 0.99 0.03 0.02 ND ND ND ND North Carolina Wilkes 3-1-1 0.08 ND 0.02 ND ND ND ND Macon 3-1-3 0.51 ND 0.03 ND ND ND ND Pender 3-J-l 1.21 ND 0.20 0.18 0.03 ND 0.11 North Dakota McLean l-E-3 0.03 ND 0.01 ND ND ND ND Grand Forks 1-F-l 0.43 ND ND ND ND ND ND Ransom l-F-4 0.07 0.01 ND 0.16 ND ND ND Ohio Pickaway 2-1-1 0.05 ND 0.05 ND 0.04 0.73 0.05 Wood 2-1-2 0.08 ND 0.15 ND 0.05 0.06 0.01 Noble 2-1-3 0.08 0.04 0.01 ND 0.02 ND 0.03 Oklahoma Beckham 3-E-4 0.14 ND 0.03 ND 0.02 ND ND Canadian 3-F-l 0.06 ND 0.03 ND 0.05 0.03 ND Nowata (9) 3-F-3 1.52 ND 0.05 ND 0.02 ND 0.03 Okmulgee 3-F-4 0.12 0.05 0.10 ND 0.01 ND 0.01 Oregon Yamhill l-A-3 0.67 ND 0.10 ND 0.15 0.10 0.01 Lane l-A-4 0.32 ND 0.05 ND 0.05 ND ND Benton l-A-5 0.27 ND 0.06 ND 0.02 ND ND Klamath 2-A-4 0.20 ND ND ND 0.02 ND ND Baker (9) l-B-4 0.06 ND ND ND ND ND ND Harney 2-B-2 0.15 ND ND ND ND ND ND Pennsylvania Somerset (6) 2-J-2 0.46 ND 0.05 ND 0.06 ND 0.10 Luzerne 2-J-3 0.59 0.04 0.06 0.48 0.06 ND 0.13 South Dakota Potter 1-E-l 0.07 ND 0.02 ND ND ND ND Butte l-E-2 0.02 ND ND ND ND ND ND Hughes 1-E^ 0.03 ND 0.02 ND ND ND ND Brown l-F-3 0.03 ND 0.02 ND ND ND ND Tennessee Davidson 3-H-3 0.09 0.02 0.14 0.22 0.01 ND 0.05 Texas Kinney 4-E-3 1.05 ND 0.05 ND 0.89 ND 0.05 Cochran 4-E^ 0.11 ND 0.04 ND 0.04 0.01 ND Bexar (7) 4-F-l 0.15 ND 0.02 ND 0.04 0.02 0.04 Clay 4-F-3 0.97 ND 0.04 ND 0.47 0.07 0.07 San Patricio 5-F-l 0.23 ND ND ND 0.01 ND ND Utah Weber 2-C-l 0.91 0.04 0.04 0.55 ND ND ND Duschesne 2-C-2 0.10 ND ND ND 0.02 ND ND Millard 3-C-l 0.42 ND 0.01 ND ND ND ND Grand 3-C-2 0.93 ND ND ND 0.08 ND 0.02 Vermont Addison 1-K-I 0.14 ND 0.01 0.11 0.04 ND 0.10 Virginia Amherst (8) 3-1^ 0.52 ND 0.02 ND ND 0.02 ND Prince George (9) 3-J-2 0.38 ND 0.02 0.11 0.02 0.04 0.05 Caroline 3-J-3 0.11 ND 0.06 ND 0.07 0.20 0.07 Washington Yakima l-A-2 0.26 ND 0.12 ND 0.03 0.54 ND Spokane (5) 1 B-2 0.38 ND 0.24 ND ND 2.01 ND Whitman l-B-3 0.27 ND ND ND ND 0.51 ND Wisconsin Trempealeau (9) l-G-3 1.16 ND 0.01 ND 0.01 ND ND Marathon (9) l-G-2 0.07 ND ND ND ND ND ND Wyoming Big Horn l-D-2 0.02 ND 0.01 ND 0.03 ND ND Crook (9) 1-D 3 ND ND ND ND ND ND ND Goshen 2-D-l 0.21 ND ND ND ND ND ND Washakie 2-D-2 0.07 ND 0.03 ND 0.02 ND ND NOTE: ND = not detected. 'Most samples consist of a pool of 10 birds. Numbers in parentheses indicate samples made up of fewer birds. -PCBs were quantihed on the basis of Aroclor 1254. If PCBs were detected, the extracts were subjected to silicic acid separation. Ten ml of the extract from the gel permeation chromatograph was placed on a 15-g standardized Silicar CC-4 column. Typical ekitions were as follows: Fraction : 60 ml petroleum ether, contains HCB and mirex Fraction II: 350 ml petroleum ether, contains PCBs and some DDE Fraction 111: 150-ml mixture of 1 percent acetonitrile, 19 percent hexane. and 80 percent methylene chloride, contains the remaining organochlorine compounds Fractions I and II were concentrated on a steam bath to 1-2 ml; Fraction III was concentrated on a flash evaporator to 1-2 ml. All were diluted to 10 ml with petroleum ether. Quantities of 4 /il per solution were injected into a gas chromatograph equipped with an electron-capture detector. Determinations were made on a Hewlett-Packard Model 5710A gas chromatograph equipped with a linear Ni'^^ detector and automatic injector, attached to a Hewlett- Packard Model 3352C data acquisition system. Instru- ment parameters and operating conditions for determin- ing clilorinated insecticides and PCBs follow: Vol. 12, No. 4, March 1979 195 Column: glass, 1219 mm X 4 mm ID. packed with a mixture of 1.95 percent OV-17 and 1.5 percent QF-1 on 80-100-mesh .Supelcoport Temperatures, "C: column 200 injector 250 detector .100 Carrier gas; a mixture of 95 percent argon and 5 percent methane flowing at ,^3 ml minute Instrument parameters and operating conditions for determining chlordane isomers were: Column: glass, 1219 mm X 4 mm ID. packed with 3 per- cent OV-1 on SO-lOO-mesh Gas-Chrom Q Temperatures, *C: column 190 injector 250 detector 300 Carrier gas: a mixture of 95 percent argon and 5 percent methane flowing at 32 ml/minute Residues in 5 percent of the samples were confirmed by mass spectrometry. Recoveries were 74-120 percent; analytical results were not corrected. All residues are expressed as ppm wet weight. They may be converted to dry or lipid weight by dividing a given wet-weight value by 0.30 or 0.05, the mean pro- portions of dry and lipid material in the samples. Quan- tification limit was 0.01 ppm for organochlorine com- pounds. Trace residues were not reported. Results and Discussion Residues of DDE, DDT, dieldrin, PCBs, heptachlor epoxide, hexachlorobenzene (HCB), and chlordane isomers in starlings collected in 1976 are shown in Table 1. Since collections were made in the fall, residues do not necessarily reflect year-round levels. Also, find- ings should not be interpreted strictly on a statewide basis because some starlings are migratory. However, samples from certain localities consistently contain fairly high residues, suggesting that samples reflect local en- vironmental contamination. For example, when results from previous monitorings (1-4) are compared, samples from certain parts of Arizona, Arkansas, California, Louisiana, and New Mexico usually contain higher DDE levels than do those from other states. A summary of DDE, dieldrin, and PCB residues in starlings from 1970 through 1976 is shown in Table 2. The average DDE level in 1976 was similar to the 1970 level, before the use of technical DDT had been sus- pended. In fact, DDE residues were significantly higher nationwide {P<0.00\ ) in 1976 than in 1974 (Table 2). It is difficult to explain why DDE residues have in- creased sharply since 1974, when residues were at their lowest level in 7 years. Possibly, DDT or its related FIGURE I. Starting collection sites, continental United States, 1976 196 Pesticides Monitoring Journal TABLE 2. Comparison of DDE. dieldriii, and PCB residues in starlings, continental United States, 1970-76 No. Pools Residues, ppm wet weight DDE DlELDRlN PCBs Year x±SEi Range Geom. X x±SE Range Geom. x x±SE Range Geom. x 1970 125 0.839 ±0.138 (125) 0.037-48.2 0.355 0.117 ±0.038 (125) 0.005-3.59 0.036 0.663 ±0.196 (125) 0.09-24.3 0.358 1972 130 0.788 ±0.124 (130) 0.047-14.8 0.387 0.098 ±0.018 (130) 0.005-1.56 0.035 0.425 ±0.153 (130) 0.04-19.9 0.215 1974 126 0.617±0.118 (126) 0.007- 9.1 0.229 0.057 ±0.011 (122) 0.005-1.01 0.019 0.112±0.016 (126) 0.01- 1.9 0.068 1976 126 0.827 ± 0.174-' (124) 0.010-12.4 0.254 0.059 ± 0.006 (96) 0.010-0.28 0.039 0.290 ±0.036 = (26) 0.11- 0.85 0.243 ^Figure in parentheses represents number of pools having detectable residues. 2 Residues in 1976 significantly higher than in 1974 (/'<0.001, Students i-tesi, log-transformed data). compounds may have been used, especially in certain geographical regions of the country. Dieldrin residues declined steadily between 1970 and 1974, but the average dieldrin level in 1976 was almost identical to the 1974 average (Table 2), indicating no further decline of dieldrin during the 2-year period. PCBs have increased significantly nationwide (P<0.001 ) since 1974, although 1976 residues remained below those reported for 1970 and 1972 (Table 2). Only 26 samples contained PCBs in 1976 compared to 126 in 1974; although the average PCB level was higher in 1976 than in 1974, the number of sites reporting PCB residues decreased fivefold in 1976. The distribution of DDE, dieldrin, and PCBs by fre- quency of occurrence at collection sites for 1976 is shown in Table 3. In general, residues were low; most values were between 0 and 1.0 ppm for the three com- pounds. Dieldrin and PCBs were not detected in star- lings at levels greater than 1.0 ppm. In addition to organochlorine compounds in Table 1, certain other chemicals were detected in starlings less frequently. TDE occurred in six samples, ranging from TABLE 3. Distribution of residues in starlings by frequency of occurrence, continental United States, 1976 Number of Sites with Residues Range, ppm DDE Dieldrin PCBs ND- 0.01 3 43 99 >0.01- 0.10 36 65 0 >0.10- 1.0 63 17 26 >1.0 -13.0 23 0 0 NOTE: ND = not detected. 0.01 to 0.10 ppm; mirex was found in 13 samples, mostly from southeastern states, ranging from 0.01 to 1.24 ppm; lindane was detected in six samples, ranging from 0.01 to 0.15 ppm; and endrin occurred in only three samples, ranging from 0.02 to 0.18 ppm. Conclusions Nationwide, residues of DDE in starlings have increased significantly since 1974 to approximately the level re- ported in 1970 samples. Average PCB levels also in- creased, but the actual number of samples containing PCB residues declined. Dieldrin levels have remained unchanged since 1974. These data indicate that starlings can serve as indicators of environmental contamination and thus provide in- formation on residue trends over time. Geographical differences in residue levels also were detected. A cknowledgments Special thanks are extended to the following for their help with starling collections: James Elder, Robert Hillen, Arnold Julin, Harry Kennedy, David Lenhart, and David Walsh. LITERATURE CITED (/) Martin, W. E. 1969. Organochlorine insecticide resi- dues in starlings. Pestic. Monit. J. 3(2): 102-1 14. (2) Martin. W. E., and P. R. Nicker.son. 1972. Organo- chlorine residues in starlings — 1970. Pestic. Monit. L 6(l):33-40. (i) Nickerson, P. R., and K. R. Barbehenn. 1975. Organo- chlorine residues in starlings, 1972. Pestic. Monit. J. 8(4):247-254. (4) White. D. H. 1976. Nationwide residues of organo- chlorines in starlings, 1974. Pestic. Monit. J. 10(1): 10-17. Vol. 12, No. 4, March 1979 197 SOILS Pesticide Application and Cropping Data from 37 States, 1972- NationaJ Soils Monitoring Program Ann E. Carey' and Jeanne A. Gowen" ABSTRACT This report siininKirizcs pesticide application and cropping data collected in 1972 from 1 ,402 agricultural sampling sites in 37 states as part of the National Soils Monitoring Pro- gram. Pesticide application data are summarized by all sites, state, and crop. Tables generally give the number of sites re- porting, number of times a compound was applied, percent occurrence, and arithmetic mean application rate. Pesticides applied most frequently were atrazine, 2,4-D, captan, and trifliiralin. Among selected major crops, pesti- cides were most frequently applied to sites growing field corn and cotton, least frequently to sites growing alfalfa/bur clover and mi.xed hay. Introduction The increasing use of chemical pesticides in agriculture in the past 30 years has helped fewer farmers feed more people than at any other time in h'story. Today, the American farmer not only feeds and clothes this Na- tion's population, but also contributes significantly to the rest of the world. Yet the sensible use of toxic com- pounds also carries the responsibilitv to minimize their effects on nonlarget components of the environment. In 1963, the President's Science Advisory Committee recommended that appropriate federal agencies "develop a continuing network to monitor residue levels in air, water, soil, man. wildlife and fish" (/). As a result of the recommendation, the National Pesticide Monitoring Pro- gram fNPMP) was established to determine levels and trends of pesticides and their degradation products in various components of the environment (2). The federal responsibility for monitoring pesticides was oflficially codified in Section 20 of the amended Federal Insecticide, Fungicide and Rodenticidc Act of 1972 (PI. 92-516). ' Ecclogical Monilorinp Branch. Bcncfns and Field .Studies Division. Office of Peslicidc Propr.ams, U.S. Environmcnial Protection Agency. TS-768. Washington. DC 2046fl. '•'Extension Agent, Colorado Slate Extension Service. Golden. CO. The National Soils Monitoring Program (NSMP) is an integral part of the NPMP and monitors residues in agricultural soils and raw agricultural crops. It was established in 1968 by the U.S. Department of Agricul- ture and is administered by the U.S. Environmental Pro- tection Agency. The present report summarizes pesticide application and cropping data collected during 1972 (FY-73) from 1.402 sampling sites in 37 states. Data for composite soil and crop samples, collected from the sites for pesticide residue analysis, are presented in a separate report (.?). Sampling The site selection criteria and statistical design of the NSMP have been described (4). In 1972. 1.533 sites in 37 states were scheduled for sampling (Fig, 1 ). At each 4-hectare ( 10-acre) site, the landowner or operator was interviewed concerning crops grown and the kinds and amounts of pesticides applied during the 1972 growing season. Results and Discussion CO.MPOUNDS APPLIED TO CROPLAND Cropping and pesticide use data were received from 1.402 of the scheduled 1,533 sites or 91 percent. Of these, 742 or 53 percent of the sites had one or more pesticides applied during the 1972 growing season. Tables summarizing the application data show the number of sites reporting a pesticide application, the percent of sites reporting the pesticide application, and the average rate of application, expressed in poimds per acre and kilograms per hectare. Table I lists the frequency of pesticide use on sample sites in various states and state groups. Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to obtain more representative data. State groups used were Mid-Atlantic: Delaware, Maryland, 198 Pesticides Monitoring Journal FIGURE I. Slates scheduled jor sampling, 1972 — National Soils Monitoring Program TABLE 1. Pesticide application data jrom 1 .402 reporting sites in 37 stales, 1972 — National Soils Monitoring Program Pesticides No Pesticides No. OF Used Used Sites eporting State R No. Co No. % Alabama 20 9 45 11 55 Arkansas 47 29 62 18 38 California 52 22 42 30 58 Florida 15 7 47 8 53 Georgia 27 13 48 14 52 Idaho 30 15 50 15 50 Illinois 139 94 68 45 32 Indiana 74 45 61 29 39 Iowa 149 106 71 43 29 Kentucky 16 7 44 9 56 Louisiana 27 18 67 9 33 Michigan 50 26 52 24 48 Mid-Atlanlic' 18 10 56 8 44 Mississippi 27 24 89 3 11 Missouri 81 39 48 42 52 Nebraska 97 40 41 57 59 New England 1 11 1 9 10 91 New York 31 13 42 18 58 North Carolina 31 17 55 14 45 Ohio 67 31 46 36 54 Oklah:>tna 43 27 63 16 37 Oregon 37 15 41 22 59 Pennsylvania 34 14 41 20 59 South Carolina 16 10 63 6 37 South Dakota 106 45 42 61 58 Tennessee 22 10 45 12 55 Virginia/West Virginia 1 24 4 17 20 83 Washington 45 26 58 19 42 Wisconsin 66 25 38 41 62 TOTAL ,402 742 53 660 47 'Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to obtain more representative data. State groups used were Mid-Atlantic: Delaware. Maryland, and New Jersey. New Eng- land: Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont; and Virginia and West Virginia, and New Jersey; New England: Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont; and Virginia and West Virginia, Among individual states and state groups, frequency of pesti- cide use ranged from 9 percent in the New England states to 89 percent in Mississippi. ALL SITES The 121 compounds applied to all sites included 54 herbicides, 38 insecticides, 20 fungicides, 4 acaricides, 2 defoliants, 2 soil fumigants, and 1 growth retardant (Table 2), The most commonly applied compounds were atrazine, 2,4-D, captan, and trifluralin, which were used on 14, 10, 8, and 7 percent of the sites, respectively. BV STATE Table 3 presents the application data by state or state group. Because of the number of states sampled, it is not feasible to discuss in detail the pesticide data from each state. However, pesticide application data from each state tended to reflect both the crops grown and the intensity of agricultural land use in the state. For ex- ample, Iowa, predominantly a corn- and soybean- producing state, recorded the use of 17 compounds on 149 sites. California, a fruit and vegetable producer, recorded 29 compounds used on 52 sites. In Figure 2, the frequency of reported pesticide applica- tions in each state was arbitrarily classified as follows: low, less than 25 percent of the sites reported pesticide application; medium, 25-59 percent reported applica- VoL. 12, No. 4, March 1979 199 TABLE 2. Siininitiry of compounds applied to 1,402 cropland sites in 37 stales, 1972- National Soils Monitoring Program Sites Reporting Average Total Sites Reporting Average Total Trade Application Application Trade Appltcation Application Name - Name Compound IF Noted No % Lb/ Acre Ko/Ha Compound If Noted No % Lb/ Acre Kg/Ha Alachlor Lasso 86 6.1 1.38 1.55 Fluomeluron Coloran 23 1.6 0.93 1.04 Aldicarb Temik 2 0.1 0.40 0.45 Folex 5 0.4 1.10 1.23 Aldnn 33 2.4 1.57 1.76 Hepiachlor 5 0.4 1.26 1.41 Amitrole 1 0.1 0.15 0.17 Hexachloro- Ancrack 4 0.3 1.08 1.20 benzene No-Bunt U 0.8 0.04 0.04 Atrazine AAlrex 2(K) 14.3 1.56 1.75 Lead arsenate 1 0.1 4,00 4.48 Azinphosmclhyl Gi'lhion 4 0.3 1.23 1.37 Lindane 1 0.1 0.01 0.01 Bcncfin Balan 6 0.4 0.83 0.93 Linuron Lorox 39 2.8 111 1.24 Benoniyl Beiilate 3 11. 1 2.58 2.90 Malathion 83 5.9 0.04 0.04 Benzene Malcic hydrazide MH 5 0,4 2.25 2.52 hexachloride 2 0.1 1.25 1,40 Maneb 3 0.2 0.70 0.78 Bromacil Hyvar 2 0.1 0.42 0.47 MCPA MCP 5 0.4 1.40 1.56 Bromoxvnil 1 0.1 1.25 1.40 MCPB 5 0.4 0.85 0.95 Butylale Sutan 17 1.2 1.68 1.89 Mercury 10 0.7 0.04 0.04 Bux 25 1.8 0.88 0.98 Melhomyl Lannale 1 0.1 0.34 0.38 Captafol Difolatan 3 0.1 3.83 4.29 Methoxythlor 11 0.7 0.19 0.21 Caplan 106 7.6 0.19 0.22 MelhyliTierciiry Carbaryl Sevin 23 1.6 2.49 2.79 aceiate Ceresan L 7 0.5 0.01 0.01 Carbofuran Furadan 17 1.2 1.07 1.19 Meihylmercury Carbophenoihion Triihion 3 0.2 0.78 0.87 dicyandiamide Panogen 3 0.2 0.01 0.01 Chloramben Amiben 51 3.6 1.38 1.55 Methyl trithion 1 0.1 0.25 0.28 Chlorobcnzilate Acaraben 4 0.3 3.45 3.87 Metnbuzin Senear 1 0.1 0.50 0.56 Chlordane 5 0.4 3.18 3.57 Mevinphos Phosdrin 1 0,1 0.25 0.28 Chloroneb Demosan 8 0.6 0.02 0.02 Ml rex 7 0.5 0.01 0.01 Chloropropham Chloro-IPC 1 0.1 0.59 0.66 Molinate O.dram 2 0.1 3.00 3.36 Chloropropylate Acarolaie 1 0.1 3.50 3.92 Monocrolophos Azodri.n 3 0.2 1.67 1.87 Chloroxuron Tenoran 1 0.1 2.00 2.24 MSMA 2i 1.5 2..36 2.65 Copper carbonate Naled Dibrom 1 0.1 1.00 1.12 (basic) 1 0.1 3.50 3.92 Napialam Alanap 8 0.6 1.35 1.52 Cyanazine Bladex 2 0.1 2.15 2.41 Nilralin Planavin 9 0.6 1.16 1.30 Cycloale Ro-Neel 3 0.2 1.95 2.19 Norea Herban 3 0.2 1.57 1.76 2,4-D 136 9.7 0.69 0.77 Oil spray 2 0.1 55.00 61.64 Dalapon Dowpon 2 0.1 7.80 8.74 Oxyihioquinox Mores:an 1 0.1 0,08 0.09 2.4-DB Buiyrac 7 0.5 0.91 1.02 Paraqual 7 0.5 0.43 0.48 DDT 21 1.5 5.83 6.53 Paralhion, elhyi 17 1.1 2.29 2.57 DEF 6 0.4 0.99 1,11 Paralhion, nielhyl 40 2.9 2.99 3.35 Diazinon 8 0.6 0.52 0,59 PCNB 7 0.5 0.02 0.02 Dibromochloro- Pebulaie Tillam 1 0.1 4.00 4.48 propane Nemagon 1 0.1 0.50 0.56 Penlachloro- Dicamba Banvel D 12 0.9 0.34 0.38 phenol PCP 1 0.1 0.05 0.06 Dichlone Phygon 1 0.1 0.50 0.56 Phenylmercury Dichloropropene Telone 1 0.1 60.00 67.25 aceiate PMA 4 0.3 0.02 0.02 Dichlorprop 2.4-DP 1 0.1 2.00 2.24 Phorale Thimet 26 1.9 1.79 2.01 Dicofol Kelihane 2 0.1 0.75 0.84 Picloram Borolin 1 0.1 0.75 0.84 Dicroiophos Bidrin T 0.1 0.08 0.09 Polyram 1 0.1 1,00 1.12 Dimethoate Cygon 6 0.4 0.58 0.65 Prolate Imidan 3 0.2 3,92 4.39 DNBP Premerge 16 1.1 1.24 1.39 Prometryn Caparol 4 0.3 0,87 0.98 Diniirocresol 2 0 1 1,63 1,82 Propachlor Ramrod 40 2.9 1.93 2.16 Diphenamid Enide 1 0.1 1 .00 1,12 Propanil St am 2 0 1 3 50 3.92 DisuUoton Di-Syston 13 0.9 0.38 0.43 Propargite Omilc 2 0.1 1,59 1.78 Diuron Karmex 11 0.8 0.71 0.80 Propham IPC 2 0.1 1,75 1.96 Dodine Cyprex 1 0.1 0.98 1.09 Pyrazon Pyramin 1 0.1 0.94 1.05 DSMA 8 0.6 2.51 2.81 Simazine Pnncep 5 0.4 2.82 3.16 Dyfonate 3 0.2 0.97 1.08 Sodium chlorate 2 0.1 1 .00 1.12 EMTS Ceresan M t) 0.6 0.01 0.01 Sulfur 10 0.7 27.85 3J.21 EPN 1 0.1 3.00 3.36 TCA 2 0.1 5.63 6.30 EPTC Ethion Ep:am HI 3 0.7 0.2 2.19 3,35 2.45 3.75 TCBC 1 0.1 8.00 8.97 Ethoprop Mocap 1 0.1 1.00 1.12 TEPP 1 0.1 0.25 0.28 Hihylmercury Terbacil Sinbar t 0.1 1.75 1.96 chloride Ceresan Red 5 0.4 0.01 0,01 Ihiram 14 0.9 0.03 0.03 Fenac 1 0.1 1.25 1,40 Toxaphene 30 2.1 9,36 10.49 Fenaminosulf D^xon 1 0.1 0.01 0,01 Ti ielazine 1 0.1 0.25 0.28 Fensulfothion Dasanit 4 0.3 2.79 3,13 Trifluralin Trellan 97 6.9 0,86 0.96 Fentin hydroxide 2 0.1 8.75 9,81 Vernolate Vernam 6 0.4 1,20 1.35 200 Pf.sticides Monitoring Journal TABLE 3. Compounds applied to cropland sites by state, 1972 — National Soils Monitoring Program Sites Reporting Average Total Sites Reportino Average Total Trade APPLICATION Application Trade Application Application Name IF Noted Compound Name Compound No. % Lb/Acre Kg/Ha IF Noted No. % Lb/ Acre Kg/Ha ALABAMA, 20 SITES FLORIDA. 15 SITES Atrazine Azinphosmethyl Carbophenoihion Chlorobenzilate Copper carbonate (basic) Ethion AAirex Guthion Triihion AcaruJen Ethodan 1 1 1 4 1 3 6.7 6.7 6.7 26.7 6.7 20.0 2.00 2.00 1.50 3.45 3.50 3.35 2.24 2.24 1.68 3.87 3.92 3.76 Atrazine Benefin Benomyl Captan Disulfoton 2,4-D AAtrex Balan Benlale Di-Syston 5.0 15.0 10.0 5.0 5.0 5.0 1.00 0.75 3.50 0.01 1.00 1.00 1.00 1.00 2.00 1.12 0.84 3.92 0.01 1.12 1.12 1.12 1.12 2.24 DNBP Linuron Naptalam Premerge Lorox Alanap 5.0 5.0 5.0 Fensulfolhion Oil spray Sulfur Dasanit 1 2 4 6.7 13.3 26.7 7.50 55.00 36.88 8.41 61.64 41.33 Parathion, methyl Trellan 5.0 10.0 10.0 13.00 8.50 2.00 14.57 9.53 2.24 Toxaphene Trifluralin GEORGIA, 27 SITES Vernolale Vernam 15.0 0.75 0.84 Alachlor Lasso 3.7 2.50 2.80 Alrazine Benefin Captan Carbaryl AAtrex Balan Sevin 3.7 3.7 3.7 18.5 4.00 1.13 O.OI 2.40 4.48 ARKANSAS. 47 SITES 1.27 0.01 Alachlor Lasso 2 4.3 3.25 3.64 2.69 Ancrack 1 2.1 0.50 0.56 DDT 3.7 4.50 5.04 Captan 3 6.4 0.01 0.01 Captafol D;folatan 3.7 10.00 11.21 Chloroxuron Tenoran 1 2.1 2.00 2.24 Disulfoton Di-Syslon 3.7 1.00 1.12 DEF 1 2.1 0.50 0.56 Fentin hydroxide Du-Ter 7.4 8.75 9.81 DDT 5 10.6 3.90 4.37 Mirex 7.4 0.01 0.01 Dicrotophos Bidrin 2 4.3 0.08 0.09 Maleic hydrazide MH-30 3.7 6.00 6.72 Disulfoton Di-Syston 1 2.1 O.OI 0.01 Parathion. ethyl 7.4 2.75 3.08 Diuron Karmex 2 4.3 1.25 1.40 Parathion. methyl 3.7 4.50 5.04 DNBP Pre.merge 4 8.5 0.94 1.05 Sulfur 3.7 34.00 38.11 DSIVIA 2 4.3 2.50 2.80 Toxaphene 2 7.4 5.25 5.88 2.4-DB Butyrac 4 8.5 0.88 0.98 Trifluralin Treflan 1 3.7 1.00 1.12 EMTS Ceresan M -> 1 7 1 4.3 2.1 14.9 2.1 0.01 3.00 0.96 1.50 O.OI 3.36 1.08 1.68 EPN Fluometuron Folex IDAHO, 30 SITES Cotoran Atrazine AAirex 2 6.7 0.75 0.84 Linuron Loiox -) 4.3 0.50 0.56 Bromoxynil 1 3.3 1.25 1.40 Mercury 7 14.9 0.05 0.05 2,4-D 7 23.3 1.21 1.36 Metribuzin Sencor 1 2.1 0.50 0.56 DDT 1 3.3 1.00 1.12 MSMA 9 19.1 1.94 2.18 EMTS Ceresan M 2 6.7 0.01 0.01 Naptalam Alanap 3 6.4 0.83 0.93 EPTC Ep;am 1 3.3 0.25 0.28 Nitralin Planavm 2 4.3 1.00 1.12 MCPB 1 3.3 2.00 2.24 Paraquat 1 2.1 0.02 0.02 Sulfur I 3.3 20.00 22.42 Parathion. ethyl 1 2.1 3.00 3.36 Trifluralin Treflan 2 6.7 0.25 0.28 Parathion. methyl Prometryn 9 3 8 19.1 6.4 4.3 17.0 2.69 1.08 0.12 4.84 3.02 1.21 0.13 5.43 Caparul Sii.Tiusoy ILLINOIS, 139 SITES Thiram Toxaphene Alachlor Aldrin Lasso 10 6 7.2 4.3 1.24 1.10 1.38 1.23 Trifluralin Treflan 12 25.5 0.77 0.86 Atrazine AAtrex 23 16.5 1.33 1.49 Bulylaie Bux Sutan 9 T 45 3 6.5 1.4 32.4 T 2 0.94 1.30 0.01 0.75 1.06 CALIFORNIA. 5 2 SITES 1.46 0.01 0.84 Alachlor Lasso 1.9 0.50 0.56 Captan Carbofuran Furadan Carbophenothion Tri.hion 1.9 0.09 0.10 Chloramben Amiben 20 14.4 1.25 1.40 Chloroneb Demosan 1.9 0.01 0.01 Chlordane 3 ■) 2 0.97 1.09 2.4-D 3.8 0.50 0.56 2.4-D 14 10.1 0.43 0.49 DNBP Premerge 1.9 0.50 0.56 2.4-DB Buiyrac 1 0.7 0.50 0.56 Dibiomochloro- Diazinon -) 1.4 2.01 2.25 propane Nemagon 1.9 0.50 0.56 Dicamba Eanvel-D 2 1.4 0.17 0.18 Dicofol Kel thane 3.8 0.75 0.84 Dvfonate 1 0.7 0.50 0.56 Disulfoton Di-Syston 1.9 1.00 1.12 EPTC Ep:am 1 0.7 0.42 0.47 EPTC Eptam 1.9 3.00 3.36 E-hyimercury Fenaminosulf Dexon 1.9 0.01 0.01 chloride Ceresan Red 1 0.7 0.01 0.01 Malathion 1.9 1.00 1.12 Heplachlor 2 1.4 1.65 1.85 MCPA MCP 3.8 2.00 2.24 Lindane 1 0.7 0.01 0.01 jVlethornyl Lannale 1.9 0.34 0.38 Linuron Lorox T 1.4 1.25 1.40 Mevinphos Phosdrin 1.9 0.25 0.28 Malathion 44 31.6 O.OI 0.01 Molinate Oidram 3.8 3.00 3.36 Meihoxychlor 5 3.6 0.01 0.01 Naled Dibrom 1.9 1.00 1.12 Nitralin Planavin 1 0.7 2.80 3.14 Nitralin Planavin 1.9 0.75 0.84 Phorate Thimet 3 -> 2 0.80 0.90 Paraquat 3.8 0.63 0.70 Propachlor Ra.xrod 15 10.8 1.71 1.92 Parathion. ethyl 9.6 0.76 0.85 TCBC Randox-T 1 0.7 8.00 8.97 Parathion, methyl 3.8 0.36 0.40 Simazine Princep 1 0.7 3.00 3.36 Phorate Thimet 3.8 1.00 1.12 Trietazine Gesafloc 1 0.7 0.25 0.28 Prolate Imidan 1.9 0.75 0.84 Toxaphene 1 0.7 0.40 0.45 Propanil Slam bmite 1.9 4.00 4.48 Trifluralin Treflan 12 8.6 0.73 0.82 Propargite 1.9 1.68 1.88 Vernolale Vernam 1 0.7 0.45 0.50 Simazine Princep 3.8 3.8 1.9 1.9 2.75 0.80 0.25 3.00 3.08 0.90 0.28 3.36 Sulfur INDIANA, 74 SITES TEPP Toxaphene Alachlor Lasso 15 20.3 1.86 2.08 Trifluralin Treflan - 3.8 0.38 0.42 Aldnn 7 9.5 1.33 1.49 {Continued next page) Vol. 12, No. 4, March 1979 201 TABLE 3 (cont'd.). Compounds applied to cropland sites by stale, 1972 — National Soils Monitoring Program Sites Reporting Average Total Sites Reporting Average Total Trade Application Application Trade Application Application Name IF NolED Compound Name IF Noted Compound No. % Lb/Acre Kg/Ha No. % Lb/Acre Kg/Ha Atrazine AAtrex 20 27.0 1.83 2.05 Linuron Lorox 3 6.0 1.67 1.87 Capian 6 8.1 0.01 0.01 Malaihion 10 20.0 0.01 0.01 Chloramben Amiben 5 6,8 1.20 1.35 Pyrazon Pyramin 1 2.0 0.94 1.05 2.4-D 4 5.4 0.50 0.56 TCA 1 2.0 0.25 0.28 EPTC Eplam 1 1.4 10.00 11.21 Trifiuralin Treflan 1 2.0 1.00 1.12 Ltnuron Lorox Treflan 8 6 10.8 8.1 4.1 1.38 0.01 1.00 1.55 0.01 1.12 Malathion Trifliiralin MID-ATLANTIC STATES,> 18 SITES Alachlor Lasso 5 27.8 2.06 2.31 IOWA. 149 SITES Atrazine AAtrex 2 11.1 1.75 1.96 Azinphosmethyl Guihion 1 5.6 0.90 1.01 Alachlor Lasso 10 6.7 0.86 0.97 Captan 4 22.2 0.01 0,01 Aldrin 8 5.4 1,20 1,35 Carbaryl Se%in 2 11.1 1.92 2.15 Airazine AAtrex 38 25.5 1,38 1,55 Chlordane 5.6 5.00 5.60 Butylate Suian 6 4.0 2,75 3.08 2.4-D 5,6 0.50 0.56 Bux 13 8.7 0,90 1.01 Dichlone Phygon 5,6 0.50 0.56 Carbofuran Furadan 4 2.7 0.98 1,09 Dieldrin 11,1 0.26 0.29 Chloropropham Chloro-lPC 1 U.7 0.59 0.66 Dimethoate Cygon 5,6 0.66 0.74 Chloramben Ami:en 16 1(1,7 0.96 1.08 5,6 3.00 3.36 2.4-D iS 12.1 0,51 0.57 Linuron Lorox 5,5 0.38 0.43 Diazinon 1 0,7 0,07 0.08 Maneb 5,6 1.44 1.61 Dicamba B.mvel D 6 4.0 0,25 0.28 Ma'aihion 11,1 0.01 0.01 Dyfonale 1 0.7 1.40 1.57 Parathion. ethvl 5,6 1.30 1,46 Ethoprop Mocap 1 0.7 1 .00 1.12 Prolate imidan 5,6 2.00 2,24 Hepiachlor 1 0.7 1.00 1.12 Sulfur 5,6 37.00 41.47 Phoraic Ihimel 8 5.4 1.06 1,19 Thiram .Arasan 5,6 0.01 0.01 Propachlor Ramrod 14 9.4 1.74 1.95 Trifiuralin Treflan 5.6 1.20 1.35 Trifiuralin Treflan 22 14.8 0.80 0.89 KENTUCKY. 16 SITES MISSISSIPPI, 27 SITES Atrazine Carbaryl 2,4-D Linuron Malathion Methoxychlor Trifiuralin AAirex Sevin Lorox Treflan 31.3 12.5 6.3 6.3 6,3 6.3 6.3 1.00 1.50 1.00 0.75 1.00 2.00 1,00 1.12 1.68 1.12 0.84 1.12 2.24 1.12 LOUISIANA. 27 SITES Alachlor Aldrin Azinphosmethyl Chloramben 2.4-D 2.4-DB DCPA DDT DSMA Dalapon DEF Dichlorprop Diphenamid Diuron DNBP EMTS Fcnac Ruomcturon Folex MSMA Norea Parathion. meihyl Propanil TCA Terbacil Thiram Toxaphenc Trifiuralin Vernolale Lasso Guthion Amiben Butyrac Dacihal Dowpon 2.4-DP Enide Karmex Premcrge Ceresan M Coioran Ansar He.fcan S.am Sinbar Ircflan Vernam 3.7 3.7 3.7 3.7 11.1 3.7 3.7 18.5 14.8 3.7 3.7 3.7 3.7 11,1 7,4 3,7 3,7 14,8 3,7 11,1 3.7 29.6 3.7 3.7 3.7 3,7 18,5 29,6 3,7 1.00 0.01 1.50 1,50 1,12 2,00 0.75 11,30 3,15 2,l» 1,50 2,00 1,00 1,25 1,25 0.01 1.25 1,03 1,(KI 2,50 0,60 3,66 3,00 1 1 ,00 2,00 0,01 23,40 1,41 2,50 1,12 0,01 1,68 1,68 1.25 2.24 0,84 12,67 3.53 2.24 1.68 2.24 1.12 1.40 1.40 0.01 1.40 1.15 1.12 2.80 0.67 4.10 3.36 12.33 2.24 0.01 26.23 1.58 2.80 Alachlor Aldicarb Ancrack Azinophosmethyl Captan Carbaryl Chloroneb 2,4-DB DDT DEF DSMA DNBP Disulfolon Diuron Fluometuron Folex Linuron MSMA Methylmercury acetate Mirex Monocrotophos Naptalam Nitralin Norea Parathion. methyl Sodium chlorate Toxaphene Trifiuralin Lasso Temik Guthion Sex in Demcsan Butyrac Premerge Di-Syston Karmex Cotoran Lorox Ceresan L Azodrin Alanap Planavin Herban Treflan 4 3 1 3 1 10 2 8 10 3.7 7.4 11.1 3.7 3.7 3.7 25,9 3,7 25,9 14,8 7.4 25,9 18,5 7,4 25,9 7,4 11,1 25.9 22,2 14,8 11,1 3,7 11.1 3.7 37.0 7.4 29.6 37.0 2.00 0,40 1.27 0.50 0.03 1,00 0,03 0,40 5,71 0,98 1,24 1,70 0,01 0.30 0.70 0.75 1.83 2.75 0.01 0.01 1.67 3.00 1.33 1.60 4.38 1.00 10.25 0.85 MISSOURI, 81 SITES MICHIGAN. 50 SITES Alachlor Aldrin Atrazine Capian 2,4-D Dicamba EPTC Lasso AAIrex Banvcl D Eptam 1 1 15 10 6 1 2 2.0 2.0 .30.0 20.0 12(1 2.0 4.0 0.50 1.40 2.09 0.01 1.29 1.00 2.00 0.56 1.57 2.35 0.01 1.45 1.12 2.24 Alachlor Atrazine Aldrin Chloramben 2.4-D Diuron Fluometuron L inuron MSMA Norea Trifiuralin Lasso AAtrex Amiben Karmex Cott)ran Lorox Herban Treflan II 13 3 T 3 1 3 6 1 I 11 13.6 16.0 3.7 2.5 3,7 1,2 3,7 7.4 1.2 1.2 13.5 1.42 1.67 1.67 3.01 0.42 0,25 1,31 0,87 3.40 2.50 0.73 NEBRASKA. 97 SITES Alachlor Atrazine Bux Carbofuran Lasso AAtrex Furadan 4 1« 7 5 4.1 18.6 7.2 5.2 1.11 1.40 0.73 0.69 (Continued next page) 202 2.24 0.45 1,42 0,56 0.03 1.12 0.03 0.45 6.40 1.10 1.39 1.91 0.01 0.34 0.78 0.84 2.05 3.08 0.01 0.01 1.87 3.36 1.49 1.79 4.90 1.12 11.49 0.95 1.59 1.87 1.87 3.37 0.47 0.28 1.46 0.97 3.81 2.80 0.82 1.25 1.57 0.82 0.78 Pesticides Monitoring Journal TABLE 3 (cont'd.). Compounds applied to cropland sites by state, 1972 — National Soils Monitoring Program Compound Trade Name IF Noted Sites Reporting Application Average Total Application Lb/Acre Ko/Ha Chloramben Cyanazine Cycloaie 2,4-D Diazinon Dyfonale EPTC Fensulfothion Linuron Parathion, ethyl Propachlor Phorate Simazine Amiben Bladex Ro-Necl Epiam Dasanit Lorox Ramrod Thimet Princep 1.0 1.0 1.0 8.2 1.0 1.0 1.0 1.0 2.1 2.1 5.2 3.1 I.O 1.50 2.80 0.40 0.61 0.98 1. 00 1.75 0.90 0.94 0.65 2.13 0.88 4.00 1.68 3.14 0.45 0.68 1.10 1.12 1.96 1.01 1.05 0.73 2.39 0.99 4.48 NEW ENGLAND,! 11 SITES Captan Carbophenothion Chloropropylate Dodine Prolate Propargite Trilhion Acarolate Cyprex Omite 9.1 9.1 9.1 9.1 9.1 9.1 19.20 0.75 3.50 0.98 0.38 9.00 NEW YORK. 31 SITES Alachlor Airazine Benomyl Bux Captan Carbaryl Carbofuran 2.4-D Diazinon Dinitrocresol DNBP EPTC Methoxychlor Parathion, ethyl Thiram Lasso AAtiex Benlate Sevin Furadan Premerge Ep:am 10 1 1 3 2 1 1 "> 1 I 1 4 I 4 7.1 32.3 3.6 3.6 10.7 7.1 3.6 3.6 7.1 3.6 3.6 3.6 12.9 3.6 12.9 0.88 2.03 0.75 0.70 0.01 4.25 1.00 0.25 0.51 0.25 0.21 0.25 0.01 0.33 0.01 NORTH CAROLINA, 31 SITES Alachlor Atrazine Carbaryl 2,4-D Dichloropropene Fensulfothion Lead arsenate Linuron Maleic hydrazide Maneb Naptalam Nitralin Parathion. ethyl Paraquat Pebulaie Phorate Penlachlorophenol Toxaphene Trifluralin Lasso AAtrex Sevin Telone Dasanit Alanap Planavjn Tillam Thimet PCP Treflan 9.7 12.9 12.9 3.2 3.2 3.2 3.2 3,2 12.9 3.2 6.5 3.2 6.5 6.5 3.2 3.2 3.2 3.2 3.2 1.00 1.63 3.38 1.00 60.00 2.00 4,00 1.50 1.31 0.41 0.92 0.50 10.50 0.38 4.00 0.50 0.05 10.00 0.80 OHIO, 67 SITES Alachlor Lasso 4 6.0 Aldrin 6 9.0 Atrazine AAtrex 13 19.4 Butylate Sutan 1 1.5 Bux 1 1.5 Captan 1 1.5 Carbofuran Furadan 1 1.5 Chloramben Amiben 5 7.5 2,4-D 5 7.5 Dicamba Banvel D 2 3.0 Linuron Lorox 5 7.5 Melhylmercury acetate Ceresan L 1 1.5 Picloram Borolin 1 1.5 Propachlor Ramrod 1 1.5 1.14 3.33 1.89 2.00 0.80 0.0 1 1.00 2.60 1.00 1.00 0.92 0.01 0.75 8.00 21.52 0.84 3.92 1.10 0.43 10.09 0.98 2.27 0.84 0.78 0.01 4.76 1.12 0.28 0.57 0.28 0.24 0.28 0.01 0.37 0.01 1.12 1.82 3.78 1.12 67.25 2.24 4.48 1.68 1.47 0.46 1.03 0.56 11.77 0.42 4.48 0.56 0.06 11.21 0.90 1.27 3.74 2.12 2.24 0.90 0.01 1.12 2.91 1.12 1.12 1.03 0.01 0.84 8.97 Compound Trade Name IF Noted Sites Reporting Application No. Average Total Application Lb/Acre Kc/Ha OKLAHOMA, 43 SITES Alachlor Benefin Captan Carbaryl 2,4-D EMTS Ethylmercury chloride MCPB Parathion, methyl PCNB Polyram Thiram Trifluralin Lasso Baian Sevin Ceresan Red Arasan Treflan 4.7 2.3 4.7 7.0 9.3 9.3 2.3 4.7 1S.6 14.0 2.3 11.6 2.3 2.00 2.24 1.00 1.12 0.01 O.OI 2.17 2.43 0.50 0.56 0.01 O.OI 0.01 O.OI 0.50 0.56 0.50 0.56 0.02 0.02 1.00 1.12 O.OI 0.01 0.50 0.56 OREGON, 37 SITES Amitrole Bromacil Captan Cvcloate 2,4-D Diazinon Diuron Ethylmercury chloride Hexachloro- benzene Malathion Maneb Melhylmercury dicyandiamide Parathion. ethyl Phenylmercury acetate Propham Ro-Neet Karmex Ceresan Red Pancgen PMA IPC 11 1 2.7 2.7 5.4 2.7 29.7 2.7 2.7 5.4 5,4 2.7 2.7 2.7 2.7 5.4 2.7 0.15 0.09 0.01 5.20 0.72 0.10 0.10 0.01 0.04 0.50 0.25 0.01 0,09 0.02 0.50 PENNSYLVANIA, 34 SITES Alachlor Airazine Butylate Captafol 2,4-D Disulfoton Lmuron Phorate Lasso AAtrex Sutan Difolatan Di-Syston Lorox Thimet 26.5 2.9 2.9 8.8 2.9 2.9 2.9 0.75 1.60 1.60 1.00 0.58 0.50 0,50 2.50 SOUTH CAROLINA, 16 SITES SOUTH DAKOTA, 106 SITES Alachlor Lasso 4 3.8 Airazine AAtrex 5 4.7 Bux 1 0.9 Captan 20 18.9 Carbofuran Furadan 2 1.9 Chloramben Amibe.n 1 0.9 2.4-D 27 25.5 Dieldrin 2 1.9 Dimelhoate Cygon 4 3.8 Disulfoton Di-Syston "> 1.9 Malathion 18 17.0 MCPA 1 0.9 1.06 0.90 1.00 0.01 0.25 2.00 0,41 0,01 0.21 0.31 0.01 0.50 0.17 0.10 O.OI 5.83 0.81 0.11 O.U O.OI 0.04 0.56 0.28 O.OI 0.10 0.02 0.56 0.84 1.79 1.79 1.12 0.65 0.56 0.56 2.80 Benefin Balan 6.25 0.60 0.67 Captan 6.25 O.OI 0.01 Carbaryl Sevin 6,25 1.00 1.12 DDT 12,50 0.50 0.56 Methyl trilhion 6,25 0.25 0.28 Mirex 6,25 0.01 0,01 Nitralin Planavin 6,25 0.35 0.39 Parathion, ethyl 6.25 2.40 2.69 Parathion, methyl 6.25 0.25 0.28 Sulfur 6.25 38.40 43.04 Toxaphene 12.50 1.00 1.12 Trifluralin Treflan r 18.75 0.58 0.65 Vernolale Vernam 6.25 2.00 2.24 1.19 1.01 1.12 0.01 0.28 2.24 0.45 0.01 0.23 0.35 O.OI 0.56 (Continued next page) Vol. 12. No. 4, March 1979 203 TABLE 3 (cont'd.). Compounds iipplicd to cropland sites by state. 1972 — National Soils Monitor ini; Program Sites Reporting Average Total Sites Repohting Average Total Trade Application Application Trade Application Application Name - IF Noted Compound Name IF Noted Compound No % Lb/ Acre Kg/Ha No. % Lb Acre Kg/Ha Melhoxychlor 1 0.9 0.01 0.01 Bromacil Hyvar , 2.2 0.75 0.84 Melhylmercury Captan 5 11. 1 0.03 0.03 dicyandiamidc Panogen 2 1.9 0.01 0.01 Cvcloate Rc-Neet 1 2.2 0.25 0.28 Paraihion, ethyl I 0.9 0.25 0.28 2,4-D 12 26.7 1.31 1.47 Propachlor Ramrod 5 4.7 1.69 1.89 Dicamba Banvcl D 1 2 2 0.25 0.28 Phoraie Thimei I 0.9 0.70 0.78 Dieldrin Diuron EPTC Hexachloro- Karmex Eptam 1 1 1 2 2 2 2 2 2 0.04 0.50 0.25 0.04 0.56 TENNESSEE 22 SITES 0.28 Alachlor Lasso 1 4.5 2.00 2.24 henzene No-Bunt 9 20.0 0.05 0.05 Atrazine AAtrex J n.6 1.60 1.79 Heptachlor 1 2.2 0.01 0.01 Dimethoate Cygon 1 4.5 2.00 2.24 MCPA ■) 4.4 1.25 1.40 Diuron Karmex 1 4.5 0.11 0.12 Mercury 3 6.7 0.01 0.01 Disulfoton Di-Syslon 1 4.5 0.72 0.81 Oxyihioquinox Morestan 1 2 2 0.08 0,09 Ethylmercury Phcn>lmercury chloride Ceresan Rec I 4.5 O.OI 0.01 acetate PMA 2 4.4 0,01 0.03 Folex 1 4.5 1.50 1.68 Phorate Thimet 1 2 2 0,03 0.03 Fluometuron Cntoran 2 9.1 0.91 1.01 Propham IPC 1 1 T 3.00 3.36 Linuron Lorox 2 9.1 0.63 0.70 Propargite Omite 1 T 1 1.50 1.68 MSMA 1 4.5 2.00 2.24 Terbacil Sinbar 2 2 1.50 1.68 Paraquat PCNB Prometryn Terrachlor Trctlan 1 4.5 4.5 4.5 IS. 2 0.50 0.01 0.24 1.04 0.56 0.01 0.27 1.16 I 1 4 WISCONSIN, 66 SITES Trifluralin Alachlor Lasso 5 7.6 0.95 1.06 Atrazine Captafol AAtrex Difolatan 16 24,2 1,5 1.33 0,50 1.49 VIRGINIA, WEST VIRGINIA,' 24 SITES U.56 Carbaryl Sevin 1.5 1,50 1.68 Atrazine AAtrex 1 4.2 1.60 1.79 Carharyl Sevin 2 8.3 3.17 3.55 Carbofuran Furadan 1.5 6,00 6.72 Daiapon 4.2 13.60 15.24 Chlordane 1.5 8.00 8.97 Naptalam Alanap 4.2 1.50 1.68 Cyanazine Biadex 1.5 1.50 1.68 Paraquat 4.2 0.50 0.56 2.4-D 4 6.1 0.69 0.78 Phorate Thimei 4.2 0.70 0.78 Diazinon 1.5 0.01 0.01 Simazine 4.2 1.60 1.79 EPTC Fensulfothion Heptachlor Eptam Di.sanit 1.5 1.5 1.5 2.011 0.75 2.00 2.24 0.84 WASHINGTON STATE. 45 SITES 2.24 1 iniirnn 1.5 1.25 1.40 Aldrin 1 f T 0,05 0.06 L.IIILII t'li MCPB -> 3.0 0.63 0.70 Benzene Phorate Thimet 5 7.6 5.32 5.96 hexachloride BHC 2 4.4 1.25 1.40 Thiram Aiasan 1 1.5 0.01 0.01 ^Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to obtain more representative data. State groups used were: Mid-Atlantic: Delaware, Maryland, and New Jersey; New England; Connecticut. Maine. Massachusetts, New Hampshire, Rhode Island, and Vermont; and Virginia and West Virginia. 204 Pesticides Monitoring Journal >25% ^^:3^ 26-59% 1 <60% ^^^ FIGURE 2. Percent of sites reporting pesticide applications, 1972 — National Soils Monitoring Program tion; and high, states where more than 60 percent of the sites reported pesticide application. BY CROP Table 4 lists crops grown on sample sites in 1972, and illustrates the diversity of crops grown in the United States. Application data for several major crops are presented in Table 5. Pesticide use varied widely among these crops. Thirty-nine different compounds were ap- plied to field corn sites but only five compounds were applied to more than 10 percent of the sites. Cotton- growing sites also received applications of 39 com- pounds, but only 1 1 compounds were applied to more than 10 percent of the sites. Table 6 shows pesticide applications on several crops by state. Differences in pesticide use among selected crops are apparent. For example, only 10.6 p>ercent of the sites growing alfalfa and/or bur clover reported any pesticide applications, but 81.5 percent of the cotton sites did. A cknowledgments It is not possible to list all the persons who contributed to this study. However, the authors are especially grate- TABLE 4. List of crops grown on 1 ,402 sampling sites, 1972 — National Soils Monitoring Program No. OF No. OF Crop Sites Crop Sites Field corn 364 Potatoes 3 Soybeans 266 Blueberries 2 Wheat 111 Apples 2 Mixed hay 105 Peaches 2 Alfalfa and/or bur clover 104 Turf 2 Pasture 66 Almonds 2 Cotton 54 Chick peas 2 Grass hay 42 Range 2 Oats 41 Sweet corn 2 Sorghum 24 Apricots 1 Barley 12 Plums 1 Oranges 9 Lespedeza sericea 1 Dry beans 9 Sweet clover 1 Silage (ccrn or sorghum) 8 Mint 1 Peas 7 Hops 1 Grapes 6 Sweet sorghum 1 Rye 6 Celery 1 Tobacco 5 Green peppers 1 Sugar beets 5 Lettuce 1 Rice 4 Pumpkins 1 Milo 4 Tomatoes 1 String beans 4 Millet 1 Pecans 3 Sunflowers 1 Flax 3 Other 9 Sugarcane 3 Fallow sites 129 Asparagus 3 Vol. 12, No. 4, March 1979 205 TABLE 5. Coin[>oiiiuls applied to cropland sites, by most common crop. 1972 — National Soils Monitoring Program Sites Reporunc Application Average Total Application Sites Reporting Application Average Total Application Compound No. % Lb/Acre Kg/Ha ALFALFA and BUR CLOVER, 104 SITES Carbaryl Carbofuran EPTC IPC Malalhion Melhoxychlor Parathion, eihyl Picloram Prolaie 2.9 1.0 1.0 1.0 1.0 I.O 1.9 1.0 1.0 2.33 0.25 2.00 3.00 1.00 2.00 0.38 0.75 0.75 COTTON. 54 SITES Aldicarb Azinphosmethyl Captan Carbaryl Chloroneb DDT DEF Dibromochloro- propane Dicroicphos Dimt.hoale DisuUoIon Diuron DNBP DSMA EMTS EPN Ethylmercury chloride Fenaminosulf Fluomeiiuon Folex Linuron MCPB Mercury Methylmercury acetate Monocrotophos MSMA Naled Nitralin Norea Paraquat Parathion. methvl PCNB Phorate Prometryn Propargile Sodium chlorate Thiram Toxaphene Trifluralin 2 1 3 1 8 16 6 5 3 20 1 2 2 1 24 1 1 4 I 2 1 21 3 3.7 1.9 5.6 1.9 14.8 29.6 11.1 1.9 3.7 1.9 13.0 16.7 7.4 14.8 5.6 1.9 1.9 1.9 40.7 9.3 5.6 3.7 13.0 9.3 5.6 37.0 1.9 3.7 3.7 1.9 44.4 1.9 1.9 7.4 1.9 3.7 1.9 38.9 55.6 0.40 0.50 0.02 1.00 0.2 7.44 0.99 0.50 0.08 2.00 0.11 0.80 1.06 2.51 0.01 3.00 0.01 0.01 0.98 l.IO 1.33 0.50 0.05 0.01 1.66 2.38 1.00 0.88 1.10 0.02 4.61 0.01 1.00 0.87 1.68 1.00 0.01 12.76 0.91 FIELD CORN. 364 SITES Alachlor Aldrin Atra/ine Butylalc Bux Captan Carbaryl Carbofuran Chlorambeii Chlordane Cyanazine 2,4-D Dalapon Diazinon Dicamba Dicofol Dieldrin Disulfoton Dyfonaie EPTC Elhoprop Fcnsulfolhion Hcplachlor Lindane 36 31 188 17 25 82 1 14 2 4 1 73 1 5 10 I 1 1 2 9.9 8.5 51. S 4.7 6.9 226 0.3 3.9 0.6 1.1 0.3 20.1 0.3 1.4 2.8 0.3 0.3 0.3 0.6 0.6 0.3 0.6 1.1 0.3 1.19 1.67 1.56 1.68 0.92 0.01 1.33 0.78 0.75 3.79 2.80 0.62 13.60 1.10 0.38 1.00 0.0 1 0.50 0.95 5.21 1.00 0.83 1.58 0.01 2.61 0.28 2.24 3.36 1.12 2.24 0.43 0.84 0.84 0.45 0.56 0.02 1.12 0.03 8.34 1.11 0.56 0.09 2.24 0.12 0.90 1.19 2.81 0.01 3.36 0.01 0.01 1.09 1.23 1.49 0.56 0.05 0.01 1.87 2.67 1.12 0.98 1.23 0.02 5.17 0.01 1.12 0.98 1.88 1.12 0.01 14.30 1.02 1.33 1.88 1.74 1.89 1.03 0.01 1.49 0.87 0.84 4.25 3.14 0.69 15.24 1.13 0.43 1.12 0.01 0.56 1.06 5.84 1.12 0.92 1.77 0.01 Compound No. % Lb/ Acre Ko/Ha Linuron 3 0.8 0.95 1.06 Malalhion 75 20.7 0.01 0.01 Melhoxychlor 8 2.2 0.01 0.01 Methylmercury acetate 1 0.3 0.01 0.01 Mirex 2 0.6 0.01 0.01 Naplalam 1 0.3 0.83 0.93 Paraquat 1 0.3 0.50 0.56 Pentachloronhcnol 1 0.3 0.05 0.06 Phorate 19 5.2 1.67 1.88 Propachlor 35 9.6 1.83 2.05 Simazine 2 0.5 2.80 3.14 TCBC 1 0.3 8.00 8.97 Thiram 4 1.1 O.OI 0.01 Toxaphene 1 0.3 0.40 0.45 Trietazine 1 0.3 0.25 0.28 MIXED HAY, 105 SITES Carbofuran I 1.0 1.00 1.12 Chlordane 1 1.0 0.75 0.84 2.4-D 2 1.9 0.42 0.47 EPTC 1 1.0 3.00 3.36 Malathion 1 1.0 0.50 0.56 Propham 1 1.0 0.50 0.56 SOYBEANS, 266 SITES Alachlor 44 Ancrack Butyrac Captan Carbaryl Chloramben 49 Chloropropham Chloroxuron :.4.D 2,4-DB DDT Dimethoaic Dinitrocresol DNBP Fluomctiiron Linuron 32 Methyl trithion Metribuzin Mirex MSMA Naplalam Nitralin Paraquat Paiathion. methvl Phorate Propachlor Simazine Thiram Toxaphene Trifluralin 59 Vernolate 3 16.5 1.5 0.4 1.9 2.6 18.4 0.4 0.4 1.5 2.3 1.1 0.4 0.4 3.4 0.4 12.0 0.4 0.4 0.4 0.4 1.9 2.3 0.8 2.3 0.4 0.8 0.4 1.1 1.9 1.1 1.54 1.08 0.40 0.01 1.83 1.38 0.59 2.00 0.96 1.00 0.66 0.66 3.00 1.54 0.50 1.11 0.25 0.50 0.01 2.00 1.30 1.36 0.38 0.71 0.70 1.90 3.00 0.08 1.00 0.87 1.65 WHEAT, 111 SITES Aldrin 1 Benzene hcxachloride 2 Bromacil Captan 2.4-D Dicamba Diuron EMTS E.hylmercury chloride Heptachlor Hexachlorobenzene Malalhion Mercury Methylmercury * dicyandiamide Parathion, methyl PCNB Phcn>lincrcury acetate Thiram Trilluralin 0.9 1.8 0.9 4.5 24.3 0.9 0.9 2.7 3.6 0.9 9.0 0.9 1.8 0.9 6.3 5.4 1.8 1.8 0.9 0.05 1.25 0.75 0.03 0.84 0.25 0.50 0.01 0.01 0.01 0 05 0.01 0.01 0.01 0.50 0.02 0.03 O.OI 0.50 1.72 1.20 0.45 0.01 2.06 1.54 0.66 2.24 1.07 1.12 0.74 0.74 3.36 1.73 0.56 1.24 0.28 0.56 0.01 2.24 1.46 1.52 0.42 0.79 0.78 2.13 3.36 0.09 1.12 0.97 1.85 0.06 1.40 0.84 0.03 0.94 0.28 0.56 0.01 0.01 0.01 0.06 0.01 0.01 0.01 0.56 0.03 0.03 O.OI 0.56 206 Pesticides Monitoring Journal TABLE 6. Pesticide applications on selected crops, by state, 1972 — National Soils Monitoring Program ALFALFA/BUR CLOVER COTTON Pesticides No Pesticides Pesticide Pestici DES N o Pesticides Pesticide State No. OF Sites Applied Applied Use Unknown No OF Sites Applied Applied Use Unknown Alabama 0 3 3 _ _ Arkansas 0 — — — 13 12 1 — California 8 2 4 2 4 2 1 1 Florida 0 — — — 0 — — — Georgia 0 — — — 2 1 — I Idaho 5 1 4 — 0 — — — Illinois 4 — 4 — 0 — — — Indiana 4 — 4 — 0 — — — Iowa 10 — 10 — 0 — — — Kentucky 1 1 — — 0 — — — Louisiana 0 — — — 6 6 — «— Michigan 5 — 5 — 0 — — — Mid-Atlantic> 0 — — — 0 — — — Mississippi 0 — — — 10 9 — 1 Missouri 2 — 2 — 6 6 — — Nebraska 10 — 9 1 0 — — — New England' 0 — — — 0 — — — New York 2 1 1 — 0 — — — N. Carolina 0 — — — 0 — _ — Ohio 4 1 3 — 0 — — — Oklahoma 3 2 1 — 7 2 5 Oregon 2 — 2 — 0 — — — Pennsylvania 3 — 3 — 0 — — — S. Carolina 0 — — — 0 — — — S. Dakota 14 1 13 — 0 — — — Tennessee 0 — — — 3 3 — — Virginia/W. Virginia' 0 — — — 0 — — — Washington state 6 1 5 — 0 — — — Wisconsin 21 i 20 — 0 — — — Total 104 li 90 3 54 44 7 3 % 100.0 10.6 86.5 2.9 100.0 81.5 l.VO 5.5 FIELD CORN SOYBEANS Alabama 7 1 6 — 2 2 — — Arkansas 0 — — — 25 16 9 — California 2 1 — 1 0 — — — Florida 1 1 — — 1 — 1 — Georgia 5 2 3 — 5 5 — — Idaho 1 1 — — 0 — — — Illinois 56 54 2 — 50 36 14 — Indiana 27 , 25 2 — 24 19 5 — Iowa 73 65 7 1 48 41 5 2 Kentucky 8 5 — 3 3 1 1 1 Louisiana 2 1 1 — 8 7 1 — Michigan 22 18 4 — 4 4 — — Mid-Atlantic' 6 4 2 — 5 5 — — Mississippi 1 1 — — 13 n 2 — Missouri 16 14 2 — 23 18 4 1 Nebraska 31 26 5 — 3 2 1 — New England' 0 — — — 0 — — — New York 13 9 4 ^ 0 — — — N. Carolina 8 4 4 — 9 4 5 — Ohio 23 19 4 __ 16 10 6 — Oklahoma 0 — . 0 — — — Oregon 2 1 — 1 0 — — — Pennsylvania 14 12 2 1 1 — — S. Carolina I 1 . 10 7 3 — S. Dakota 16 16 — — 4 3 1 — Tennessee 4 3 1 — 6 4 2 — Virginia/W. Virginia' 1 1 — _ 5 2 2 1 Washington state 0 — — — 0 — — — Wisconsin 24 17 5 2 1 1 — — Total 364 302 54 8 266 199 62 5 % 100.0 82.9 14.9 2.2 100.0 74.S 23.3 1.9 WHEAT MIXED HAY Alabama 0 1 — 1 — Arkansas 0 — — 1 — 1 — California 2 — 1 1 1 1 — — Florida 0 — — — 0 — — — Georgia 0 — — — 0 — — — Idaho 4 4 3 — 3 — Illinois 7 2 5 — 6 1 5 — Indiana 9 — 9 — 0 — — — Iowa 0 — — — 1 — I — Kentucky 0 — — — 1 — 1 (Continued next page) Vol. 12, No. 4, March 1979 207 TABLE 6 (conl'd.). PcstUiile appUcutions on .sclccU-cl crops, by \lulc, 1972 — Nulionul Soils Monitoring I'ronrum WHEAT MIXED HAY Stats No. OF Sites Pesticides Applied Louisiana 0 Michitian 0 Mid-Allanlic' 0 Mississippi 0 Missouri 5 Nebraska 14 New EnKland ' 0 New York 0 N. Carolina U Ohio 7 Oklahoma 25 Oregon 6 Pennsylvania 0 S. Carolina 0 S. Dakota 14 Tennessee 2 Virginia^W. Virginia • 0 Washington Male 0 Wisconsin 16 Total 1 1 1 % 100.0 1 16 6 IS 53 47.8 No Pesticides Applied Pesticide Use Unknown 5 12 1 55 49.5 3 2.7 No. OF Sites 0 8 0 0 11 0 2 12 0 12 0 10 8 1 7 1 8 0 12 106 lOU.O Pesiicides Applied No Pesticides Applied 5 5.0 Pesticide Use Unknown 2 12 12 7 8 1 7 1 8 12 101 fill to the inspectors from the Plant I'roteetion and Quar- antine Programs, Animal and Plant Health Inspection Service, U.S. Department of Agriculture, for collecting the data. LITERATURE CITED (/) Bennitl. I. L.. Jr. 1967. Foreword. Pestic. Monil. J. 1(1). (2) Panel on Pesticide Monitoring. 1971. Criteria for defin- ing pesticide levels to he considered an alert to potential problems. Pestic. Monit. J. .'i(l):36. (3) Carey. A. /:., J. A. Cowcn, //. lai, W . G. Mitchell, ami G. B. Wiersniu. 1978. Pesticide residue levels in soils and crops from 37 slates, 1972 — National Soils Monitor- ing Program (IV). Pestic. Monit. J. 12(4) :2()K-228. (4) Wicrsnia. C. H., I'. I\ Sand, and E. /.. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(l):63-66. 208 PisTiciDES Monitoring Journal Pesticide Residue Levels in Soils and Crops from 37 States, 1 972 — National Soils Monitoring Program (IV) Ann E. Carey,' Jeanne A. Gowen,' Han Tai,' William U. Mitchell,' and G. Bruce Wiersma ' ABSTRACT Residue data from the 1972 IFY-7J) National Soils Moni- toring; fro^ram are summarized. Composite samples of agricultural soil and mature crops were collected from 1 ,483 of the 1,533 selected 4-hectare sites in 37 states. Analyses were performed for organochlorine and orf-anophosphorus compounds, trifliiralin, and polychlorinated hiphenyls (PCBs): analysis for atrazine was performed only wlien pesticide application data indicated current-year use. Organochlorine pesticides were delected in 45 percent of the soil samples. The most frequently detected compound was dieldrin, found in 27 percent of all soil .samples. Other compounds de- tected, in order of frequency, included 1)1)1 . aldrin, chlor- dane, and heptachlor epoxide, found, respectively, in 21,9, 8, and 7 percent of all soil .samples. Crop samples were col- lected from 727 sites. All were analyzed for or/janochlo- rines; analyses were performed for orf;anophosphales and atrazine only when pesticide application data indicated current-year use. For all crops, 40 percent of the samples contained detectable levels of orf;anochlorines and 10 per- cent contained detectable levels of orfianophosphales. Atra- zine was not detected. Introdiiclion The National Pcsticitlc Monitoring Program (NPMP) was initiated at the recommendation of the President's Science Advisory Committee in 1963 to "develop a con- tinuing network to monitor residue levels in air, water, soil, man, wildlile and fish" {H). The primary objective of the NPMP is to determine levels and trends of pesti- cides and their dcgratlation products in various com- ponents of the environment (5). The National Soils Monitoring Program (NSMP) was established in 1968 as an integral part of NPMP to monitor residues in agricultural soils and raw agricultural crops. 'Ecological Moniiorinn Branch, Bcnefils and Field Studies Division, Office of Pesticide Programs, U.S. Environmental Protection Agency, TS-768, Washinglon, DC 20460. -Extension Agent, Colorado Stale Extension Service, Golden, CO. ■'Ecological Monitoring Branch, Benefits and Field Studies Division, Office of Pesticide Programs, U.S. Environmental I'roteclion Agency, Pesticides Monitoring Laboratory. Bay St. I.ouis. MS. 'Chief, I*ollutant Pathways Branch, Environmental M()nitoring and Support Laboratory, U.S. Environmental l*rotection Agency, Las Vegas, NV. The present report summarizes soil and crop pesticide concentration data collected from 1,48.? sampling sites in .37 states during 1972 (FY-73). Data were not col- lected from all conterminous states because of budgetary limitations. The states omitted from the survey were generally large, western states either having little wide- spread agriculture or growing primarily wheat and other small grains, which require fewer pesticides than do other nongrain crops, Sampliitg Procedures A total of 1,533 sites in 37 states were scheduled for sampling during late summer and fall of 1972 (Fig, 1), .Site selection criteria, statistical design, and sampling techniques involved in the present study have been described (i, 8). At each 4-hectare (lO-acre) site, a composite soil sample and a composite mature crop sample, if available, were collected accoriling to estab- lished procedures (6), In addition, information on cropping practices and a history of pesticide applications for the current cropping season were obtained in a personal interview with the landowner or operator. These data have been summarized and published sepa- rately (/). A nalytical Procedures OKCANOC HI ORINI S ANIl OKCi ANOPMOSPH AI l;S Sample Preparatiim. Soil — A lOO-g subsample was taken from a thoroughly mixed field sample. The subsample was moistened with 25 ml distilled water and extracted with 200 ml 3:1 hexaneiisopropanol solvent by shaking for 4 hours on a reciprocating shakei . The isopropanol was removed by three distilled water washes and the hexane extract was dried through anhydrous sodium sulfate. The sample extract was then stored at low temperature for subsequent gas-liquid chromatographic (GLC) analysis. Crops — For samples containing less than 2 percent tat (e.g., alfalfa, bur clover, corn stalks, cotton stalks, green bolls, miscellaneous hay), a 100-g sample of the crop was dry blended for 3 minutes and then blended for 5 Vol. 12, No. 4, MaR( ii 1979 209 Not Sampled FIGURE I. States where agricultural soils and crops were sampled. 1972 (FY 197.^) — National Soils Monitoring Program minutes in 800 ml acetonitriie. An aliquot of the sample extract, representing 10 g of the original sample, was decanted into a 500-ml Erienmeyer flask. The extract was concentrated under a three-ball Snyder column to approximately 10 ml, 100 ml hexane was added, and the hexane-acetonitrile azeotrope was again concentrated to 10 ml. The process was carried out three times to re- move essentially all acetonitriie. The hexane extract was dried through anhydrous sodium sulfate, the volume was adjusted to 50 ml, and the extract was stored at low temperature. chloride was essentially removed. Each extract volume was adjusted to 2.5 ml for separate injection on the gas-liquid chromatograph. GLC — Analyses were performed on gas chromatographs equipped with tritium foil electron-affinity detectors for organohalogens and thermionic or flame photometric detectors for organophosphates. A multiple-column sys- tem of polar and nonpolar columns was used to identify compounds. Instrument parameters and operating con- ditions follow: For crop samples containing more than 2 percent fat (e.g.. corn kernels, cottonseed, sovbeans), a 100-g sam- ple was prewashed with 100 ml isopropanol and then with 100 ml hexane. Both prewashes were discarded. The sample was extracted as described in the preceding paragraph. A separate aliquot of the extract, not sub- jected to Florisil cleanup, was reserved for flame photo- metric analysis for organophosphates. Florisil Cleanup — An extract equivalent to 5 g original crop sample was fractionated through a 15-g Florisil column into two fractions bv use of 100 ml 10 percent methvlene chloride in hexane and 100 ml methylene chloride for fractions 1 and 2, respectively. Methylene chloride was removed by concentrating each extract to low volume under a three-ball Snyder column, adding 100 ml hexane, and concentrating again to low volume. After two additions of hexane, the methylene Gas chromatographs: Hewlett-Packard Model 402A Hewlett-Packard Model 402B Tracer Model MT-::o Cohinins: glass. 6 mm OD x 4 mm ID. 183 cm long, packed with one of the following; 5 percent OV-2I0 on 811-100-mesh Chromosorb W-HP; 3 percent DC-20U on l(H)-120-mesh Gas-Chrom Q; a mixture of 1.5 percent OV-17 and 1.95 per- cent QF-1 on 100-1 20-niesh Supelcopon Temperatures. "C: thermionic detector housing 250 detector (EC and FPD) 200 injection port 250 column OV-210 166 column DC-200 170-175 mixed column 185-190 Carrier gases: 5 percent methane-argon flowing at 80 mr min- ute; prepuritied nitrogen flowing at 80 ml.'minule Sensitivity or minimum detection levels for organo- chlorines and trifluralin were 0.002-0.0.'* ppm except for combinations of polychlorinated hiphenyls (PCBs), chlordane, toxaphene, and other chemicals which had minimum detectable levels of 0.05-0.1 ppm. Minimum detectable levels for organophosphates were approxi- mately 0.01-0.0.^ ppm. Compounds detectable by this 210 PtiSTiciDES Monitoring Journal methodology are listed in Table 1 . When necessary, residues were confirmed on a Dohrmann microcoulo- metric detector or a Coulson electrolytic conductivity detector. Because trifluralin is detected by the organo- chlorine methodology, it appears with the organochlo- rine analyses in the tables. TABLE 1. Compounds detectable by chemical methodology of the present study Organochlorines Alachlor Endrin ketone Aldrin Heptachlor Benzene hexachloride Heptachlor epoxide Chlordane Hexachlorobenzene SDDT Isodrin Dieldrin Lindane (-^,-BHC) DCPA Methoxychlor Dicofol Ovex Endosulfan 1 PCBs Endosulfan II PCNs Endosulfan sulfate Propachlor Endrin Toxaphene Orcanophosphates DEF Parathion. ethyl Diazinon Parathion. methyl Ethion Ronnel Malathion Trithion Phorate Other Halogenated Hydrocarbons Trifluralin 1 'Although trifluralin is a dinitroaniline compound, it is detected by the organochlorine methodology and thus appears with organochlorines in Tables 2-7. Recovery Studies — Pesticide recovery values from soil were 80-110 percent, but usually were close to 100 percent. Values from crops ranged from 70 to 100 per- cent, depending on the amount of pesticide present, the individual pesticide, and the type of crop involved. Residue concentrations detected in both soil and crop samples were corrected for recovery. Soil samples were also converted to a dry-weight basis. ATRAZINE To analyze soil samples for atrazine, a 50-g subsample was taken from a thoroughly mi.xed field sample. The subsample was placed in the Soxhlet thimble and moist- ened with 40 ml 1:1 distilled water: methanol. After addition of 250 ml nanograde methanol, the sample was extracted for 4 hours. The extract in the Soxhlet flask was evaporated to about 50 ml on a hot plate and by use of a three-ball Snyder column. The sample extract was then decanted into a 1 -liter separatory funnel. The extract was partitioned three times with 150 ml Freon 1 13 each time. The Freon 113 fractions were combined and concentrated to incipient dryness on a rotary evaporator. The extract was dissolved in isooctane and adjusted to 5 ml for injection into a gas-liquid chromatograph. GLC — A Coulson electrolytic conductivity cell detector in the nitrogen mode was used for detection and quanti- fication of the atrazine. Positive samples were con- firmed by alkali flame detection. Recovery rate was 90-1 10 percent; minimum detection level was 0.01 ppm. Results and Discussion Tables 2-5 show concentrations of pesticides in soil samples, and Tables 6-8 show concentrations of pesti- cides in mature agricultural crops. Soil concentration data are also summarized by all sites and by state or state groups. Most tables list the number of analyses, the number of times a compound was detected, percent occurrence of the compound, the arithmetic mean, the estimated geometric mean, and the minimum and maximum positive concentrations detected. The estimated geometric mean is routinely presented in the tables as an alternative to the arithmetic mean as a measure of central tendency for the data evaluation. Pesticide residue data frequently contain a large number of zero values, resulting either from the absence of pesticides or their presence at levels below the analytical sensitivity. Such data are seldom distributed normally, as shown by tests for skewness and kurtosis, but often tend to approximate a log-normal distribution. After repeated tests for significant skewness and/or kurtosis, the log (Z-fO.Ol) transformation was used to deter- mine the logarithmic means. The antilogs of these fig- ures, minus 0.01, were taken to obtain the estimates of the geometric mean in the untransformed dimension. The estimated geometric mean was calculated only for those compounds with more than one positive detection. COMPOUND CONCENTRATIONS IN CROPLAND SOIL All Sites — Soil samples were received from 1,483 of the scheduled 1,533 sites in 37 states. Results of analyses for organochlorine and organophosphorus pesticides and atrazine are presented in Table 2. The most fre- quently detected chemical was dieldrin, found in 27 per- cent of all samples analyzed. Other compounds, in order of frequency, included 2DDT, aldrin, chlordane, and heptachlor epoxide found, respectively, in 21, 9, 8, and 7 percent of all samples analyzed. Table 3 lists the occurrence of pesticide residues in the agricultural soil samples collected during 1972. The frequency of detection varied widely among the states surveyed. The detection frequencies of atrazine appear to be much higher for individual states than in other analyses because atrazine analyses were performed only when site application records indicated its use during the current growing season. Table 4 presents the percent incidence of residues of selected pesticides at specific levels. For most of the compounds listed, the highest percentage of positive Vol. 12, No. 4, March 1979 211 TABLE 2. Compound concentrations in cropland soil for all sample sites in 37 stales, 1972 (FY 1973) — National Soils Monitoring Program Compound Positive Detections No. Residues, ppm dry weiokt % Arithmetic Mean Estimated Geometric Mean' Extremes of Detected Values MiN. Max. ORGANOCHLORINES ( 1,483 samples) Aldrin 129 Benzene hexachloride 1 Chlordane 117 DCPA 1 o.p'-DDE 10 p.p'-DDE 299 o.p'-DDT 161 p,p'-DDT 275 o.p'-TDE 1 p.p-TDE 46 SDDT 314 Dicofol 7 Dieldrin 403 Endosulfan I 1 Endosulfan II 1 Endosulfan sulfate 1 Endrin 10 Endrin ketone 2 Heptachlor 57 Hepiachlor epoxide 97 Hexachlorobenzene 11 PCB 2 PCNB 3 Propachlor 1 Ronnel 1 Toxaphene 76 Trifluralin- 81 8.7 0.1 7.9 0.1 0.7 20.2 10.9 I8.S 0.1 3.1 21.2 0.5 27.2 0.1 0.1 0.1 0.7 0.1 3.9 6.6 0.7 0.1 0.2 0.1 0.1 5.1 5.5 0.03 <0.01 0.05 <0.01 <0.01 0.05 0.03 0.13 <0.01 0.01 0.22 <0.01 0.04 <0.0I <0.0I <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0,01 <0.01 0.24 0.01 0.002 0.003 <0.001 0.006 0.003 0.007 0.001 0.010 <0.001 0.008 <0.001 <0.001 0.001 0.001 <0.001 <0.001 <0.001 0.003 0.001 0.0 1 0.02 0.01 0.18 0.01 0.01 0.01 0.01 0.31 0.01 0.01 0.06 0.01 0.08 0.25 0.31 0.01 0.02 0.01 0.01 0.01 0.80 0.22 0.10 0.19 0.22 0.01 13.28 7.89 0.09 7.16 5.62 18.93 8.20 29.45 2.15 6.18 2.13 0.38 0.60 0.72 0.44 1.49 2.61 46.58 1.86 ORGANOPHOSPHATES ( 1,246 samples) DEF 4 Diazinon 3 Malathlon 2 Paralhion, ethyl 7 Parathion, methyl 1 Phorate 13 0.3 0.2 0.2 0.6 0.1 <0.01 <0.01 <0.01 <0.01 <0.01 <0.001 <0.001 <0.001 <0.001 0.06 0.07 0.08 0.02 O.OI 0.67 0.17 0.13 0.19 Phorate 13 1.0 <0.01 <0.001 0.01 0.04 TRIAZINE (151 samples) Atrazine 134 88.7 0.10 0.051 0.01 0.77 'Not calculated when fewer than two positive detections present. 'See footnote, Table I. 212 Pesticides Monitoring Journai TABLE 3. Occurrence of pesticide residues in cropland soils from 37 states, 1972 — National Soils Monitoring Program Organochlorines^ Organophosphates ATRAZINE2 No. OF State Analyses Alabama TT Arkansas 43 California 64 Florida 17 Georgia 29 Idaho 29 Illinois 139 Indiana 78 Iowa 150 Kentuckv 28 Louisiana 27 Michigan 53 Mid-Atlantic" 14 Mississippi 30 Missouri 82 Nebraska 101 New England ' 20 New York 36 N. Carolina 31 Ohio 67 Oklahoma 64 Oregon 37 Pennsylvania 37 S. Carolina 17 S. Dakota 106 Tennessee 25 Virginia W. Virg nia '25 Washington state 45 Wisconsin 67 Positive Detections No. No. OF Analyses Positive Detections No. No. of Analyses Positive Detections No. 18 37 45 12 22 15 100 27 101 10 21 9 7 25 33 39 7 13 19 20 7 11 11 15 12 15 6 9 82 86 70 71 76 52 72 35 67 36 78 17 50 83 40 39 35 36 61 30 11 30 30 88 11 60 24 20 12 22 43 53 17 28 25 87 59 113 15 26 44 14 25 66 86 20 35 28 53 64 33 37 17 90 21 25 43 57 14 2 1 11 18 4 34 3 17 4 34 2 94 100 100 67 14 1 14 0 100 13 19 13 17 100 90 6 6 100 8 7 88 7 5 71 2 2 2 0 100 16 15 94 1 Although trifluralin is a dinitroaniline compound, it is detected bv the organochlorine methodology and thus appears with organochlorines in Tables 2-7. -Samples analyzed only when application records indicated atrazine use during the current growing season. ^Because some small eastern states had very few sites, those with similar geographic location and/or agricultural characteristics were combined to obtain more representative data. Stale groups used were Mid-Atlantic: Delaware, Maryland and New Jersey; New England: Connecticut. Maine, Massachusetts. New Hampshire. Rhode Island, and Vermont: and Virginia and West Virginia. TABLE 4. Percent incidence of selected pesticides in cropland soil from all sampling sites in 37 states, 1972 — National Soils Monitoring Program Concentration, Heptachlor PPM DRY WT i:DDT Aldrin Dieldrin Chlordane Heptachlor Epo.vide TOXAPHENE Trifluralin Not detected 78.8 91.3 72.8 92.1 96.2 93.5 94.9 94.5 0.01- 0.25 11.7 7.3 23.6 3.3 3.6 6.4 0.1 5.0 0.26- 1.00 5.3 1.0 3.2 3.2 0.2 0.1 1.1 0.4 1.01- 5.00 3.1 0.3 0.3 1.3 — — 2.6 0.1 5.01-10.00 0.7 0.1 0.1 — — 0.9 — >10.00 0.4 0.1 — — — — 0.4 — TOTAL 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Vol. 12, No. 4, March 1979 213 TABLE 5. Compound concentrations in cropland soils, l>y state, 1972 — National Soils Monitoring Program Positive Detections Compound No. % Arithmetic Mean Concentration Residues, ppm dry weight Estimated Geometric Mean ^ Extremes of Detected Values MiN. Max. ALABAMA Organochlorines,= 22 samples Chlordane 1 P.p'-DDE 14 o.p-DDT 8 p.p'-DDT 15 XDUT 15 Dieldrin 2 Endrin 1 Ronnel 1 Toxaphene 7 Trifluralin 4 Organophosphates, 22 samples Phorate 1 4.6 63.6 36.4 68.2 68.2 9.1 4.6 4.6 31.8 18.2 4.6 0.01 0.08 0.03 0.16 0.27 <0.01 <0.01 <0.01 0.67 0.02 <0.01 0.028 0.009 0.042 0.062 0.001 0.038 0.006 0.16 0.01 0.01 0.01 0.01 0.01 0.10 0.19 0.22 0.07 0.04 0.58 0.19 1.24 1.97 0.01 5.94 0.17 ARKANSAS Organochlorines." 43 samples Chlordane 2 o.p'-DDE 1 p.p'-DDE 25 o.p'-DDT 22 p,p'-DDT 27 p.p'-TDE 5 2DDT 27 Dieldrin 10 Endrin 2 Toxaphene 1 1 Trifluralin 17 4.6 2.3 S8.1 51.2 62.8 11.6 62.8 23.3 4.6 25.6 39.5 <0.01 <0.01 0.16 0.13 0.54 0.02 0.85 0.02 0.01 1.01 0.04 0.001 0.036 0.027 0.083 0.002 0.114 0.005 0.001 0.033 0.015 0.03 0.03 0.01 0.01 0.01 0.01 0.03 0.01 0.02 0.48 0.01 0.08 1.87 0.92 4.49 0.45 7.35 0.24 0.24 9.11 0.31 Organophosphates, 43 samples; no residues detected CALIFORNIA Organochlorines," 64 samples Chlordane 2 o.p'-DDE 3 p.p'-DDE 44 o,p-DDT 23 P.p'-DDT 32 P.p'-TDE 7 2DDT 45 Dicofol 4 Dieldrin 7 Hexachlorobenzene 1 PCBs 1 Toxaphene 9 Trifluralin 1 Organophosphates 53 samples DEF 1 Malathion 1 Parathion, ethyl 4 3.1 4.7 68.7 35.9 50.0 10.9 70.3 6.3 10.9 1.6 1.6 14.1 1.6 1.9 1.9 7.6 0.02 <0.01 0.16 0.06 0.26 0.01 0.49 0.05 0.01 0.01 0.02 0.25 <0.01 <0.01 <0.01 0.01 0.001 0.001 0.042 0.011 0.033 0.002 0.074 0.003 0.002 0.010 0.002 0.02 0.01 0.01 0.01 0.02 0.01 0.01 0.38 0.01 0.44 1.49 0.46 0.05 0.10 0.13 0.02 1.02 0.03 2.72 1.38 5.62 0.27 9.72 2.15 0.36 6.45 0.19 FLORIDA Organochlorines, 17 samples Aldrin I Chlordane 4 p.p'-DDE 10 o.p'-DDT 2 P.p'-DDT 10 P.p'-TDE 1 2DDT 11 Dicofol 3 Dieldrin 3 Heptachlor epoxide 1 Toxaphene 3 5.9 23.5 58.8 11.8 58.8 5.9 64.7 17.6 17.6 5.9 17.6 loxapnene .* 17. t Organophosphates. 17 samples: no residues detected Triazines, 1 sample: no residues detected 0.01 0.03 0.08 0.03 0.21 0.04 0.37 0.03 0.08 <0.01 0.83 0.007 0.017 0.004 0.022 0.035 0.006 0.009 0.019 0.16 0.02 0.01 0.02 0.01 0.74 0.01 0.06 0.15 0.01 2.04 0.22 0.66 0.56 2.16 3.38 0.23 1.09 9.00 GEORGIA Organochlorines,' 29 samples Benzene hexachloridc I Chlordane 1 o.p'-DDE 1 p.p'-DDE 20 3.4 3.4 3.4 69.0 <0.01 <0.01 <0.01 0.11 0.031 0.02 0.01 0.01 0.01 1.30 (Continued next paf>e) 214 Pi sTiciDEs Monitoring Journal TABLE 5 (Cont'd.). Compound concentrations in cropUmd soils, by state, 1972 — National Soils Monitoring Program Residues, ppm dry weight Compound No o,p'-DDT 6 p.p'-DDT 20 P.p'-TDE 2 2 DDT 22 Dieldrin 4 Endrin 1 Toxaphene 8 Trifluralin 2 Positive Detections % Arithmetic Mean Concentration Estimated Geometric Mean' extkemes of Detected Values MiN. Max. Organophosphates, 28 samples Phorate 4 20.7 69.0 6.9 75.9 13.8 3.4 27.6 6.9 14.3 0.08 0.33 0.01 0.52 <0.0I <0.0I 2.22 <0.01 <0.01 0.008 0.043 0.002 0.072 0.001 0.036 0.001 0.002 0.04 0.01 0.03 0.01 0.01 0.01 0.65 0.01 0.02 1.71 6.11 0.15 9.12 0.02 46.58 0.09 0.04 IDAHO Organochlorines, 29 samples Chiordane 1 p.p'DDE 11 o,p -DDT 4 p.p'-DDT 10 P.p'-TDE 2 2 DDT 12 Dieldrin 11 Heptachlor epo xide 1 Hcxachlorobenzene 1 3.4 37.9 13.8 34.5 6.9 41.4 37.9 3.4 3.4 Organophosphates, 25 samples: no residues detected 0.01 0.02 0.01 0.05 Not calculated when fewer than two positive detections present. 2 See footnote 1, Table 1. ='See footnote 3, Table 3. TABLE 6. Occurrence of pesticide concentrations in standing agricultural crops from 1 ,483 sampling sites. 1972 — National Soils Monitoring Program Orcanochlorines Organophosphates Triazines No. OF Positive Detections No. OF Positive Detections" No. OF Positive Detections Crop Materials Analyses No. % Analyses No. % Analyses No. % Alfalfa/bur clover 43 25 58 39 3 7 Asparagus 1 1 100 1 0 Beans, dry 3 1 33 3 0 Clover {Trifolium) 8 5 63 8 0 Corn, sweet (kernel s) 2 0 2 0 . . Corn, field (kernels ) 288 31 U 167 0 . 12 0 — Corn stalks 283 132 47 247 6 -> 16 0 — Cotton stalks 40 39 98 40 32 80 Cotton 2 0 2 0 Cotton seed 38 31 82 32 13 41 Grass hay 21 14 67 21 6 29 Leipedeza 1 1 100 1 1 100 Mixed hay 47 31 66 43 3 7 Oat hay 1 0 — ■ 1 0 Pasture forage 10 5 50 9 1 11 Peanut vines 2 2 100 2 0 .^^ Soybean hay 1 1 100 _ Sugar beet lops 1 0 _ Silage (corn or sorghum) 3 1 33 2 1 50 Milo 3 1 33 2 0 Peanuts 9 6 67 0 Peas 1 0 0 __^ Pecans 1 0 0 Rye 1 1 100 0 Sorghum (grain) 14 5 36 11 2 18 Sorghum (stalks) 18 8 44 15 3 20 Soybean.^ 199 73 37 66 0 . . ^ Sugarcane 2 0 2 0 ^ Sweet sorghum 2 2 100 __ Tobacco 2 2 100 2 1 50 — 220 Pesticides Monitoring Journal TABLE 7. Occurrence of organochlorine concenlrations in selected, maiiire crops, from 1,483 sites by state or stale group, 1972 — National Soils Monitoring Program Field Corn, Kernels Soybeans Mixed Hay State No. OF Analyses Positive Detections No. No. of Analyses Positive Detections No. Positive Detections No. OF Analyses No. % Alabama Arkansas California Florida Georgia Idaho Illinois Indiana Iowa Kentucky Louisiana Michigan Mid-AtlanliQi Mississippi Missouri Nebraska New England^ New York N. Carolina Ohio Oklahoma Oregon Pennsylvania S. Carolina S. Dakota Tennessee 2 Virginia/W. Virginia^ 1 Washington state — Wisconsin 13 41 24 71 6 1 21 3 10 27 11 6 18 1 10 11 2 17 1 5 33 7 73 17 90 100 4 19 1 5 28 14 41 3 7 4 3 15 15 3 4 10 0 2 16 6 17 0 3 0 0 1 6 0 100 53 40 57 43 41 7 40 10 10 100 100 100 100 100 14 1 1 100 1 I 100 g 1 13 1 1 100 1 1 64 1 I 100 1 I 100 1 1 100 4 I 50 1 1 100 3 1 33 J See footnote 3; Table 3. Vol. 12, No. 4, March 1979 221 TABLE 8. Compound concentrations in standing agricultural crops, 1972 — National Soils Monitoring Program Positive Detections Compound No. Arithmetic Mean Concentration Residues, ppm dry weight Estimated Geometric Meani Extremes of Detected Values MiN. Max. ALFALFA/BUR CLOVER Organochlorines, 43 samples Chlordane 7 p.p'-DDE 12 o.p'-DDT 12 p.p'-DDT 15 i:DDT 15 Dieldrin 16 Hepiachlor epoxide I Toxaphene 2 Organophosphates. 39 samples DEF 1 Diazinon I Malathion 3 Organochlorines, I sample p.p'-DDE o.p'-DDT p.p'-DDT 3: DDT 16.3 0.02 27.9 0.01 27.9 0.01 34.9 0.02 34.9 0.04 37.2 0.01 2.3 <0.01 4.6 0.01 2.6 <0.01 2.6 <0.01 7.7 0.01 ASPARAGUS 100.0 0.11 lOO.O 0.03 100.0 0.33 100.0 0.47 o.oos 0.003 0.004 0.009 0.012 0.007 0.002 0.002 0.04 0.01 0.01 0.02 0.03 0.01 0.01 0.17 0.02 0.01 0.03 0.11 0.03 0.33 0.47 0.24 0.05 0.09 0.23 0.28 0.09 0.19 0.26 Organophosphales, I sample: no residues delected BEANS, DRY (all varieties) Organochlorines, 3 samples Dicofol 1 Organophosphates, 3 samples: 33.3 no residues detected 0.05 0.15 CLOVER (Trifolium sp.) Organochlorines, 8 samples Chlordane p,p'-DDE o.p'-DDT p.p'-DDT ZDDT Dieldrin 25.0 37.5 50.0 50.0 50.0 Dieldrin 5 62.5 Organophosphates. 8 samples: no residues detected 0.02 0.02 0.03 0.05 0.10 0.03 0.008 0.009 0.014 0.022 0.031 0.018 0.07 0.01 0.01 0.03 0.04 0.02 0.10 0.08 0.07 0.14 0.29 0.11 CORN, SWEET (kernels) Organochlorines, 2 samples: no residues detected Organophosphates, 2 samples: no residues detected CORN STALKS Organochlorines, 283 samples Alachlor 1 0.3 Chlordane 17 6.0 P.p'-DDE 28 9.9 o.p'-DDT 37 13.1 p.p'-DDT 62 21.9 P.p'-TDE 2 0.7 SDDT 62 21.9 Dieldrin 99 35.0 Endrin 3 l.I Hepiachlor 1 0.3 Hcptachlor epoxide 14 5.0 Hexachlorobenzene 1 0.3 Toxaphene 9 3.2 Organophosphates, 247 samples Diazinon 2 0.8 Malathion 3 1.2 Phorate 4 1.6 Triazines, 16 samples; no residues detected Organochlorines, 288 samples Chlordane ■» o.p'-DDT P.P'-DDT vDDT Dieldrin 0.7 0.3 0.7 0.7 2.8 <0.01 0.01 <0.01 <0.01 0.02 <0.01 0.03 0.01 <0.01 <0.01 <0.01 <0.01 0.04 <0.01 <0.01 <0.01 FIELD CORN (kernels) 0.002 O.OOl 0.002 0.004 <0.00l 0.005 0.005 <0.001 <0.001 0.002 <0.00l <0.00l <0.00I <0.01 <0.0I <0.01 <0.01 <0.01 <0.00l <0.00l <0.001 0.001 0.09 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.19 0.04 0.06 0.01 0.01 0.03 0.03 0.03 0.0 1 0.41 0.16 0.25 2.33 0.01 2.74 0.29 0.04 0.06 4.14 0.10 0.25 0.02 0.15 0.07 0.10 0.21 (Continued next page) 222 Pesticides Monitoring Journal TABLE 8 (Cont'd.). Compound concentrations in standing agricultural crops, 1972 — National Soils Monitoring Program Residues, ppm dry weight Extremes of Positive Detections Arithmetic Mean Estimated CiEOMElRir Detected Values Compound No. % Concentration Mean! Min. Max. Endrin 2 0.7 <0.01 <0.001 0.01 0.02 Heptachlor 1 0.3 <0.01 0.02 Heptachlor epoxide 23 8.0 <0.01 0.001 0.01 0.02 PCNB 1 0.3 <0.01 — 0.01 Organophosphates. 167 samples no residues detected Triazines, 12 samples: no residues detected COTTON STALKS Organochlorines,- 40 samples Chlordane 6 15.0 0.05 0.006 0.15 1.00 o,p'-DDE 1 2.5 <0.0I — 0.13 P.p'-DDE 29 72.5 0.67 0.089 0.01 8.89 o.p-DDT 28 70.0 0.79 0.116 0.01 13.40 p,p'-DDT 38 95.0 7.36 0.739 0.02 102.00 p.p-TDE 12 30.0 0.04 0.010 0.01 0.41 ;:DDT 38 95.0 8.87 0.913 0.02 115.79 Dieldrin 14 35.0 0.02 0.008 0.01 0.19 Endosulfan sulfate 1 2.5 0.07 — 2.70 Endrin 2 5.0 0.01 0.002 0.15 0.15 Heptachlor epoxide 3 7.5 <0.01 0.001 0.01 0.02 Toxaphene 28 70.0 25.44 1.078 0.66 462.30 Trifluralin 1 2.5 <0.01 — 0.02 Organophosphates, 40 samples Carbophcnothion 1 2.5 <0.01 — 0.08 DEE 25 62.5 1.20 0.069 0.01 24.19 Diazinon 1 2.5 <0.01 — 0.02 Malathion 4 10.0 0.03 0.003 0.01 0.94 Parathion. ethyl 5 12.5 0.01 0.003 0.01 0.12 Parathion. methyl 16 40.0 0.15 0.026 0.02 1.39 Phorate 1 2.5 <0.01 — 0.01 COTTON SEED Organochlorines. 38 samples P,p-DDE 16 42.1 0.01 0.008 0.01 0.12 o,p'-DDT 15 39.5 0.03 0.012 0.02 0.19 p,p'-DDT 31 81.6 0.22 0.082 0.01 1.40 P.p'-TDE 2 5.3 <0.01 0.001 0.04 0.14 ZDDT 31 81.6 0.27 0,091 0.01 1.79 Dieldrin 2 5.3 <0.01 0.001 0.01 0.03 Toxaphene 20 52.6 0.49 0.082 0.20 3.71 Organophosphates, 32 samples DEE 13 40.6 0.09 0.016 0.02 0.71 Parathion, methyl 2 6.3 <0.01 0.001 0.04 0.05 COTTON Organochlorines, 2 samples: no residues detected Organophosphates, 2 samples: no residues detected SILAGE Organochlorines, 3 samples Chlordane 1 33.3 0.05 — 0.16 p.p-DDT 1 33.3 <0.01 — 0.01 VDDT 1 33.3 <0.01 — 0.01 Organophosphates, 2 samples Diazinon 1 50.0 0.05 — O.Il Malathion 1 50.0 1.32 — 2.64 GRASS HAY Organochlorines, 21 samples Chlordane 2 9.5 0.01 0.003 0.09 0.09 o,p-DDT 12 57.1 0.02 0.014 0.01 0.08 p,p'-DDT 13 61.9 0.07 0.033 0.01 0.23 p.p-DDE 9 42.9 0.02 0.009 0.01 0.08 2DDT 13 61.9 0.11 0.044 0.01 0.30 Dieldrin 7 33.3 0.01 0.006 0.01 O.U Toxaphene 6 28.6 0.15 0.020 0.30 1.19 Organophosphates, 21 samples DEE 1 4.8 0.0 1 — 0.12 Diazinon 6 28.6 0.04 0.011 0.02 0.34 Malathion 5 23.8 0.03 0.007 0.02 0.22 (Continued next page) Vol. 12, No. 4, March 1979 223 TABLE 8 (Cont'd.). Compound concenlration.s in stanclinf; iif>riciillurtil crops, 1972 — National Soils Monitoring Program • Positive Detections Compound No. Residues, ppm dry weight Arithmetic Mean Concentration Estimated Geometric Meani Extremes of Detected Values MiN. Max. LESPEDEZA SERICEA Organochlorines, I sample p,p'-DDT 1 i:DDT I Dieldrin 1 Endrin 1 Toxaphene 1 Organophosphales, 1 sample DEF 1 lOO.O 100.0 100.0 100.0 100.0 100.0 O.IS 0.15 0.03 0.02 0.48 0.15 0.15 0.15 0.03 0.02 0.48 0.15 MILO Organochlorines, 3 samples p.p'-DDT I P,p-DDE 1 2 DDT 1 Toxaphene Organophosphates. 2 samples: no residues detected 33.3 33.3 33.3 33.3 0.02 <0.01 0.02 0.04 PASTURE FORAGE 0.06 0.01 0.07 0.13 Organochlorines. 10 samples Chlordane 1 o,p'-DDT 3 p.p'-DDT 4 p.p'-DDE 3 I DDT 4 Dieldrin 4 Toxaphene 2 Organophosphates, 9 samples Diazinon 1 10.0 30.0 40.0 30.0 40.0 40.0 20.0 11.1 0.05 0.01 0.08 0.01 0.10 0.01 0.15 <0.01 0.006 0.021 0.004 0.026 0.007 0.014 0.48 0.02 0.08 0.01 0.17 0.01 0.59 0.01 0.07 0.40 0.03 0.40 0.04 0.86 MIXED HAY Organochlorines. 47 samples Chlordane 10 o.p'-DDE 1 p.p-DDE 21 o.p'-DDT 23 p.p'-DDT 26 p.p'-TDE I 2 DDT 26 Dieldrin 22 Endrin 2 Heptachlor epoxide 1 Organophosphates, 43 samples Diazinon 2 Malathion 3 Parathion, methyl 1 Phorate 1 21.3 2.1 44.7 48.9 55.3 2.1 55.3 46.8 4.3 2.1 4.6 7.0 2.3 2.3 0.03 <0.01 0.02 0.02 0.04 <0.01 0.08 0.02 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.008 0.008 0.009 0.019 0.027 0.012 <0.001 <0.001 0.001 0.05 0.04 0.01 0.01 0.01 0.02 0.02 0.01 0.01 0.05 0.01 0.02 0.01 0.02 0.44 0.13 0.12 0.44 0.69 0.11 0.01 0.02 0.09 PEANUTS Organochlorines, 9 samples p.p'-DDE 2 2 DDT 2 Toxaphene 6 Organophosphates, 3 samples: 22.2 22.2 66.7 no residues detected <0.01 <0.01 0.25 0.003 0.003 0.100 0.02 0.02 0.17 0.02 0.02 0.65 PEANUT VINES Organochlorines, 2 samples p.p'-DDT 1 2 DDT 1 Dieldrin 2 Toxaphene 1 Organophosphates, 2 samples: 50.0 SO.O 100.0 50.0 no residues detected 0.42 0.42 0.21 106.82 0.102 0.85 0.85 0.02 213.65 0.41 PEAS (all varieties) Organochlorines, I sample: no residues detected Organophosphates, I sample: no residues delected PECANS Organochlorines. I sample: no residues detected Organophosphates, I sample: no residues detected (Continued next page) 224 Pesticides Monitoring Journal TABLE 8 (Cont'd.). Compound concenlnilions in standing agrkultiinil crops, 1972 — National Soils Monitoring Program Residues, ppm dry weight Positive Detections Compound No. Arithmetic Mean Concentration Estimated Geometric Mean ^ RYE Organochlorines, 1 sample Chlordane 1 lOO.O Dieldrin 1 100.0 Organophosphates, 1 sample; no residues detected 0.08 0.02 Extremes of Detected Values MiN. 0.08 0.02 Max. SORGHUM (grain) Organochlorines, 14 samples o,p'-DDT 1 p.p'-DDT 5 p,p'-DDE 2 2DDT 5 Dieldrin 2 Organophosphates, 11 samples Malalhion 2 Parathion, ethyl 1 Parathion, methyl 1 Phorate 1 7.1 35.7 14.3 35.7 14.3 18.2 9.1 9.1 9.1 <0.01 0.01 <0.01 0.01 <0.01 0.03 <0.01 <0.01 <0.01 0.006 0.001 0.006 0.001 0.006 0.02 0.01 0.01 0.01 0.01 0.04 0.03 0.01 0.01 0.07 0.02 0.10 0.01 0.29 SORGHUM STALKS Organochlorines, 18 samples Chlordane 1 o.p'-DDT 5 p.p'-DDT 8 p.p'-DDE 6 p.p'-TDE 1 2 DDT 8 Dieldrin 5 Toxaphene 1 Organophosphates, 15 samples Malathion 3 Parathion, ethyl 1 5.6 27.8 44.4 33.3 5.6 44.4 27.8 5.6 20.0 6.7 0.01 0.01 0.02 0.01 <0.01 0.04 0.01 0.01 0.02 <0.01 0.004 0.012 0.004 0.017 0.004 0.006 0.15 0.01 0.03 0.01 0.07 0.04 0.01 0.25 0.06 0.02 0.03 0.11 0.04 0.20 0.05 0.13 SUGAR BEET TOPS Organochlorines, 1 sample: no residues detected SOYBEANS Organochlorines, 199 samples Chlordane 1 0.5 o.p'-DDT 1 0.5 p.p-DDT 12 6.0 p.p'-TDE 1 0.5 2DDT 13 6.5 Dieldrin 47 23.6 Endrin 16 8.0 Heptachlor 1 0.5 Heptachlor epoxide 8 4.0 Toxaphene 12 6.0 Organophosphates. 66 sa mples no residues detected ■'.■;'.'< ^^•'- '■•., 'I--; ■.'.•."■.'.■.• 'i\: ■''■ii'.~ '■■':'-'' \:r:'K- :'■■•: - V 1 ■ '•'• FIGURE 5. Percent occurrence of ZDDT residue detections in cropland soil of 37 stales, by state, 1972 — National Soils Monitoring Program 228 Pesticides Monitoring Journal 1/2 X < C FIGURE 6. Percent occurrence of chlordane residue detections in cropland soil of 37 states, by state, 1972 — National Soils Monitoring Program Acknowledgments It is not possible to list by name all persons who con- tributed to this study. The authors are especially grate- ful to the staff of the Pesticides Monitoring Laboratory, Bay St. Louis, Mississippi, who received, processed, and analyzed samples for compojnd residues, and to the inspectors of the Animal and Plant Health Inspection Service, U.S. Department of Agriculture, who collected the samples. LITERATURE CITED (/) Carey. A. E., and J. A. Gowen. 1978. Pesticide appli- cation and cropping data from 37 states, 1972 — Na- tional Soils Monitoring Program. Pestic. Monit. J. 12(3):137-I48. (2) Carey, A. E., J. A. Gowen, H. Tai, W. G. Mitchell, and G. B. Wiersma. 1978. Pesticide residue levels in soils and crops, 1971 — National Soils Monitoring Program (III). Pestic. Monit. J. 12(3) : 1 17-136. (3) Carey. A. £., G. B. Wiersma. H. Tai. and W. G. Mit- chell. 1973. Organochlorine pesticide residues in soils and crops of the corn belt region, United States — 1970. Pestic. Monit. J. 6(4) :369-376. (4) Crockett. A. B.. G. B. Wiersma, H. Tai, W. G. Mit- chell, P. F. Sand, and A. E. Carey. 1974. Pesticide residue levels in soils and crops, FY-70 — National Soils Monitoring Program (II). Pestic. Monit. J. 8(2):69-97. (5) Panel on Pesticide Monitoring. 1971. Criteria for de- fining pesticide levels to be considered an alert to poten- tial problems. Pestic. Monit. J. 5(1):36. (6) U.S. Environmental Protection Agency. 1973. PM Memorandum No, 3. Sample Collection Manual. Guide- lines for collecting field samples: soil, crops, water, sediment. 71 pp. (7) Wiersma. G. B., H. Tai. and P. F. Sand. 1972. Pesti- cide residue levels in soils, FY-69 — National Soils Monitoring Program. Pestic. Monit. J. 6(3) : 194-228. (8) Wiersma, G. B.. P. F. Sand, and E. L. Cox. 1971. A sampling design to determine pesticide residue levels in soils of the conterminous United States. Pestic. Monit. J. 5(l):63-66. Vol. 12, No. 4, March 1979 229 Organochlorine Pesticide Residues in Soils from Six U.S. Air Force Bases, 1975-76 Jerry T. Lang,' Leopoldo L. Rodriguez,- and James M. Livingston " ABSTRACT Soil samples coUcctcd during 1975 and 1976 from United States Air Force installations in California, Georgia, Ohio, Oklahoma, Texas, and Utah were analyzed for organochlo- rine pesticide residues. :s.DDT, chlordane, and dieldrin were the pesticides most commonly found. In 1975, ZDDT resi- dues were significantly higher in samples from residential areas than in samples from golf courses or areas free of pesticide application. Chlordane residues in 1975 were sig- nificantly liighcr in both residential and golf course areas than in areas where pesticides had not been used. No sig- nificant differences were found in 1976 in residue levels of any pesticide monitored among various land use areas. cm) with a j-inch (7. 6-cm) -diameter bulb planter. Twenty core samples from each site were composited in a plastic bucket, thoroughly mixed by hand, and poured back and forth into a similar bucket. The composite sample was sieved through 'i-inch (6.4-mm) hardware cloth to remove large particles and debris. A subsample of the composite sample was placed in a clean hexane- rinsed 8-oz (240-ml) amber glass salve jar. Salve jars were capped with aluminum foil-lined lids and sub- samples were kept frozen until being prepared for analy- sis. All sampling equipment was thoroughly rinsed with water after each stratum was sampled to avoid cross contamination. Introduction In 1975, the United States Air Force Occupational and Environmental Health Laboratory at Kelly Air Force Base, Texas, initiated a two-year pilot pesticides monitor- ing program to gather preliminary data on organochlo- rine residues in soils and sediments from Air Force bases and to determine the feasibility of developing a full-scale Air Force pesticides monitoring program. Only the base- line data on soil samples are discussed here. The feasi- bility study and the baseline data for sediment samples have been discussed elsewhere by Lang (4). Sample Collection and Preparation Six Air Force Logistics Command bases were sampled, including Hill AFB, Utah; Kelly AFB, Texas: McClellan AFB, California: Robins AFB, Georgia: Tinker AFB, Oklahoma; and Wright-Patterson AFB, Ohio. All bases represent urban environments with substantial indus- trialization and histories of considerable pesticide use. Soil samples were collected from residential, open or nonuse, and golf course areas. Core samples from each use stratification were taken from the top 3 inches (7.6 ' Present address: Chief. EntDmology Services. OL-AD. U.S. Air Force Occupatii>naI and Fnvironmenlal Health Laboratory. APO San Fran- cisco. CA 96274. 7he opinions and assertions contained herein arc those of the authors and are not to be construed as the views of the Departtrent of the Air Force. ^U.S. Air Force Occupational and Environmental Health Faboratory, Brooks Air Force Base, TX 782.15. At each residential sampling site, 10 individual core samples were taken from both sides of randomly selected streets. At those sites with sidewalks, all samples were taken within 1 ft (30.5 cm) of the sidewalk in the direction of the house. At sites without sidewalks, sam- ples were taken approximately 4 ft (1.37 m) from the street. At each open sampling site, 10 core samples were collected at 45-ft (13.7-m) intervals along two parallel straight lines 45 ft (13.7 m) apart which originated at a randomly selected point. Golf course samples were col- lected from random starting points at 45-ft (13.7-m) intervals along both sides of the fairway at the edge of the rough. A Italy tical Procedures I'RFPARATION OF SAMPLES Two grams of dry-sieved subsample (sieve size No. 14) were placed in a 15-ml test tube with a Teflon-lined screw cap, and 10 ml 3: 1 hexane-isopropanol was added. Tubes were rotated for 4 hours, and the subsample was centrifuged. The solution was transferred to a 60-ml separatory funnel and washed three times with water to remove the alcohol. The solution was dried with anhydrous sodium sulfate, the solvent was reduced by evaporation, and the sample was cleaned by passage through a Florisil microcolumn. Subsample extracts were stored at low temperature for subsequent gas-chromat- ographic (GC) analysis. 230 Pesticides Monitoring Journal GAS CHROMATOGRAPHY The analytical procedures were basically the same as those described by Wiersma et al. (6). Samples were analyzed for organochlorines and PCBs with a Tracor Model 222 gas chromatograph equipped with two Ni-63 electron-capture detectors (EC) and four glass columns. Two sets of polar and nonpolar columns were used to identify and confirm the organochlorine pesticides and PCBs. The gas chromatograph was equipped with a Model 8000 Varian Auto Sampler and interfaced with a Model 3354 Hewlett-Packard Data System. Instrument parameters and operating conditions follow: Columns: glass. 6 ft long. 6 mm OD X 4 mm ID, packed with (1)3 mixture of 1.5 percent SP-2250 and 1.95 percent SP-2401 on 100-120-mesh Supelcon. AW, DMCS (2) a mixture of 4 percent SE-30 and 6 percent SP-2401 on 100-1 20-me5h Supelcon, AW, DMCS Temperatures, °C: detector 300 injection port 225 column 200 Carrier gas: 5-10 percent methane-argon flowing at 60 ml/minute Compounds and their quantitative detectable levels are listed in Table 1. Minimum detectable levels of organo- chlorine pesticides were 0.01-2.00 mg/kg. RECOVERY STUDIES Recovery of the components listed in Table 1 ranged from 91 to 102 percent. Data presented in Tables 2 and 3 were not corrected for recovery. Results and Discussion Because a similar data pattern emerged on each base, data for a given year on the same pesticide on the same land use area were combined from all six bases (Table 2). i;DDT residues were the most ubiquitous organochlorines on the six bases (Table 2). 2DDT resi- dues were also quantitatively higher overall than were residues of any other organochlorine except chlordane, which in 1975 had arithmetic mean levels consistently TABLE 1. Qitanlitative detection limits of organochlorines found in soils of six U.S. Air Force bases, 1975-76 Compound Residue, ppm 2 DDT Aldrin Heptachlor Lindane Toxaphene Chlordane Dieldrin Endrin Heptachlor epoxide Methoxychor PCBs 0.05 0.01 0.01 0.01 2.00 0.20 0.02 0.02 0.01 0.04 0.40 O HI 03 < I I I I I I I o o o o o -n O O »r, Q l-H hh: o q q Q O "X z o C3 q O O wi Z ^ ^ ^ o o r- P 9 P O O iri — o o^ d z r-i^° in M-1 >/"i r- o ^ Q Z f^ o o I CO Q z as o I I I I I I I I I I o o o O d r-^ z I I I I I I O O m S d ■rt z o q q d d r-^ dv- z — q o d o ■* I rt Q z f, q Tj- d d r-^ Q Z 'J QO ^ -^ q m O ^ Q ^O ON r- o O -: d -^ o o = Q Z 0S<^ rr, rt 9^ ^ d trt Q Z mom Q Z C O OS (^ <:i >n I I I I I I I I I I OOP-; d d r-' z O O 00 (6 o ^ z o 9 '0 d o f-^ I r4 Q Z m — O ^ w^ d w m Q Z Q O OO a z O "-^ *>D ^ S (£ I t- H (A u as s Vol. 12, No. 4, March 1979 231 TABLE 3. Geometric means and 9!! percent confidence intervals for pooled -DDT. chlordanc from use-stratified areas on six U.S. Air Force bases — 1975-76 and dicldrin residue data 2 DDT Chlordane DiELDRIN AKEA 95^0 CI Lower Mean 95% CI Upper 95% CI Lower Mean 95% CI Upper 95% CI Lower Mean 95% CI Upper 1975 Residues, ppm Residential Open Golf course 0.0791 0.0124 0.0347 0.2276'" 0.0235"" 0.0599"'> 0.6549 0.0443 0.1033 0.0440 0.1875"" 0.0091 0.0158"" 0.0338 0.1049"" 0.7153 0.0275 0.3253 0.0100 0.0089 0.0091 0.0246"" 0.0119"" 0.0122"" 0.0606 0.0159 0.0163 1976 Residues, ppm Residential Open Golf course 0.0257 0.0134 0.0110 0.0782'"> 0.0361'"' 0.0437'-) 0.2382 0.0960 0.1729 0.0033 0.0150'«> 0.0100 0.0182i«> 0.0084 0.0320"» 0.0694 0.0329 0.1218 0.0094 0.0099 0.0089 0.0117"" 0.0129"" 0.0110"" 0.0145 0.0157 0.0136 NOTE: For a given year, means in a vertical column followed by the same letter are not significantly different at the 5 percent level. higher than -DDT. The high arithmetic mean for chlor- dane residues in residential areas during 1975 was mainly attributable to the high levels found at Wright- Patterson AFB. This finding is notable in light of past problems with chlordane contamination in Capehart housing units on Wright-Patterson (7, 2). Except for chlordane levels found in residential soils in 1975, the arithmetic means shown in Table 2 closely appro.vimate mean levels of the same pesticides in various nonmilitary urban areas of the United States (i). data. Therefore, standard t-tests were used to compare mean differences in -DDT data, and t'-tests (5) were used on the chlordane data. In 1975, -DDT residues were significantly higher in resi- dential areas than in open and golf course areas. Chlor- dane levels were significantly higher in both residential and golf course areas than in open areas. There was no significant difference in chlordane levels between resi- dential and golf course areas. Since residue data are not normally distributed, the arithmetic means in Table 2 are useful for comparison only in a relative sense. Therefore, the more statistically useful geometric means and associated 95 percent con- fidence limits based on data normalized with the In {X 4- 0.01) transformation discussed by Carey et al. (i) are given in Table 3 for the three most ubiquitous pesticides: -DDT, chlordane, and dieldrin. To obtain an overall picture of the data, a three-factor analysis of variance was used to evaluate pesticide by land use by year interactions. The only significant inter- action was for land use areas between the two years. Further examination showed that only the residential area means for 1975 and 1976 differed significantly {P < 0.001). There was no significant difference for the open area means (P < 0.10) and only an indication of a difference for the golf course means (P < 0.10). One-way analyses of variance were used to evaluate data on a particular pesticide during a given year. Significant F values were found only for -DDT and chlordane in 1975. Bartlett's test (5) was used to check homogeneity of variances in the two cases. Variances were homo- geneous for the -DDT data but not for the chlordane Large differences between 1975 and 1976 2DDT and chlordane data (Table 3) are puzzling. From what is known generally of organochlorine degradation rates, microbial or other forms of degradation could not ac- count for the decreases in 2DDT and chlordane levels between 1975 and 1976. The most likely explanation for the rather drastic reduction in -DDT residues in resi- dential areas and chlordane residues in residential and golf course areas between 1975 and 1976 is the irregular distribution of pesticide residues in the environment and the relatively small number of samples collected from each land use area. Conclusions Organochlorine residues on the six Air Force installa- tions generally were the same generic type and quantity as those found in nonmilitary urban environments. -DDT residues were the most abundant followed by chlordane and dieldrin. Residential areas generally were contaminated more heavily with organochlorincs than were open or nonuse and golf course areas. Large variations between 1975 and 1976 data on some pesti- cides indicate that, if the Air Force program is contin- ued, more samples should be taken from each sampling site and increased emphasis should be placed on sampling protocol to ensure the gathering of comparative data. 232 Pesticides Monitoring Journal LITERATURE CITED (/) Air Force Logistics Command Headquarters. 1975. Summary and comparison of two-hour baseline chlor- dane air sampling results from Air Force military family housing (AF MFH). Office of the Surgeon, Wright-Patterson Air Force Base, Ohio, 62 pp. (2) Air Force Logistics Command Headquarters. 1976. Report on four chlordane sampling protocols conducted in military family housing at Wright-Patterson AFB, Ohio. Office of the Surgeon, Wright-Patterson Air Force Base, Ohio, 136 pp. (.?) Carey, A. E.. G. B. IViersma, and H. Tai. 1976. Pesti- cide residues in urban soils from 14 United States cities, 1970. Pestic. Monit. J. 10(2) :54-6(). (4) Lang. J. T. 1978. USAF Occupational and Environ- mental Health Laboratory, Tech. Repl. 78-33, Evalua- tion of the USAF pesticides monitoring pilot program, 1975-1976. (5) Snedecor, G. W.. and W. G. Cochran. 1967. Statistical Methods (6th ed.). Iowa State University Press, Ames, Iowa. 593 pp. (6) Wiersma. G. B., H. Tai. and P. F. Saiul. 1972. Pesticide residue levels in soils, FY 1969 — National Soils Mon- itoring Program. Pestic. Monit. J. 6(3) : 194-201. Vol. 12, No. 4, March 1979 233 APPENDIX' Chemical Names of Compounds Discussed in This Issue ACEPHATE ALDRIN CHLORDANE DDE DDT DELNAV DIAZINON DIELDRIN DURSBAN ENDRIN ETHION HCB HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE MALATHION METHAMIDOPHOS MIREX NONACHLOR OXYCHLORDANE PCBs {Polychlorinaicd Biphenyls) TDE TOXAPHENE TRITHION O, ^-Dimethyl acetylphosphoramidolhioaie Not less than 95% of l,2.3.4.10.IO-hexachloro-I,4,4a,5.8,8a-hexahydro-l.4:5,8-dimcihanonaph- ihalene 1.2,3.4,5.6,7,8.8-Ociachloro-2,3,3a,4,7.7a-hexahydro-4.7-meihanoindene. The technical product is a mixture of several cotiipounds including heptachlor, chlordene, and two isomeric forms of chlordane. Dichlorophenyl dichloro-ethyletic (degradation product of DDT); />,//-DDE: I .l-Dichloro- 2.2-bis{/J-chloIophe^yl) ethylene; *>.//-DDE: 1 .1 -Dich!oro-2-(o-chlorophenyl)-2-(/;-chIorophenyl) ethylene Main component {p,p'-DDT) : n-Bist/j-chlorophenyl ) /i,/?./i.-trichloroethane. Other isomers are possible and some are present in the commercial product. ri.p'-DDT: [l.l,l-Trichloro-2- (o-chlorophenyl)-2-(p-chlorophenyl) ethane] 2,3-p-DiozanedithioI 5..y-bis (0,0-diethyl phosphorodiihioate) O.O-Diethyl 0-{2-isopropyl-6-melhyl-4-pyrimidinyI } phosphorothioate Not less than 85% of 1.2, .1.4,10. 10-Hexachloro-6,7-epoxy-l.4,4a. 5,6, 7:8.8a-octahydro-l,4- e«rfo-e>:o-5,8-dimethanonaphthalene 0,0-Dielhyl 0-( 3,5,6-trichloro-2-pyridyl ) Hexachloroepoxyoctahydro-f«(io.i'/if/o-dimethano-naphthalene O,O,0'.O'-Telraethyl 5,5'-methylene bisphosphorodithioate Hexachlorobenzene 1.4,5.6,7,8,8-Heptachloro-.1a,4.7,7a-tetrahydro-4.7-ra