GOVDOC 7-f BOSTON PUBLIC LIBRARY GOVfiRMMENT DOCUMENTS UEPARTMEMT RECEIVED ] FEB 1 6 2000 I The Pesticides Monitoring Journal is published quarterly under the auspices of the FEDERAL WORKING GROUP ON PEST MANAGEMENT (responsible to the Council on Environ- mental Quality) and its MONITORING PANEL as a source of information on pesticide levels relative to man and his environment. The WORKING GROUP is comprised of representatives of the U.S. Departments of Agricul- ture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; Transportation; and Labor; and the U.S. Environmental Protection Agency. The pesticide MONITORING PANEL consists of representatives of the Agricultural Research Service, Animal and Plant Health Inspection Service, Extension Service, Forest Service, Depart- ment of Defense, Fish and Wildlife Service. Geological Survey, Food and Drug Administration, Environmental Protection Agency, National Marine Fisheries Service, National Science Founda- tion, and Tennessee Valley Authority. Publication of the Pesticides Monitoring Journal is carried out by the Technical Services Divi- sion, Office of Pesticides Programs of the Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies repre- sented on the pesticide MONITORING PANEL which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and interpretive articles. However, pertinent data in summarized form, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institu- tions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Manuscripts received for publication are reviewed by an Editorial Advisory Board established by the MONITORING PANEL. Authors are given the benefit of review comments prior to publication. Editorial Advisory Board members are; John R. Wessel, Food and Drug Administration, Chairman Paul F. Sand, Agricultural Research Service, Vice Chairman Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Thomas W. Duke, 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 Mention of trade names or commercial sources in the Pesticides Monitoring Journal is for identification only and does not represent endorsement by any Federal agency. Address correspondence to: Paul Fuschini Editorial Manager PESTICIDES MONITORING JOURNAL U.S. Environmental Protection Agency Room B49 East, Waterside Mall 401 M Street, S.W. Washington, D. C. 20460 Martha Finan Joanne Sanders Editors CONTENTS Volume 9 June 1975 Number 1 BRIEF Page DDT residues in stailiiiQs, 1974^ Paul R. Nickerson and Kyle R. Barhehenn RESIDUES IN FISH. Wll DLIFE. AND ESTUARIES Chlorinaleil pcsticitles ami polychlorimited hipfienyls in marine species, Orcfion, Washinnlon coast — 1972 Robert R. Claeys, Richard S. Caldwell, Norman H. Cutshall, and Robert Helton Residues oj ornanochlorine pesticides and polychlorinaled hiphenyls and autopsy data for bald eagles. 1971-72 Eugene Cromartie. William L. Reichel. Louis N. Locke, Andre A. Belisle, T. Harl Kaiser. Thair G. Lamont. Bernard M. Mulhern. Richard M. Proiity. and Douglas M. Swineford Mercury concentralicms in fish, Morth Atlantic offsliore waters — 197 1 ^ R. A. Greig, D. Wenzloflf, and C. Shelpuk Baseline cnncenlrations of polychlorinaled hiphenyls and DDT in Lake Michi-^an fish. 1971 Oilman D. Veith II 15 21 GENERAL Distribution of nr'janochlorine pesticides in an agricultural environment, Holland Marsh. (>iit,irio~l97n-72 John R. Brown. Lai Ying Chow, and Fong Ching Chai Cliloriiialed livdrocarhon pesticides and mercury in coastal biota, Puerto Rico and the U.S. I'lrgin Islands — 1972-74 Robert J. Reimold Total mercury in » ater. scdimenl. and selecleil aquatic organisms, Carson River. ,\'e\iula — 1972 Robert T. Richins and Arthur C. Risser, Jr. ERRATA APPENDIX Chemical names of compounds discussed in this issue. In/onnntion for eontrihntors 30 Organochlorine pesticide residues in a farming urea, i\ova Scotia — 1972-73 34 B. G. Burns. M. F. Peach, and D. A. Stiles 39 44 55 56 57 BRIEF DDT Residues in Starlings, 1974 Paul R. Nickerson ' and Kyle R. Barbehenn 2 ABSTRACT In the preceding issue of this journal, the authors suggested that the mean level of DDT plus metabolites in starlings should drop below 0.1 ppm for the 1974 collection. They based their prediction on an analysis of the relationship be- tween mean levels of DDT and its metabolites in starlings and estimates of domestic disappearance of DDT. The pres- ent brief summarizes initial findings from the 1974 starting collection. Authors indicate that their earlier estimates for disappearance of total DDT were optimistic: the geometric mean for 1974 was 0.282, a 36 percent reduction from the 1972 mean of 0.442. Introduction Based upon an analysis of the relationship between mean levels of DDT and its metabolites in starlings and estimates of domestic disappearance of DDT, authors suggested in the preceding issue of this periodical that 'Division of Technical Assistance, Fish and Wildlife Service, U.S. Department of the Interior, Washington, D.C. 20240. 2 Criteria and Evaluation Division, Office of Pesticide Programs, U.S. Environmental Protection Agency, Washington, D.C. Vol. 9, No. 1, June 1975 the residue levels of these organochlorines in starlings should drop below a mean of 0.1 ppm for the 1974 collection (/). Analytical Results Residue analysis results from the 1974 collection are now in hand and it is apparent that the extrapolation from a small data base was overly optimistic. The geo- metric mean of DDT plus metabolites is 0.282 ppm for 1974. Of the 122 sites sampled. 17 of the values exceeded 1.0 ppm and 2 (3G3 in Arkansas and 4C1 in Arizona; see Tables 1,3) reached a level of 9.2 ppm. Although the reduction of 0.160 ppm (36 percent) from the mean level of 1972 (0.442 ppm) is substantial it is clear that DDT remains by far the most abundant source of pesti- cide residues found in starlings two full growing sea- sons after the major uses of DDT were cancelled. LITERATURE CITED (7) Nickerson, Paul R., and Kyle R. Barbehenn. 1975. Organochlorine residues in starlings, 1972. Pestic. Monit. J. 8(4):247-254. 1 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Chlorinated Pesticides and Polychorinated Biphenyls in Marine Species, Oregon/ Washington Coast, 1972 ^ Robert R. Claeys,= Richard S. Caldwell,' Norman H. Cutshall,* and Robert Holton' ABSTRACT Concentrations of chlorinated pesticides and polychlorinated biphenyls (PCB's) Here determined in three offshore marine species from the Oregon/Washington coast: pink shrimp, euphausiids, and flatfish: five species of bivalve mollusks from five estuaries along the Oregon coast: several fish species from the Coos Bay and Columbia River estuaries: and a summer run of steelhead from the Rogue River. The compounds p,p'-DDE and PCB's were detected most frequently. Euphausiids and pink shrimp contained approxi- mately 2 ppb (pg/kg) wet-weight DDE and 8 and 25 ppb PCB's, respectively. Offshore flatfish contained an average of 9 ppb DDE and 29 ppb PCB's. DDE residues in estuarine mollusks approximated 0.5 ppb. PCB levels were not de- tectable f<5 ppb) except in collections from the mouth of the Columbia River where levels averaged 400 ppb PCB's and 17 ppb DDT. Selected Columbia River fish species con- tained 38 ppb DDE and 480 ppb PCB's: summer-run steel- head in the Rogue River contained 97 ppb DDE and 125 ppb PCB's. PCB chromatograms of most euphausiids closely resembled those of Aroclor 1254. Chromatograms of shrimp and fiat- fish indicated selective metabolism of two compounds in the Aroclor 1254 formulation. Biphenyls of higher chlorine content were also detected in the shrimp and flatfish. Introduction A global program to determine baseline levels of metals, hydrocarbons, and chlorinated hydrocarbons was initi- ^ Research conducted under National Science Foundation International Decade of Ocean Exploration Grant 6X28744, National Marine Fisheries Contract N-042-14-72(N), and U.S. DHEW Public Health Service Grant ES00040. 2 Environmental Health Sciences Center, Oregon State University, Corvallis. Oreg. 97331. 3 Marine Sciences Center, Oregon State University, Newport, Oreg. * Department of Oceanography, Oregon Slate University, Corvallis, Oreg. ated in 1971 by the International Decade for Ocean Exploration (IDOE) Program of the National Science Foundation. Baseline data for chlorinated hydrocarbons in the North Pacific Ocean are reported here. In addi- ction, baseline levels in mollusks were determined in sev- eral Oregon estuaries as part of the National Estuarine Monitoring Program. Several species of fish were col- lected from two of these estuaries along with some sum- mer-run steelhead (Salmo gairdnerii), a type of rainbow trout, from the Rogue River. Chlorinated hydrocarbon levels obtained under the IDOE Program from the Atlantic Ocean (/) and the Gulf of Mexico (2) surveys have already been published. Sampling and Analytical Procedures Pink shrimp {Pandalus jordani), euphausiids (Euphausia pacifica), and several species of flatfish were collected at ocean stations from Newport, Oreg., to the Straits of Juan de Fuca during September and October 1971 (Fig. 1). An otter trawl and an Isaacs-Kidd midwater trawl were used in these collections. Estuarine bivalves were collected quarterly from De- cember 1971 through October 1972 in five Oregon estuaries: Columbia River, Tillamook Bay, Yaquina Bay, Umpqua River estuary, and Coos Bay (Fig. 1). Species collected were the cockle clam (Clinocardium nuitallii). Eastern softshell clam (Mya arenaria), bay mussel (Mytilus edulis), Asiatic clam (Corbicula flu- minea), and a species of Anodonta. The latter two species inhabit only fresh water and were the most abundant mollusks in the Columbia River; estuarine clams were not readily available. In addition, several sp;cies of estuarine fish were collected in the Coos Bay and Columbia River estuaries during January 1973 and Pesticides Monitoring Journal August 1972, respectively; summer-run steelhead were obtained from the Rogue River in September 1970. Ex- cept for the steelhead, samples were frozen in glass jars washed with acetone. Special care was taken to avoid contamination because of the possible presence of poly- chlorinated biphenyls (PCB's) aboard ship. I I ANADfl Vs A " Nouhcal M>les FIGURE I. Stations on Oregon/ Washington coast sampled for residues in marine species Analytical procedures were similar to those of Porter et al. (3) except for hexane-acetonitrile partitioning; for that, analysts followed the method of Giuffrida et al. (4). Briefly, the shrimp, euphausiids, and small fish were ground whole in a meat grinder and a subsample not exceeding 3 g lipid or 100 g tissue was taken for analy- sis. Steelhead were analyzed individually by taking a cross section posterior to the anal opening. Mollusks were prepared and extracted as described by Butler (5). They were ground with a desiccant mixture of 10 per- cent QUSO (precipitated silica) and 90 percent an- hydrous sodium sulfate. The sample and desiccant were mixed at an exact ratio of 1:3 by weight before taking a 120-g subsample. Fish and shrimp were extracted in a blendor with 2:1 hexane: acetone (v/v) and mollusks were extracted by Soxhiet with 1:1 hexane: acetone. A 25- 50-g sample was extracted, the solvent evaporated, and the residue weighed for an approximate lipid con- tent. Approximately 90 percent of the lipid was separated from the organochlorines by chromatographic column elution (4). The extract was evaporated under a stream of air and the lipid residue was mixed with florisil and loaded on a dry-packed florisil column. Pesticides were then cluted with 9:1 acetonitrile:water and partitioned into hexane after aqueous dilution. Additional cleanup was obtained on a second florisil column. PCB's, DDT, BHC, chlordane, mirex, and toxaphene compounds were eluted from the second column with 5 percent benzene in hexane (v/v). Dieldrin, endrin, heptachlor epoxide, and methoxychlor were eluted with hexane containing 10 percent ethyl ether and 0.25 percent acetone (v/v). Major PCB isomers were separated from pesticides by a modification of the procedure of Armour and Burke (6) by substituting a 1 percent water deactivated silicic acid column. The 4-10 chloro PCB compounds were eluted with hexane and the 1-3 chloro PCB"s and pesti- cide compounds were eluted with 5 percent aqueous methanol. Pesticides were partitioned into hexane after aqueous dilution of the methanol. Compounds were normally separated and quantitated by gas-liquid chromatography on 122-cm-by-3-mm-ID py- rex columns filled with a 2:1 mixture of 7 percent QF-1 and 7 percent DC-1 I liquid phases on high-performance chromosorb W, 1 00/ 1 20 mesh, or with 7 percent DC- 1 1 . Columns were operated at 195° C with 20 ml/min N^ flow. The flow rate employed was 1.5 times the optimum rate for maximum PCB resolution. Both electron-cap- ture and microcoulometric-halide detectors were em- ployed. Sensitivity of the microcoulometric detector was 1-3 ng dieldrin or DDE. Base hydrolysis was used to confirm the presence of DDD and DDT in selected samples by conversion to DDE and DDMU. respectively (7). PCB's remain stable although the a and -, BHC isomers are destroyed during this procedure. A 1:1 fuming HNO,: concentrated sul- furic acid nitration test (8) was used to confirm the presence of chlordane and toxaphene; these are the only compounds which are not nitrated. Special precautions were employed to improve analysis of low pesticide concentrations. Glassware was baked at 250°-300° C in a large oven (9) and other items such as glass wool, sodium sulfate, and florisil were baked at 450° C in a muffle furnace to reduce blank levels. In addition, blanks were analyzed before any samples were begun. For PCB quantitation peak heights of the sample and standard were added. When peaks were missing, a zero was inckided in the summation. For two different rea- sons PCB values may be low: no attempt was made to Vol. 9, No. 1, June 1975 identity 8-10 chloro biphenyls; and 1-3 chloro hiphcnyls elutc with the pesticide fraction from the silicic acid column. Selected samples were spiked with known standards prior to extraction at a concentration of 10 higher than that previously analyzed. Mean recoveries were 75 per- cent for DDE. 63 percent for DDT. 83 percent for dieldrin. and 100 percent for Aroclor 1260 when silicic acid column separation of PCB's was employed (10). Recoveries from the silicic acid column were only 85 percent for DDE and DDT, thus accounting for low DDT recovery. Mean recovery of DDE for mollusks was 92 percent without silicic acid column separation. Values reported here are uncorrected for recovery or blank levels, except for mollusks, in which case blank levels were subtracted. Results Levels of chlorinated hydrocarbons in offshore species, cstuarine fish, and Rogue River steelhead are given in Tables 1 and 2; offshore results are summarized in Table 3. Most of these data were presented in 1972 at a work- shop of the International Decade of Ocean Exploration (10). TABLE 1. Clilorinutcd hydrocarbon cuncenlralions in marine species, Washington/Oregon — 1972 CONCENIRATION, ^G/KG WET WEIGHT /../'-DDE /),/'-TDE p.p'-DDT Total DDT PCB'S Ettphausia pucifica Pandalus jordani Flatfish (genus and species unknown l Blanks Samples analyzed .Samples with residues Mean Range .Samples analyzed Samples wilh residues Mean Range Samples analyzed Samples with residues Mean Range Samples analyzed Samples with residues Mean Range 14 14 s S 0,2-5.8 13 13 1,9 0,9-3.7 13 13 8 5 3,4-18 II 11 0,06 0.02-0 13 14 5 0.2 0-0.6 13 8 0 3 0,2-1.0 13 12 1,0 0,7-1.7 11 5 0,03 041.12 14 5 0,6 11-4.0 13 8 0.5 0.2-3.0 13 12 1.0 0,6-2.0 11 4 0.03 0-0.10 14 14 3.0 0.2-5.9 13 13 2.7 1.1-5,0 13 13 10.5 4-19.7 9 7 0.12 0-0.25 11 11 7.5 1-22 13 13 25 11-69 10 10 29 16-121 9 7 <2 0^ TABLE 2. Chlorinated hydrocarbons in selected marine species collected off Oregon/Washington coast, September 1971 Sampling Stauon Location : Latitude, Longitude Concentration, /iG/kg wet weight P./J'-DDE p.p'-TDE P.P'-DDT Total DDT AROCLOll 1254 Arcklok 1260 (Continued next page) 4 Euphausia pacifica 44° 39' 124° 31' 1.0 0,6 0.9 3 5 44° 43' 124' 41' 5.8 6 5 44° 39- 124° 52' 4.5 6 44 ■ 41' 125° 09' 1.1 8 3 44' .39' 125° 14' 3.3 3 g 44° 43' 126° 29' 2,6 22 8 44° 43' 126 29' 0.8 8 9 44° 43' 127=35' 1.0 25 5 10 45° 10' 125° 39' 1.1 4 11 45° 46' 125° 49' 2,3 0,1 0.5 13 12 45° 56' 127° 40' 3.3 (1,4 ' 0,5 1 1 5 46° 21' 124° 27' IS - 4 4 46° 31' 124° 30- 0,2 - 0.2 NA Pesticides Monitoring Journal TABLE 2 (cont'd.). Chlorinated hydrocarbons in selected marine species collected off Oregon/Washington coast, September 1971 Pandaliis iuniuni Sand Shrimp Sergestid Shrimp Sampling Station Location : Latitvtoe, Longitude Concentration, ^o/ko wet weight P,P'-DDE P,p-TDE p,p-DDT Total DDT Dieldrin Aroclok 1254 Aroclor 1260 4 3 46° 41' 124° 46' 47° ir 124° 48' 2.1 = 1.3 ' 0.6 = 0,6 1 3 = 4 1 7 6 5 = 4 1 NA NA 7 44° 39- 124° 35' 2.4 0.7 0.3 9 10 7 44° 43' 124° 41- 3.7 0.2 0.3 11 6 45° 55' 124° 14' 1.1 12 6 45° 55' 124° 28' 1.2 36 8 6 45° 56- 124° 41' 2.0 9 5 46° 21' 124° 27' 0.9 0.5 0.3 35 10 4 46° 37' 124° 26' 2.5 0.3 0.2 33 4 46° 39' 124° 39' 1.4 14 4 46° 41' 124° 37' [.8 0,4 0.6 16 3 47° 06' 124° 41' 1.9 1.0 19 50 3 47° 06' 124° 47' 1.0 0.5 0.2 15 3 47° 11' 124° 48' 2.0 = 3 = 44 2 47° 39' 125° 05' 3.0 0.3 ■ 1.1 • 4 20 6 45° 55' 124° 14' <1.3 1 ND 2 47° 39' 124° 36' <0,3 7 2 47° 40' 124° 54' 1.1 0,3 0,3 2 28 1 48° 06' 124° 51' 6 44° 43' 124° 41' Galathea Shrimp 46° 41' 124° 37' Flatfish 6 45° 54' 124° 02' 6,4 0,7 1,1 8 ND 12 6 45° 55' 124° 14' 10.4 1,0 1,1 13 52 6 45° 56' 124° 12' 10 = <3 = <5 = 18 NA 6 45° 55' 124° 28' 12,6 0,9 0,8 14 24 6 45° 56' 124° 41' 12,7 1,7' 1,8' 25 28 4 46° 37- 124° 14' 11,0 1,8 ' 2,0' 15 85 36 4 46° 37' 124° 26' 3.4 1,0 1,2 6 25 2 47° 28' 124° 41' 6,7 1,0 1.5 9 28 2 47° 39' 124° 36' 5,0 0,9 6 24 (Continued next page) Vol. 9, No. 1, June 1975 TABLE 2 (cont'd.). Chlorinated hydrocarbons in selected marine species collected off Oregon /Washington coast, September 1971 Sampling Station Location : Latitude, Longitude CONCENTllATION, fiO/KG WET WEIGHT p,p'-DDE P,P'-TDE P,P'-DDT Total DDT DiELDRIN Aroclob 1254 Aroclor 1260 2 2 2 2 2 2 1 47° 39- 124° 36' 47° 40' 124° 54' 47° 41' 124° 46' 47° 39' 125° 05' 47° 39' 125° 05' 47° 39' 125° 05' 48° 06' 124° 51' 5.7 1 0.0 5.7 17.4 16,6 20.0 4.3 NA 0.6 0.9 0.8 0.8 NA 0.8 NA 0.7 0.7 0.9 0.9 NA 0.9 6 17 7 19 18 20 6 12 18 16 30 18 21 16 Salpa 44° 43' 127° 35' 20 Clttpea harengtts pallasii 46° 37' 124° 14' 19 4.0 1.6 Small Fish 48° 12' 124° 56' 2 1.2 NOTE: NA = not analyzed. ND = no data because of interference with analytical process. Blank spaces imply residues below detectable levels. Representative Euphansia pacifica sample contained 1.8 percent lipid; Pandalus jordani, 2.0 percent; sand shrimp, 2.4 percent. ' Alcoholic base hydrolysis. 2 Microcoulometric detector confirmation. TABLE 3. Chlorinated hydrocarbons in esluarine fish and Rogue River steelhead, 1970-73 Species Concentration, yiiG/KO wet weight p.p'-DDE I p.p'-TDE I p.p'-DDT Total DDT DiELDRIN Aroclor 1254 Aroclor 1260 Coos Bay Estuary, January 1973, Station 18 Striped Seaperch (Embiotoca lateralis) Sand Sole (Pseltichlhys melanostictus) Staghorn Sculpin iLeptocoitus armatits) Starry Flounder (Platichtbys stellalits) Blank Percent recovery of sample spiked at 17 ppb 6 0.02 87 5 7 3 6 0.02 NA 23" 26 > 14 > 27 1 Columbia River Estuary, August 1972, Station 13 = Starry Flounder (Plalichlhys stellaliis) 18 8 8 34 310 Tom Cod (Microgadtis proximus) 90 Peamouth Chub iMvlochilus causinitsi 81 62 143 1160 Finescale Sucker {Caiosiomus svncheilus) 14 28 11 ,5 3 350 Blank <1 <1 0.4' NS 7/11 0.2 0.3 NS NS 10/2 1.2 NS NS NS Mytilus ediilis 1/26 0,7 NS NS NS 5/19 1.0 NS NS NS 7/12 0.8 0.3 NS NS 10/2 1.8 NS NS NS Yaquina Mya arenaria 1/24 0.2 NS NS NS 4/15 0.5 NS NS NS 7/8 0.2 NS NS NS 9/25 0.6 NS NS 5 Clinocardtittn nntiiillti M NS NS NS NS 4/15 0.2 11.5 NS NS 7/8 0.2 NS NS NS 9/25 0.3 NS NS 7 Blanks =■' Winter 0.2 0.3 0.5 19 Spring 0.2 0.2 0.4 9 Summer 0.1 0.2 0.4 5 Fall 0,2 0.2 0.4 1 NOTE: Values have been correcled for sea water blanks. ND = no data because of interference with analytical process. NS = residues not significant (less than twice the blank values). ' Confirmed by base hydrolysis. -Values assume 30-g sample weight. ■' Average of two blanks. Pesticidls Monitoring Journal lower than those determined for blank samples. Like Coibiciila, Anodonta displayed the highest PCB level in the spring. During the fall sampling period, low levels (5-7 ppb) of PCB's were detected in the two bivalve species from Yaquina Bay, and 26 ppb PCB's were found in the Coos Bay Mya population. Discussion Relative concentrations of DDT and PCB compounds differed in the three offshore species. Residues of 5DDT were 3 ppb in both euphausiids and pink shrimp, but PCB levels differed between the two species by a factor of three: 7.5 versus 25 ppb, respectively (Table 3). Levels of DDT in flatfish were three times higher than in euphausiids and pink shrimp, but PCB levels were similar to those in the pink shrimp. Considering that all three species have nearly the same lipid content, ap- proximately 2 percent, other factors probably account for these differences. Both euphausiids and pink shrimp feed on zooplankton and smaller animals. Euphausiids are found in the water column, however, and pink shrimp are found near the ocean floor. Another possible explanation for the difference between these levels is that the two species were collected from different geo- graphic locations. Most euphausiids were collected west of Newport (station 7); pink shrimp were collected farther north at stations 2 and 5. DDT levels reported by Giam et al. (2) for the Gulf of Mexico are considerably higher. DDT levels for Gulf shrimp (family Panaeidae) ranged from 33 to 165 ppb; PCB chromatograms lacked sufficient resemblance to an Aroclor formulation for quantitation. DDT levels in Gulf fish were also much higher than those from the study reported here, but PCB levels were comparable. Atlantic Ocean levels (7) are similar to those reported from the present study of the Northeast Pacific. Ice- landic shrimp (Pandaliis borealis) contained 1 and 18 ppb DDT and PCB compounds, respectively. In 1968 Stout (72) reported pesticide residues in fish and shellfish in the Northeast Pacific. Residues in hake collected along the Oregon/ Washington coast ranged from 115 to 285 ppb total DDT; DDE represented only 26-36 percent of the total DDT residue. Some PCB interference may have accounted for higher DDD and DDT residues. In the authors' 1972 collections, DDE often represented the major portion of the total DDT residue; Columbia River collections, which showed signs of recent DDT contamination, were the excep- tion. Little is known about biological effects of PCB's on the marine environment. Duke et al. {13) exposed shrimp (Penaeus duorarum) to 5 ppb Aroclor 1254 in sea water for 20 days. Shrimp that died after 10 days had only 1,600 ppb PCB's; those living after 20 days had 3,300 ppb PCB's. Thus mortality probably was not caused by PCB poisoning. If 1 ,600 ppb is taken as a toxic residue level for shrimp, then pink shrimp (Panda- lus jordani) in the Northeast Pacific contain only 1/60 the toxic residue level. Similar studies for DDE were not located. DDE and PCB levels in the Coos Bay fish were slightly less than those found in the offshore flatfish collections (5 vs. 9 ppb DDE and 22 vs. 29 ppb PCB's, respec- tively). Traces of chlordane and thiodan found in the steelhead may have originated from agricultural use in Medford, Oreg., a fruit-growing area. Only minor quantities of these chemicals are presently being applied in this area. Dieldrin found in those collections may have originated in the Rogue River, although dieldrin was also found in a few offshore collections. PCB chromatograms of shrimp samples indicate selected metabolism of some isomers. All shrimp species had very low peaks for isomers 21 and 23 although euphau- siids contained the expected ratio of isomers. The lower quantities of isomers 21 and 23 in flatfish may be a result of their feeding on pink shrimp. The larger fish, herring, salpa, and steelhead, had chromatograms close- ly resembling Aroclor 1254. PCB chromatograms of common murres collected in this area were very similar to the shrimp chromatogram {11). It is significant that three of the four fish collected in the Coos Bay estuary had PCB patterns closely resembling Aroclor 1254. The pattern of the fourth, a starry flounder, resembled Aro- clor 1260. Except for the Columbia River collections, organo- chlorine residues reported here for Oregon estuarine mollusks are consistently lower than those reported for mollusks from many other coastal States. Coos Bay mollusks had higher 2DDT residues than had mollusks from the small coastal drainage estuaries, but even these did not exceed 5 ppb. In contrast, a very high percentage of mollusks sampled in other States con- tained between 11 and 100 ppb 2DDT; significant num- bers contained even more than 100 ppb (5). Residues found in Columbia River Corbicula (53-78 ppb) more closely paralleled those reported in other States, but Anodonta collected in the same area con- tained less than 15 ppb 2DDT. In general, a higher level of DDT tissue residues would be anticipated in Columbia River mollusks considering the enormous area of agricultural land drained by this river system. However, high levels of 2DDT found in Corbicula may also be a result of the extraordinary ability of this species to accumulate organochlorine compounds. Like DDT, PCB's accumulated far more heavily in Corbicula than in the other mollusks examined. The higher levels of PCB's in the Columbia River fish sug- gest that PCB contamination of the Columbia River greatly exceeded that of adjacent coastal waters. Vol. 9, No. 1, June 1975 A cknowledgment Authors gratefully acknowledge the National Science Foundation IDOE Program for financial support of the offshore investigation and the National Marine Fisheries Service for financial support of the moUusk study. LITERATURE CITED (/) Harvey, George R., and H. P. Miklas. 1972. Baseline studies of pollutants in the marine environment. Inter- national decade of oceanography workshop, Brook- haven National Laboratory, May 24-26 1972 Pp 469-492. (2) Gium, C. S., A. R. Hanks, R. C. Richardson, W. M. Sackett, and M. K. Wong. 1972. DDT, DDE, and polychlorinated biphenyls in biota from the Gulf of Mexico and Caribbean Sea — 1971. Pestic Monit J 6(3):139-143. {3) Porter, Mildred L., S. J. V. Young, and J. A. Burke. 1970. A method for the analysis of fish, animal, and poultry tissue for chlorinated polychaete pesticide resi- dues. J. Ass. Oflic. Anal. Chem. 53(6) : 1300-1303. {4) Giuffrida, Laura, D. C. BoslMkk, and N. F. Ivcs. 1966. Rapid cleanup techniques for chlorinated pesti- cide residues in milk, fats, and oils. J. Ass. Ofhc. Anal Chem. 49(3):634-638. (5) Butler, Philip A. 1973. Organochlorine residues in estuarine mollusks. 1965-72. National Pesticide Moni- toring Program. Pestic. Mont. J. 6(4) :238-362. (6) Armour, Judith A., and J. A. Burke. 197(1. Method for separating polychlorinated biphenyls from DDT and its analogs. I. Ass. OfRc. Anal. Chem. 53(4): 761-768. (7) Klein. A. K.. and J. O. Watts. 1964. Separation and measurement of perthane, DDD (TDE) and DDT in leafy vegetables by electron capture gas chromatog- raphy. J. Ass. Offic. Anal. Chem. 47(2) :311-316. (iS) Kuwano, Y. A., A. Bcvenue, H. Beckman, and F. Erro. 1969. Studies on the effect of sulf uric-fuming nitric acid treatment on the analytical characteristics of toxaphene. J. Ass. Offic. Anal. Chem. 52(1):167- 172. (9) Lamherton, J. G., and R. R. Claeys. 1972. A large inexpensive oven to decontaminate glassware for en- vironmental pesticide analysis. J. Ass. Offic. Anal. Chem. 55(4):898-899. (10) Claeys, R. R. 1972. Baseline studies of pollutants in the marine environment. International decade of oceanography workshop, Brookhaven National Lab- oratory, May 24-26, 1972. Pp. 499-514. (//) Scott. J. M., ]. A. Wiens, and R. R. Claeys. Organo- chlorine levels associated with a common murre die- off in Oregon. I. Wildl. Mgmt. (In press). {12) Stout, Virginia F. 1968. Pesticide levels in fish of the Northeast Pacific. Bull. Environ. Contam. Toxicol. 3(4):240-246. (13) Duke, T. W., J. I. Lone, and A. J. Wilson, Jr. 1970. A polychlorinated biphenyl (Aroclor 1254) in the water, sediment, and biota of Escambia Bay, Florida. Bull. Environ. Contam. Toxicol. 5(2) : 171-180. 10 Pesticides Monitoring Journal Residues of Organochlorine Pesticides and Polvchlorinated Biphenyls and Autopsy Data for Bald Eagles,' 1971-72' Eugene Cromartie, William L. Reichel, Louis N. Locke, Andre A. Belisle, T. Earl Kaiser, Thair G. Lamont, Bernard M. Mulhern, Richard M. Prouty, and Douglas M. Swineford ABSTRACT Thirty-seven bald eagles found sick or dead in 18 Stales during 1971-72 were analyzed for organochlorine pesticides and polychlorinated biphenyls (PCB's). DDE and PCB's were detected in all bald eagle carcasses; 30 carcasses con- tained DDD and 28 contained dieldrin. Four eagles con- tained possibly lethal levels of dieldrin and nine eagles had been poisoned by thallium. Autopsies revealed that illegal shooting was the most common cause of mortality. Since 1964 when data were first collected, 8 of the 17 eagles obtained from Maryland, Virginia, South Carolina, and Florida possibly died from dieldrin poisoning: all four speci- mens from Maryland and Virginia were from the Chesa- peake Bay Tidewater area. Introduction The purpose of this paper is to report and evaluate residue and autopsy data on bald eagles (Haliaeetiis leiicocephalus) collected in 1971 and 1972. Data for specimens collected in 1964 through 1970 have been previously reported (/-5). Sampling Bald eagles found dead or moribund in the field are collected by Federal, State, and private cooperators, packed in dry ice, and shipped air express to the Patuxent Wildlife Research Center in Laurel, Md., where they are stored intact in plastic bags at —25° C, Thus sampling for the present study was not systematic because of the relatively low population and protected status of these birds. Table 1 shows the collection areas of the 37 birds analyzed; 25 birds were collected in 1971 and 12 in 1972. Decomposed specimens were not analyzed. TABLE 1. Distribution of eagles collected by State and year of death, 1971-72 No. Eagles Collected State 1971 1972 California 1 Florida 1 Illinois 4 Indiana I Iowa 1 Maine 1 Michigan 1 Minnesota 2 Missouri 4 1 New Mexico 1 New York 1 Ohio 1 South Carolina 1 Texas 1 Utah 2 Virginia 1 2 Wisconsin 1 Wyoming 8 1 TOTAL 25 12 ' Patuxent Wildlife Research Center. Fish and Wildlife Service, U.S. Department of Interior, Laurel. Md. 20811. Autopsy and Analytical Procedures Procedures for autopsy followed those reported previ- ously by Belisle et al. (.?). After removal of the skin, feet, wings, liver, and gastrointestinal tract, the carcass was ground and homogenized in a Hobart food cutter. A 10-g aliquot of the carcass and the entire brain were Vol. 9, No. 1, June 1975 mixed separately with anhydrous sodium sulfate in a blendor and extracted for 7 hours with hexane in a Soxhlet apparatus. Extracts were evaporated, lipid weights were determined, and the extracts were redis- solved in 20 ml hexane. A 10-mI aliquot of extract containing not more than 0.5 g lipid was cleaned on a florisil column. The florisil had been washed and recalcined at 675° C according to Hall's method (4) and partly deactivated with 1.0-1.5 percent water to permit the elution of diel- drin with the other pesticides. Approximately 21 g of the treated tlorisil was placed in each 2-by-20-cm column with a 250-ml reservoir and topped with 1 cm anhy- drous sodium sulfate. Columns were prewashed with 50 ml hexane and the extract was eluted with 200 ml 6 percent ethyl ether in hexane. The florisil eluate was concentrated to 5 ml and a 4-ml aliquot was placed on a silicic acid column to separate pesticides from PCB's. Armour and Burke's separation method (5) was used with the following modifications: the silicic acid, Mallinckrodt Silicar CC-4, was heated at 130° C for 24 hours in a pan covered with alumi- num foil containing a few pinholes; celite and air pres- sure were eliminated; and the petroleum ether eluate was collected in two separate fractions of 100 ml and 300 ml followed by 200 ml of the polar eluate. The adsorbent usually was deactivated with 3 percent water, and the flask was .sealed with paraffin tape, shaken for 3 hours on a reciprocating shaker, and allowed to equilibrate for 24 hours before use. The amount of water was adjusted by running standards to assure that all the DDE was in the second fraction. Using this procedure, hexachlorobenzene (HCB) and mirex were collected in the first 100 ml petroleum ether, PCB's and DDE were in the second fraction, and the remaining pesticides were in the polar eluate. Silicar CC-4 did not require celite or air pressure to maintain the specified flow rate. Covering the pan with alumi- num foil during the heating process eliminated certain interfering background peaks. Samples were analyzed with a Hewlett-Packard 5753 gas-liquid chromatograph equipped with a Ni^^ detector, automatic sampler, digital integrator, and a 4 percent SE-30/6 percent QF-1 column at 190° C. The flow rate of 5 percent methane in argon was 60 ml/min for col- umns and 40 ml/min for purge. DDE was quantitated by peak height to avoid possible errors from PCB inter- ference; other pesticides were measured by digital inte- gration of area, and PCB's were estimated by compar- ing total peak area with Aroclor 1254 or 1260. Residues in 15 specimens (40 percent) were positively identified with an LKB gas-liquid chromatograph/mass spectrometer (GLC/MS). Operating procedures have been described (3) except that a 1 percent SE-30 col- umn was temperature-programmed. Program rate was 2° C/min; initial temperature was 135° C, rising to a maximum of 220° C. Average recoveries from spiked mallard carcass tissue were: DDE, 96 percent: ODD, 103 percent; DDT, 110 percent; dieldrin, 101 percent; heptachlor epoxide, 104 percent; mirex, 106 percent; oxychlordane, 98 percent; (■/.y-chlordane. 100 percent; rw-nonachlor, 98 percent; HCB, 69 percent; and Aroclor 1254, 101 percent. Resi- due levels for eagle samples were not corrected for recovery. The lower limit of sensitivity was 0.05 ppm; residue levels less than 0.05 ppm were not reported "trace" as in the previous reports. Samples were not analyzed for oxychlordane, cw-chlor- dane, c/.y-nonachlor, or HCB in 1971. GLC/MS analy- ses using temperature programming revealed both cis- chlordane and /ro/w-nonachlor. In one sample, only fra/i.v-nonachlor was detected. Authors were unable to obtain a GLC column for the electron-capture detector that would separate both compounds without interfer- ence from another pesticide. The peak was quantitated as r/j-chlordane because standards of these compounds have the same detector response. Thallium levels in eagle kidneys were determined by flame atomic absorption using the method described by Curry et al. (6) except that a sampling boat was not used. The lower limit of sensitivity was 2.0 ppm. Results and Discussion ursiDUE.s Table 2 summarizes residues of organochlorine pesti- cides and PCB's in 37 bald eagle carcasses and brains; all data are reported on a wet-weight basis. All carcasses contained PCB and DDE residues, 30 contained DDD, and 28 contained dieldrin. Four specimens had concentrations of dieldrin in the brain within the range known to have caused death by dieldrin. Table 3 shows dieldrin levels in the brains of these specimens to range from 4.0 to 7.8 ppm. Stickel et al. (7) concluded from an experimental study on Japanese quail (Coiiiniix coturnix) and from residues in brains of several kinds of animals found dead in the field following heavy dieldrin treatments that a concen- tration of 4-5 ppm indicated that the animal was in the danger zone. Linder et al. (8) concluded from studies of capsule-dosed pheasants that a level of 3-4 ppm, or greater, of dieldrin in the brain indicates death by dieldrin. During the 1964-72 period, 190 eagles were analyzed; 19(10 percent) of these specimens were suspected cases of dieldrin poisoning. The incidence of dieldrin poison- ing is high, particularly among specimens from Mary- land, Virginia, South Carolina, and Florida. Of the 17 eagles collected (3 from Md., 4 from Va., 4 from S.C., and 6 from Fla.), 8 (47 percent) were possible victims 12 Pesticides Monitoring Journal TABLE Pesticide and PCB residues in 37 bald eagles, 1971-72 YEAR Residues, ppm WET WEIGHT Compound Cabcass Brain No. Specimens i Median ' Range No. Specimens" Median i Range p.P'-DDE 1971 25 5.7 0.77- 210,0 25 0,95 0.07- 89.0 1972 12 11.0 0.83- 110.0 12 3.3 0.14- 55.0 p.p'-DDD 1971 IS 0.40 0,10- 33.0 9 0,19 0.05- 9,9 1972 12 0.54 0.14- 18,0 8 0.35 0.06- 2,9 P.P'-DDT 1971 4 0.33 0.26- 3.2 2 0.08 0.05- 0,11 1972 S 0.42 0.12- 0.94 1 0.34 Dieldrin 1971 16 0.72 0.10- 33.0 12 0.30 0.05- 7.8 1972 12 0.65 0.14- 12.0 8 0.61 0.23- 4.6 Heptachlor epoxide 1971 9 0.36 0.06- 5.5 6 0.18 0.05- 1.5 1972 5 0,72 0.06- 2.7 3 0,35 0,11- 1.7 Mirex 1971 10 0.30 0.10- 1.3 4 0.10 0.10- 0.13 1972 6 0.26 0.06- 0.60 2 0.13 0.11- 0.13 Oxvchlordane 1972 6 0.34 0.18- 1.4 6 0,09 0.05- 0,34 ci^-Chiordane- 1972 10 0.30 0.11- 7.4 7 0.11 0,05- 1,7 cij-Nonachlor 1972 6 0.29 0.07- 0.95 2 0.59 0,19- 0,98 Hexachlorobenzene 1972 4 0.30 0.11- 0.50 4 0.14 0.05- 0.18 PCB's 1971 25 8.6 0.30- 290.0 24 1.1 0.10-150.0 1972 12 26.0 0.60-1200,0 11 16,0 0,65-190.0 ' Number of specimens coDtaining residues; the median is based on this nimiber. - And/or /ran5-nonachlor. TABLE 3. Data on four suspected cases o/ dieldrin poisoning of adult eagles, 1971-72 Dieldrin State Year Sex Residue IN Brain, ppm Autopsy Findings ' Iowa 1971 F 7,8 Open, no fat deposits South Carolina 1971 M 6.5 Emaciation Virginia 1971 M 4.0 Open, no tat deposits Virginia 1972 F 4.6 Open, no fat deposits ' Open = no diagnosis could be made on the basis of autopsy findings. of dieldrin poisoning. Two eagles suspected of dieldrin poisoning were collected from each State. It is of special concern that all four eagles from Maryland and Virginia suspected of dieldrin poisoning were from the Chesa- peake Bay tidewater area. No specimens were collected from North Carolina or Georgia. A large group of bald and golden eagles found dead near Casper, Wyo., in May 1971 were suspected of having been killed by ingestion of poisoned bait. Speci- mens were analyzed for cyanide, strychnine, sodium fluoroacetate (1080), and thallium. Residues of thallium in the kidneys ranged from 14 to 59 ppm. Eight of the eleven bald eagles from this group which were suitable for residue analysis are included in this report. In an eagle from Utah, the kidney contained 63 ppm thallium. It was concluded from autopsies and chemical analyses that these eagles had died from thallium ingestion. AUTOPSY Results of the autopsies are summarized in Table 4. Illegal shooting, the most common cause of mortality, was responsible for the death of 35 percent of the eagles. Three eagles suspected of dieldrin poisoning were in good flesh but lacked deposits of fat. The other bird TABLE 4. Probable causes of bald eagle mortality, 1971-72 Cause of Death No, Eagles Shooting 13 Thallium poisoning 9 Dieldrin poisoning 4 Nephrosis 1 Drowning 1 Drowning; coccidiosis 1 Coccidiosis 1 Strychnine poisoning 11 Impact 1 Electrocution 1 Open = 4 TOTAL 37 ' Specimen from New Mexico; analyzed for strychnine by Denver Wildlife Research Center, Denver. Colo. 2 No diagnosis could be made on the basis of autopsy findings or chemical analysis. listed as emaciated showed marked atrophy of the pec- toral and leg muscles, and had no fat deposits. Coccidiosis caused by Isospora sp. was apparently re- sponsible for the death of an eagle from Minnesota. It was a contributing factor in the death of an emaciated adult female found downstream from Flaming Gorge Dam, Utah; immediate cause of her death was reported as drowning. Vol. 9, No. 1, June 1975 13 Drowning was also the immediate cause of the death of an adult female eagle from Michigan that had high levels of DDE (55 ppm) and PCB's (190 ppm) in the brain. The eagle, which had been observed perched on a snag over the water, suddenly fell into the water and drowned. No injuries were found, and both aerobic and anaerobic cultures of liver, heart blood, and in- testinal tract failed to reveal any pathogenic bacteria. The thallium-poisoned eagles usually had normal amounts of adipose tissues, were in good flesh, and had no gross lesions except congestion of vessels overlying the cerebellum. Microscopically, there were no acid-fast intranuclear inclusion bodies which sometimes indicate lead poisoning, and examination of the kidney sections stained by the Pritschow technique proved to be equivocal. An adult female eagle from Missouri had a shattered lower left leg, the result of an earlier gunshot wound. She had valvular endocarditis, probably the result of a secondary bacterial infection from the leg wound. Escherichia coli appeared in the heart blood but not in the lungs and liver; thus the cause of death is listed as shooting (Table 4). Conclusion Bald eagles are subject to a wide variety of environ- mental insults, including infectious agents, chemical pollutants, and human-related trauma. Levels of pesti- cides and PCB's in eagles continue to be high, reflect- ing widespread contamination by these compounds. A cknowledgments Authors acknowledge organizations and individuals, particularly U.S. Game Management Agents, who sub- mitted specimens and provided the field data. P. Polen, Velsicol Chemical Corporation, provided the various chlordane standards, Larry Young prepared tissue sec- tions for histological examination, and Marian Kreamer assisted in assembling the data. LITERATURE CITED ( / I Rcichcl. W. L.. E. Cronuirlie, T. G. Lamoiil, B. M. Miilheiii, ami R. M. Proiily. 1969. Pesticide residues in eagles. Pestic. Monit. J. 3(3) : 142-144. (2) Mulluin, B. A/., W. L. Reichel, L. N. Locke, T. G. Lamont. A. A. Belisle, E. Cromaiiie, G. E. Bagley, and R. M. Piouly. 1970. Organochlorine residues and au- topsy data from bald eagles 1966-68. Pestic. Monit. J. 4(3):141-144. (.^) fiWu/f, A. A.. W. L. Reichel, L. N. Loclie, T. G. Lamont, B. A/. Mulhern, R. M. Prouty, R. B. DcWolf, and E. Cromartie. 1972. Residues of organochlorine pesticides, polychlorinated biphenyls, and mercury and autopsy data for bald eagles, 1969 and 1970. Pestic. Monit. J. 6(3):133-138. (4) Hall, E. T. 1971. Variations of florisil activity: method to increase retentive properties and improve recovery and elution patterns of insecticides. J. Ass. Oftic. Anal. Chem. 54(6):1349-1351. (5) Armour, J. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Ass. OflRc. Anal. Chem. 53(4) :761-768. (6) Curry, A. S., J. F. Rend, and A. R. Knott. 1969. De- termination of thallium in biological material by flame spectrophotometry and atomic absorption. Analyst 94 (1122):744-753. (7) Slickel, W. H., L. F. Stickel, and J. W. Spanri. 1969. Tissue residues of dieldrin in relation to mortality in birds and mammals. Pp. 174-204 in M. W. Miller and G. C. Berg, editors. Chemical Fallout: Current Re- search on Persistent Pesticides. Chas. C. Thomas, Springfield, III. (5) Linder, R. L., R. B. Dalilgren, and Y. A. Greichus. 1970. Residues in the brain of adult pheasants given dieldrin. J. Wildl. Manage. 34(4) :954-956. 14 Pesticides Monitoring Journal Mercury Concentrations in Fish, North Atlantic Offshore Waters — 1971 R. A. Greig,! D. Wenzloff,' and C. Shelpuk 2 ABSTRACT Mercury concenlrations were determined in muscle and liver of 41 species of fish and a limited number of plankton, sediment, and invertebrate samples collected from North Atlantic offsliore waters in 1971. The average mercury con- centration in fish muscle was 0.154 ppm with a standard deviation of 0.124. Invertebrate samples had mercury con- centrations which were generally less than 0.1 ppm. In a single lobster sample, however, 0.31 ppm mercury was found in the tail muscle and there was 0.60 ppm in the liver. Mer- cury levels in all 9 plankton and 10 sediment samples taken were less than 0.05 ppm. Introduction Recently, much has been published about mercury in freshwater lakes in Japan. Sweden, Canada, and the Great Lakes area of the United States. Mercury dis- charged into these waters was found to accumulate in tissues of fish and other organisms to levels that in cer- tain species were considered potentially dangerous to human health (/ ). This mercury was traced to many industrial and do- mestic uses, such as the manufacture of sodium hy- droxide and chloralkali plants, paper manufacturing, plastics production, and application of fungicides to control yeast and mold growth on grass and in pulp mills. The degree and source of mercury contamination of freshwater fish and waters were readily established. Levels in marine fish and waters, however, were not so ' National Marine Fisheries Service, Middle Atlantic Coastal Fisheries Center, Milford Laboratory, Milford. Conn. 06460. = J. P. Stevens Co., Box 428. Piedmont. S.C. easily determined. The Food and Drug Administration (FDA), U.S. Department of Health, Education, and Welfare, conducted a survey of mercury levels in sev- eral species of both domestic and foreign marine fish- eries products and found that certain species of tuna and swordfish contained mercury above the 0.5 ppm action level, the maximum allowable concentration in fish intended for sale. As a result of these findings, a program was initiated within the National Marine Fisheries Service. U.S. De- partment of Commerce, to determine mercury levels in other marine fish as part of an overall program on the effects of chemical contamination of living marine re- sources. The present paper reports on part of this pro- gram, a survey of mercury concentrations in groundfish collected from U.S. waters of the North Atlantic Ocean. Experimental Methods SAMPLE COLLECTION Fish and invertebrates were collected by otter trawl dur- ing the annual assessment of groundfish stocks con- ducted by the National Marine Fisheries Service, Northeast Fisheries Center. Woods Hole. Mass. After the catch, fish and invertebrates were sorted and dis- sected aboard the vessel. Livers and a 1 -inch-thick steak immediately posterior to the head were taken from each fish. Invertebrate samples varied: whole squid were an- alyzed although scallop samples were composed of only the edible muscle and lobster samples consisted of the digestive diverticula and tail muscle. Bottom sediments were obtained from selected areas with a Smith-Mclntyre sampler. Samples were removed for analysis with a plastic tube 1 ' 'z inch in diameter and 6 inches long, which was inserted into the bottom sedi- ment, capped, and frozen. Vol. 9, No. 1. June 1975 15 Approximate geographic sampling areas arc shown in Figure 1. Common and scientific names o(" fish and in- vertebrates obtained in the survey arc presented in Table 1. FIGURE 1. Colleclion sites of fish sampled for mercury concentrations, North Atlantic ofjshore waters — 1971 TABLF 1. I'isli sampled for mercury concentrations. North Atlantic offshore waters — 1971 Common Name Scientific Name American plaice Hippoglossoides pla(essoides American shad Alosa sapidissima Angel shark Squalus dumerili Atlantic cod Gadus morhua Atlantic herring Clupea harengiis harengus Atlantic mackerel Scomber scombrits Atlantic wolffish Anarhichas lupus Beardfish Polymixia lowei Blackbelly rosefish Helicolenus dactyloptents Black sea bass Centropristis striata Butterfish Peprilus triacanthus Cusk Brosme brosme Daubed shanny Lumpenus maculatus Fawn cusk-eel Lepophidium ceninum Fourspot flounder Paralichthys oblongus Gulf Stream flounder Cttharichthys arctifrons Haddock Melanogrammus aeglefinus Lanternfish Unclassified Little skate Raja erinacea Longhorn sculpin Myoxocephalus octodecemspinosus Mailed sculpin Triglops nybelini Northern searobin Pnonotus carolinus Ocean pout Macrozoarces americanus Pollock PoUachius virens Redfish Sebostes marimts Red hake Urophycis chuss Round herring Etrumeus teres Silver hake Merluccius bilinearis Spiny dogfish Squalus acanthias Spot Leiostomus xanthurus Striped searobin Prionotus evolans Thorny skate Raja radiata White hake Urophycis tenuis Windowpane flounder Scophthalmus aquosus Winter flounder Pseudopleuronectes americanus Winter skate Raja binoculata Witch flounder Glyptocephalus cynoglossus Yellowtai! flounder Limanda ferruginea SAMPLE PREPARATION FOR CHEMICAL ANALYSIS At the laboratory fish steaks were thawed, skinned, and boned. Muscle and liver tissues of 5-10 fish from each station were combined into single composite samples for mercury analysis although some muscle and liver tissues were also analyzed individually. Invertebrates were pooled into composites of If) animals per station. Sam- ples were homogenized in an electric blendor composed of stainless steel blades and a glass jar. Plankton samples were processed in a Vir-Tis model 10- 100 freeze-drier for 48 hoLirs. Plankton data are re- ported on a wet-weight basis. Entire sediment samples about 3-5 inches deep and I'i inches in diameter were thoroughly mi.xed by hand in a plastic bag prior to analysis. MERCURY ANALYSIS Samples were analyzed according to the procedure of the Division of Laboratories. Ontario Ministry of the Environment (J). Plankton samples and ground flesh or liver samples ranging from 0.1 to 0.5 g were weighed into 30-ml Rjeldahl flasks. Ten ml 4:1 reagent grade concentrated sulfuric acidrnitric acid were added and the sample was shaken in a 50-60° C water bath. Di- gestion was considered complete after II2-2 hours when a clear solution was obtained. Flasks and samples were cooled at room temperature for 1 hour and placed in ice while 15 ml 6 percent potassium permanganate was slowly added to each sample. After addition of perman- ganate, samples were left overnight at room tempera- ture. A 20 percent sulfuric acid solution was added and sam- ples were transferred to glass washing bottles equipped with fritted stems. Twenty ml reductant consisting of 100 ml concentrated sulfuric acid. 15 g sodium chlo- ride. 30 g hyroxylamme sulfate, and 60 g stannous sul- fate made up to l.f)00 ml with distilled water were added to the sample and stirred for 1 minute. Mercury was swept by air through a 2.5-cm cell mounted in the light path of a Perkin Elmer model 305 atomic absorp- tion spectrophotometer. Air flow rate was adjusted to give about 60 percent recorder response for 0.3 Mg mer- cury. Peak heights of sample recorder response were compared to those of standards carried through the same digestion procedure described above for quantita- tion. The method was checked tor accuracy by comparing its results with those obtained by other procedures. A sample of oil-packed yellow fin tuna prepared by the National Canners Association was analyzed for mercury residues by nine laboratories using a variety of methods. The average mercLiry level obtained was 0.86 ppm; range was 0.80-1.02 ppm. The tuna sample studied at this laboratory was routinely analyzed with small batches of samples taken in the present study. An aver- age value of 0.90 ppm with a relative standard devia- tion of 17.94 percent was obtained lor 39 replicate determinations. 16 Pesticides Monitoring Journal The procedure for mercury analysis of sediment sam- ples was obtained from the Chemistry Laboratory Manual — Bottom Sediments, December 1969, compiled by the Great Lakes Region Committee on Analytical Methods, Federal Water Quality Administration, a pre- decessor of the U.S. Environmental Protection Agency. Samples ranging between 0.2 and 0.5 g were weighed into 125-ml Erlenmeyer flasks and 10 ml distilled water and 5 ml of 1:3 lactic acid:HCl (aqua regia) were added. Samples were heated lor 2 minutes in a 95° C water bath and cooled in tap water for 10-15 minutes. Fifty ml distilled water and 15 ml of a 6 percent potas- sium permanganate sokition were added to each flask. Then samples were reduced and analyzed by atomic absorption spectrophotometry as described for fish tis- sue except that sediment samples were analyzed the day they were digested. Percent recoveries of HgCL added to fish muscles and sediment prior to digestion are given in Table 2. Mer- cury was added to fish muscle before any acids or other reagents and was not allowed to equilibrate with muscle prior to addition of acid. Mercury added to sediment was allowed to stand for 2 hours prior to addition of water and acid. Sensitivity was about 0.05 ppm. TABLE 2. Percent recovery of mercury from fish and sediment. North Atlantic offshore waters — 1971 Mercury No. Recovery , % Species Mg' Analyzer Range Average Fishmeal 0.05 6 81.9-118.1 95.4 Swordfish 0.1 6 100.7-127.9 113.7 Yellow perch 0.2 6 80.9-108.0 96.9 Carp 0.2 6 89.7-102.3 95.1 Yellowfin tuna 0.3 5 95.4-105.1 98.6 Skipjack tuna 0.5 5 103.1-111.9 108.2 Sediment 0.3 6 105.0-119.0 111.5 1 HgCla used for mercury addition. Results Mercury concentrations among individual specimens were similar for most fish species although variations among individuals were observed for cusk and spiny dogfish (Table 3). One cusk collection had mercury concentrations ranging from 0.14 to 1.33 ppm in the liver and from 0.15 to 0.59 ppm in the muscle. In a sec- ond collection, variation among individuals was less: residues ranged from 0.16 to 0.34 ppm in the muscle and from 0.13 to 0.40 ppm in the liver. Variation among four of six collections of spiny dog- fish individuals was substantial. Mercury levels in these samples were: 0.20-0.61 ppm, 0.35-0.69 ppm, 0.35-0.93 ppm, and 0.22-0.65 ppm. Mercury content among indi- viduals in the other two collections ranged only from 0.17 to 0.29 ppm and from 0.14 to 0.29 ppm. MERCIJRY LEVELS AND FEEDING HABITS In an attempt to correlate mercury concentrations with feeding habits, fish were grouped according to similar feeding patterns. The majority collected were bottom- feeders, others were primarily pelagic and plankton feeders and a few species could not be grouped into a particular feeding habit and were listed as miscellaneous. Feeding habits and mercury concentrations did not correlate (Table 4). MUSCLE Highest levels of mercury in fish muscle were found in cusk, spiny dogfish, northern searobin. and striped sea- robin (Table 5). The highest mercury concentrations in these samples were 0.49, 0.53, 0.35, and 0.35 ppm, re- spectively. The 36 other fish species had mercury levels in muscle that were less than 0.30 ppm. Mercury levels in all fish muscle sample averaged 0.154 it 0.124 ppm. LIVER Highest mercury levels in fish livers were detected in blackbelly rosefish, cusk, northern searobin, and Ameri- can shad (Table 5). The highest mercury levels in these samples were 0.40. 0.83. 0.56. and 0.67 ppm, respec- tively. The other 36 species of fish had mercury levels below 0.30 ppm in the liver (Table 5). Concentrations in livers of all fish examined averaged 0.164 ± 0.157 ppm. MUSCLE AND LIVER Mercury residues in fish samples averaged 0.154 ppm in muscle and 0.164 ppm in liver. Investigators have shown that liver accumulates metals to a greater extent than do most other tissues and organs (.3-5). Data in this study, however, reflected an important difference: similar concentrations of mercury occurred in muscle and liver for most species examined. Exceptions to this rule were spiny dogfish, blackbelly rosefish, American shaJ, and Atlantic herring. Levels in spiny dogfish were two to three times higher in muscle than in liver, whereas in the other species mercury concentrations were greatest in the liver. Ratios of mercury levels in liver to those in muscle for other species were black- belly rosefish, 2:1; American shad, 13:1; and Atlantic herring, 5:1. PLANKTON, SEDIMENT, AND INVERTEBRATES Mercury levels in all 9 plankton and 10 sediment sam- ples were less than 0.05 ppm (Table 6). Pandallis shrimp, scallops, and squid generally had mercury levels less than 0.05 ppm (Table 7). However, the mercury levels of one squid sample and one shrimp sample were 0.06 ppm and 0.09 ppm, respectively. The single lobster sample obtained had mercury levels of 0.31 ppm in the tail meat and 0.60 ppm in liver (Table 7). Discussion This study measures total mercury: organic and In- organic forms. Methylmercury is considered more toxic to humans than are inorganic mercury salts and thus its occurrence in fish is of more toxicological significance Vol. 9, No. 1, June 1975 17 TABLE 3. Mercury conccntralions in individual fish samples. North Atlantic offshore waters — 1971 No. Mercury Content. Fish Ana- PPM wet weight Standard Species Tissue lyzed Range Average Deviation American dab muscle 5 0.03-0.16 0.08 0.064 Atlantic cod muscle 4 0.10-0.15 0.14 0.081 liver 4 0.08-0.15 0.12 0.017 muscle 5 0.10-0..38 0.24 0.135 liver 5 0.10-0.36 0.18 0.109 Atlantic herring liver 5 0.20-0.44 0.26 0.103 Atlantic wolffish muscle 5 0.08-0.25 0.16 0.063 Blackbelly rosefish muscle 5 0.12-0.31 0.22 0.095 Cusk muscle 6 0,16-0.34 0.27 0.089 liver 6 0.13-0.40 0.24 0.095 muscle 6 0.15-0.59 0.41 0.189 liver 6 0.14-1.33 0.65 0.440 Fourspotted flounder musde 5 0.09-0.19 0.16 0.031 Haddock liver 5 0.05-0.09 0.06 0.014 Little skate muscle 5 0.05-0.18 0.12 0.060 liver 5 0.06-0.15 0.10 0.033 Mackerel muscle 5 0.07-0.10 0.08 0.016 Pollock muscle 5 0.06-0.12 0.10 0.029 liver 5 0.05-0.09 0.06 0.016 Redflsh muscle 6 0.15-0.29 0.20 0.050 Red hake muscle 5 0.05-0.09 0.06 0.000 Silver hake muscle 5 0.06-0.14 0.09 0.034 Spiny dogfish muscle 4 0.17-0.29 0.23 0.052 muscle 10 0.20-0.61 0.34 0.160 muscle 5 0.35-0.69 0.54 0.135 muscle 5 0.35-0.93 0.58 0.270 muscle 5 0,22-0.65 0.44 0.154 muscle 5 0.14-0.29 0.18 0,064 Thorny skate muscle 5 0.11-0.41 0.19 0,116 muscle 4 0.15-0.36 0,26 0.113 liver 4 0.12-0.17 0.15 0.033 White hake muscle 5 0.08-0.17 0.12 0.037 liver 5 0.05-0.18 0.12 0.055 Windowpane flounder muscle 5 0.06-0.18 0.10 0.045 Winter flounder muscle 5 0.06-0.12 0.08 0.022 liver 5 0.12-0.26 0.18 0.044 Witch flounder muscle 5 0.08-0.11 0.09 0.000 liver 5 0.07-0.17 0.12 0.045 Yellowtail flounder muscle 5 0.07-0.13 0.10 0.022 TABLE 4. Mercury concentrations in fish grouped according to feeding habits. North American offshore waters — 1971 Fish No. Col- lections Analyzed i Mercury Content, ppm wet weight Muscle Range Average Liver Range Average Bottom Feeders American dab 2 0.06-0.08 0.07 0.11-0.14 0.13 Atlantic cod 2 0.14-0.25 0.20 0.11-0.20 0.16 Atlantic wolflish 2 <0.05-0.15 0.08 <0.05-0.06 <0,05 Blackbelly rosefish 1 0.22 0.22 0.40 0.40 Black sea bass 1 0.08 0.08 0.18 0.18 Cusk 4 0.15-0.49 0.31 0.14-0.83 0.42 Fourspot flounder 2 0.16 0.16 0.23-0.27 0.25 Gulf Stream flounder 2 0.05 0.05 ND ND Haddock 2 <0.05-0.09 0.06 <0.05 <0.05 Little skate 2 0.13-0.16 0.15 0.10-0.23 0.17 Longhorn sculpin 2 0.08-0.09 0.09 0.09-0.16 0.13 Ocean pout 2 <0 .05-0.11 0.07 <0. 05-0.09 0.06 Red hake 2 <0. 05-0.05 <0.05 <0.05-0.08 0.06 Striped searobin 1 0.35 0.35 0.38 0.38 Thorny skate 2 0.21-0.26 0.24 0.09-0.15 0.12 White hake 2 0.10-0.12 0.11 0.12-0.16 0.14 Windowpane (lounjer 1 0.10 0.10 0.12 0.12 Winter flounder 3 0.06-0.14 0.09 0.07-0.18 0.11 Winter skate 1 0.15 0.15 0.18 0.18 Witch flounder 2 0.07-0.10 0.09 0.13-0.16 0.15 Yellowtail flounder 2 0.10-0.24 0.17 0.17-0.25 0.21 Pelagic Feeders Pollock Redfish Spot Silver hake 0.08-0.10 0.10-0.20 <0.05 0.09 0.09 0.15 <0.05 0.09 <0.05-0.06 0.15 <0.05 0.10 Plankton Feeders American shad Atlantic herring Mackerel 0.05 <0.05-0.09 0.08 0.05 0.06 0.08 0.67 0.26-0.28 ND Miscellaneous Angel shark Cusk-eel Spiny dogfish 0.08 0.11 0.07-0.53 0.08 0.11 0.32 <0.05 0.19 <0.05-0.19 NOTE: ND = no data. ' Each collection includes 6-10 animals. <0.06 0.15 <0.05 0.10 0.67 0.27 ND <0.05 0.12 0.10 than is the occurrence of total mercury. Reports con- flict concerning methylmercury: total mercury ratios in fish. Japanese investigators report that methylmercury does not exceed about 15 percent of the total mercury in fish whereas Swedish scientists have reported that these mercury concentrations are mostly methylmercury (6). The Food and Drug Administration bases its adminis- trative guideline of 0.5 ppm mercury in fish on total mercury content. Thus data presented here can be com- pared to the guideline. The only muscle samples in this survey that approached this level were those in cusk and spiny dogfish. Cusk measuring 61-67 cm had an average mercury content of 0.49 ppm. Levels in three groups of spiny dogfish muscle averaged 0.44, 0.47, and 0.53 ppm, whereas levels in five other groups of dog- fish ranged from 0.07 to 0.34 ppm. The average of 0.154 ± 0.124 ppm for all fish muscle samples shows most fish well below the guideline level. With the exception of cusk and spiny dogfish, fish ex- amined in this study do not have abnormal mercury concentrations in relation to levels in marine fish re- ported by other investigators. Twelve of 15 species of Oregon groundfish had mercury levels in the range of 0.08-0.24 ppm. Yellow rockfish. lingcod. and spiny dog- fish had average levels of 0.37, 0.35, and 0.60 ppm, respectively (7). The latter concentration was higher than the level reported for spiny dogfish in the present study. Of about 21 species of marine fish and shellfish, only swordfish consistently had mercury levels at or over 0.5 ppm in an FDA study of marine and freshwater fish (8). Three thousand samples of canned tuna had an average mercury content of 0.25 ppm; less than 4 per- cent of these samples had levels over 0.5 ppm. The aver- age mercury content of 19 other species of marine fish and shellfish was 0.3 ppm although most were below 0.1 ppm. Mercury levels in fish landed in England and Wales have also been determined (9). Investigators there re- ported that mercury levels in fish from deep-water fish- ing areas averaged 0.06 ppm. Those caught away from coastal waters in the North Sea had an average concen- tration of 0.10 ppm whereas residues in fish caught in 18 Pesticides Monitoring Journal TABLE 5. Mercury concentralions in composite fish samples, North Atlantic offshore waters — 1971 Sample Data Mercury Content Average, ppm wet weight Depth. Length, Whole Species Latitude Longitude FAIHOMS ' Date CM 1 Muscle Animal Liver American dab 42° 48' 70° 38' 15-62 4-17 32-36 0.08 0.14 41° 21' 68° 46' 28-62 10-19 ND 0.06 0.11 American shad ND ND 23-62 ND ND 0.05 0.67 Angel shark 16° ir 74° 48' 58-105 4-4 43-58 0.08 <0.05 Atlantic cod 41° 44' 69° 40' 58-115 10-18 ND 0.25 0.20 42° 12' 70° 06' 15-62 11^ 54-61 0.14 0.11 Atlantic herring 41° 38' 68° 37' 28-62 10-18 ND <0.05 0.26 40' 23' 71° 02' 28-62 3-10 2(1 0.09 0.28 Atlantic wolffish 42° 42' 66° 07' 30-52 4-25 78-93 0.15 <0.05 42° 55' 65° or 5(1-105 11-7 20-74 0.07 <0.05 Beardfish 37° 07' 74° 33' 58-105 4-5 13-14 0.06 Blackbelly rosefish 39° ir 72° 32' 95-200 10-7 16-34 0.22 0.40 Black sea bass 36° 50- 74° 42' 28-62 4-5 22-24 0,08 0.18 Butterfish 36° 37' 75° 20' 10-32 4-3 10 0.06 Cusk 42° 46' 66° 37' 48-105 11-13 61-67 0.49 0.83 42° 48- 70° 07' 55-130 4-18 44-68 0.27 0.23 Daubed shanny 43° 44' 69° 08' 5-62 4-21 8-12 0.05 Fawn cusk-eel 40° 13' 71° 04' 58-105 10-8 25-29 0.11 0.19 Fourspot flounder 40° 24' 71° 57' 28-62 3-11 16-19 ND 0.27 39° 09' 73° 12' 28-62 10-6 21-34 0.16 0.23 Gulf Stream flounder 38° or 74° 14' 28-62 10-5 6-12 0.05 ND Haddock 41° 32' 69° 31' 10-35 10-18 ND 0.09 <0.05 41° or 67° 06' 28-62 3-16 46-68 <0.03 <0.05 I.anternflsh 41° 35- 61° 55' 95-200 10-22 ND <0.05 Little skate 40° 22' 68° 46' 28-62 10-16 ND 0.16 0.23 40° 57- 71° 18' 13-33 3-30 45-50 0.13 0.10 LonghorB sculpin 40° 46' 68° 35' 10-34 10-17 ND 0.09 0.16 41° 12' 71° 17' 13-33 3-10 25 0.08 0.09 Mackerel 39° 59' 71° 40' 28-62 3-11 30-35 0.08 ND Mailed sculpin 43° 35' 66° 41' 50-115 4-23 8-13 <0.05 Northern searobin 37° 53' 74° 41' 10-32 10-9 24-27 0.35 0.36 Ocean pout 40° 23' 73° 06' 11-32 3-31 45-55 0.11 0.09 40° 55' 71° 63' 11-35 3-10 46 <0.05 <0.05 Pollock 42° 48' 66° 37' 48-105 4-24 51 0.08 <0.05 41° 25' 69° 08' 58-115 10-19 ND 0.10 0.06 Redfish 41° 42' 69° 16' 58-115 3-24 38 0.20 0.15 41° 57' 69° 02' 58-115 10-19 41-57 0.10 0.15 Red hake 40° 24' 71° 57' 28-62 3-11 25-30 <0.05 <0.05 40° 33' 71° 57' 28-62 9-30 27-34 0.05 0.08 Round herring 40° 09' 73° 31' 11-32 10-4 15-16 <0.05 Silver hake 39° 55' 72° 05' 28-62 10-7 28-31 0.09 0.10 Spiny dogfish 42° 20' 65° 35' 48-105 4-29 68-75 0.23 0.07 42° 17' 66° 34' 90-160 3-21 ND 0.32 0.06 44° 16' 66° 51' 50-135 11-15 81-84 0.34 0.09 40° 32' 71° 20' 28-62 3-11 37 0.07 <0.05 36° 28' 75° 08' 10-32 4-3 80-92 0.53 0.19 38° 14' 73° 44' 58-105 4-8 82-95 0.47 0.07 40° 29' 72° 26' 11-32 10-1 60-86 0.44 0.15 40° 43' 70° 26' 11-35 10-15 ND 0.18 0.12 Spot 37° 29' 75° 13- 10-32 10-10 27-29 <0,05 <0.05 Striped searobin 36° 00' 74° 53- 28-62 4-4 28-37 0.35 0.38 Thorny skate 42° 41' 66° 12- 30-52 4-25 60-93 0.21 0.09 44° 07' 66° 35' 15-62 11-15 60-81 0.26 0.15 White hake 42° 44' 69° 40' 90-155 4-18 57-68 0.12 0.12 42° 16' 70° 22' 15-62 11-3 27-72 0.10 0.16 Windowpane flounder 41° (19' 70° 47' 11-35 9-29 22-31 0.10 0.12 Winter flounder 40° 11' 67° 56' 15-62 4-21 22-46 0.07 0.08 40° 42' 72° 31' 11-32 10-1 28-35 0.14 0.18 Winter skate 40° 46' 68° 35' 10-34 10-17 ND 0.15 0.18 Witch flounder 38° 13' 73° 51' 95-200 4-8 31-36 0.07 0.16 40° 32' 70° 57' 28-62 10-8 42-50 0.10 0.13 Yellowtail flounder 40° 16' 73° 24' 11-32 3-31 28-32 0.24 0.17 40° 29' 71° 49' 28-62 9-30 33-38 0.10 0.25 NOTE: ND = no data. • Values reported in ranges only; depth range represents a bottom contour from which the fish was taken. the Irish Sea were twiee as high. The average level ot about 0.15 ppm lor all groun(.lfish examined in the pres- ent stLKly falls midway between North Sea and Irish Sea data. A cknowledgmeiUs Authors thank Rics Collier. Wayne Cable, Charles Gib- son, Martin Newman, Darryl Christensen, and Malcolm Silverman for collecting samples. LITERATURE CITED (/) Bligh, E. G. 1970. Mercury and the contamination of freshwater fish. Fish. Res. Bd. Can., Manuscript Rep. Ser. No. 1088, April 1970. (2) Bishop. J. N.. L. A. Taylor, and P. L. Diosady. 1975. High temperature acid digestion for the determination of mercury in environmental samples. Laboratory Services Branch, Ministry of the Environment. Vol. 9, No. I, June 1975 19 (.?) Hainnrz, L. 196S. Experimental investigations on the accumulation of mercury in water organisms. Inst. Freshwater Res., Drottningholni, Sweden, Rep. No. 48. {4) Priiifilc. B. //., D. E. Hiisoiii;. E. L. Katz, and S. T. ,\tulawkci. 1968. Trace metal accumulation by estu- arine mollusks. J. Sanit. Eng. Div., Proc. Am. Soc. Div. Eng., 94(SA3, Proc. Pap. 5970) :455-475. (5) Pilerson, C. L., W. L. KUiwe. and G. D. Sharp. 1973. Mercury in tunas: a review. Fish. Bull. 71(3 ) :603-613. (6) Suzuki, T., T. Mi Yanui, and C. Toyama. 1973. The chemical form and bodily distribution of mercury in marine fish. Bull. Environ. Contam. Toxicol. 10(6): 347-355. (7) CItilds, E. A., and J. A'. Gatfke. 1973. Mercury con- tent of Oregon groundtish. Fish. Bull. 71(3 ) :7 13-717. (S) Simpson, R. E., W. Horwilz, and C. A. Roy. 1974. Surveys of mercury levels in fish and other food. Pestic. Monil. J. 7(3/4 ): 127-138. (9) Portmann, J. E. 1972. The levels of certain metals in fish from coastal waters around England and Wales. Aquaculture l(l):91-96. TABLE 6. Mercury coiicentralions in plunklon and sediment, iXorlli Atlantic offshore waters — 1971 Sample Data Mercury Content Latitude Longitude Depth, FATHOM Date Average, ppm WET weight Plankton 42° 50- 64° 32' 50-100 4-27 <0.05 43° 33' 68° 44' 55-110 4-21 <0.U5 42° 13' 69° 59' 55-130 11^ <0.05 43° 05' 68° 40' 60-120 11-17 <0.05 41° 29- 66° 47' 28-62 10-22 <0.05 36° oy 74° 52' 28-62 4-4 <0.05 36° 51- 75° 20- 10-32 4-3 <0.05 39° 19- 73° 51' 10-32 4-1 <0.05 37° 14- 74° 58' 10-32 10-12 <0.05 Sediment 42° 50' 64° 32- 50-100 4-27 <0.05 43° 33' 68° 44' 55-110 4-21 <0.05 43° 12' 70° 05' 55-130 11-8 <0.05 43° 05' 68° 40- 60-120 11-17 <0.05 43° 14' 68° 42' 60-120 11-17 <0.05 36° 03' 74° 52- 28-62 4-4 <0.05 36° 51' 75° 26' 10-32 4-3 <0.05 39° 19' 73° 51' 10-32 4-1 <0.05 40° 19- 70° 29' 23-62 10-15 <0.05 37° 14' 74° 58' 10-32 10-12 <0.05 TABLE 7. Mercury concentrations in invertebrates, North Atlantic offshore waters — 1971 Sample Data Mercury Content Average, ppm wet weight Depth, Length, Whole Species Latitude Longitude rATHOMS Date CM Muscle Animal Liver Lobster (Homarits americanus) 39° 21- 72° 15- 95-200 4-9 6-19 0.31' 0.60 Pandallid slirimp (unclassified) 42° 04' 68° 44' 58-115 4-19 ND 0.09 42° 48' 70° 38' 15-62 4-17 ND <0.05 41° 19- 61° 20' 10-35 3-23 ND <0.03 Scallops (Placopeclen magellanicus) 38° 10' 74° 07' 28-62 10-6 5-7 <0.05 — Squid (lllex illecebrosus) 40° 13' 71° 07' 58-105 3-11 ND <0.05 39° 38- 72° 60- 28-62 10^ ND <0.05 40° 02' 71° If 95-200 10-8 18-22 <0.05 36° 19' 74° 48- 95-200 4-4 ND 0.06 NOTE: ND = no data. ' Lobster muscle sample from tail only. 20 Pesticides Monitoring Journal Baseline Concentrations of Poly chlorinated Biphenyls and DDT in Lake Michigan Fish, 1971 ' Oilman D. Veilh '■ ABSTRACT Responding lo Ihe recommendations of the Lake Michigan Interstate Pesticide Committee, the author aimed to estab- lish baseline data on polychlorinated biphenyls (PCB's) and DDT in Lake Michigan fish in 1971. Because the past 2 years had witnessed unprecedented legislative action to pro- tect food resources and other aquatic species near the top of the food chain from persistent hazardous chemicals, the author also attempted to gauge the impact of cooperative legislative action on the quality of targe lakes. Thirteen species of fish taken from 14 regions of Lake Michigan in the fall of 1971 were analyzed for PCB's and DDT analogs. Mean wet-weight concentrations of PCB's similar to Aroclor 1254 ranged from 2.7 ppm in rainbow smelt to 15 ppm in lake trout. Most trout and salmon longer than 12 inches contained PCB's at concentrations greater than the tolerance level of 5 ppm established by the Food and Drug Administration, U.S. Department of Health, Edu- cation, and Welfare. Mean concentrations of total DDT ranged from less than 1 ppm in suckers to approximately 16 ppm in large lake trout. The presence of the major chlorin- ated hydrocarbons was confirmed by gas-liquid chromatog- raphy/mass spectrometry; additional PCB confirmations were obtained through perchlorination. The most abundant PCB's were tetra-, penta-, he.xa-, and heptachlorobiphenyls which are similar lo commercially prepared Aroclor 1254; lesser chlorinated PCB's were present in fish from nearshore waters. ■ Supported by U.S. Environmental Protection Agency Project 16020 PBE, University Engineering Experiment Station, and University cf Wisconsin Department of Civil and Environmental Engineering. Madison, Wis. = National Water Quality Laboratory. U.S. Environmental Protection Agency, 6201 Congdon Boulevard. Dulutli. Minn. 55804. Introduction This paper identifies and quantifies the most abundant organochlorine compounds, particularly polychlorinated biphenyls (PCB's) and DDT, in Lake Michigan fish in 1971. By establishing data on PCB's and DDT in Lake Michigan fish as recommended by the Lake Michigan Interstate Pesticide Committee, the author of the pres- ent study aimed to develop a 1971 baseline to predict trends of these themicals in the lake. Lake Michigan contains much higher concentrations of potentially hazardous and persistent organic chemicals than the other Great Lakes, in part because of their widespread usage in the watershed and their disp-oportionally brief flushing period and low biomass density. Previous stud- ies have shown that fish from Lake Michigan approach the action levels for dieldrin set by the Food and Drug Administration (FDA), U.S. Department of Health, Education, and Welfare (/); a major percentage of Lake Michigan fish exceeded the 5 ppm action level for DDT in 1969 (2), Similarly, Veith (3) has shown that PCB concentrations similar to Aroclor 1254 were greater than 15 ppm or th ee times the FDA action level in large fish captured from Lake Michigan in 1969. Despite the comparatively high levels of DDT. dieldrin, and PCB's in Lake Michigan, there is no unequivocal evidence that they are endangering aquatic life. Concen- trations of these chemicals appear to be below 10 parts per trillion (ppt) in the pelagic water and less than 100 ppt in nearshore waters. However, considerable in- direct evidence suggests that the buildup of organo- chlorine compounds may threaten biological resources of the lake. Other reports have reviewed the chronic toxicity of pesticides and PCB's (4-7). Vol.. 9, No. 1, June 1975 21 States surrounding Lake Michigan have made a major effort to restock the lake with brown, lake, and rain- bow trout and coho and chinook salmon. Between 1963 and 1970. over 600.000 rainbow trout were released by Wisconsin alone (8,9). However, Reinert (2) previous- ly noted that DDT and dieidrin levels in eggs of these fish are similar to concentrations which inhibited repro- duction in the studies of Burdick et al. (10) and Macek (11). Johansson et al. (J2) have shown that 15 ppm PCB's (lipid basis) in salmon eggs produced mortality in 50 percent of the samples tested. Death can be ex- pected in all eggs when the PCB lipid content reaches 25 ppm. Although continued stocking of fish may maintain a food resource, many fish contain residue body burdens which make them unfit for consumption. The effect of these fish on mink production in the North Central States has been studied in detail: before DDT and dieidrin concentrations in these fish had been well docu- mented, Hartsough (13) indicated that the fish were suspected to inhibit mink reproduction; Aulerich et al. (14) clearly demonstrated that the fish had been the cause of the minks' reproductive failure; and Aulerich and Ringer (15) reported that DDT and DDD did not have significant adverse effects on mink. Furthermore, dieidrin was lethal to mink at 2.5 ppm in the food when fed for extended periods, but did not appear to affect reproduction at twice this concentration during the ges- tation period. Aulerich et al. concluded that feeding coho salmon to mink did not cause reproduction prob- lems, but that the disorder is associated with other species of fish and ". . . appears to be dependent upon the species of fish and its environment" (16). Finally, after the earlier reports that PCB's were present in Lake Michigan fish. Ringer et al. (17) demonstrated that 10 ppm Aroclor 1254 in coho salmon produced 71 per- cent mortality in mink and that a mixture of 10 ppm PCB's and 0.5 ppm dieidrin in coho feed produced 100 percent mortality. No kits were born alive when the diet contained 5 ppm or more Aroclor 1254 alone. This clearly indicates that biological resources of Lake Michigan may seriously endanger other species even though concentrations of toxicants are not severe enough to produce readily discernible effects within the aquatic communities. Equally important is the coincidence of high chlori- nated hydrocarbon levels in herring gull and other bird populatons coupled with reproductive failures and sub- sequent population decline (18). Anderson (19) found that the eggs of the Great Lakes herring gull contained the highest chlorinated hydrocarbon levels ever re- ported for that species. He also found that the degree of eggshell thinning in the Lake Michigan gull, whose population declined dramatically in the ea^ly 1960's. varied from 9 percent in 1953-56 to 18 percent in 1965. In comparison, eggs of gulls on Lake Huron and Lake Superior have exhibited shell thinning of 7 percent and 8 percent, respectively, and those from gulls on the East Coast have remained essentially unchanged. Double- crested cormorants from Wisconsin had eggshells 20 percent thinner than those of gulls, and their eggs had the highest DDE concentrations of any cormorant eggs sampled from interior North America. Golden eagles, which feed primarily on mammals, do not show eggshell thinning as dramatic as that of bald eagles, which feed on fish (19). Lake Michigan is the only Great Lakes watershed where major persistent chemicals have been curtailed. Al- though use of chlorinated pesticides in agriculture was probably diminishing in the late 1960's. the Lake Michi- gan Enforcement Conference recommended regulatory actions on many uses in 1968. This recommendation led to restrictions on DDT including its sale in Illinois. Michigan, and Wisconsin. A more detailed summary is presented by Lueschow (20). Monsanto Company, the sole producer of PCB's in the United States, restricted PCB sales in 1970; by April 1971 they were sold only to close-system users. To measure the impact of the unprecedented coopera- tive legislative action regarding these chemicals, and to establish baseline data, the Lake Michigan Interstate Pesticide Committee recommended that this study be funded. Sampling Procedures Fish were collected in September and October 1971 with gill nets and pond nets from the four regions of Lake Michigan outlined in Figure 1. Whole fish were stored frozen (—20° C) in aluminum foil or polyethy- lene bags for 60 days or less and homogenized while frozen by repeatedly passing them through a meat grinder. All metal surfaces were rinsed with acetone, polyethylene bags were examined for interferences, and the grinder bearing and seal were checked periodically to assure that the sample was not contaminated during storage or preparation. Analytical Procedures REAGENTS Sodium sulfate (Fisher Scientific Co.) was washed with three volumes of 1:1 hexane-acetone and dried at 130° C. To prevent further contamination from cap liners or containers, the Na^SOj was stored in large glass bottles with aluminum foil liners in the cap. The florisil (Kensington Chemical, Fisher Scientific Co.) was extracted in an all-glass Soxhiet extractor for 24 hours with the azeotrope of hexane and acetone to re- move traces of organic impurities. The solvent was evaporated from the florisil at 100° C, and the solid was heated at 650° C for 2.5 hours for activation. If not used immediately after heating, the florisil was heated to 105° C before use. 22 Pesticides Monitoring Journal BENTOft HARBOR Ethyl ether and methylene chloride: Glass wool: FIGURE 1. Sampling regions for collecting fish, Lake Michigan — 1971 Other analytical components included: Silicic acid: Mallinckrodt Chemical, AR grade, Ramsey and Patterson. Used directly from reagent bottle. Hexane: Skelly B. Redistilled in glass from Dri- Sodium, Fisher Scientific Co. Acetone: Fisher Scientific Co.. MCB. Redis- tilled in glass from Dri-Sodium, Fisher Scientific Co. Mallinckrodt Chemical. Pesticide-qual- ity solvents. Used directly from re- agent bottle after periodic checks ■.howed no interferences. Soaked in acetone, rinsed with 1:1 acetone: hexane mixture. Glassware: Washed thoroughly with hot detergent; rinsed once with hot water, twice with distilled water, again with 1 : 1 mixture of redistilled acetone:hexane. PREPARATION OF SAMPLES Procedures to extract and remove the bulk of the lipids have been described previously (21). Because of the high relative concentration of p,p'-DDE in Lake Michigan fish, DDE was quantitated directly by dilut- ing 10 percent of the nonpolar iiorisil eluate to the appropriate volume for gas-liquid chromatographic (GLC) analysis. PCB's were separated from TDE and DDT isomers with a modified Armour and Burke pro- cedure which omitted Celite 545 (22). Quantitative gas chromatographic analyses were con- ducted on an Aerograph 1745-20 gas chromatograph equipped with dual concentric-tube electron-capture detectors (-'H, 250 mc). Columns were 2.0-m-by-l .8- mm-lD glass coils packed with 3 percent OV-101 on 120/140-mesh Gas-Chrom Q. The carrier gas, purified Nj, was maintained at 20 ml, min; the injector, column, and detector temperatures were 240 , 1 80 . and 220° C. respectively. Chromatograms were recorded on a Varian model A-25 dual pen recorder. Previous work (21) showed that fish from Lake Michi- gan contain mixtures of PCB's that closely resemble the Aroclor 1 254 produced by Monsanto Company, al- though PCB's both heavier and lighter than those most abundant in Aroclor 1254 were also present. The fish extracts contain predominantly those PCB's which elute at 70. 84. a doublet of 98 and 104. 125, 146, and 176; peak height of p.p'-DDE is represented here as 100 (Fig. 2). The presence of DDE precluded the use of the 98 and 104 PCB components in the quantita- tion, and PCB's based on Aroclor 1254 were deter- mined by summing the heights of the 70, 84. 125, 146, and 174 PCB components when peak height of DDE is 100. This method also decreased the effect of minor compositional variations on the analytical result. /UKICIXMI I2H LAKE MICHIGAN SALMON RETENTION VOLUME FIGURE 2. Chromatograms of PCB mixtures in Aroclor 1254 and fish from Lake Michigan Vol. 9, No. 1, Iune 1975 Recovery of PCB's from fish tissue averaged 85.1 ± 4.3 percent, whereas recovery of DDE was greater than 90 percent. The precision of the method outlined above is summarized in Table 1. which lists means and stan- dard deviations of the analyses of six replicates of sev- eral fish species for PCB's. DDT, and lipids. The stan- dard deviation for PCB analyses ranged from 5 percent in smaller fish to 14 percent in large coho salmon. The decrease in precision in analyses of large coho resulted from the difficulty of homogenizing larger fish. Pre- cision was poorest in DDT analyses, where the standard deviation ranged from 8 to 23 percent with a mean of approximately 14 percent. This reduced precision re- sults from losses during silicic acid chromatography which is used to quantitate the TDE and DDT isomers. The precision of DDE analyses was greater than those for DDT analyses, which was anticipated because of the fewer manipulations of the extracts. The standard deviation ranged from 7 to 18 percent, but the average deviation was approximately 10 percent. Because of the relatively simple procedure, lipid analyses were most precise, exhibiting standard deviations from 5 to 7 percent. TABLE I . Precision of chlorinated hydrocarbon determinations for PCB's, DDE. DDT, and lipids in selected fish, Lake Michigan — 1971 Species No. Repli- cates Aroclor 1254 P.P'-DDE P.P-DDT Lipid, % Coho salmon (25 in.) 6 15.2±2.2 7.5±0.6 3.2±0.6 4.2+0.2 Coho salmon (27 m.) Whitefish (13 in.) 6 6 1.1.1+1.3 4.1 ±0.2 5.5±0.4 0.35±0.04 1.8±0.4 0.56+0.04 10.0±0.6 16.2±0.9 Bloater (10 in.) 6 5.7±0.4 3.4+0.3 2.2±0.3 18.2+1.3 Alewife (8 in., composite) 6 4.0+0.2 1.1±0.2 1.0±0.2 5.7±0.3 NOTE: In columns 3-6, first number represents mean, second repre- sents standard deviation. Residues are ppm wet weight. The determinable limit for PCB analysis was approxi- mately 0.1 ppm; limits for p,p' -DDT. o,p'-DDT, p,p'- TDE. and p.p'-DDE were approximately 0.05 ppm. CONFIRMATION OF MAJOR COMPONENTS Major components of Lake Michigan fish extracts were characterized for a limited number of composite sam- ples by standard gas-liquid chromatography/ mass spec- trometry techniques. In addition, the presence of PCB's in samples from each collection area was confirmed by perchlorination of PCB's to decachlorobiphenyl and subsequent analysis of the product by GLC (23). Ali- quots of the hexane fraction of silicic acid columns were evaporated to dryness in a 5-ml vial fitted with a teflon-lined screw cap. Antimony pentachloride (0.2 ml) was added to the residue, and the vial was sealed and held at 180° C for 6 hours. Approximately 1 ml 6N MCI was added to the products to remove the SbCf-, and the solution was extracted with five 1-ml hexane portions. The hexane was passed through a disposable pipette containing anhydrous Na^,S04 to remove traces of the aqueous solution. The sample was collected in a graduated centrifuge tube and diluted to the proper volume for GLC analysis. This technique also provided semiquantitative information for PCB's to supplement direct GLC analysis of the extracts. For those samples which contained PCB's similar to Aroclor 1254, esti- mates of total PCB's by perchlorination were within 15 percent of direct GLC analysis. Results and Discussion Approximately 850 fish were analyzed for PCB mix- tures most closely resembling Aroclor 1254; a summary is presented in Table 2. Mean concentrations ranged from 2.7 ppm in smelt to 15.5 ppm in lake trout. Larger fish, such as brown, lake, and rainbow trout and Chinook and coho salmon, contained PCB's at mean concentrations two to three times the 5 ppm action level established by FDA (/). Mean PCB concentrations in redhorse suckers, smelt, and whitefish were con- siderably less than 5 ppm. Mean concentrations in the alewife, carp, chub, and yellow perch were approxi- mately 5 ppm; the range was 4.2-6.0 ppm. As expected. PCB levels increased with the percentage of fat and size of fish. In Lake Michigan fish the mean concentration of total DDT. the sum of p.p'-DDT. o.p'-DDT. p.p'-TDE. and p.p'-DDE. ranged from 0.9 ppm in carp to 7.1 ppm in lake trout (Table 2). As with PCB's, fish with higher lipid concentrations contained greater concentrations of DDT. The ratio of PCB's to total DDT ranged from 1.3 in redhorse suckers caught primarily in the northern waters to 7.6 in carp. The ratio of PCB's to DDT in the ma- jority of the fish was between 1.7 and 2.8, and only in the carp, redhorse, yellow perch, and white sucker did the ratios fall outside this range. This ratio may become important in future studies to determine the rates at which the chemicals are eliminated from the Lake Michigan system. Mean ratios of o.p'-DDT to p.p'-DDT ranged from 0.1 to 0.3; this ratio in the majority of the fish was 0.2. Since technical DDT generally contains about 30 per- cent of the o.p'-DDT isomer (ratio, 0.4), data from Lake Michigan fish suggest that degradation, other re- moval mechanisms, or both in the lake are slightly greater for the o.p' isomer than for the p.p' isomer. More than 80 percent of the total DDT residue is accounted for by p.p'-DDE and p.p'-DDT. Not only did PCB concentrations vary considerably among the 13 species captured, but the range of PCB concentrations in a single lake species was generally 24 Pesticides Monitoring Journal greater than 100 percent. The concentration range in red suckers was less, but ail were captured in the same region of the lake. Ahhough some variation in concen- trations is expected because of the norma! analytical error, the much larger ranges in Table 2 are undoubt- edly due to other factors that limit usefulness of the mean concentrations presented. Previous research has shown that the lipid content, size of fish, season of cap- ture, and concentration in the water may affect con- siderably the observed concentration of chlorinated hydrocarbons in tissue (2). CHLOROBIPHENYLS Regional variation in PCB concentrations and variations due to lipid content for each species are shown in Table 3. The wet-weight concentration of PCB's in ale- TABLE 2. Major chtorocarbons in fish, Lake Michigan — 1971 Mean Mean Mean Mean No. FISH Fish MEAN Mean Mean Mean PCB/ DDE/ o,p'-DDT/ Species ' Analyzed Weight, g Lipid, % PCBs DDE :;ddt 2 DDT 2 DDT p.p'-DDT Alewife 85 100 6.5[3.91 4.6[2.11 1.7(0.8] 2.2(1.1] 2.4 0.8 0.2 Bloater 287 249 20.0(5.9] 6.0[2.21 2.5(1.1] 3.8(2.8] 2.2 0.7 0.2 Brown trout 17 3,650 15.5[4.11 7.3[2.81 2.7(1.0] 4.2(1.6] 1.8 0.6 0.1 Carp 42 2.160 10.0[7.0] 4.2(3.61 0.7(0.9] 0.9(1.2] 7.6 0.8 0.3 Chinook salmon 21 3,100 5.0[3.91 11.4(4.0] 5.2(1.5] 6.8(2.5] 1.7 0.8 0.2 Coho salmon 56 2,720 6.5[2.11 11.5[5.7] 4.8(2.3] 6.3(2.8] 2.1 0.7 0.2 Lake trout 134 1,620 16.6[4.31 15.5(3.3] 5.0(2.8] 7.1(3.71 2.5 0.7 0.2 Yellow perch 44 148 6.U1.7] 5.8(3.5] 1.0(0.6] 1.6(1.1] 4.8 0.8 0.1 Rainbow trout 11 4,190 18.4[3.3] 9.3(4.1] 3.4[1.31 4.2(1.8] 2.3 0.8 0.2 Redhorse sucker 16 902 8.6I1.2I 3.010.7) 1.6(0.5] 2.6(0.7] 1.3 0.6 0.2 Smelt 38 51 5.8[1,8) 2.7(1.3] 0.8(0.4] 12(0.6] 26 0.7 0.1 White sucker 51 1,130 5.9[2.81 3.9(3.6] 1.0(0.5] 1.6(1.2] 3.4 0.7 0.1 Whitefish 43 1,170 17.6[4.4] 3.0[1.9] 0.8(0.3] 1.4(0.6] 2.8 0.7 0.2 NOTE: Expressions in brackets J-epresent standard deviations. Residues are ppm wet weight. ' Scientific names appear in Table 3. TABLE 3. Mean concentrations of PCB's and DDT in fish. Lake Michigan — 1971 Percent- Percent- age Fish age Fish No. Above PCB's, Above Capture Fish 5 PPM LIPID P.P'- p.p'- P.P'- o.p'- TOTAL 5 PPM Location Date Analyzed PCB's PCB's WEIGHT DDE TDE DDT DDT DDT DDT Alewife (Alosa pseudoharengus) Michigan City 10/15 10 4.4(2.0] 40 164 1.4 0.19 0.5 0.08 2.2 10 Benton Harbor 9/2 10 4.8(1.1] 40 60 1.8 0.23 0.5 0.08 2.7 0 Waukegan 8/23 2 2.5(0.1] 0 47 1.0 0.18 0.5 0.07 1.6 0 Saugatuck 4/11 12 5.3[2.21 41 51 1.8 0.22 0,8 0.10 2.7 11 Sheboygan 10/15 4 5.5(1.4] 50 79 2.2 0.20 0.7 0,07 3.2 0 Ludington 7/3 16 4.4(1.4] 18 207 ND ND ND ND ND ND Frankfort 10/5 10 3.7(1.2] 20 62 1.3 0.16 0.4 0.06 1.9 0 Manitou Island 9/10 3 3.8(2.2] 33 51 3.2 0.33 1.3 0.16 5.0 30 Rock Island 9/11 3 8.9(12.0] 66 182 1.1 0.11 0.3 0.04 1.5 0 St. Martin Island 9/11 6 3.5(1.3] 16 82 1.0 0.14 0.3 0.05 1.5 0 Brown trout (Salmo tnilta) Michigan City Sheboygan Gills Rock 10/15 7/13 9/16 1 5 10 11.9(0.0] 7.9(3.0] 6.7(2.5] 100 100 70 51 42 54 3.7 2.6 2.8 0.70 0.46 0.48 1.7 1.2 1.0 0.22 0.18 0.14 8.4 4.4 4.4 100 25 40 Bloater (Coregonus hoyi) (Continued next page) Carp (Cyprinus carpio) Michigan City 11/29 2 11.0(0.2] 100 72 3.3 0.81 0.3 0.14 4.6 50 Saugatuck 10/15 15 4.6(4.8] 26 71 0.6 0.20 0.1 0.02 0.9 0 Sheboygan 7/23 11 1.7(0.8] 0 30 0.2 0.07 0.0 0.01 0.3 0 Pensaukee Bar 11/1 9 4.2(1.4] 33 30 0.8 0.19 0.0 0.01 1.0 0 Manitou Island 9/16 5 5.8(0.8] 80 30 ND ND ND ND ND ND Benton Harbor 9/2 10 5.0(1.2] 60 24 2.5 0.31 1.5 0.19 4.5 30 Saugatuck 6/16 18 8.1(1.9] 88 46 1.9 0.47 1.8 0,19 4.3 37 Saugatuck 6/18 24 7.8(2.2] 95 43 2.4 0.63 2.4 0.25 5.7 64 Saugatuck 6/19 15 6.9(1.8] 86 34 1.8 0.47 2.5 0.31 5.1 66 Milwaukee 9/19 11 4.6(1.2] 36 28 3.4 0.36 2.0 0.26 6.0 88 Sheboygan 7/13 13 5.1(1.5] 61 31 1.3 0.40 2.2 0.24 4.1 50 Sheboygan 7/22 13 6.1(1.8] 76 21 3.4 0.34 2.0 0.24 5.9 81 Vol, 9- No, 1, June 1975 25 TABLE 3 (cont'd.)- Mean concentrations of PCB's and DDT in fish, Lake Michigan — 1971 Percent- Pekcent- age Fish AGE Fish No. Above PCBs, Above Capture Fish 5 PPM LIPID P.P'- P.P'- P.P'- o.p'- Total 5 PPM Location Date Analyzed PCBs PCB's WEIGHT DDE TDE DDT DDT DDT DDT Sheboygan 8/19 6 3.8[0.6] 0 15 2.6 0.35 1.3 0.16 4.4 20 Sheboygan 8/27 7 5.0[1.3] 57 23 3.2 0.47 2.3 0.28 6.2 80 Sheboygan 10/15 6 3. 7 [0.8] 0 21 2.4 0.28 1.7 0.17 4.5 42 Ludington 7/3 43 7.4[1.8] 93 41 2.0 0.58 T ~t 0.28 5.0 46 Frankfort 10/5 8 4.7[0.7] 12 28 2.2 0.33 1.2 0.16 3.8 0 Manitou Island 9/10 10 4.6[1.1] 30 24 3.1 0.50 1.8 0.26 56 50 Washington Island 9/9 6 4.110.6] 0 16 3.2 0.34 1.9 0.18 5.6 60 Rock Island 9/11 6 5.8[2.5] 66 97 2.8 0.36 1.1 0.08 4.4 20 Rock Island 9/14 7 5.611.6] 57 23 2.7 0.42 2,0 0.22 5.4 50 Rock Island 9/16 8 4.0(0.7] 12 18 2.8 0.29 1.3 0.14 4.5 40 St. Martin Island 7/19 9 3.4[0.6] 0 16 2.2 0.34 1.1 0.17 3.8 0 Manistique 5/27 9 4.8[0.7] 33 26 2.9 0.42 1.8 0.14 5.2 80 Chinook salmon (Oncorhynchus tscha-nytscha) Milwaukee 10/15 1 24.0[0.0] 100 117 6.6 1.67 4.7 0.53 13.6 100 Manitowoc 10/21 8 11.3[3.1] 100 209 6.3 0.62 1.2 0.21 8.3 100 Strawberry Creek 10/21 10 9.9[2.8] 100 373 4.5 0.39 1.0 0,17 8.0 88 Gills Rock 9/16 2 12.7[0.7] 100 278 5.5 0.44 1.2 0.20 7.3 100 COHO salmon (Oncorhynchus kisutch) Michigan City 4/17 8 3.6[1,7] 12 51 0.8 0.17 0.6 0.08 1.6 0 Michigan City 9/27 8 17.3[8.4] 87 255 5.3 0.46 1.2 0.20 7.2 85 Michigan City 10/7 6 14.0[4.0] 100 349 4.5 0.41 1.4 0.18 6.5 60 Sheboygan 10/21 9 12,1[2.8] 100 276 6.6 0.57 1.4 0.27 8.8 100 Ludington 8/28 4 11.2L3.3] 100 108 6.8 0..39 0.9 0.19 8.3 100 Platte River 10/7 10 12,9[1.3] 100 226 5.5 0.48 1.4 0.24 7.6 100 GiUs Rock 9/16 11 12.6(4.1] 90 166 4.9 0.45 1.2 0.20 6.7 87 Lake trout {Sahelinus namaycush) Michigan City 10/15 4 14.9(2.0] 100 89 2.9 0.88 3.1 0,35 7.3 100 Michigan City 9/8 3 21.2(6.8] 100 121 9,5 1.12 3.9 0,45 14.9 100 Saugatuck 6/21 14 11.9(3.8] 100 70 4,7 0.65 2.1 0.27 7.6 88 Saugatuck 7/10 7 15.5(2.4] 100 78 6.9 0.70 2.0 0.24 9.8 100 Saugatuck 10/1 9 18.7(4.7] 100 113 6.7 0.84 2.8 0.27 10.6 100 Milwaukee 9/14 1 21.2(0,0] 100 90 10.1 0.96 3.0 0.47 14.5 100 Milwaukee 9/19 7 21.1(6.0] 100 114 10.6 1.05 3.3 0.45 15.4 100 Milwaukee 10/15 12 10.4(3,6] 100 127 2.3 0.44 1.3 0.15 4.2 20 Sheboygan 7/1 1 14,9(0,0] 100 58 ND ND ND ND ND ND Sheboygan 7/13 36 12.5(3.2] 100 82 4.3 0.51 1.7 0.24 6.8 64 Ludington 7/1 10 8,1(1,8] 100 51 3.3 0.52 1.6 0,22 5.6 60 Ludington 7/4 8 8,5(1,7] 100 58 3.2 0,63 2.0 0,30 6.1 66 Grand Traverse Bay 10/19 8 11.3(5.3] 75 56 6.0 0,73 2.0 0,30 9,0 77 Green Island 7/21 19 9.0(1.7] 100 48 3.8 0,50 1,5 0,21 6,0 72 Gills Rock 9/16 10 14.7(6.4] 100 83 5.5 0,62 1.9 0,24 8.J 62 Yellow perch (Perca flarescens) Michigan City 10/15 14 4.2(0,7] 14 72 0.8 0.15 0,4 0.04 1.3 0 Waukegan 8/28 9 6.1(1.5] 88 78 ND ND ND ND ND ND Milwaukee 10/13 10 10.9(3.1] 90 203 1.1 0.30 0,7 0.08 2,1 0 Ludington 7/6 3 6.2(1.3] 100 139 2.2 0.30 0.9 0,13 3.6 0 Frankfort 10/12 -) 5.4(1,8] 50 69 1.7 0,43 -> ■> 0,14 4.5 0 Pensaukee Bar 8/25 10 2,7(2.1] 10 49 0.4 0,10 0.0 0.01 0,5 0 Rainbow trout (Salmo gairdneri) Michigan City Gills Rock 10/15 9/16 12,0(0.0] 8.8(4.3] 100 77 66 47 ND 3.1 ND 0,.34 ND 0.9 ND 0.16 ND 4.5 Redhorse (Moxdstoma sp.) Rock Island St. Martin Island 9/11 9/11 2.8(0.9] 3.2(0.5] 33 37 1.7 1.5 0.30 0.35 0.6 0.8 0.09 0.09 2.7 2.7 Rainbow smelt {Osmerus eperlanus modrax) Michigan City 10/15 15 3.2(0.9] 0 45 0.9 0.11 0.4 0.04 1.4 0 Sheboygan 10/15 0.7(0,2] 0 18 0.6 0.12 0.3 0.03 1.0 0 Green Island 7/21 5 2.6(1.1] 0 57 0.7 0.12 0.2 0.02 1.0 0 Rock Island 9/11 8 2.9(1.7] 25 49 1.0 0.14 0.5 0.05 1.6 0 St. Martin Island 7/19 4 1.3(0.3] 0 31 0.7 0.09 0.2 0.04 1.0 0 White sucker (Caiosiomus commersoni Michigan City 10/15 6 10.6(4.0] 100 100 1.8 0.32 1.8 0.08 4.6 66 Saugatuck 10/15 3 6.0(2.9] 66 149 0.7 0.14 0.2 0,03 1.0 0 Saugatuck 10/18 5 2.3(0.4] 0 40 ND ND ND ND ND ND Pensaukee Bar 8/6 7 3,2(3.1] 14 57 0.3 0.15 0.2 0.04 0.7 0 Grand Traverse Bay 10/19 14 2.3(0.7] 0 68 0.4 0.31 0.4 0.03 2.1 0 Green Island 7/21 1 2.1(0.0] 0 20 0.7 0.19 0.4 0.08 1.3 0 Rock Island 9/11 14 2.5(0.9] 0 46 0.9 0.20 0.3 0.04 1.4 0 (Continued next page) 26 Pesticides Monitoring Journal TABLE 3 (cont'd.). Mean concentrations of PCB's and DDT in fish, Lake Michigan — 1971 Percent- — " Percent- age Fish age Fish No. Above PCB's, Above Capture Fish 5 PPM LIPID CP'- P.P'- I'.n'- II. p'- Total 5 PPM Location Date Analyzed PCB's PCB's WEIGHT DDE TDE DDT DDT DDT DDT Lake whitefish (Coregonus clupea/ormis) Michigan City 10/15 4 6. no 9] 100 25 0.5 0.32 0.5 0,06 1.4 0 Saugatuck 6/19 7 2.7[0.5] 0 15 n.6 0.21 0.4 0.08 1.3 0 Saugaujck 6/21 1 3U1.31 0 18 ND ND ND ND ND ND Grand Haven 9/6 7 5.8[0.91 71 25 0.7 0.38 0.8 0,10 1.9 0 Grand Traverse Bay 10/19 11 1.8(0,3] 0 1.1 1.2 0,25 0.4 0.08 2.0 0 Rock Island 9/11 10 1.5I0.2] 0 9 0.7 0.16 0.4 0.05 1.4 0 NOTE; Expressions in brackets represent standard deviations. ND = not determined. Residues are ppm wet weight, wives was greater in southern Lake Michigan than in the northern regions, although anomalies are apparent. Most alewives captured south of a line between Sauga- tuck and Sheboygan contained between 4.4 and 5.5 ppm PCB's, whereas those caught north of the line con- tained between 3.5 and 4.4 ppm. An interesting excep- tion occurred in alewives from Rock Island just off the Door County Peninsula in Wisconsin; mean PCB con- centration was 8.9 ppm. Analysis of brown trout suggested similar trends; those from Michigan City at the southern end of the lake contained 11.9 ppm PCB's. whereas those from She- boygan and Gills Rock contained 7.9 and 6.7 ppm PCB's, respectively. Carp from Michigan City also had higher levels of PCB's than had those from the northern region. In contrast to the 11.0 ppm found in the Michigan City carp, those from Saugatuck and Sheboygan contained 4.6 and 1.7 ppm, respectively. PCB's in bloaters in southern Lake Michigan ranged from 4.6 ppm near Milwaukee to 8.1 ppm near Sauga- tuck. In general, bloaters from the northern regions had concentrations below 5 ppm. The concentration of PCB's in the five groups of bloaters collected near Sheboygan during a 3-month period varied from 3.7 to 6.1 ppm. although the mean was below 5 ppm; no trend was indicated. The variation is somewhat less when data are expressed on a lipid basis; for example. PCB concentrations in the August 27 and October 15 bloaters were 5.0 and 3.7 ppm wet weight, respectively. In contrast, the concentration of PCB's in lipids was 23 ppm and 21 ppm, respectively. Thus much of the observed variation is caused by the variation in lipid content of fish. All Chinook salmon captured in Wisconsin contained more than 5 ppm PCB's; mean concentrations ranged from 9.9 ppm in Strawberry Creek (Sturgeon Bay) to 24 ppm at Milwaukee. In concentrations of PCB's among coho salmon, authors observed little evidence of a trend dependent upon sam- pling region. Except for coho caught early in 1971 near Michigan City, mean concentrations of PCB's ranged from 11.2 ppm in salmon near Ludington to 17.3 ppm in those near Michigan City. Among lake trout PCB concentrations were greatest in those from Michigan City, Saugatuck, and Milwaukee, where mean concentrations were generally between 15 and 21 ppm. Trout from the northern areas such as Sheboygan, Ludington. Grand Traverse Bay, and Gills Rock contained considerably less, and mean concen- trations ranged between 8 and 15 ppm. Mean concentration of PCB's was unexpectedly high, 10.9 ppm, in the 10 yellow perch caught near Milwau- kee. Perch from other regions averaged less by a factor of two, and those from lower Green Bay contained 2.7 ppm. In seven Rock Island redhorse, PCB residues averaged 2,8 ppm. In nine specimens from St. Martin Island, mean concentration was 3,2 ppm. Rainbow trout were caught only near Michigan City and Gills Rock. The Michigan City rainbow trout had 12.0 ppm PCB's. whereas those from Gills Rock aver- aged only 8.8 ppm. Concentrations of PCB's in white suckers and smelt were generally between 2 and 4 ppm, although the average concentration was 6.0 ppm in the three white suckers from Saugatuck on October 15 and 10.6 ppm in the six from Michigan City the same day. Except for whitefish caught at Grand Haven and Michigan City, the PCB concentration in whitefish was less than 3.1 ppm. DDT AND ANALOGS Concentrations of p.p'-DDT, o.p'-DDT. p,p'-TDE. and p.p'-DDE are presented in Table 3 along with the total DDT and percentage of fish that contained residues above the 5ppm action level established by FDA (1). Total DDT in alewives ranged from 1.6 ppm near Wau- kegan to 5.0 ppm near the Manitou Islands. There was no trend in the variations according to region, A brown trout from Michigan City contained 8.4 ppm total DDT, whereas those from Sheboygan and Gills Rock averaged 4.4 ppm. Except for the carp from Michigan City, which averaged 4.6 ppm total DDT, average concentra- tions in Lake Michigan carp were 1 .0 ppm or less. Vol. 9, No. 1. June 1975 27 Total DDT in bloaters ranged from 3.8 ppm at Frank- fort and St. Martin Island to 6.2 ppm at Sheboygan. There are no trends tor DDT in chubs (Table 3). Except lor eight coho salmon caught near Michigan City in the spring, which averaged 1.6 ppm total DDT. total DDT in this species varied little throughout the lake. Mean concentrations ranged between 6.5 and 8.8 ppm. Lake trout from Michigan City averaged 14.9 ppm total DDT on September 8. 1971; those caught October 15. 1971. averaged only 7.3 ppm. The discrepancy is likely due to size differences. For example, the lake trout caught near Milwaukee in September also contained a mean concentration of approximately 15 ppm; how- ever, the smaller trout caught near Milwaukee in Octo- ber averaged only 4.2 ppm total DDT. DDT concentra- tions in lake trout from northern areas of the lake were less than 8 ppm; approximately 60-70 percent of the lake trout contained over 5 ppm total DDT. Yellow perch from Pensaukee Bar in lower Cjreen Bay had the lowest DDT content. 0.5 ppm; perch from other areas contained between 1.3 and 4.5 ppm total DDT. None of the perch contained more than 5 ppm total DDT. Concentration of DDT in smelt, whitefish. and white suckers averaged approximately 1-2 ppm. although white suckers from Michigan City averaged 4.6 ppm total DDT. SiiDiDiary Concentration of PCB's ranged from less than 2 ppm in small fish with low lipid content to over 20 ppm in larg- er fish with higher lipid content. The concentration of PCB's in Lake Michigan coho salmon is two to three times greater than in coho from Lake Huron, approxi- mately 1.5 times greater than in Lake Ontario coho salmon, and approximately 10 times greater than in coho from Lakes Erie and Superior. Essentially 100 percent of large salmon and trout, both popular food sources, and 50-80 percent of bloaters from Lake Michi- gan contain PCB concentrations greater than the 5 ppm tolerance level set by FDA. Additional monitoring of this watershed is needed to determine whether tissue concentrations will reflect restrictions in domestic PCB sales and possible decreases in PCB usage in the water- shed even though U.S. production of Aroclor 1254 has remained essentially the same as in 1969 {2-1). Acknowledgments Fish for this study were collected by the Bureau of Sport Fisheries and Wildlife Great Lakes Fishery Lab- oratory, U.S. Department of Interior; State agencies from Michigan, Indiana, Illinois, and Wisconsin; and numerous private research and commercial fishing or- ganizations. Their assistance, essential to this study, is sincerely appreciated. LITERATURE CITED (/) Heallon, D. C. 1975. A review of PCB's in the Great Lakes area. Food and Drug Administration, U.S. DHEW. Governors' Great Lakes Pesticide Council. Jan. 30. Chicago. III. (Minieo.) (2) Reinert. R. E. 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4) :233-240. (-') I'eitli, G. D. 1970. Environmental chemistry of the chlorobinphenyls in the Milwaukee River. Ph. D. thesis. Univ. Wisconsin. Madison, Wis. 180 pp. (4) Zitko. v., and P. M. K. Choi. 1971. PCB and other industrial halogenated hydrocarbons in the environ- ment. Fish. Res. Bd. Can. Tech. Rep. 272. 55 pp. {,5) \'ciiional Insiiliilcx of Health. 1972. Environ. Health Perspect. 1( I ): 1-185. (6) Qtiinhy. G. E. 1972. Polychlorobiphenyls (PCB's) and related chlorophenyls: Effects on health and en- vironment. I. Bibliography 1881-1971. Oak Ridge Na- tional Laboratory, TIRC-I, ORNL-EIS-72-20. 140 pp. (7) Niiiioncil Technical Information .Service. 1972. Poly- chlorinated biphenyls and the environment. Inter- departmental Task Force on PCB's. Springfield, Va., COM-72-l()4l9. 18! pp. (<"() Kernen, L. 1970. Rainbow and brown trout — Lake Michigan 1970. Rep. Wisconsin Dep. Nat. Resour., Green Bay, Wis. 6 pp. (Mimeo.) (9) Great Lakes Fi.shery Laboratory. 1972. Annual prog- ress report — 1971. Ann Arbor, Mich. 318 pp. (/rt) Burdick, G. £., £. 1. Harris. H. ]. Dean, T. M. Walker. J. Skea, and D. Colby. 1964. The accumula- tion of DDT in lake trout and the effect on reproduc- tion. Trans. Amer. Fish. Soc. 93( 2 ) : 127-1 36. (//) Macek, K. J. 1968. Reproduction in brook trout, Salvelinus fontinalis. fed sublethal concentrations of DDT. J. Fish. Res. Bd. Can. 25( 9 ): 1787-1796. {12) Johansson, A'. S.. S. Jensen, and M. Olsson. 1970. PCB indications of effects on salmon. PCB Confer- ence, Swedish Salmon Institute. Stockholm, Sweden, Pp 59-68. (Mimeo.) {13) Hartsough, G. R. 1965. Great Lakes fish now suspect as mink food. Amer. Fur Breeder 38( I ) :25, 27. {14) Aulerich, R. J., R. K. Ringer. P. J. Schaible. and H. L. Seagran. 1970. An evaluation of processed Great Lakes fishery products for feeding mink. Feed- stuffs 42(3) :48-49. {15) Aulerich. R. J., and R. K. Ringer. 1970. Some effects of chlorinated hydrocarbon pesticides on mink. Amer. Fur Breeder 42( I ): lO-l I. (/6) Aulerich. R. J.. R. K. Ringer. H. L. Seagran. and W . G. Yoitalt. 1971. Effects of feeding coho salmon and other Great Lakes fish on mink reproduction. Can. J. Zool. 49(5) :6I 1-616. {17) Ringer. R. A'., R. J. Aulerich. and M. Zabik. 1972. Effect of dietary polychlorinated hiyhenyls on growth and reproduction of mink. Presented at the American Chemical Society. New York. Division of Air, Water, and Waste. Pp. 149-154. {IS) Ratclifle, D. A. 1970. Changes attributable to pesti- 28 Pesticides Monitoring Journal cides in egg breakage frequency and eggshell thickness in some British birds. J. Appl. Ecol. 7( 1 ) :67-l 13. (19) Anderson, D. W. 1970. Chlorinated hydrocarbons: their dynamics and eggshell effects on herring gulls and other species. Ph.D. thesis. Univ. Wisconsin, Madison, Wis. 166 pp. (20) Lueschow, L. A. 1972. Lake Michigan Pesticide Con- ference pesticide report. Final report to U.S. Environ- mental Protection Agency by Wisconsin Department of Natural Resources, Madison, Wis. 139 pp. (21) Veith, G. D., and G. F. Lee. 1971. PCB's in fish from the Milwaukee River. Proc. 14th Conf. Great Lakes Res. Pp. 157-169. (22) Armour, J. A., and J. A. Burke. 1970. Method for separating PCB's from DDT and its analogs. J. Ass. Oflic. Anal. Chem. 53(4) ;761-768. (23) Berg, O. W., P. L. Diosady, and G. A. V. Rees. 1972. Column chromatographic separation of PCB's from chlorinated hydrocarbon pesticides, and subsequent gas chromatographic quantitation in terms of deriva- tives. Bull. Environ. Contam. Toxicol. 7(6) :338-347. (24) Popageorge, W. B. 1974. Testimony on behalf of Monsanto Company, Transcript of Proceedings, U.S. Environmental Protection Agency. In the Matter of: Toxic Pollutant Etfluent Standards, Washington, D.C., May 8. P. 2756. Vol. 9, No. 1, June 1975 29 GENERAL Distribution of Organochlorine Pesticides in an Agricultural Environment , Holland Marsh, Ontario — 1970-72 ^ John R. Brown,2 Lai Ying Chow,^ and Fong Ching Chai 3 ABSTRACT Analysis of organochlorine pesticides in soil, fish, and human blood samples from Holland Marsh, Ontario, indicates that although total DDT is present in detectable amounts, it does not constitute a hazard to human health and longevity. Among soils tested, residues were highest in surface sam- ples. DDT levels in human blood samples were similar to those in U.S. and British studies. Introduction Holland Marsh, a 7,500-acre area devoted primarily to intense vegetable farming, is located 30 miles north of Toronto. Ontario. It is 7 miles long. 1-3 miles wide, and cultivated by 400 farmers. Soil is classified as peat muck and the average farm size is 25-30 acres. The marsh is served by eight cooperative packing houses which process 90 percent of the crop. Produce is then de- livered to Toronto and Hamilton. Ontario; Detroit. Mich.; and areas of upper New York State including Buffalo and Rochester. Aldrin, dieldrin. and DDT and its metabolites have been applied to soil and crops for the past 40 years. It is pro- posed that this survey of residues in the Holland Marsh ecosystem form a basis from which the ultimate fate of DDT residues in agricultural environments of southern Ontario may be determined. This study was commenced in 1970, 6 months after use of DDT was banned in Ontario. Materials and Methods Blood samples were taken from farm workers and pack- ing house employees of both sexes. Ten-ml blood sam- ^ Institute for Environmental Studies and School of Hygiene. Univer- sity of Toronto, Toronto. Ontario, Canada. 2 School of Hygiene. University of Toronto, 150 College Street, Toronto, Ontario, Canada M58 lAl. Reprints are available from this address. 3 Institue for Environmental Studies, Haultain Building, University of Toronto, Toronto, Ontario, Canada. pies were collected in glass tubes containing potassium oxilate as an anticoagulant. Blood was collected in June (217 samples) and September (108 samples), the com- mencement and the end of the most active growing period. Four farms situated along the north-south axis of the marsh were randomly selected for monitoring. Farm size and agricultural history are listed in Table 1. The four farms sampled were larger than average for the marsh, enhancing authors' opportunities for a large sampling area, personal interviews with each farmer, and accurate detailed history of the farm. Soil samples were collected during late spring from six sites ran- domly selected on each farm. Individual samples were taken from the soil surface, composite samples were taken from 0-7.5 cm deep, and five 7.5-cm cores were sampled in one location to a total depth of 45 cm on each farm. Sampling sites are shown in Figure 1. TABLE 1. History of farms sampled for DDT and related compounds. Southern Ontario — 1970-72 Approxi- Acres mate Age, Crops Farm Size, Yeari Soil Description Grown 1 135 20 Deep woody muck soil near canal but also sphagnum muck at north end. Very wet below 22.5 cm Lettuce Celery Onions Carrots Potatoes Parsnips 2 180 28 Deep muck-peat soil. Little wood Lettuce Carrots Celery Onions 3 30 30 Half is shallow muck with heavy clay underneath. Half is mineral soil with heavy clay underneath Carrots Cauliflower Cauliflower Cabbage 4 100 10 Deep, wet muck soil. Very woody in places Carrots Onions Lettuce ^Age of farm implies period of time land has been cultivated since first homesteaded. 30 Pesticides Monitoring Journal C.anrmnatnn 1^ -^ Sampling locations, farms 1-4 ■«" Dyke limit nniiiti Drainage canal limit ■MOfORO FIGURE 1. Four farms in Holland Marsh, Ontario, sampled for DDT and related compounds Forty-eight fish were obtained by gill net or hook and line from streams throughout the marsh. Three ml whole blood was extracted with 10 ml acetonitrile using a Niagara shaker, 25 ml distilled water was added to the acetonitrile extract, pesticides were partitioned into hexane. and the hexane was concentrated to dryness with a rotary vacuum evaporator. The residue was redis- solved in 2 ml hexane and used for subsequent gas- VoL. 9, No. 1. June 1975 31 liquid (.hromatographic (GLC) analysis. A Varian model 2100 gas chromatograph equipped with 250-mCi trituim electron-capture detectors was used. Columns measuring 1.8 by 4 mm ID were packed with 4 per- cent SE-30 + 6 percent QF-I on 100-200-mesh chrom- osorb W. Average recovery rates for DDT. DDD. and DDE were 78. 82. and 79 percent, respectively. Ten-g samples of fish and soil were mixed with 10 g anhydrous sodium sLilfate and extracted by Soxhiet. Acetonitrile extracts were evaporated to approximately 5 ml. 50 ml sodium chloride solution was added, and the aqueous mixture was extracted three times with .50 nil redistilled hexane. The hexane extract was then evaporated to 10 ml and placed on top of a column containing a mixture of florisil and Celite in a 4:1 ratio by weight. The entire column was eluted with 200 ml of 6 percent ether in hexane and the eluate was evapo- rated to dryness with a rotary vacuum evaporator. The residue was redissolved in 4 ml hexane and used for subsequent GLC analysis. Average recovery rates for DDT, DDD. and DDE were 93, 93. and 91 percent, respectively. Results have been corrected for recovery. Sensitivity was 0,001 ppm for DDT, 0.0005 ppm for DDD. and 0.0001 ppm for DDE. Total DDT is calcu- lated by adding DDT and the equivalent values for DDE (1 . 1 1 48 ) and DDD ( 1 . 1 076 ) . Total DDT concen- trations in human blood samples are listed in Table 2. TABLH 2, Total DDT in hiintan Mood samples, Hoilaiicl Marsh. Ontario— 1970-72 No, SAMPLES Total DDT, ppm Mean ± stan- dard ERROR Median Range, ppm Whole group Farmers Packers and Otliers 356 92 264 0.016-1-0.001 0.019-1-0.002 0.014-1-0,001 O.OIl 0.01.1 0.011 0.011-0.084 0.005-0.084 0.001-0.077 TABl.F. 3, Hemof;lobin in human hlood, Holland Marsh, Ontario— 1970-72 No, Mean -^ Stan- Sex Samples dard Error Whole group M 230 15,7-1-0,1 F 126 14.2-1-0,2 Farmers M 92 15.5-1-0,2 Packers and others M 138 16.1 -1-0,1 F 126 13,8-1-0.2 40H 4.0 30 E a a. ui UJ I 20 i/i LU EC 10 TOTAL EQUIVALENT DDT I P 3.0 2.0- 1.0 T~r ALDRIN 4.0 3.0- 2.0- 0 7.5 15.0 22.S 30.0 37.5 45.0 i 1 DIELDRIN jpa SURFACE SOIL 7.5 15.0 22.5 30.0 37.5 45.0 DEPTH, cm 0 7.5 15.0 22.5 30.0 37.5 45.0 32 FIGURE 2. Concentrations of organochlorine pesticide residues by soil depth Pesticides Monitoring Journal TABLE 4. Organochlorine pesticide residues in soil sam- ples from four farms, Holland Marsh, Ontario — 1970-72 Residues, ppm Depth, cm No. Samples Aldrin DlEL- DRIN P.P'- DDE DDD P,P'- DDT Total DDT Surface 36 0.51 1.61 1.26 0.79 21.13 23.27 0- 7.5 18 0.86 2.19 1.64 1.02 27.41 30.38 7.5-15.0 18 0.78 2.03 1.49 1.07 23.49 26.38 15.0-22.5 18 0.62 1.40 0.86 0.85 12.35 14.25 22.5-30.0 18 0.03 0.08 0.07 0.02 0.73 0.83 30.0-37.5 18 0.02 0.06 0.08 0.03 0.85 0.97 37.5-45.0 18 0.04 0.08 0.08 0.03 0.82 0.95 Results and Discussion Total DDT levels in human blood from Holland Marsh are similar to those given by Dale (/) for the general population in the United States (0.019 ppm) and by Robinson (2) for the general population in England (0.013 ppm). Marchand et al. (i) and Mastromatteo (4) have discussed the possibility of blood dyscrasias arising from the widespread use of chlorinated hydro- carbon pesticides. In view of these hypotheses, hemo- globin in all samples was analyzed using cyanomethemo- globin. Values derived (Table 3) were within clinically acceptable limits for both men and women and did not indicate blood dyscrasia. Results of all human blood analyses were separated by month of sampling. Median values of total DDT from these two periods (0.013 and 0.011 ppm. respectively) were not significantly different. Quartiles around the medians are 0.010. 0.015. 0.010. and 0.012. respectively. Samples from packing house employees had a median value of 0.011 ppm; those from the farmers had a median value of 0.013 ppm. As in the study by Wasser- mann et al. (5). people over 40 years of age had higher organochlorine pesticide residues than had those in younger age groups. Mean residue levels of organochlorine soil samples are listed by farm and sample depth in Table 4 and illus- trated in Figure 2. Most compounds detected are con- centrated in the first 7.5 cm of soil, a distribution pro- file similar to that in soil of Norfolk County. Ontario (6). Similar results have also been obtained by Albright et al. in Alabama soils (7). Organochlorines are subject to decomposition by weathering and normal tillage. It is likely that total DDT concentrations in soil will diminish because DDT is no longer used in Ontario. Fish samples had lower total DDT levels (Table 5) than those in similar species collected from other areas where DDT has been used extensively, such as Nor- folk County. Ontario. Holland Marsh fish had higher DDT levels than fish taken recently from the base of the Bruce Peninsula, an unsettled area in Lake Huron. The total DDT equivalent has been determined in vari- ous ecological systems in the Holland Marsh region. Results indicate that no serious health hazard is asso- ciated with total DDT concentrations present. TABLE 5. Total DDT in fish muscle, Holland Marsh, Ontario— 1970-72 Species No. Samples Mean Total Common Name Scientific Name DDT, ppm Brown bullhead Iclalurus nebulosus 13 0.56 Bowfin Amia calva 0.18 Carp Cyprinus carpio 0.75 Goldfish Carassius auratus 0.38 Golden shiner Notemigonus crysoleucas 0.54 Yellow perch Perca flarescens 0.39 Northern pike Esox lucius 0.27 Rock bass Ambloplites rupestris 0.71 Smallmouth bass Micropterus dolomieui 0.73 White sucker Catostomus commersoni 5 0.53 Sunfish (Pumpkinseed) Leponiis gibbosits 15 0.46 NOTE: Fish were collected from ponds, streams, and rivers through- out the marsh. LITERATURE CITED (/) Dale, W. E., A. Curley, and C. Cueto, Jr. 1966. Hexane extractable chlorinated insecticides in human blood. Life Sci. 5(l):47-54. (2) Robinson, J., and C. G. Hunter. 1966. Organochlorine insecticides: concentrations in human blood and adi- pose tissue. Arch. Environ. Health 13(5) :558-563. (3) Marchand, A/., P. Dubrulle, and M. Goudemand. 1956. A case of agranulocytosis in a subject who has been exposed to vapours of benzene hexachloride. Arch. Ma. Prof. I7(3):256-258. (4) Mastromatteo, E. 1964. Hematological disorders follow- ing exposure to insecticides. Can. Med. Ass. J. 90(20): 1166-1168. (5) Wassermann, M., D. Wassermann, and I. Ivriani. 1970. Organochlorine insecticides in plasma of occupationally exposed workers. Inter-American Conference on Toxi- cology and Occupational Medicine, Seventh Conference, Coral Gables, Fla. (6) Brown, J. R. 1971. DDT in the agricultural soil and human tissue in Norfolk County, Ontario. Proceedings of the Second International Congress of Pesticide Chemistry, Israel. Pp. 551-571. (7) Albright, R., N. Johnson, T. W. Sanderson, R. M. Farb, R. Melton, L. Fisher, G. R. Wells, W. R. Parsons, V. C. Scott, J. L. Speake, J. R. Staltworth, B. G. Moore, and A. W. Hayes. 1974. Pesticide residues in the top soil of five West Alabama Counties. Bull. Environ. Contam. Toxicol. 12(3):378-384. Vol. 9, No. 1, June 1975 33 Organochlorine Pesticide Residues in a Farming Area, Nova Scotia— 197 2 -7 3''^ B. G. Burns, M. E. Peach, and D. A. Stiles ABSTRACT Soil, silt, and water samples from the Habitant Creek water- shed. Nova Scotia, a tobacco-growing area, have been monitored for organochlorine insecticides. Most samples contain measurable quantities of many persistent pesticides used in farming during the past decade. Sediment levels indicate that residues settle in sluggish parts of the stream. Drainage ditches show highest residual content caused in part by mass transport of soil in runoff. Residue content of water samples is normally one-tenth to one-hundredth that of silt, but is much higher during periods of heavy runoff. Levels vary with the seasons and are highest in the fall. decrease through the spring and summer, and are lowest in the winter. Although samples of well water taken fairly close to the stream showed virtually no residual content, a natural drainage reservoir had a pesticide content similar to that in the stream. Introduction In recent years the use of organochlorine insecticides in Canada has come under increasing scrutiny because of their long-term persistence. Although their role as gen- eral agricultural insecticides has diminished over the past 5 years, they were, until the early 1970's, used ex- tensively to control infestation in tobacco. Several reports {1-5) have appeared on the long-term persistence of organochlorine insecticides in a variety of settings, most of which were experimental plots. Al- though Harris (2.6,7) has extensively studied organo- chlorine residues in natural agricultural settings in southwestern Ontario, such work has generally received little attention. 1 Portions of this paper presented at the Third International Congress of Pesticide Chemistry, Helsinki, Finland, July 1974. 2 Acadia University, Wolfville, Nova Scotia, Canada BOP 1X0. Study supported in part by Agriculture Canada Contract EMR 7103. During the past few years, the chemistry department at Acadia University has been investigating organochlorine pesticide residues in the Habitant Creek watershed of Nova Scotia. This region, approximately 10 square miles, is located in the Annapolis Valley and supports a variety of agriculture including tobacco farming. Soils in the agricultural part of the watershed are predomi- nantly loam. Sampling Procedures Habitant Creek has both a tidal and a nontidal portion separated by an aboideau. This study deals with the nontidal section only and more specifically with the two main tributaries. Sleepy Hollow Brook and North Brook, which directly border farmland. Sampling locations are shown in Figure 1, SILT Samples were collected from readily accessible points along the banks and bed of the stream, natural drainage ditches, and other special areas such as the exit from a reservoir, Streambed samples were taken at a depth of 5-10 cm with a ladlelike device having a total volume of about 12 ml. Samples taken from stream banks and dry land were collected as soil cores of 2.5-cm diameter and 25-cm depth. Generally, at least three samples from the same site were thoroughly mixed prior to storage at 1.5° C. WATER Water samples were collected in 25-liter glass containers 1 m from the bottom of the stream. Because the water- way is relatively narrow (< 3 m) at all locations except site 30, no attempt was made to obtain vertical or hori- zontal profiles. However, it was felt necessary to ensure that all samples represented the stream as a whole rather 34 Pesticides Monitoring Journal FIGURE 1 . Habitant Creek drainage system showing sampling locations than localized pockets. Consequently, three samples were collected at each location from positions as close as possible to the center of the stream. These were com- bined for analysis. A nalytical Procedures Organochlorine insecticides were extracted from previ- ously moistened silt samples according to the method of Peach et al. (8). Water samples were filtered through glass wool and extracted by the procedure of Kahn and Wayman (9). The combined water extracts were then cleaned in standard fashion {8). Residues were identified by gas-liquid chromatography using the following operating parameters: Gas chromatopraph: Column: Delector; Temperature; Puryc carrier gas: Flow rate: Attenuation: Hewlett-Packard F and M model 700 pyrex 1.22 m by 0.73 cm, packed with 1 percent OV-17 on acid-washed chro- mosorb-W. 60 811 mesh, or 1.8.^ m by 0.73 cm, packed with 3.8 per- cent UCW-98 on acid-washed chromo- sorb-W, 60, 80 mesh electron-capture, pulsed at 50 ^s column 190' C detector 205° C 95 percent argon / 5 percent methane I. inde, dried by p.issine ihroujjh molecu- lar sieve purge gas 40 ml 'min carrier gas 30 ml mm 50 by 1 Peaks were identified by comparing their retention times with those of analytically pure standards applied to the above columns. Quantification was achieved by com- paring peak areas. Calibration curves for each insecti- cide were prepared daily using analytical standards sup- plied by Montrose Chemical Corporation, Torrance. Calif.; Shell Canada Limited, Toronto, Ontario; and Velsicol Corporation, Chicago, 111. Percent recoveries ranged from 65 to just over 100 per- cent. Residue levels in soil and water samples were cor- rected for recovery. Results and Discussion The first series of samples was collected during the spring and early summer of 1972, mostly in the form of sediment from streambeds (Table 1). The sample from site 1 9 was taken from an uncultivated piece of land directly across the road from a drainage ditch serv- ing tobacco fields. Most samples contained measurable quantities of commonly used organochlorine insecticides and their breakdown products. Most frequently found were the two isomers of DDT in quantities which might be expected from a typical agri- cultural settinc (2). Other residues were more localized Vol.. 9, No. 1. JuNi 1975 35 but difficult to link with particular field applications be- cause these had been many and varied over a consider- able period of time. Highest residue levels were detected in a sample taken directly from site 18, the drainage ditch of a field on which tobacco had grown for 3 years. However, a sam- ple talcen just across the road at site 19, where little surface erosion could have occurred, had the lowest residues in the studied area. Samples were also collected during the summer of 1973 from places where natural drainage ditches led into the creek system. Results of these analyses are shown in Table 2. Residue concentrations decrease in streambeds at points where water has moved slowly for some time. The exit to the holding pond (site 10) and the exit to Canning Reservoir (site 3) are the most obvious examples of sites where no residue was detected in 1972 or 1973. Results also agree with water analyses conducted at two other drainage ditches where samples were collected during heavy prolonged rainshowers and about 3 days later (Table 3). Soil, especially the sandy loam of the Habitant Creek watershed, erodes during shower activ- ity. Although the eroded soil was filtered off before water analyses were undertaken, the water still retained a substantial amount of insecticide. After the shower, the soil settled once more and aqueous pesticide con- centrations reverted to more usual levels. Water analyses have also been conducted on aqueous samples collected from several sites during different seasons. Although it was impossible to sample at some sites during the summer and winter because of too low a water flow or too much ice, overall results clearly chow maximum pesticide concentration during fall and spring when rainfall is highest and the ground is most subject to erosion (Table 4). Finally, samples of artesian water were taken from wells on properties bordering North Brook. Residue levels of water samples taken directly from the holding pond and the natural drainage reservoirs serving the towns of Canning and Wolfville are shown in Table 5. Artesian water contains virtually no residue, but wells depending on surface runoff have concentrations comparable to those of streams within the watershed. Although the Wolfville reservoir is not fed from the Habitant Creek system, analyses show that it has an organochlorine con- tent similar to that of the creek. TABLE 1. Organochlorine insecticide residues in streambed sediments. Habitant Creek, Nova Scotia — 7972 Collec- tion Site Residues, ppb Hept*- Hepta- chlor NONA- a-CHLOR- -y-CHLOR- Me- thoxy- 'y-BHC CHLOR Aldrin Epoxide CHLOR DANE DANE DiELDRIN Endrin o,p'-DDT p.p'-DDT CHLOR 1 7.9 0.0 5.3 0.0 6.2 42.2 2.5 3.0 5.1 0.9 154.0 0.0 2 11.6 0.0 42.0 0.0 5.0 38.0 0 0 6.0 5.6 22.0 274.0 0.0 .1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 4 1.5 5.0 18.0 0.0 10.0 28.0 0.0 6.5 26.6 19.0 109.0 0.0 5 2.6 4.8 7.4 0.0 1.2 12.0 17.0 0.0 36.0 9.1 572.0 0.0 6 6.6 9.0 2.7 0.0 0.0 8.0 9 5 0.0 28.0 27.0 28.0 0.0 7 14.4 12.0 11.0 0.0 0.0 22.0 9.0 0.0 12.0 16.0 46.0 0.0 8 79.5 0.0 7.1 0.0 0.0 4.(1 0.7 0.0 13 8 223.0 74.0 0.0 9 0.0 11.5 37.4 1.2 4.6 6.0 0.7 3.2 8.6 79 20.5 0.0 10 0.0 0.0 0.0 0.0 0.0 0.0 00 0.0 0.0 0.0 0.0 0.0 11 0.0 0.0 21.0 0.0 13.0 664.0 50.0 86.0 309.0 122.0 79.0 0.0 12 89.0 9.0 1.7 0.3 0.0 0.9 1.2 13.4 39.4 45.7 140.0 0.0 13 64.5 17.9 103.0 6.5 12.3 39.0 17.4 0.0 12.5 80.0 10.5 0.0 14 126.0 0.0 36.0 0.0 36.0 6.7 5.1 0.0 21.3 130.0 47.0 0.0 15 3.4 15.0 0.0 0.0 0.2 85.0 0.0 0.0 1.5 25.0 101.0 0.0 16 0.0 0.0 3.5 0.0 0.0 136.0 47.0 0.0 22.0 49.0 22.0 0.0 17 34.0 15.0 0.0 0.0 0.2 0.9 0.0 0.0 1.5 25.0 101.0 0.0 18 0.0 174.0 83.5 30.0 83.0 306.0 0.0 0.0 923.0 261.0 603.0 0.0 19 36.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20 0.0 0.0 8.6 0.0 15.0 9.2 2.1 0.0 145.0 123.0 340.0 0.0 21 0.0 85.0 0.0 30.0 0.0 38.0 40.0 0.0 0.0 64.5 40.0 0.0 22 0.0 0.0 0.0 0.0 0.0 80 0.0 0.0 0.0 64.5 40.0 0.0 23 0.0 104.0 0.0 11.5 0.0 120.0 51.0 0.0 750.0 261.0 110.0 0.0 24 0.0 29.5 368.0 0.0 0.0 285.0 U.O 3.8 46.0 4.2 22.5 0.0 25 10.0 11.3 11.3 0.0 0.0 0.0 0.0 0.0 5.5 4.0 263.0 43.0 TABLE 2. Organochlorine insecticide residues in sediments of natural drainage ditches entering Habitant Creek system, 1973 Residues, ppm Site Hepta- Hepta- CHLOR NONA- a-CHLOR- 7-Chlor- Me- THOXY- 7-BHC CHLOR Aldrin Epoxide CHLOR DANE DANE DiELDRIN Endrin o,p'-DDT p.p'-DDT CHLOR 26 0.00 0.67 0.53 0.00 0.00 0.75 0.00 5.95 0.67 0.83 3.75 0.00 27 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.95 2.68 6.67 6.25 0.00 28 0.00 4.76 2.22 17.30 0.94 0.19 0.31 13.75 0.38 2.75 4.83 0.00 29 0.00 2.67 1.60 0.40 0.00 0.44 0.00 1.19 0.27 2.33 7.00 0.00 36 Pesticides Monitoring Journal TABLE 3. Organochlorine insecticide residues in drainage ditch water, Habitant Creek Watershed— 1972 Residues, ppb Site 7-BHC Hepta- CHLOR Aldrin Hepta- CHLOR Epoxide NONA- CHLOB a-CHLOR- DANE 7-Chlor- DANE Dieldrin Endrin o.p'-DDT P.p'-DDT Me- thoxy- CHLOR During Thunderstorm 18 Near site 6 n.(l8 fl06 0.38 0.00 0.33 0.02 1.04 0.00 0.47 0.00 0.46 0.45 0.42 0.04 0.00 0.00 1.07 0.31 0.49 0.56 0.45 0.64 0.05 0.02 3 Days After Thunderstorm 18 Near site 6 O.UO 0.00 0.02 0.00 0.00 0.01 0.00 0.00 0.02 0.00 0.02 0.02 0.00 0.00 0.05 0.02 0.06 0.03 0.01 0.01 0.03 0.03 0.00 0.00 TABLE 4. Organochlorine insecticide residues in water, Habitant Creek — 1972 Residues, PPB Site. Date 7BHC Hepta- CHLOR Aldrin Hepta- CHLOR Epoxide Nona- CHLOR a-CHLOR- DANE -y-CHLOR- DANE Dieldrin Endrin o.p'DDT p.p'-DDT Me- THOXY- CHLOR 22 Spring o.on 0,00 0.01 0.00 0.00 0.01 0.00 0.01 0.03 0.23 0.36 0.01 Summer Fall Winter 23 Spring Summer Fall Winter 24 Spring Summer Fall Winter 0.1)1) 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.04 0.00 0.25 0,00 0.35 0,00 0.04 0.00 0.00 0.00 o.u 0.01 0.10 0.36 0.46 0.00 0.55 0.42 0.61 0.00 0.43 005 0.86 0.00 0.41 0.08 1.67 0.02 3.72 0.56 2.41 0.05 0.00 0.00 0.30 0.00 0.29 0.47 1.12 0.00 0.12 0.01 0.73 0.01 0.15 0.18 0.36 0,05 0.15 0.18 1.49 0.08 0.09 0.00 0.09 0.00 0.01 0.01 0.02 0.03 0.02 0.01 0.00 0.01 0.00 0.01 0.38 0.43 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.03 0.00 0.00 25 Spring 0.01 0.26 0.03 0.02 0.04 0.01 0.00 0.04 0.03 0.05 0.05 0.00 Summer Fall Winter 30 Spring Summer Fall 0.02 0.03 0.08 0.00 0.12 0.00 0.20 0.03 0.67 0.03 0.25 0.07 0.08 0.00 0.03 0.05 0.04 0.00 0.04 0.02 0.09 0.06 0.00 0.00 0.00 0.06 0.03 0.09 0.05 0.42 0.16 0.04 0.66 0.16 0.02 5.14 0.03 0.03 7.83 0.04 0.12 16.94 0.00 0.02 4.13 0.03 0.01 11.80 0.02 0.03 4.61 2,32 0,04 1,40 0.36 0.12 0.39 0.00 0.00 0.00 Winter 31 Spring Summer Fall Winter 21 Spring Summer Fall Winter — — — — — — — — — — — — 0.01 0.00 0.01 0.00 0.02 0.00 0.03 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.01 0.00 0.13 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.03 0.11 0.04 0.00 0,05 0,01 0.05 0.00 0.01 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.35 0.00 0.01 0.00 0.67 0.00 0.00 0.00 6.10 0.00 0.02 0.01 6.10 0.00 0.02 0.01 31.30 0.00 0.00 0.00 17.89 0.00 0.05 0.03 10.48 0.00 0.06 0,05 18.46 0.00 0.01 0,01 28.38 0.00 0.03 0.02 1.68 0.00 000 0.00 0.00 0.00 NOTE: — ^ no sample taken. TABLE 5. Organochlorine insecticide residues in waters within and outside Habitant Creek watershed, 1972-73 Residues, ppb Site Hepta- Hepta- CHLOR Nona- a-CHLOR- 7-CHLOR- Me- THOXY- 7-BHC CHLOR Aldrin Epoxide CHLOR DANE DANE Dieldrin Endrin o.p'-DDT p.p'-DDT chlor Artesian Wells 1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3 0,00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4 0,00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Holding Pond 0.04 0.U8 0.03 0.01 0.05 0.41 0.00 0.06 0.04 0.01 0.28 0.06 Caiming Reservoir 0.02 0.05 0.04 0.08 0.21 0.86 0.27 0.22 0.16 0.09 0.30 0.00 WolfviUe Reservoir 0.07 0.07 0.04 0.05 0.08 0.23 0.08 0.20 0.21 0.45 0.37 0.00 NOTE: Only the holding pond and Canning Reservoir are fed from Habitant Creek system. Vol. 9, No. 1, June 1975 37 LITERATURE CITED (/) Harris, C. R. 1966. Influence of soil type on the activ- ity of insecticides in soil. J. Econ. Entomol. 59(5): 1221-1225. (2) Harris, C. R., and W. W. Satis. 1971. Insecticide resi- dues in soils on 16 farms in southwestern Ontario — 1964. 1966, and 1969. Pestic. Monit. J. 5(3) :259-267. (i) MacPhee, A. W., D. Chishotm, and C. R. MacEachcrn. 1960. The persistence of certain pesticides in the soil and their effect on crop yields. Can. J. Soil Sci. 40(1 ) : 59-62. {4) Lichtensteirt, E. P., T. W. Fuhremann, and K. R. Schiilz. 1971. Persistence and vertical distribution of DDT, lindane, and aldrin residues, 10 and 15 years after a single soil application. J. Agr. Food Chem. 19(4):7I8-721. (5) Lichtenstein, E. P., T. W. Fuhremann, K. R. Schiilz, and R. F. Skrentny. 1967. Effect of detergents and inorganic salts in water on the persistence and move- ment of insecticides in soils. J. Hcon. Entomol. 60(6): 1714-1721. (6) Miles, J. R. W., and C. R. Harris. 1971. Insecticide residues in a stream and a controlled drainage system in agricultural areas of southwestern Ontario, 1970. Pestic. Monit. J. 5( 3 ) :289-294. (7) Miles. J. 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. (S) Peach, M. E., J. P. Schafjner, and D. A. Stiles. 1973. Movement of aldrin and heptachlor residues in a slop- ing field of sandy loam texture. Can. J. Soil Sci. 53(4): 459-463. (9) Kahn, L., and C. H. Waynian. 1964. Apparatus for continuous extraction of nonpolar compounds from water applied to the determination of chlorinated pesti- cides and intermediates. Anal. Chem. 36(7) : 1340-1353. 38 Pesticides Monitoring Journal Chlorinated Hydrocarbon Pesticides and Mercury in Coastal Biota, Puerto Rico and the U.S. Virgin Islands — 1972-74 * Robert J. Reimold " ABSTRACT Baseline lereh of mercury and chlorinated hydrocarbons were determined for Caribbean coastal biota as part of the U.S. Environmental Protection Agency estuarinc moni- toring program. Forty-one percent of the 150 environmental samples taken had significant levels of these compounds. Concentrations of chlorinated hydrocarbons suggest spatial and temporal variations within the plant or animal. In some cases residues in biota could be related to the land-use practices in ihe sampled watershed. Introduction The presence of chlorinated hydrocarbons in continental U.S. marine and estuarine organisms has been routinely monitored since 1965 (1.2). There is. however, a paucity of data concerning concentrations of these chlorinated hydrocarbons in estuarine and marine fauna and Hora from ihc Caribbean (.^). As part of the estuarine monitoring program of the U.S. Environmental Protection Agency (EPA), a biannual survey of selected Caribbean islands was initiated in October 1972. The purpose of this paper is to report baseline concentrations including negative results in selected environmental samples collected from U.S. ter- ritories in the Caribbean. Methods The study area includes Puerto Rico and the U.S. Vir- gin Islands of St. John, St. Thomas, and St. Croix. Col- 'Conlribution No. 286, Marine In^litute, University of Getirgia, S.ipelo Island. Ga. 31.127. Project funded in part by U.S. EPA Con- tract 68-02-1254. -iVlarine Resources Extension Center, University oi Georgia, P.O. Box 517, Brunswick, Ga. .11520. Vol. 9. No. 1. June 1975 lection locations for each of the four island areas are identified in Figures I and 2. At each location, samples were collected within 1 km of the edge of shore. Sites were selected in watersheds which respond quickly to rainfall and produce runoff which might contribute pol- f.itants to coastal biota. Samples were collected by seine, trap, hook and line, or by hand during fall 1972, spring 1973, fall 1973, and spring 1974. They were immediately placed on ice in aluminum foil packets. Within 4 hours of collection, samples were processed for analysis according to pre- viously developed techniques (4.5). Operating param- eters of the gas-liquid chromatographic (GLC) tech- niques were: Column: glass, 5 ft by 18 in., packed with i percent DC-200 on 80/100 mesh Gas-Chrom Q Temperatures; Oven 190^ C Injector 210' C Detector 210° C Carrier Gas; Prepurilied nitrogen at a flow rate of 40 ml/min. Three columns of different polarity were used for confirmation. PUNTA CANGREJOS / r •^ ^ ^ - w— ^""^ — s. i PUERTO RICO / Ly CARieeEAN SEA I _/ — -^ N A FIGURE 1. Collection sites for coastal biota, Puerto Rico 39 U. S. VIRGIN ISLANDS LINO POINT CINNAMON BAY DAVI POINT CORAL BAY MANGROVE LAGOON BORDEAUX N KILOMETERS 0 5 10 SALT RIVER TAGUE BAY\ BUTLER BAY EAST 'point -7 I \ good CARLTON BETTYS HARVEY HOPE HOPE DITCH FIGURE 2. Collection sites: St. Croix, St. Thomas, and St. John, U.S. Virgin Islands Analyses were performed by the EPA Pesticide Monitor- ing Laboratory, Bay St. Louis, Miss., and by the Marine Institute Laboratory, University of Georgia. Sapelo Island. In an earlier monitoring program for chlorinated hydrocarbon pesticides, the two laboratories synchro- nized methodologies and analyzed split samples. Results from this study were not significantly different. Samples processed by the EPA laboratory were ana- lyzed using Butler's technique (2). Specific chloinnated hydrocarbons determined were DDT, DDE, TDE, diel- drin, and polychlorinated biphenyls (PCB's). The PCB's were separated from pesticides and identified as Aroclor 1254 by matching chromatograms of field samples with chromatograms of standard Aroclor samples. All con- centrations are reported as Mg/kg or ppb on a whole- body, wet-weight basis. Relative recovery from the sam- ples was between 85 and 90 percent. Data are not cor- rected for recovery. Concentrations less than 5 ppb are not considered in this study. All analyses for mercury were conducted by the EPA laboratory using the techniques of Uthe et al. (6) and Brandenberger and Bader (7.8). These results are also expressed in Mg/kg or ppb on a whole-body, wet-weight basis. Mercury concentrations less than 0.02 Mg/kg are not considered. Results Of 1 50 environmental samples collected and analyzed. 41 percent had significant concentrations (^- 5 ppb) of mercury or chlorinated hydrocarbons (Table 1). Table 2 lists scientific names of the biota and summarizes sample collection data. Low concentrations of dieldrin were found in red man- grove leaves collected from St. Croix and St. John. There were also very low concentrations of dieldrin in a Nassau grouper and a soldier crab, both from St. John. Occurrence of dieldrin in St. John samples from the Coral Bay coincides with the presence of dieldrin in well and cistern water from a church at the bay (9). Cistern water sampled in 1970 contained 0.01 ppb diel- drin. 40 Pesticides Monitoring Journal TABLE 1. Chlorinated hydrocarbon concentrations in biota, U.S. Virgin Islands and Puerto Rico, 1972-74 REsrouES, PPB Date Location Common Name DiELDRIN DDT DDE TDE PCB's Mercury FaU '72 Mayaguez PR Snook 157 162 Spring '7J Mayaguez PR Great barracuda 69 103 968 Spring '7J Mayaguez PR Red drum 114 Fall '73 Mayaguez PR Bluestriped grunt 70 Spring '74 Mayaguez PR Yellowfin mojarra 399 Spring '74 Mayaguez PR Barbu 157 824 Fall '72 Punta Cangrejos PR West Indian sardine 39 25 201 Spring '73 Punta Cangrejos PR West Indian sardine 416 271 Spring '73 Punta Cangrejos PR Atlantic spadefish 240 194 Spring '73 Punia Cangrejos PR Red mangrove 40 Spring '73 Punta Cangrejos PR Great barracuda 69 103 968 Fall '73 Punta Cangrejos PR Yellowfin mojarra 87 Spring '74 Punta Cangrejos PR Striped mullet 579 Spring '74 Punta Cangrejos PR Silver jetmy 89 Spring '74 Punta Cangrejos PR Red mangrove 68 80 Spring '74 Punta Cangrejos PR Fiddler crab <10 12 <10 Fall '72 David Point STT Red grouper 133 Spring '73 David Point SI 1 Queen triggerfish 400 Spring '73 David Point SI 1 Red snapper 736 Fall '73 David Point STT Queen triggerfish 822 Fall '73 David Point STT Rock hind 290 Spring '74 David Point STT Rock hind 304 Spring '74 David Point STT Gray snapper 700 Spring '74 Mangrove Lagoon SI 1 Red mangrove 64 20 Fall '72 Cruz Bay STJ Soldier crab 36 44 14 Fall -72 Cruz Bay STJ Red mangrove 129 Fall '73 Cruz Bay STJ Rock hind 40 Fall '72 Cinnamon Bay STJ Mongoose (liver only) 22 47 11 Fall '72 Coral Bay STJ Soldier crab 43 132 14 Fall '72 Coral Bay STJ Red mangrove 21 Fall '72 Coral Bay STJ Turtle grass 40 Fall '72 Coral Bay STJ Nassau grouper <10 Spring '73 Coral Bay STJ West Indian sardine 719 Spring '73 Coral Bay STJ Mangrove oysters 58 Spring '73 Coral Bay STJ Schoolmaster 155 Spring '73 Coral Bay STJ Porcupine fish 78 Fall '73 Coral Bay STJ Red mangrove 50 Spring '74 Coral Bay STJ Mangrove oysters 110 Fall '73 Bordeaux STJ Soldier crab <10 30 112 Fall '73 Bordeaux STJ Soldier crab 758 17508 Fall '73 Lind Point STJ Soldier crab 21 Fall '72 East End Point STX Jewfish 495 Fall '73 East End Point STX Yellowtail snapper 83 Fall '73 East End Point STX Ocean surgeon 25 Fall '73 East End Point STX Queen triggerfish 75 Fall -72 Harvey Ditch STX Red mangrove 181 Fall '72 Harvey Ditch STX Red mangrove 181 Spring '73 Harvey Ditch STX Red mangrove 38 Spring '74 Harvey Ditch STX Striped mullet 809 Spring '74 Harvey Ditch STX French grimt 467 Spring '74 Harvey Ditch STX Spotted pink shrimp 4630 Spring '74 Harvey Ditch STX Fiddler crabs <10 8624 Spring '74 Harvey Ditch STX Striped mullet 5391 Fall '72 Bettys Hope STX Red mangrove 132 Fall '72 Bettys Hope STX Checkered puffer 1817 Fall '72 Carleton STX Red mangrove 61 Spring '73 Carleton STX Red mangrove 11 FaU '72 Good Hope STX Fish doctor 166 FaU '72 Butler Bay STX Great barracuda 129 Spring '73 Salt River STX Mangrove oysters 39 Spring '73 Tague Bay STX Great barracuda 271 NOTE: All residues are given on a whole-fish, wet-weight basis. PR = Puerto Rico, STJ = St. John, STT = St. Thomas, STX Blank spaces indicate no residues detected. St. Croix. DDT and DDE were found in mongoose liver collected from Cinnamon Bay, St. John, and soldier crabs col- lected at Coral Bay and nearby Bordeaux on St. John. Earlier studies of the cistern water and sediments at these sites did not reveal DDT or DDE (9), although they reported 0.14 ppm DDE in sediment of a cistern at Coral Bay. DDT and DDE were found in East Indian sardines, snook, and great barracuda from Mayaquez, P.R, In the great barracuda, there were 69 Mg/kg DDT and 103 fig/ kg DDE on a whole-fish basis. Giam et al. (3) sam- pled great barracuda east of the Yucatan peninsula and detected 8 Mg/kg DDT in the muscle and 42 ^g/kg DDT in the liver. TDE was found only in soldier crabs (14 iJ-g/kg) and mongoose liver (11 Mg/kg) from Cruz, Coral, and Cin- namon Bays, St. John. Earlier research efforts (9) did not reveal TDE at these sites. Aroclor 1254, the only PCB compound identified, was found in West Indian sardines collected from Mayaguez, Vol. 9, No. 1, June 1975 41 P.R. f201 Mg/kg), Punta Cangrejos, P.R. (416 Mg/kg), and Coral Bay. St. John (719 ^g/kg). This compound also appeared in red mangrove leaves from Cruz Bay. St. John (129 Mg/kg); and from Harvey Ditch (181 Mg/ kg), Bettys Hope (132 Mg/kg). and Carleton (61 Mg/kg), all in St. Croix. Aroclor 1254 was also detected in sev- eral other fish (Table 1) including a great barracuda from Butler Bay, St. Croix (129 f'g/kg), and striped mullet (5,391 ,"g/kg) and fiddler crabs (8,624 ^g/kg) from Harvey Ditch, St. Croix. This is a considerably greater concentration of Aroclor 1254 than that re- ported in a great barracuda collected by Giam et al. (3), which had 9 Mg/kg in the muscle and 57 A^g/kg in the liver. TABLE 2. Genera, species, and common names of biota sampled, U.S. Virgin Islands and Puerto Rico, fall 1972~spring 1974 Species I PR I STJ I STt| STX PLANTS Red mangrove (Rhizophora mangle) Turtle grass (Thalassia tesludinum) X X INVERTEBRATES Spotted pink shrimp {Fenaeits brasiliensis) Fiddler crab {Uca pugilator) Soldier crab {Coenobita clypeatus) Pacific oysters' (Crassostrea gigas) Mangrove oysters (Crassostrea rhizophorae) Scallops' (Argopeclen irradians) FISH Ocean surgeon { Acanthurus bahianus) Spotted eagle ray (Aelabalus narinari) Queen triggerfish (Batistes vetula) Bar jack iCaranx ruber) Snook (Centropomits undecimalis) Atlantic spadefish (Chaetodipterus jaber) Banded butterflyfish {Chaelodon striatus) Porcupinefish iDiodon hystrix) Rock hind ( Epinephelus adscensionis ) Jewfish (Epinephelus itaiara) Red grouper ( Epinephelus morio ) Nassau grouper (Epinephelus striatus) Silver jenny (Eucinostomus gula) Yellowtin mojarra (Gerres cinereus) Fish doctor (Gymnelis viridis) Margate (Haemulon album) French grunt (Haemulon flavolinealum ) White grunt (Haemulon plumieri) Blueslriped grunt (Haemulon sciurus) Schoolmaster (Lutjanus apodus) Red snapper (Lutjanus campechanus) Sand tilefish (Malacanthus plumieri) Striped mullet (Mugil cephalus) White mullet (Mugil curema) Yellowtail snapper (Ocyurus chrysurus) Barbu (Polydactylus virginicus) Spotted goalfish (Pseudupeneus maculatus) West Indian sardine (Sardinella sardina) Striped parrotfish (Scarus croicensis) Red drum (Sciaenops ocellata) Redtail parrotfish (Sparisoma chrysopterum) Stoplight parrotfish (Sparisoma viride) Checkered puffer (Sphoeroides lesludineus) Great barracuda (Sphyraena barracuda) MAMMALS Mongoose (Herpestes javanicus) X X X X X X X X X X X X X X X X X X X X X X NOTE: PR = Puerto Rico, STT = St. Thomas, STJ = St. John. STX = St, Croix. ' Sample obtained from artificial upwelling mariculture project, Lamont-Doherty Geological Observatory, Columbia University. The highest concentration of mercury, 968 Mg/kg, was found in a great barracuda collected near Mayaguez, P.R., in spring 1973. It was also detected in the red snapper (400 ^g/ke) collected at David Point. St. Thomas. Mercury also occurred in the red mangrove from Punta Cangrejos. P.R. (40 Mg/kg) and from Har- vey Ditch, St. Croix (38 Mg/kg); and in other compo- nents low in the food chain, such as mangrove oysters from Coral Bay. St. John (58 Mg/kg), and from Salt River. .St. Croix (39 Mg/kg). Discussion The author's findings supplement information recently published by Giam et al. (3) and Lenon et al. (9). In all three studies, concentrations of chlorinated hydro- carbons suggest spatial and temporal variation within the same plant or animal. In some instances, residues in the biota could be related to the land-use practices in the watershed. At Coral Bay, St. John, the Virgin Islands Department of Health had employed both DDT and dieldrin in an insect control program. Lenon et al. (9) reported both DDT and diel- drin in cistern water at Coral Bay. As shown in Table 1 of the present study, dieldrin and DDT were found in measurable concentrations in fauna collected from Coral Bay. In another instance illustrated in Table 1 and Figure 2, Aroclor 1254 was found in red mangroves on the south side of St. Croix. Residues in samples collected west- ward along the ocean shore during fall 1972 declined from the first measured concentration, 181 Mg/kg at Harvey Ditch, to 132 Mg/kg at Bettys Hope and 61 Mg/kg at Carleton. By spring 1974. Aroclor 1254 had trophically magnified to levels of 8.624 Mg/kg in the fiddler crabs and 5,391 Mg/kg in striped mullet, both potential detrivores. The source of this PCB compound is not known. One might speculate that it is local, con- sidering that residues are found at such low trophic levels in the primary producers and detrivores. It is not yet possible to determine whether the detected measured pollutants are increasing, decreasing, or main- taining status quo. Data in this study do establish base- line conditions for future comparisons in these relatively uncontaminated areas of Puerto Rico and the U.S. Virgin Islands. Acknowledgments The author acknowledges Philip A. Butler and the EPA Pesticide Monitoring Laboratory, Bay St. Louis, Miss., for analysis of all the mercury samples and many of the pesticide samples. Dr. Butler also contributed edi- torial suggestions. Particular thanks are extended to Jeannette E. Durant for the analytical portion of this work. The author also 42 Pesticides Monitoring Journal appreciates the assistance of Alan Robinson and the National Park Service of St. John; Kenneth Haines, Lamont-Doherty Geological Observatory. Columbia University. New Yorlc City; and John Ogden and Lee Cicrhard, West Indies Laboratory, Fairleigh Dickinson University, St. Croix, U.S. Virgin Islands. Of special value was the space provided by the West Indies Laboratory for part of the field portion of this research. James R. Duerbig, Owen M. Ulmer, Charles J. Durant, John L. Gallagher, Patrick C. Adams, and Rick A. Linthurst made field collections. LITERATURE CITED (/) Butler, P. A. 1969. Monitoring pesticide pollution. Bio- Science 19(10):889-891. (J) Butler, P. A. 1973. Organochlorine residues in estuarine mollusks. 1965-1972. National Pesticide Monitoring Program. Pestic. Monit. J. 6(4) :238-362. (.?) Gicim, C. S., A. R. Hanks, R. L. Rkluird.wn, W. M. Sackett, and M. K. Wong. 1972. DDT, DDE, and poly- chlorinaled biphenyls in biota from the Gulf of Mexico and Caribbean Sea— 1971. Pestic. Monit. J. 6(3):139- 143. (4) Reimold, R. J., and C. J. Durant. J973. Toxaphene con- tent of estuarine fauna and flora before, during, and after dredging loxaphene-contaminated sediments. Pestic. Monit. J. 8( 1 );44-49. (5) Durant, C. J., and R. J. Reimold. 1972. Effects of es- tuarine dredging of toxaphene-contaminated sediments in Terry Creek, Brunswick, Ga. — 1971. Pestic. Monit. J. 6(2);94-96. (6) Uthe, J. F., F. A. J. Armstrong, and M. P. Stainton. 1970. Mercury determination in fish samples by wet digestion and flameless atomic absorption spectropho- tometry. J. Fish. Res. Bd. Can. 27(4 ) :805-8 II. (7) Brandenberger, H., and H. Bader. 1967. The determi- nation of nanogram levels of mercury in solution by a nameless atomic absorption technique. Atomic Ab- sorption Newsletter 6: 101. (S) Brandenberger, H.. and H. Bader. 1968. The determi- nation of mercury by flameless atomic absorption II. A static vapor method. Atomic Absorption Newsletter 7:53. (9) Lenon. H., L. Curry. A. Miller, and D. Patulski. 1972. Insecticide residues in water and sediment from cisterns on the U.S. and British Virgin Islands— 1970. Pestic. Monit. J. 6(3): 188-193. Vol. 9, No. 1, JUNt; 1975 43 Total Mercury in Water, Sediment, and Selected Aquatic Organisms, Carson River, Nevada — 1972^ Robert T. Richins - and Arlhur C. Risser. Jr.'' ABSTRACT A 1971-72 study of the Nevada Carson River drainage sys- tem by the Geological Survey, U.S. Department of Interior, revealed suhslantial amounts of mercury from pre- 1 900 gold and silver milling operations of the Comstock Lode. A monitoring survey was initiated to determine the extent of mercury uptake from corresponding surface water and sediments for seven aquatic species collected from five .'Sam- pling stations along the watercourse. Total mercury content in fish ranged from 0.02 to 2.72 ppm: highest concentra- tions occurred in pi.scivorous white hass (0.50-2.72 ppm) sampled from Lahontan Reservoir. Residue levels appeared to be related to fish size, as demonstrated by highly signi- ficant correlations between wet weight and mercury content of five of the six species. Concentrations also appeared to be directly influenced by the species' position on the aquatic food chain. These results indicate that mercury levels in some fish from the Carson River drainage system may ex- ceed the 0.50 ppm maximum concentration considered by the Food and Drug Administration. U.S. Department of Health, Education, and Welfare, to be safe for human con- sumption. Introduction Increased mercury levels in various localized areas, par- ticularly the aquatic environment, are often influenced hy people. Their use of mercury has threatened bird populations in Sweden (/) and contaminated lakes and rivers in some areas of the United States, rendering fish unsafe for consimiption (2). Consequences of exposure to such acute concentrations are evident in reports from Minamata and Niigata, Japan {3.4). Natural sources also contribute to mercury contamina- 1 Department of Biology, University of Nevada, Reno, Nev. •Ada County Council of Governments, 525 W. Jefferson St., Boise, Idaho 895U2. Reprints available from this address. > San Diego Zoo, San Diego, Calif. tion (5). I evels of naturally occurring mercury as high as 1,200 ppb have been reported in air over heavy ore deposits (6). It has been estimated that the earth re- ceives approximately 100.000 tons of mercury annually from precipitation. This compares to the yearly human production of about 10.000 tons (7). Since the first century B.C. elemental mercury has been used to extract gold and silver from their ores by amal- gamation {8). Thus when the Nevada Comstock Lode was discovered in the spring of 1859 near Virginia City, Nev. (9), large amounts of the liquid metal were im- ported to 75 gold-milling sites in the area. In 1869 rail- road lines connected Virginia City with the 12 millsites along the Carson River in the Brunswick Canyon area. Alter this link was completed nearly all milling in the Comstock Lode was carried out at these sites because water power was available (10). The Patio process, which employed an average charge of 1:10 quicksilver ( mercury ) to the weight of the ore ( 9 ) . was used for extraction (//). Though records are in- complete. Hatch and Otfs estimates of total mercury lost during the 30-year peak of the Comstock (1865- 1 895 ) are as high as 200.000 flasks, or approximately 15,000.000 lb (12). These authors also make further reference to the recovery of quicksilver from tailings at the Douglas Mill in Six-Mile Canyon below Virginia City. Here, using cyanide and flotation methods which had first been perfected for extracting gold and silver. the site's tailings were refined around 1906. Between 1906 and 1914 the operation recovered over 1.000 flasks of mercury. Until the last decade it was generally accepted that metallic mercury settled to the bottom of a body of water, posing no threat to the aquatic environment. Westoo (13). however, reported that 90 percent of the 44 Pesticides Monitoring Journal mercury in tissues of Swedish fish was present as methyl- mercury, an organic form highly toxic to wildlife and people. Johnels et al. (14) subsequently published the opinion that methylmercury could be created anaerobic- ally by bacterial action in bottom sediments. This theory was verified by Jernclov and Jensen (/5). A 1971 study by the Geological Survey, U.S. Depart- ment of Interior, on surface water and sediments from the streams, canals, drains, and lakes in and below Brunswick Canyon, reported that substantial amounts of mercury from pre-1900 milling activity had entered the Carson River drainage system. Total mercury levels as high as 20.0 ppm were reported for bottom-sediment samples collected near the upstream end of Lahontan Reservoir; the highest level in sediment from the Carson River near Fort Churchill was 1 1 .0 ppm. Attention immediately focused on the accumulation of mercury by domestic plants and animals raised in the area. A study was undertaken in 1971 by the College of Agri- culture Extension .Service. University of Nevada. Reno (16). Equally important was the determination of mercury levels in tissues of native fish populations because aquatic organisms are known to concentrate mercury (17-18). Although numerous studies on mercury levels in fish of contaminated areas exist (19-21), data for the Carson River system were sparse and inconclusive (22). Previous work was concerned with data collected only from Lahontan Reservoir, a project completed in 1915 by the U.S. Department of Interior — Reclamation Service (predecessor of the Bureau of Reclamation). No references to fish size or weight had been published, nor had any attempt been made to correlate mercury levels in sediment with those in fish. Thus the present study was undertaken to ascertain total mercury levels for water and accompanying sediment, the relation be- tween individual fish species and mercury levels, and the effect of fish weight on individual mercury concen- trations in the Carson River drainage system. The Carson River flows in a northeasterly direction from its origin in the Blue Lake area, Alpine County, Calif, (elevation 3.176 m). From the convergence of the east and west forks between Genoa and Minden. Nev.. the river drops approximately 243 m to its termination at the Carson sink located 12.5 km north of Fallon, Nev. (elevation 1,173 m). Flow rates range from an average monthly high of 320 m'/sec during maximum discharge in May, to an average monthly low of 4 m-Vsec in August (23). Bottom sediment ranges from coarse sand to clay, with turbidity and alkalinity generally increas- ing as the stream nears Lahontan Reservoir 10 km west of Fallon (24). Initially, a 22-km stretch of the Carson River drainage system between New Empire. Nev.. and Lahontan Reservoir was chosen for sampling. On the basis of pre- sumed total mercury content of bottom sediment from pre-1900 ore milling, five collecting sites were designat- ed representative of mercury content increasing progres- sively downstream. Areas were chosen for sampling on the basis of accessibility and previous data (23). .Sampling sites are shown in Figure I. Site 1 was located 2.5 km east of Carson City. Nev., at the Brunswick Canyon Bridge. River width was approximately 24 m; the bed sloped to a maximum depth of 1.25 m. Water was moderately turbid and the bottom substrate was composed of materials ranging from very coarse sand to silt. Protective rock cover was generally poor and aquatic vegetation was sparse. This site represented an uncontaminated area above the 12 millsites associated with the drainage system, showing no evidence of pre- vious milling activity. Site 2 was located 5 km east of Carson City in Bruns- wick Canyon. It was immediately adjacent to the Eureka millsite, approximately 3 km below site 1. The water- course at this station narrowed markedly to about 1 8 m as the river cut through the steep canyon. Depth in- creased from less than 1 m to a maximum of 2.12 m and bottom sediment was characterized by rock rubble. The current was considerably faster than it was up- stream because of the river's decreased width and in- creased elevation decline. Jutting rock formations pro- vided maximum shelter for fish and other aquatic organisms. Tailings from three Comstock milling opera- tions extended to the water's edge. This area had been directly contaminated by pre-1900 milling activities. Station 3 was located 1 .25 km below Dayton. Nev., at the river's maximum width of 45.5 m. Depth varied from 1 to 2 m, channeling was prevalent, and turbidity generally increased as the waterflow slowed to a mini- mum for the four sampling sites. The bottom substrate was composed of sand ranging from coarse to very fine, with a brownish top coating of organic material. Although rock rubble was scarce, rooted vegetation was heavy and supplied adequate protective cover for aquatic organisms. Irrigation diversions for agriculture became numerous downstream from this site. No evi- dence of milling activity was observed near station 3 al- though a sand and gravel operation was located approxi- mately 0.6 km upstream. Site 4 was located 10 km east of Dayton midway be- tween Break-A-Heart Ranch Number 1 and Break-A- Heart Ranch Number 2. The site was situated in the center of farmland and was characterized by numerous irrigation diversions. The river widened to approximate- ly 24.2 m and reached a maximum depth of 2 m. The bottom substrate was mostly fine sand with little rock rubble. Banks were steep and channeled. No rooted vegetation was observed although flow was calm and turbidity moderate. This area represents a section of the river indirectly contaminated by milling operations. Vol. 9, No. 1, June 1975 45 CHURCHILL COUNTY NLAHONTAN RESERVOIR xl STOREY / COUNTY/ / / / OviRGINIA CITY I \WASHOE ^N-*/-' 2/0 DAYTON CARSON y%S^ CITY ' DOUGLAS COUNTY / 0 FALLON SAMPLE SITE AND NUMBER KILOMETERS I 6.2 I 1 1 FIGURE 1. Mercury sampling locations, Carson River, Lyon County, Nevada — 7972 Sampling site 5 was located at the upstream end of Lahontan Reservoir, which is located approximately 10 km west of Fallon, and is 10.5 km long. At conser- vation level during an average water year (under nor- mal rainfall conditions), Lahontan impounds some 293,000 acre-feet of water, reaching depths in excess of 30 m (24). Bottom sediment is composed of clay, silt, and some fine organic material. This site represents a location remote from early milling operations. Materials and Methods SAMPLING Samples of fish including crayfish were collected by electrofishing from the four Carson River sites during the months of July through October 1972, with a dual- electrode shocking apparatus. The electrical source was a 115-volt AC Briggs and Stratton gasoline-powered generator. Each sampling effort consisted of a run between two predetermined points at the particular collecting site. Stunned fish were retrieved with a long-handled dip net. Emphasis was placed on collecting the largest fish of as many species as possible from each site. The electrofishing gear was effective for the river collec- tions but proved inadequate at the reservoir. Sampling at this site consisted of individual angler catch trolling and bankfishing; species numbers and size of fish varied uncontrollably. Samples were labeled according to wet weight, species identification, and date and site of collection. They were preserved by freezing in water-filled polyethylene bags. Bottom sediment samples collected in July 1972 from the four river sites consisted of composites of the upper- most 2.5-7.6 cm of fine-grained sedinient from the right bank of the river. Samples for the Lahontan station were obtained in the shallows near the upstream end of the reservoir. All sediments were collected in acid- rinsed quart jars, characterized by sediment type, and labeled according to location. Unfiltered samples were preserved by acidification with 10 ml 1:1 distilled 46 Pesticides Monitoring Journal water: nitric acid of low mercury content, and refriger- ated until analysis (25). Special attention was given to the stream flow rate dur- ing the sampling period because total mercury content of sediment and surface waters is related to stream dis- charge (23). Flow rates were supplied by the Geo- logical Survey office in Carson City. Surface water samples were also collected in July. Five dipped samples were taken across the stream from each site at a depth of approximately 15 cm, placed in acid- rinsed quart jars, dated, and preserved for future analysis by acidification with 10 ml 1:1 distilled water:nitric acid. Samples were then refrigerated. Water aliquots were not filtered because they were to be tested pri- marily for total mercury content. A nalytical Procedures Cold vapor, flameless atomic absorption was selected as the analytical technique. Design samples were analyzed in triplicate with a Beckman Atomic Absorption Sys- tem/Beckman model DB-G grating spectrophotometer, and reported as mean values. If sample variation be- tween any duplicate set exceeded 5 percent, analyses for that set were repeated. General procedures for fish samples followed those of Hatch and Ott (26), as modified by Uthe et al. (27) and Armstrong and Uthe (28). A 0.1-0.5-g sample of flesh taken from the trunk region below the dorsal fin and above the lateral line was dissolved in a 250-ml flask with 5 ml of a 4:1 solution of concentrated sul- furic acid : nitric acid and was oxidized with 15 ml 6 percent KMnOj and 2 ml 6 percent K^SjOs after cool- ing. Excess permanganate was reduced with a 30 per- cent HoOo solution and the sample was made to 100 ml with distilled water. The sample was further reduced with 4 ml 10 percent SnCl.j and aerated through the atomic absorption apparatus. Recovery studies of spiked fish samples averaged 92.7 percent with a sensitivity of 0.02 ppm. Standard deviations were 0.040 for samples analyzed at the 0.05 ppm spike level and ± 0.050 for tissues containing 0.5 ppm total mercury. For sediment analysis, a 0.5-g sample was digested with 2 ml of the sulfuric acid : nitric acid solution and per- mitted to stand for 5 hours. After cooling, an oxidation- reduction procedure identical to that employed for fish tissues was followed. Recoveries for seeded sediment samples averaged 89.4 percent, with standard deviations of ± 0.041 at 0.05 ppm and ± 0.068 at 0.5 ppm. A modified version of the Federal Water Quality Ad- ministration provisional method (25) was employed for water analysis. Samples consisted of unfiltered 50-ml aliquots digested for 5 hours with 5 ml of the sulfuric acid: nitric acid solution. After cooling, the portions were oxidized with 1 ml of a 6 percent KMn04 solution and 2 ml of a 6 percent K^S^O^ solution. Samples were then reduced with a 10 percent hydroxylamine hydrochloride solution and 4 ml of a 10 percent SnCL. Recoveries averaged 94.1 percent with a sensitivity of ± 0.065 at the 0.2 ppb level and ± 0.040 at the 2.0 ppb level. Results Total mercury levels in surface waters of the drainage system are listed in Table 1. Values shown were not corrected for recovery. Based on triplicate analyses of unfiltered samples collected during a mean stream flow of 10. 1 m''/sec, results for the Brunswick Canyon Bridge, Eureka Mill, and Dayton Bridge collecting sta- tions showed mean total mercury concentrations of less than 0.20 ppb, the minimum detectable level for water. TABLE 1 . Total mercury levels in surface water, Carson River. Nevada— July 18, 1972 Site No. Source Total Hg, ppb 1 Carson River, Brunswick Canyon Bridge, 2.5 km east of Carson City <0.20 2 Carson River, Eureka Millsite, 5 km east of Carson City <0.20 3 Carson River, Dayton, 1.25 km below Dayton Bridge <0.20 4 Carson River, 10 km east of Dayton, below Break-A-Heart Ranch No. 1 0.87 5 Lahontan Reservoir, Lyon County, at upstream shallows 2.10 NOTE: Concentrations based on average of triplicate analysis of un- filtered samples. If no absorbance was detected, Hg level was recorded as <0.20 ppb, minimum detectable level in water. Levels in water from the two downstream sites increased as the river neared Lahontan Reservoir. At site 4 levels averaged 0.87 ppb. Site 5 levels suggested an accumu- lation of mercury by surface water: mean total mer- cury level based on triplicate analysis reached 2.10 ppb. The Food and Drug Administration (FDA), U.S. De- partment of Health, Education, and Welfare, considers 5.0 ppb to be the maximum level acceptable in drink- ing water (8). Although normal background levels for unpolluted surface waters vary widely and are affected by many parameters, the 2.10 ppb concentration at the Lahontan site was well above the 0.03 ppb level pre- sumed to be the mean natural mercury content for un- contaminated waters (8). Total mercury levels of sampled bottom sediment are shown in Table 2; they are not corrected for recovery. Based on triplicate analysis of unfiltered samples col- lected during a mean discharge flow of 10.1 m^/sec on July 18, 1972, levels at the five stations also suggested that mercury content increased as water flowed down- stream farther from previous milling activity. Mercury concentrations at Brunswick Canyon Bridge, site 1, ranged from 0.111 to 0.130 ppm with a mean level of 0.122 ppm. Corresponding levels of total mercury at the Eureka millsite, site 2, were as high as 0.447 ppm and averaged 0.349 ppm. Vol. 9, No. 1, June 1975 47 TABLE 2. Total mercury in fine-grained sediment, Carson River and Lahontan Reservoir, Nevada — July 18, 1972 Total Site Hg, No.i PPM Source DESCRIPIION 1 0.122 Off right bank, 25 m below bridge Dark brown silt and clay 2 0.349 Off riuht banlt. 5 m below mill^ite Coarse silt and sand 3 0,209 Off right bank, 0.6 km below Dayton Bridge Hark brown clay 4 0.722 Off right bank, 100 m below Break-A-Heart Ranch No. I Sill and clay 5 1.345 10 m off bank below water Dark brown silt and clay surface NOTE: All samples represent the top 2.5-7.6 cm sediment. Concentrations based on average of triplicate analysis of un- filtered samples. ' See Table 1 for specitic site locations. An exception to the trend of mercury levels increasing in a downstream direction was observed at site 3. Here the mean level was only 0.209 ppm. Although stream flow decreased at this site, no apparent cause for this decline was observed. Total mercury levels at site 4 were markedly higher than those observed at Dayton. Concentrations averaged 0.722 ppm for the three samples analyzed. Levels of mercury at Lahontan averaged 1.345 ppm. Such infor- mation implies that variations in mercury distribution in sediment along the river are caused by the washing action of local currents, which progressively enrich the mercury content of bottom sediments in a downstream direction. Si.x species of fish and one species of crustacean were collected between July and October 1972 (Table 3) when mean stream discharge was 13.4 cm. Wet weight, average mercury concentration, standard deviation, and total mercury range were recorded for the species at each site in Tables 4-8. Residues were not corrected for recovery. TABLE 3. Aquatic organisms sampled for mercury content, Carson River drainage system — July-October 1972 Species Site No.i Golden shiner {Noiemigomis crysoleucras) 1^ Crayfish (Pacific as tacus liniusculus) 1-4 Tahoe sucker (Catostomus tahoensis) lA Carp (Cypriritts carpio) 1-5 White bass iMorone chrysops) 5 White catfish llcfalurits catus) 5 Brown bullhead (Ictaliirus nebulosus) 5 1 See Table I for specfic site locations. As was the case for water and sediment samples, total mercury concentrations for individual aquatic species increased as the river approached Lahontan Reservoir. Table 4 shows mercury concentrations in organisms col- lected at the Brunswick Canyon Bridge. Mercury con- centrations ranged from 0.020 to 0.520 ppm for the 24 samples collected; 12.5 percent exceeded 0.50 ppm. Highest levels were present in carp, which had an aver- age level of 0.258 ppm total mercury. Levels in cray- fish ranged from 0.100 to 0.520 ppm; two of the five samples had residues in excess of 0.50 ppm. Mean total mercury contents for the golden shiner and the sucker were notably low, averaging 0.183 and 0.189 ppm, re- spectively. Only three samples analyzed from this site contained less than 0.020 ppm total mercury. A paired t-test showed no significant diflference between mean total mercury concentrations. Wet-weight range and sample size of individual species collected at this site were lower than those of species from other stations. Mean total mercury levels of organisms from the Eureka Millsile are presented in Table 5. Residues were consistently higher than at the Brunswick Bridge in all species except golden shiners. Likewise, mean wet weights of all species except the shiner were consistently higher. The greatest increase in mercury concentrations appeared in carp: five of eight specimens ranging from 1.02 to 411.20 g had wet weights exceeding 0.50 ppm. Levels in crayfish averaged 0.435 ppm total mercury with a range of 0.114 to 0.732 ppm. Suckers at this site demonstrated slightly higher levels of mercury than at Brunswick Bridge. Overall. 16.2 percent of the sam- ples contained residues in excess of 0.50 ppm total mer- cury: 10.8 percent represented levels less than 0.02 ppm. the minimum detectable concentration for fish. At the Eureka site mercury levels in carp were sig- nificantly greater than in golden shiners and suckers (p<0.01). Differences between residues found in all other species comparisons were insignificant. At the Dayton collecting station residues in shiners de- creased appreciably (Table 6) and had a mean mercury concentration of 0.097 ppm, the lowest recorded mean level of any species at any site. Mercury content in cray- fish and suckers also dropped. Concentrations averaged 0.105 and 0.103 ppm, respectively. Levels in carp, how- ever, remained relatively high. Of eight carp specimens analyzed, levels in six exceeded 0.50 ppm. A t-test comparison of levels present at the Dayton site demonstrated no significant difference in mercury levels accumulated by shiners, crayfish, and suckers. Mercury concentrations in carp, however, were significantly greater (p < 0.01 ). averaging five times more total mer- cury than the other three species. Table 7 demonstrates corresponding mercury levels in fish tissue samples from site 4. Although one would have expected mercury concentrations to decrease some- what proportionately with distance from milling sites, levels actually increased substantially. Of particular in- terest were concentrations found in crayfish. Ranging 48 Pesticides Monitoring Journal from 0.534 to 0.969 ppm. mercury content in all six specimens exceeded the FDA 0.50 ppm tolerance level. Higher residues averaging 0.524 ppm were also found in sucker tissues. Although wet weights for this species were considerably greater than those for suckers at any of the previous sites, the wet-weight range for crayfish at this station was relatively small. Mercury levels in shiners were consistent with those at the other river sites, ranging up to 0.318 ppm. Concentrations for carp also remained rather constant although there was a high individual total mercury level of 1 .360 ppm. Of the 37 samples collected at site 4, 45.9 percent contained total mercury concentrations in excess of 0.50 ppm. This represents the highest levels found in fish tissue at any of the four collection sites along the Carson River. Mean total mercury levels in crayfish, suckers, and carp were significantly greater than those in shiners at this station (p < 0.05). Concentrations in crayfish were also significantly greater than those in suckers (p < 0.05). Residue variances between crayfish and carp did not differ significantly from those between suckers and carp. Total mercury levels for aquatic species collected from Lahontan Reservoir are shown in Table 8. Wet weights of all species were greater than those of samples taken from the four river sites. Likewise, mercury content in sample tissues was higher. Highest concentrations were observed in white bass in which levels ranged from 0.501 to 2.720 ppm. Of eight specimens analyzed, all contained residues exceeding 0.50 ppm. White catfish had a mean total mercury content of 0.394 ppm. Levels in carp analyzed from this site were also high. One specimen contained 1.087 ppm total mercury. Every sample from the reservoir contained mercury residues above 0.020 ppm; 62.5 percent exceeded 0.50 ppm. TABLE 4. Total mercury residues in aquatic organisms, Brunswick Canyon Bridge, Carson River, Nevada (site 1) — 1972 No. Mean Wet Wet Mean Total Samples Fish in Weight, g Weight Ho, PPM Total Positive (%) Over Species Sample (±S.D.) Range, o (±S.D.) Ho. PPM Samples, % i 0.50 ppm Shiners 6 6.66(±3.33) 2.50-10.50 0.183(±0.157) 0.020-0.356 67.0 0.0 Crayfish 5 13.98(±4.09) 9.60-20.05 0.21U±0.176) 0.100-0.520 100.0 40.0 Suckers 7 50.07(±36.93) 7.22-105.33 0.189(±0.n8) 0.020-0.333 85.7 0.0 Carp 6 73.58(±76.19) 8.29-182.30 0.258(±0.180) 0.069-0.503 100.0 16.6 ' Samples considered positive if total mercury residue exceeded 0.020 ppm. minimum detectable level in fish. TABLE 5, Total mercury residues in aquatic organisms, Eureka millsite, Nevada (site 2) — 1972 No. Mean Wet Wet Mean Total Samples Fish in Weight, g Weight Hg, ppm Total Positive (%) Over Species Sample (±S.D.) Range, g (±S.D.) Hg, ppm Samples, % i 0.50 PPM Shiners 10 5.19(±3.14) 1.75-10.53 0.172(±0.128) 0.020-0.353 80.0 0.0 Crayfish 5 29.59(±13.92) 10.45-42.50 0.435( ±0.278) 0.114-0.732 100.0 20.0 Suckers 14 77.88(±53.50) 5.10-178.40 0.222(±0.104) 0.122-0.476 100.0 0.0 Carp 8 158.58(±207.21) 1.02-411.20 0.637(±0.367) 0.020-0.919 75.0 62.5 ^ Samples considered positive if total mercury residue exceeded 0.020 ppm, minimum detectable level in fish. TABLE 6. Total mercury residues in aquatic organisms, Dayton, Nevada (site 3) — 1972 No. Mean Wet Wet Mean Total Samples Fish in Weight, g Weight Hg, PPM Total Positive (%) Over Species Sample (±S.D.) Range, g (±S.D.) Hg, ppm Samples, % i 0.50 ppm Shiners 10 3.67(±1.25) 1.98-5.20 0.009(±0.069) 0.020-0.170 50.0 0.0 Crayfish 7 15.90(±5.66) 9.55-21.35 0.1 05 (±0.054) 0.020-0.149 85.7 0.0 Suckers 14 42.97(±31.46) 14.95-105.10 0.103(±0.070) 0.033-0.250 100.0 0.0 Carp 8 109.36(±139.48) 1.59^00.20 0.536(±0.113) 0.355-0.650 100.0 75.0 ^ Samples considered positive if total mercury residue exceeded 0.020 ppm, minimum detectable level in fish. TABLE 7. Total mercury residues in aquatic organisms, Break-A-Heart Ranch No. 1, Nevada (site 4) — 1972 No. Mean Wet Wet Mean Total Samples Fish in Weight, g Weight Hg, ppm Total Positive (%) Over Species Sample (±S.D.) Range, g (±S.D.) Hg, ppm Samples, % i 0.50 ppm Shiners 11 2.43 (±1.75) 0.87-6.31 0.136(±0.127) 0.020-0.318 54.5 0.0 Crayfish 6 13.24(±3.99) 9.20-20.20 0.756(±0.n8) 0.534-0.969 100.0 100.0 Suckers 11 127.29(±69.22) 24.20-210.70 0.524(±0.227) 0.205-0.965 100.0 63.6 Carp 9 95.41(±167.11) 1.40-399.12 0.616(±0.385) 0.020-1.360 88.9 55.5 ' Samples considered positive if total mercury residue exceeded 0.C20 ppm, minimum detectable level in fish. Vol. 9, No. 1, June 1975 49 These data suggest that the elevated mercury levels in fish species sampled from Lahontan are probably due to the presence of tluvia! sediment high in mercury content deposited at the upper end of the reservoir. A statistical comparison showed that mean total mer- cury concentrations in white bass collected from La- hontan Reservoir were significantly greater than those in white catfish or brown bullhead {p<0.01). No other comparisons of the various species demonstrated major differences in mercury levels although a larger sample size would be desirable for this observation to be con- sidered significant. A t-test was performed to evaluate variation of mean total mercury contents among species of the four Carson River sites. Results demonstrated several distinct trends. In general, total mercury concentrations in shiners did not vary significantly from site to site. Levels in cray- fish collected at site 4, however, were significantly greater than those sampled at the other river sites fp<0.01). Levels in suckers from this area were also significantly greater than those from the other river sites (p<0.01). Residues in the Brunswick Bridge carp samples were significantly less than those in carp collected from downstream sites (p < 0.05). A relationship also appeared between mercury concen- trations and species' weight. Further statistical analyses were performed to determine whether there was a posi- tive correlation strong enough to establish weight limits within which safe mercury concentrations could be found. Table 9 presents simple correlation coefficients for mercury versus weight. The relationship was ex- amined for the seven species collected in the study area, although sample sizes for white bass, white catfish, and brown bullhead were too small for accurate prediction. Several points are noteworthy. Among species, the rela- tion between mercury concentrations and fish weight was not consistent. Within species, there was generally a strong positive correlation between mercury content and fish weight, as indicated by shiner, sucker, carp, brown bullhead, and white bass populations. The absence of such a correlation in white catfish is probably attribut- able to small sample size and wet-weight range. No such explanation was apparent for crayfish. Statistical analyses were also performed to determine the relationship between mercury levels in bottom sedi- ments and mean residues in individual fish species at each site (Fig. 2). Data demonstrated no significant correlation between mercury concentrations in shiners and carp and levels of accompanying sediments for the four river sites. There was, however, a significant cor- relation between mean residue levels in suckers and crayfish and mercury concentrations in bottom sediment at individual collecting stations (p<0.10). Similar an- alyses for white bass, white catfish, and brown bullhead were not initiated because these species were collected only from Lahontan Reservoir. More individual sam- pling sites are necessary to insure validity of correlations between mean mercury concentrations in aquatic species and those in respective bottom sediments. TABLE 8. Total mercury residues in aquatic organisms, Lahontan Reservoir, Nevada (site 5) — 1972 No. Mean Wet Wet Mean Total Samples Fish in Weight, g Weight He, PPM Total Positive ( % ) Over Species Sample (±S.D.) Range, g (±S.D.) HG. PPM Samples. % > 0.50 PPM Wliite bass 8 414.23(±72.79) 320.80-527.20 1.297( ±0.845) 0.501-2.720 KKl.O 100.0 White catfish 5 .156.29(±76.73l 280.35-440.11 0.374(±0.227) 0.211-0.769 KXl.O 20.0 Brown bullhead 6 419.49(±I12.54) 300.98-540.20 0.554( ±0.394) 0.250-1.083 100.0 33.3 Carp 5 284.17(±126.97) 120.00-392.35 0.743 (±0.285) 0.382-1.087 itw.o 80.0 ^Samples considered positive if total mercury residue exceeded 0.020 ppm, minimum detectable level in fish. TABLE 9. Analyses for homogeneity of mercury-weight conditions in aquatic organisms, Carson River drainage system, Nevada — 7972 No. Fish Mean Hg Species IN Sample Content, ppm Size, g CORREL. COEFF. p-Value Shiners 36 0.129 0.87-10.53 0.6818 0.001 Crayfish 23 0.345 9.2{M2.50 0.0204 NS Suckers 45 0.245 5.10-210.70 0.7633 0.001 Carp 36 0.547 1.02-411.20 0.6165 0.001 White bass 8 1.297 320.80-527,20 0.9750 0.001 White catfish 5 0.374 280.35-440.11 0.7746 NS Brown bullhead 6 0.554 300.98-540.20 0.8971 0.02 NOTE: NS = not significant. 50 Pesticides Monitoring Journal KEY; CA =CA«P CK = CHAYFISH SH = SHINER SU = SUCKER ■ SEDIMENT SAMPLING SITE FIGURE 2. Total mercury in fine-drained bottom sediineni and aquatic organisms, Carson River, Nevada — 7972 Discussion Mercury concentrations in the environment are difficult to assess. Before one declares a water body or organisms present in that water contaminated with mercury waste from people's activities, it is necessary to know the nat- urally occurring background levels of the metal in both water and organisms. Because the full extent of the mer- cury problem has only recently become apparent, at- tempts to establish background levels have been limited. Background data on mercury concentrations in the Carson River consist of surface water and sediment an- alyses taken upstream from pre- 1900 ore milling sites in 1971-72 by the Geological Survey. No previous in- formation exists on baseline levels present in Carson River fish, although random spot samplings of various locations throughout the .State were performed by the U.S. Environmental Protection Agency in cooperation with the Nevada State Fish and Game Commission in 1970-71. In general, mercury content for surface water above the Brunswick Canyon area is less than 0.20 ppb (23). Total mercury present in corresponding sediments ranges between 0.04 and 0.10 ppm. These concentra- tions compare with the accepted 0.03 ppb mean natural background level for uncontaminated stream and river waters and the 0.073 ppm mercury content found in uncontaminated stream and river sediments (8). The present study and the Geological Survey findings (2i)^indicate that mercury concentrations in the Carson River drainage system downstream from pre- 1900 gold and silver mines far exceed naturally occurring back- ground levels in the river. Apparently total mercury in water and sediment increases in proportion with in- creased distance downstream from early milling sites. This trend is presumably due to contributions from mill- ing tailings along the river which progressively enrich mercury content downstream, reflecting the flushing action of seasonal runoff. Greatest concentrations are within and immediately upstream from Lahontan Reservoir. Mercury concentrations in water and sediment are greatly infliienced by stream How becaiisc an increase in flow enhances scrubbing action on geological de- posits. Samples collected during periods of high dis- charge generally rellect higher mercury content (23). This is evidenced by contrasting values of water and sediment collected from the Carson River by the Geo- logical Survey during a period of high snow runoff in May with those recorded in this study from similar sites during the months of minimum discharge, July and August 1972. Of six surface waters sampled by the Geological Survey, total mercury content ranged from 0.2 to 6.3 ppb. Two samples exceeded the FDA 5.0 ppb tolerance limit for drinking water. Corresponding sedi- ment analyses revealed mercury levels ranging from 9.5 to 20.0 ppm. Concentration in samples from the pres- ent study showed total mercury content ranging from 0.20 to 2.10 ppb for water, and from 0.122 to 1.345 ppm for sediment. Extrapolation of these data suggests that mercury content for surface water and sediment can vary markedly, depending on stream discharge. On this basis, it can further be assumed that since maxi- mum discharges during 1971-72 were well below those of many recent years, peak mercury concentrations during the same years were probably also less than those associated with higher flows (23). The ability of aquatic organisms to concentrate mercury above the levels found in their environment is well known (17,29). Mechanisms by which fish accumulate organomercury compounds, however, are not fully un- derstood. It is believed that all microorganisms capable of vitamin B^^ systhesis are also capable of methyl and dimethylmercury synthesis (30). Apparently carbon, phosphates, nitrogen, and various trace elements pro- vide these organisms with the food they require to grow and multiply. This food supply in turn determines the size of populations of bacteria and molds present, and thus the rate of organic mercury conversion. The re- action is viewed as a detoxification of the microorga- nisms' environment at the expense of the fish, and is important because the solubilities of these organomer- curials permits the compounds to be directly absorbed in fish by diffusion across the gills (31). Numerous investigators have shown mercury residue in fish tissues to be present as methylmercury. Kamps et al. (32) demonstrated that methylmercury comprises 95 percent of the total mercury present in white bass. Wcstoo has shown mercury in pike to be at least 90 per- cent methylmercury (13). Although a detailed evalua- tion by the Geological Survey showed most mercury in the water and bottom sediments of the Carson River present as a component of the sulfide or nonmethyl Vol. 9, No. 1, June 1975 51 organic substance (23). it became apparent after an- alyzing some 200 fish samples in the present study that methylmercury conversion was occurring in the system. Results in Table 8 demonstrate mercury concentrations in while bass and brown bullhead collected from La- hontan Reservoir exceeding 2.70 and 1.08 ppm. respec- tively. Levels for carp and crayfish from the Carson River near site 4 ranged from 0.20 to 1.360 ppm, aver- aging 0.616 and 0.756 ppm, respectively. These data represent a substantial uptake of mercury from the aquatic environment, the majority of which must be assumed methylmercury. These levels also represent residues which are considerably higher than 0.20 ppm. generally accepted as the naturally occurring back- ground level for most lish (S). As noted earlier, residues varied widely between indi- vidual fish within a species. This was particularly evi- dent in carp from site 4, whose individual mercury resi- dues ranged from 0.020 to 1 .360 ppm, and in white bass from Lahontan, whose levels varied from 0.501 to 2.720 ppm. This variance appeared to be, in part, a function of fish weight as demonstrated by the highly significant correlations between fish weight and total mercury content shown in Table 9. Similar studies have also shown significant correlations between fork length and total mercury content, and age and mercury ac- cumulation for several species of fish (32,33). Neither of these relationships was explored in the present study. In order to predict weight ranges with a mercury con- tent less than 0.50 ppm, regression analyses were per- formed on species which reflected highly significant cor- relation between mercury content and weight. Values for intro-species regressions of total mercury appear in Table 10; estimated regression lines for each of the five species are shown in Figure 3. Extrapolation of these data permits prediction of individual mercury levels within species, providing wet-weight values are given. For example, it can be predicted that the total mercury content of a carp weighing 200.0 g corresponds to 0.623 ppm. This prediction is reached by direct interpretation from the carp regression line (Fig. 3); or by calculation from the equation Y = a + b(X). substituting the values 0.395 for a, and 1.139 ^ lO'^ for b (Table 10), and 200.0 g for X. Similar computations show the fol- lowing practical wet-weight limits below which indi- viduals of the five species can be expected to contain less than 0.500 ppm total mercury: shiner. 18.00 g: sucker, 180.00 g; carp, 100.00 g; brown bullhead, 430.00 g: and white bass, 350.00 g. Sample sizes for white bass and brown bullhead were too small for accurate prediction. A wider range would also have been desirable because predicted values are likely to fall far outside the sample range. The merit of such predictions might possibly be found by selective fishing; the person fishing could weigh each fish to determine mercury content. 10.0- 9.0^ 8.0^ KEY: = FDA GUIOEilNE / BB= BIOWN BULLHEAD / CA = CABP / SH = SHINEI *y 70 J / e 0- SU = SUCKEB / W8= WHITE BASS / / 5.0- / 7 E o. a. c o a: 40- 3.0- / / / V Z 2 0- / / A^ o t- 1,0- 0.5- .j/^, 4 7_ ^ //c>.— \^ -300 \..,-200 - 100 o o 1 o o o o 1 r T-n 3 S gg o o og FISH WET WEIGHT, 9 FIGURE 3. Lineiir regressions of total mercury content on fish wet weight, Carson River, Nevada — 1972 TABLE 10. Regression equations for total mercury content versus wet weight in fish. Carson River drainage system, Nevada— 1972 .Species No. Fish in Sample Total Mercury Content ' Shiner ?6 7.623 y 10--1 -1- 2.955 X 10-2(FW) Sucker 45 6.290 X 10--' -1- 2.416 X 10 -^CFW) Carp 36 0.395 + 1.139 X 10-HFW) White bass 8 — 3.2S4 + 1.115 X 10-=(FW) Brown bullhead 6 — 1.121 + 4.016 X lO-i(FW) 1 FW — fish weight, g. Another conclusion was that mercury levels varied widely between species, indicating marked differences in ability to concentrate mercury (Fig. 4), There is also increasing variance between species and increasing fre- quency of mean levels exceeding 0.50 ppm total mer- cury in a downstream direction. These differences are probably explained by variations in feeding activities of the different groups and the accompanying mercury content in surface water and bottom sediments of the respective stations. Levels in golden shiners ranging from 0.097 to 0.183 ppm were consistently lower than concentrations found in other species at each site. McKechnie has shown that algae and plankton arc the principal food of shiners when available (34). Algae and plankton represent minimum mercury sources be- cause of their position at the base of the food pyramid. Mean total mercury levels for suckers and crayfish were also consistently low from site to site. In general, mean mercury concentrations in suckers ranged from 0.103 to 0.524 ppm and those for crayfish ranged from 0.105 52 Pesticides Monitoring Journal to 0.756 ppm. The exception for both species was ob- served at site 4, where t-test comparisons showed mean mercury residues of 0.524 ppm for suckers and 0.756 ppm for crayfish. These were significantly greater than levels in the other species from the site (p < 0.01 ) and mean values for individuals of the same species at the three upstream sites (p < 0.01 ). KEY: BB= BtOWN BULLHEAD CA= CA«f E ,5 CR> CRAYFISH a SH< SHINER X SU= SUCKER we- WHITE BASS Xwa _, r.o WC= WHITE CATFISH g ^^ ,CA 5 0.8 - S OSH ■bb D WC 1 1 1 1 2 3 1 4 1 s SAMPLINS SITE FIGURE 4. Mean total mercury in aquatic organisms, Carson River, Nevada — 1972 This again reflects feeding activities. Suckers are bottom- dwellers, grazing mainly on green algae, insects, and mollusks (35). Crayfish are also bottom-dwellers, feed- ing on nearly anything that is edible (24). Because total mercury content of surface water and sediments was also significantly higher at site 4. and because fish have been shown to absorb mercury compounds directly through their gills and through ingestion of food (i/), authors had expected tissue levels of bottom-feeders to be higher as well. Average residues in carp ranged from 0.258 to 0.743 ppm in the five collecting stations. A t-test comparison demonstrated significantly lower levels (p<0.01) in carp taken from the New Empire location above pre- 1900 milling activity. Further t-test comparison showed mean mercury concentration in carp significantly higher than in shiners except at site 1 (p < 0.01 ). Mean concentrations varied insignificantly from mean content of other species at individual stations. Authors made these comparisons with the hope of arriv- ing at a single fish species as an indicator of trends in mercury levels within a station or the entire drainage system over a period of years. Carp, then, represent the species most suitable for such an indicator in the Carson River system: they are present at all five sampling sites; mercury levels within the species do not vary signifi- cantly except above milling operations where evidence of natural background concentration exists; and mer- cury concentrations in carp are similar to those in the other species except shiners. Carp also reflect an increasing omnivorous diet. Fila- mentous green algae make up the bulk of their food (36); aquatic insects, crustaceans, and small fry are secondary items. Some large carp are even cannibalistic, as demonstrated in downstream sites where most of the large carp were captured by angling with live minnow bait. The species, therefore, provides a good index of mercury accumulation for fish that are both herbivorous and omnivorous. Because mercury levels in white catfish, brown bullhead, and white bass were determined only for samples col- lected from Lahontan Reservoir, a comparison of mer- cury variation among sites was not possible. A t-test comparison of the three species sampled at site 5 showed that mean levels in white bass were significantly higher than in brown bullhead and white catfish (p<0.05). Concentrations of 0.554 ppm in brown bullhead and 0.374 ppm in white catfish varied insigni- ficantly. The differences between mercury levels in the three species can again be explained in terms of feeding habits. White catfish and brown bullhead are omnivor- ous, feeding near the bottom. Major food items include algae, diatoms, and Crustacea; secondary items include insects and other fish (24). White bass are primarily piscivorous, consuming a greater volume of fish than all other foods combined (37); this habit was reflected in their average total mercury level of 1.297 ppm. Ac- companying sediment and water analyses from the reservoir were correspondingly high, undoubtedly in- fluencing mercury uptake by fish. DTtri has categorized fish according to their ability to accumulate mercury (8). Category I, encompassing predators such as bass and pike, accumulate the highest quantities of mercury. Category II includes such fish as carp and bluegills, which usually contain less mercury. Fish in category III, generally including bottom-feeders such as catfish and suckers, have the least tendency to concentrate mercury. This categorization is corroborated by observations in the present study, especially from Lahontan Reservoir, where mean total mercury content for white bass averaged 1.297 ppm. Category II carp demonstrated a mean content of 0.743 ppm at site 5 although one specimen at this site contained 1.087 ppm. Category III catfish, brown bullhead, averaged 0.554 ppm total mercury at site 5. Results imply biological magnification of mercury among fish or an increase in levels of mercury in fish food organisms at each trophic level of the generalized food chain. A cknowledgments Authors thank the University of Nevada. Reno, Nev., for cooperating with this study: particularly Ben Payne, Department of Biochemistry, for valuable assistance; personnel of the Water Resources Laboratory, Desert Research Institute, for making necessary equipment available and for constructive comments on the study; Vol. 9, No. 1, June 1975 53 and Michael J. O'Farrell. lor helping to collect samples and interpret data. We acknowledge the Nevada State Fish and Game Commission lor Scientific Collection Permit G628. and Geological Survey. USDI. Carson City. Nev., for hydrological information on the Carson River Basin. LITERATURE CITED (/) Borg, K., H. Wunnlorp, K. Erne, and E. Haiiko. 1966. Mercury poisoning in Swedish wildlife. J. Appl. Ecol. 3(supplement): 171-172. (2) Dales, L., E. Kahn, and E. Wei. 1971. Methylmercury poisoning — an assessment of the sportfish hazard in California. Calif. Med. 114:13-15. (3) Blair, J. A. 1972. Quicksilver and slow death. Nat. Geogr. 142:518-527. (4) Iriikayama, K. 1966. Minamata Disease. Third Inter- nal. Conf. on Water Pollution Research. Paper No. 8. Water Pollution Control Federation, Washington, D.C. (5) Goldwater, L. J. 1971. Mercury in th; environment. Sci. Amer. 224(5) : 15-21. (6) Geological Survey. USDI. 1970. Mercury in the en- vironment. Geol. Surv. Prof. Paper 713, U.S. Govt. Printing Office, Washington, D.C. 67 pp. (7) Wallace, R. A., W. Fulkerson, W. D. Shiilts, and W. S. Lyon. 1971. Mercury in the environment. The human element. Oak Ridge Nat. Lab, Publication ORNLNSF-EP-1. 61 pp. (S) D'ltri, F. M. 1972. The environmental mercury prob- lem. CRC Press, Cleveland, Ohio. 124 pp. (9) Smith, G. H. 1943. The history of the Comstock Lode, 1850-1920. Univ. Nev. Bull. 37(3):41-47. (70) Schilling, J. 1972. Personal communication. Depart- ment of Geology, University of Nevada, Reno, Nev. (//) Riegel, E. R. 1955. Industrial chemistry. Reinhold Publishing Corp., New York. 1015 pp. (12) Bailey, E. H., and D. A. Phoeni.x. 1944. Quicksilver deposits in Nevada. Univ. Nev. Bull. 38(5): 12-46. (13) Westoo, G. 1966. Determination of methylmercury compounds in foodstuffs. I. Methylmercury com- pounds in fish, identification and determination. Acta Chem. Scand. 20(8) :2131-2137. (14) Johnels, A., T. Westermark, W. Berg, P. Persson. and B. Sjostrand. 1967. Pike (Esox lucius L.) and some other aquatic organisms in Sweden as indicators of mercury contamination in the environment. Oikos 18(2);323-333. (15) Jernelov, A., and S. Jensen. 1969. Biological methyla- tion of mercury in aquatic organisms. Nature 223 (5207): 753-754. (16) Smith, H. G. 1972. Personal communication and un- published data. College of Agriculture, University of Nevada, Reno, Nev. (17) Abelson, P. H. 1970. Methyl mercury. Science 169: 237. (18) Hammond, A. L. 1971. Mercury in the environment — natural and human factors. Science 171:788-789. (19 {20 (21 (22 (23 {24 (25 (26 (27 (28 (29 (30 (31 (32 (33 (34 (35 (36 (37 Knight, L. A., and J. Herring. 1972. Total mercury in largemouth bass (Micropterus salmoides) in Ros Barnett Reservoir, Miss. — 1970 and 1971. Pestic Monit. J. 6(2):1U3-106. :\ielson, O. 1969. Mercury in fish from the Saskatche wan River system. A report to the Saskatchewan Min istry of Fisheries, Saskatchewan, Canada. Sumner, A. K., J. G. Saha. and Y. W. Lee. 1972 Mercury residues in fish from Saskatchewan water: with and without known sources of pollution — 1970 Pestic. Monit. J. 6( 2 ): 122-125. Trelease, T. 1972. Personal communication. Nevad; Department of Fish and Game, Reno, Nev. Clendenon, D. 1972. Personal communication ant unpublished data. Geological Survey, USDI, Carsor City, Nev. LaRivers, 1. 1962. Fishes and fisheries of Nevada Nev. Fish and Game Comm., Carson City, Nev 782 pp. Federal Water Quality Administration. 1970. Tenta- tive method for mercury (flameless AA procedure) Anal. Quality Control Lab., Cincinnati, Ohio. Hatch, W. R.. and W. L. Ott. 1968. Determination ol submicrogram quantities of mercury by atomic ab- sorption spectrophotometry. Anal. Chem. 40(14): 2085-2087. Utile, J. F., F. A. J. Armstrong, and M. P. Stainton. 1970. Mercury determination in fish samples by wet digestion and flameless atomic absorption spectropho-j tometry. J. Fish. Res. Bd. Can. 27(4) ;305-31 1. Armstrong, F. A. J., and 1. F. Uthe. 1971. Semi-' automated determination of mercury in animal tissue. At. Absorption Newslett. 10:101-103. Aaronson, T. 1971. Mercury in the environment. En- vironment 13(4): 16-23. Wood, J. A/. 1972. A progress report on mercury. En- vironment 14( l):33-39. Rucker. R. R.. and D. F. Amend. 1969. Absorption and retention of organic mercurials by rainbow trout and Chinook and sockeye salmon. Prog. Fish Cult. 31(4):197-20I. Kamps, I. R., R. Carr, and H. Miller. 1972. Total mercury-monomethylmercury content of several spe- cies of fish. Bull. Environ. Contam. Toxicol. 8(5); 273-279. Scott, B. P., and F. A. J. Armstrong. 1972. Mercury concentrations in relation to size in several species of freshwater fishes from Manitoba and Northwestern Ontario. J. Fish Res. Bd. Can. 29( 12) : 1685-1690. McKechnie. R. J. 1966. Golden shiner. In Inland Fisheries Management (A. Calhoun, ed.). Pp. 448- 492. Calif. Dept. Fish and Game. Kimsey, J. B.. and L. O. Fisk. 1964. Freshwater non- game fishes of California. Calif. Dept. Fish and Game. 54 pp. Burns. J. A. 1966. Carp. In Inland Fisheries Manage- ment (A. Calhoun, ed.). Pp. 510-515. Calif. Dept. Fish and Game. Bonn, E. W . 1953. The food and growth rate of young white bass (Morone chrysops) in Lake Texoma. Trans. Amer. Fish. Soc. 82:213-221. 54 Pesticides Monitoring Journal ERRATA PESTICIDES MONITORING JOURNAL, Volume 8, Number 4, pp. 247-254. In the paper "Organochlorine Residues in Starlings, 1972," the following corrections are in order: Page 250 Column 2, line 6, should read, "Residue values of DDT and its metabolites from each station were compared, as were those of dieldrin, for the periods summer-winter 1967-68 versus fall 1968, fall 1968 versus fall 1970, and fall 1970 versus fall 1972." Table 2, title, should read, "Geometric and arithmetic means of DDT and dieldrin residues in starlings, 1967-72." Page 251 Column 2, line 1 : "periods" should be "period." Column 2, lines 16-17: "metabolic" should be "metabolite." Page 252 Table 5: footnotes 1 and 2 should be reversed; the former refers to sites and the latter to PCB's. Page 254 Column 2, line 1, should read: "A metabolite of chlordane, oxychlordane, was found in nearly all samples at very low levels." Column 2, Literature Cited, reference 1 : publi- cation date should be 1969. Vol. 9, No. 1, June 1975 55 APPENDIX Chemical Names of Compounds Discussed in This Issue ALDRIN BHC (BEN7FNE HEXACHIORIDE) CHIORDANE DDD DDE DDMU DDT DIELDRIN ENDOSULFAN ENDRIN HCB HEPTACHLOR HEPTACHLOR EPOXIDt METHOXYCHI OR MIREX NONACHLOR OXYCHLORDANE PCB'S (POLYCHLORINATEIi BIPHENYLS) TDE THIODAN TOXAPHENE Not less than 95% of l,2,3,4.10.10-HexachIoro-I,4,4a,5,8,8a-hexahydro-l,4-fnrfo-eAro-5,8-dimethanonaphthalene l.-,3.4,5.fi-Hexachlorocyclohexane (mixture of isomers). Commercial product contains several isomers of whicf gamma is most active as an insecticide. 1.2.'*.S.6.7.S,«-()clachloro-2. V.''a.4.7.7a-he\ah\dro-4.7-meth;momdene The technical product is a mixture o several ctimpoiinds includinp hcptachlor, chlordene. and twt> isomeric forms of chlordane. See TDE. Dichlorodiphen\ 1 dichloro-ethylene (degradation product of DDT) P.p'-DDE: l,l-Dichloro-2,2-bis(^»-chIorophenyl) ethylene ('.P'-DDE: I.l-Dichloro-2-(o-chlorophenyI )-2-( p-chlorophen> 1 l etlnlene 1 , 1 '-( ChJorc^ethenylidene ) bis ( 4-chloroben/enc ) Nfain component i r.r'-DDJ I a-Bis( />-cliloro phenyl )/^.,^.,^-ti ichli>roe(hane Other isomers are possible and some are present in the commercial product. o.p'-DDT; (l,l.l-TrichIoro-2-(o-chlorophenyl)-2-(p-chlorophenyl ) ethane | Not less than 85% of 1 ,2.1,4,10,in-Hexachlorod.7-epoxy-l ,4.4a,5,6,7.8,8a-octahydro-l ,4-f ni/()-«o-5,8-dimcthano- naphthalene 6,7.8.9,10.10-Hexachloro-l,5,5a.6,9.9a-hcxaliydro-6,9-methano-2,4,.'^-benzodioxathiepin 3-oxide l,2,3.4,10,10-Hexachloro-6,7-epoxy-1.4,4a.5,6,7,8,8a-octahydro-l,4-#nrfo-endo-5.8-dimethanonaphthalene Hexachlorobenzene 1.4.5.6,7,8,8-HeptachIoro-3a,4,7,7a-telrahydro-4,7-e'ndo-methanoindenc I.4,5,6,7,8,8-Heptachloro 2,3-epoxy-3a.4,7,7a-tetrahydro-4.7-methanoindane l.l,l-Trichloro-2,2-bis(p-methoxy phenyl) ethane DodecachlorooctahN dro-l .3.4-nietlieno-2H-c\cloliiiia[cd]pentalene 1.2.3,4.5,6.7.S-Nonachlor-.'la.4,7.7.i-lelrah>dro-4.7-methannindjn 2.3.4,5,6,6a,7,7-Octachloro-la,lb,5,5a.6,6a-hexahydro-2,5-methano-2ff-indeno( l,2-/;i)oxirene Mixtures oi chlorinated biphenyl compounils having-' various percenlaycs of chlorine 2.2-Bis(/'-chlorophenyl)-l,l-dichloroethane See endosulfan. Chlorinated camphene (67-69% chlorine); product is a mixture of polychlor bicyclic terpenes with chlorinated camphenes predominating. 56 Pesticides Monitoring Journal Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretive information which contribute to the understanding and evaluation of pesticides and their residues in relation to man and his environment. The publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries; medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. 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Correspondence on editorial matters or circulation mat- ters relating to official subscriptions should be addressed to: Paul Fuschini, Editorial Manager, PESTICIDES MONITORING JOURNAL, Technical Services Divi- sion, Office of Pesticides Programs, U. S. Environmental Protection Agency, Room B49 East, Waterside Mall, 401 M Street, S.W., Washington, D. C. 20460. if U.S. GOVERNMENT PRINTING OFFICE: 1975—621-568/4 Vol. 9, No. 1, June 1975 57 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 man and his environment. The WORKING GROUP is comprised of representatives of the U.S. Departments of Agricul- ture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; Transportation; and Labor; and the U.S. Environmental Protection Agency. The pesticide MONITORING PANEL consists of representatives of the Agricultural Research Service, Animal and Plant Health Inspection Service, Extension Service, Forest Service, Depart- ment of Defense, Fish and Wildlife Service, Geological Survey, Food and Drug Administration, Environmental Protection Agency, National Marine Fisheries Service, National Science Founda- tion, and Tennessee Valley Authority. Publication of the Pesticides Monitoring Journal is carried out by the Technical Services Divi- sion, Office of Pesticides Programs of the Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies repre- sented on the pesticide MONITORING PANEL which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and interpretive articles. However, pertinent data in summarized form, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institu- tions, both domestic und foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Manuscripts received for publication are reviewed by an Editorial Advisory Board established by the MONITORING PANEL. Authors are given the benefit of review comments prior to publication. Editorial Advisory Board members are: John R. Wessel, Food and Drug Administration, Chairman Paul F. Sand, Agricultural Research Service, Vice Chairman Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Thomas W. Duke, 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 Mention of trade names or commercial sources in the Pesticides Monitoring Journal is for identification only and does not represent endorsement by any Federal agency. Address correspondence to: Paul Fuschini Editorial Manager PESTICIDES MONITORING JOURNAL U.S. Environmental Protection Agency Room B49 East, Waterside Mall 401 M Street, S.W. Washington, D. C. 20460 Martha Finan Joanne Sanders Editors CONTENTS Volume 9 September 1975 Number 2 PESTICIDES IN PEOPLE Total mercury levels in selected human tissues, Idaho — 1973-74 59 J. Gabica, W. Benson, and M. Loomis Organochlorine pesticide residues in human milk. Western Australia — 1970-71 g4 Conway I. Stacey and Brian W. Thomas RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury residues in breast muscle of wild ducks, 1970-71 (,-j Thomas S. Baskett Organochlorine pesticide residues in small migratory birds, 1964-73 • 79 David W. Johnston Insecticide residues in the Tuttle Creek Reservoir ecosystem, Kansas— 1970-71 gp Harold E. Klaassen and Ahmed M. Kadoum RESIDUES IN FOOD AND FEED Pesticide residues in total diet samples (VllI) 94 D. D. Manske and R. D. Johnson GENERAL Occurrence of chlorinated hydrocarbon insecticides, )Uthern Florida — 1968-'/ Harold C. Mattraw, Jr. APPENDIX Chemical names of compounds discussed in this issue II5 Information for Contributors jig southern Florida — 1968-72 jOg PESTICIDES IN PEOPLE Total Mercury Levels in Selected Human Tissues, Idaho — 1973-74 ''^ J. Gabica, W. Benson, and M. Loomis ABSTRACT Total mercury levels were determined in hitman tissues taken at autopsy from six hospitals in the three basic geographical areas of Idaho. Of the 242 specimens analyzed, 76 percent contained detectable mercury. Levels were compared with respect to the age, sex, and geographic residence of autop- sied individuals. Mean levels detected were 1.04 ppm in kidney tissue, 0.34 ppm in liver, and 0.08 ppm in brain. Mean mercury levels for the three geographical areas were: southeastern Idaho, 0.22 ppm: southwestern Idaho, 0.80 ppm: and northern Idaho, 0.43 ppm. The relatively high means in southwestern Idaho specimens may be related to the preponderance of natural cinnabar deposits in that por- tion of the State. Mercury levels were higher in women than men for all tissues in both the southwestern and northern areas, but the reverse was true in the .southeast. Data were compared with findings of other investigators in an attempt to arrive at background levels of total mercury residues in human tissues. Introduction Data on mercury levels in human tissues are limited. Mercury has not been included in most comprehensive studies on trace metals in human tissues. Analytical diffi- culties may offer a partial explanation for this exclusion (1.2). Knowledge of background levels of mercury in vari- ous human tissues is important because of the possible mutagenic effects or toxic properties of this element and its various compounds. Any use of mercurials as diure- tics, antiseptics, cathartics, or pesticides (3-6) would presumably contribute to mercury found in various body tissues. Naturally occurring cinnabar ore deposits may be an additional source of exposure in Idaho with its extensive history of mining in which large quantities of ^Research performed under U.S. Environmental Protection Agency Contract No. 68-02-0552 by the Epidemiologic Studies Program (for- merly Pesticide Community Studies Program), Office of Pesticide Programs, EPA, through the Idaho Department of Health and Wel- fare. -Epidemiologic Studies Program. Department of Health and Welfare, Statehouse, Boise, Idaho 83720. metallic mercury were used to extract gold from ore (7). Some of this mercury is still present in large quantities in certain locations, especially streambeds throughout the State (8). The present study was intended to be a preliminary screening of a survey of mercury levels in certain tissues of humans and a wide variety of wildlife. Cause of death was noted in each instance but was not compared to mercury concentrations found. Autopsy and Sampling Procedures The State was roughly divided into three general areas, northern Idaho, southwestern Idaho, and southeastern Idaho, relating to the locations of the six participating hospitals (Fig. 1). The hospitals, two of which were O Cold extcacClon: produciim o- FIGURE 1. Map of Idaho showing sites of sampling, natural mercury deposits, and gold mining Vol. 9, No. 2, September 1975 59 located in each of these three areas, contributed 242 autopsy samples of kidney, liver, and brain tissues from patients who had died during the previous 12 months from a variety of causes unrelated to mercury poison- ing. Because tissues analyzed were from autopsies, they could not be considered normal. However, mean levels drawn from individual cases should be close to normal. Specimens were placed immediately in formaldehyde at the respective hospitals and sent to the laboratory at once or, in some cases, no more than 2 weeks before analysis. Formalin was analyzed before use and again after autopsy specimens had been stored in the solution. In no instance was mercury or any other background contaminant detected which might invalidate values ob- tained. Researchers selected homogeneous samples from each organ for analysis, taking care to prevent pre- analytical contamination from handling. All glassware used was scrupulously cleaned with nitric acid and rinsed with distilled water. Tissue specimens were placed on blotting paper and allowed to dry until most of the formalin had been absorbed or evaporated. Subsequently, a 1-5-g sample was ground in a Dual glass tissue grinder; a 1-g wet- weight sample was then removed for analysis. Results are based upon this 1-g sample. The sample was digested according to procedures outlined by the American Asso- ciation of Analytical Chemists (9). Fifty ml distilled water was added to a 50-ml aliquot of the digest and placed in a 200-ml biological oxygen demand (BOD) bottle. Two ml of a 5 percent potassium persulfate solution, 4 ml of a 5 percent KMnO^ solution, 2 ml of a 100-ml water solution containing 12 g NaCl and 12 g hydroxylamine, and 5 ml of a 10 percent SnCL solution were added. The mixture was stirred between additions (8) and was immediately put under an air vaporizer. Results were recorded on a Coleman 50 ana- lyzer by cold vapor. A standard curve of 0.01-2.00 /zg mercury was used. Results and Discussion Mercury was found in 76 percent of all tissues tested; the mean value was 0.73 ppm. Mean levels by age, sex, and geographic area of the State for each of the tissues tested are listed in Table 1. Roughly 3.5 times more mercury occurred in kidney tissue than in liver and about 10 times more than in brain tissue. Kidney levels ranged to a high of 15.70 ppm, whereas highest con- centrations for liver and brain were 5.80 and 0.94 ppm, respectively. Corresponding mean levels in the current study were 1.04, 0.34, and 0.08 ppm for the same tissues. In comparison, Matsumoto (70) reported levels of 6.60, 4.0, and 0.50 ppm in kidney, liver, and brain, respectively, in Japanese fetuses which succumbed to Minamata disease {10, II). Hospitals with the highest mercury levels in all three organs were located in southwestern Idaho where most of the natural mercury deposits are found (see Fig. 1 in reference 7). The combined mean level for all tissues was 0.80 ppm in the southwest, whereas the mean level was only 0.22 ppm in the southeast and 0.43 ppm in the north. Nevertheless, it cannot be assumed that these deposits caused the higher levels. High concentrations were not found in this geographical area during a pre- vious study by Benson and Gabica in which 1.000 hair samples from residents throughout the State were ana- lyzed for total mercury (12). Table 2 and the Benson/Gabica study (12) show that mercury levels vary according to sex of the subject once they approach or exceed 1 ppm. In general, levels in women were higher than those in men. Women over 65 years of age had more mercury in their tissues than had men in the same age group. The converse was true for people in the 46-55- and 20-45-year age groups although it was less marked in the latter. The higher mercury levels in females of advanced age have not been explained. No available data show evidence of differences in the environmental exposure of males and females. Differences between residue levels in the differ- ent sexes cannot be attributed to cosmetics used on skin and hair because the same distribution with respect to sex was found in all organs. Mean residue concentrations in liver were higher in women than in men from all areas. Women also had higher average levels in the brain and kidney except for kidney tissue in the southeast and brain tissue in the north. Total residues for all three areas were higher among women in all tissues except kidney; in those tissues total values for men were slightly higher (Table 1). Dal Cortivo et al. (/.?) found that brain, liver, and kidney tissue from autopsy specimens had respective mean mercury levels of 0.05, 0.10, and 0.20 ppm. On the other hand, Kevorkian et al. (2) found much higher mean levels: 0.25, 7.70, and 10.36 ppm, respectively. Hyland et al. (7) and Howie et al. (5) reported re- sults similar to those of the present study except that Hyland found only 0.65 ppm mercury in kidney sam- ples. Howie's results were corrected from dry to wet weight for comparison by dividing values by five. Takeuchi (14) showed that mercury levels in cats averaged 2.00 ppm in the liver, 0.41 ppm in the kidney, and less than 0.10 ppm in the brain. This differs from the findings of the present study and from those of others in which highest concentrations were in kidneys. Takeuchi, however, is in accord with the present study in finding lower mercury levels in human brain tissue than in liver and kidney tissue. This is probably due to the selectivity of the blood/brain barrier, especially with respect to inorganic mercury (75). This barrier would not be active in the deposition of mercury into tissue of such organs as liver or kidney. 60 Pesticides Monitoring Journal TABLE 1. Distribution of mercury concentrations in tissue from human autopsy samples, ldaho~1973-74 Area Tissim Sex No. Samples Positive Samples, % Mean, ppm Range, ppm Southeast K M F M and F 14 3 17 93 67 88 1.07 0.06 0.56 0-3.04 0-0.20 0-3.04 B M F M and F 13 1 14 92 100 96 0.02 0.02 0.02 0-0.06 0-0.02 0-0.06 L M F M and F 18 8 26 78 38 58 0.06 0.15 0.11 0-0.41 00.25 0-0.41 Total M F M and F 45 12 57 88 68 78 0.39 0.05 0.22 0-3.04 0-0.25 0-3.04 Southwest K M F M and F 24 22 46 71 96 83 1.27 1.90 1.57 0.02-15.70 0.18-12.50 0.02-15.70 B M F M and F 9 11 20 89 91 90 0.11 0.28 0.19 0 0.16 0-0.95 0-0.95 L M F M and F 25 24 49 100 100 100 0.34 0.95 0.64 0.1-2.11 0-5.07 0-5.07 Total M F M and F 58 57 115 87 96 91 0.57 1.04 0.80 0-15.70 0-12.50 0-15.70 North K M F M and F 20 11 31 75 91 83 0.84 1.14 0.99 0-7.56 0-5.78 0-7.56 B M F M and F 6 2 8 83 50 66 0.04 0.01 0.03 0-0.25 0-0.01 0-0.25 L M F M and F 18 13 31 28 23 26 006 0.48 0.27 00.49 0-5.80 0-5.80 Total M F M and F 44 26 70 62 55 58 0.31 0.54 0.43 0-7.56 0-5.80 0-7.56 Statewide K M F M and F 58 36 94 80 92 86 1.06 1.03 1.04 0-15.70 0-12.50 0-15.70 B M F M and F 28 14 42 88 80 84 0.06 0.10 0.08 00.25 00.94 0-0.94 L M F M and F 61 45 106 69 54 61 0.15 0.53 0.34 0-2.11 0-5.80 0-5.80 Total M F M and F 147 95 242 79 73 76 0.64 0.82 0.73 0-15.70 0-12.50 0-15.70 NOTE: K = kidney L = liver B = brain M = male F = female Vol. 9, No. 2, September 1975 61 TABLE 2. Mercury levels in tissue from human autopsy samples Idaho— 1973-74 Age Range, years Tissue Sex No. Samples Range, ppm Mean, ppm B M F 7 5 0.000.73 0.00-0.35 0.07 0.14 0-19 L M F 8 7 O.OO-I.ll 000-5.07 0.12 0.95 K M F 4 5 0.01-O.64 0.00-1.16 0.11 0.37 B M F 3 4 0.00-0.08 0.06-0.16 0.05 0.05 20-45 L M F 8 5 0.00-0.37 0.000.41 0.19 0.14 K M F 8 4 0.00-3.04 0.05-0.85 0.77 0.33 B M F 2 1 0.00-0.05 0.00-0.04 0.02 0.06 46-55 L M F 8 9 0.00-2.40 0.00-1.06 0.33 0.25 K M F 11 7 0.01-7.56 0.00^.40 2.95 0.95 B M F 7 2 0.00-0.16 0.000.14 0.02 0.08 56-65 L M F 12 8 0.00-0.31 0.00-2.26 0.06 0.63 K M F 12 7 0.00-7.56 0.00-0.91 0.58 0.50 B M F 6 2 0.00-0.01 0.000.26 0.00 0.56 66-75 L M F 16 9 0.02-0.09 0.00-0.31 0.11 0.75 K M F 15 7 0.00-0.66 0.04-9.40 0.26 5.37 B M F 1 1 0.00-0.02 0.00-0.33 0.02 0.33 76-86 L M F 8 8 0.00-0.90 0.00-5.80 0.11 1.00 K M F 8 6 0.02-1.55 0.00-12.50 0.48 0.74 NOTE: B = brain L = liver K = kidney M = male F = female 62 Pesticides Monitoring Journal Acknowledgments Authors wish to thank the following Idaho hospitals for supplying autopsy specimens: St. Lukes and St. Alphon- sus Hospitals, Boise; Bannock Memorial Hospital, Poca- tello; Idaho Falls (LDS) Hospital, Idaho Falls; and Kootenai Memorial Hospital, Coeur d'Alene. We are grateful to personnel of Sacred Heart Medical Center, Spokane, Wash., for obtaining autopsy tissues from persons who lived in northern Idaho communities. LITERATURE CITED (/) Hyland, ]. R., J. Kevorkian, and D. P. Cento. 1971. Total mercury levels in human tissues — a preliminary study. Lab. Med. 2(8):46-49. (2) Kevorkian. Jack, D. P. Ccnlo. J. R. Hyland, W. M. Bagozzi, and Eunice Van Hollebeke. 1972. Mercury content of human tissues during the twentieth century. Amer. J. Pub. Health. 62(4) :504-513. (i) Ahlmark. A. 1948. Poisoning by methyl mercury com- pounds. Brit. J. Ind. Med. 5:117-119. (4) Lundgren, Karl-David, and A. Swens^on. 1949. Occu- pational poi;oning by alkyl mercury compounds. J. Ind. Hyg. Toxicol. 31(4) : 190-200. (5) Howie, R. A., and H. Smith. 1967. Mercury in human tissue. Dept. Forensic Med., Univ. Glasgow, Glasgow, Scotland, U.K. 7:90095. (6) Taylor, W. H., A. Guirgis. and K. Steward. 1969. In- vestigation of a population exposed to organomercurial seed dressing. Arch. Environ. Health. 19(4) :505-509. (7) Ross, S. H., and C. N. Savage. 1967. Idaho Earth Sciences. Earth Sciences Series No. 1. Idaho Bur. Mines Geol. Moscow, Idaho. P. 100. (S) Federal Water Quality Administration. 1970. Tentative method for mercury (flameless AA procedure). Anal. Quality Control Lab., Cincinnati, Ohio. (9) Association of Analytical Chemists. 1970. Official Methods of Analysis, Eleventh Ed. Official Final Ac- tion 25.058, 25.059, 25.060. 418 pp. {10) Matsumoto, H., G. Koya, and T. Takeuchi. 1965. Fetal Minamata disease — a neuropathological study of two cases of intrauterine intoxication by a methyl mercury compound. J. Neuropathol. Exp. Neurol. 24(4) :563- 574. (//) Tobuomi, H., T. Okajima, J. Kanai, M. T.sunoda, Y. Ichiyasu, H. Misumi, K. Shimomura, and M. Takaba. 1961. Minamata disease. World Neurol. 2(6) :536-545. (12) Benson, W. W., and ]. Gabica. 1971. Total mercury in hair from 1,000 Idaho residents. Pestic. Monit. J. 6(2):80-83. (13) Dal Corlivo, L. A., S. B. Weinberg, P. Ciaquinta, and M. B. Jacobs. 1964. Mercury levels in normal human tissue. J. Forensic Sci. 9(4) :501-510. (14) Takeuchi, T. 1970. Biological reactions and pathologi- cal changes of human beings and animals under the condition of organic mercury contamination. Intern. Conf. Environ. Mercury Contam., Ann Arbor, Mich. Pp. 1-29. (15) Clarkson. T. W. 1973. The pharmacodynamics of mer- cury and its compounds with emphasis on the short- chain alkylmercurials. Mercury in the western environ- ment. Buhler, D. R., ed. Proceedings of a Workshop, Portland, Oreg., Feb. 25-26, 1971. Corvallis, Oreg. Vol. 9, No. 2, September 1975 63 Organochlorine Pesticide Residues in Human Milk, Western Australia — 1970-71 Conway I. Stacey > and Brian W. Thomas 2 ABSTRACT Milk samples from 22 nursing mothers in the metropoli- tan area of Perth, Western Australia, have shown the pres- ence of DDT, DDE, dieldrin. and HCB in amoimts con- sistent with similar surveys in other countries. Although mean values tend to be slightly lower than expected, their wide range, 0.002-0.025 ppm for DDT, suggests that a much larger sample should be examined to obtain a more accurate mean. This view is supported by values obtained in another survey of the same area. Introduction During the past decade there has been considerable interest in the presence of organochlorine pesticide resi- dues in human milk and their effect on breast-fed in- fants. The United Nations World Health Organization (WHO) has determined that 0.01 mg/kg/day is the maximum safe intake of DDT. A number of surveys (1-4) indicate that the DDT intake of many breast-fed infants has exceeded that level. With the advent of worldwide publicity, however, accompanied by more vigorous controls in many countries, DDT residues in human milk appear to be decreasing and the trend is expected to continue. The present investigation was initiated by the Nursing Mothers' Association (NMA) of Western Australia in 1970 when the local press was carrying articles on the use and effects of DDT and other chlorinated hydro- carbons. Members of NMA supplied samples which were examined for DDT, DDE, dieldrin, and HCB. Sampling Procedues In 1970-71, 22 donors supplied a total of 23 samples of approximately 50 ml each in specially prepared glass iDepartmem of Chemistry, Western Australian Institute of Technology. Hayman Road. South Bentley, Western Australia 6102. = Department of Physics, Western Australian Institute of Technology, Hayman Road. South Bentley, Western Australia. containers. Samples were frozen and stored until used. All donors lived within a 30-mile radius of the General Post Office, Perth, Western Australia, the area termed the Perth metropolitan area. Each donor was asked to fill out a questionnaire indi- cating her weight and diet, and the frequency and form of pesticide use in her home. Apart from oned woman who indicated a slight reduction of meat intake,, no donor was on a special diet. All donors were con- sidered to be in good health. Analytical Procedures Each 40-ml sample was homogenized and the milk; fats were extracted using the single extraction method described in the Pesticide Analytical Manual (5) of the Food and Drug Administration, U.S. Department ofij Health, Education, and Welfare. A modified Moats column cleanup was employed using a florisil column eluted with 20 percent methylene chloride / hexane, and acetonitrile. The acetonitrile residue was further eluted from a MgO/celite column with hexane. Analyses were performed using the following instru- ment parameters: Chromatograph: Gas. Varian model 1400 Detector: Concentric tube; electron-capture, tritium Columns: Glass, 2 m, packed with equal parts 3 percent QF-1 and 1 percent DC-200 on 100-120 mesh Varaport 30. For confirmation: glass, 1.5 m, packed with 5 per- cent SE-30 on 100-120 mesh Varaport 30. In addition to gas chromatography, peak identities were confirmed by thin-layer chromatography using AgNO, -incorporated alumina. Results were corrected to 100 percent recovery. This method detected organo- chlorines at a sensitivity level of 0.001 ppm (Table 1). Excess milk from each sample was combined. Part of this composite was supplied to the Government 64 Pesticides Monitoring Journal rABLE 1. Organochlorine pesticide residues in human milk. Western Australia — 1970-71 Residues in Whole Milk, ppm Sample No. DDT DDE Total DDT DlELDRIN HCB 1 0.013 0.063 0.083 0.003 0.022 2 0,010 0.057 0.074 0.003 0.026 3 0.011 0.063 0.081 0.005 0.034 4 0.011 0.043 0.059 0.004 0.033 5 0.012 0.085 0.107 0.004 0.031 6 0.002 0.015 0.019 0.004 0.012 7 0.004 0.045 0.054 0.004 0.026 8 0.010 0.077 0.096 0.009 0.027 9 0.003 0.030 0.036 0.005 0.023 10 0.004 0.040 0.049 0.005 0.025 U 0.010 0.037 0.051 0.005 0.024 12 0.009 0.080 0.098 O.OOS 0.027 13 0.012 0.112 0.137 O.OII 0.022 14 0.011 0.110 0.134 0.005 0.028 15 0.009 0.055 0.070 0.004 0.022 16 0.004 0.033 0.041 0.003 0.026 17 0.020 0.068 0.096 0.005 0.022 18 0.025 0.073 0.106 0.005 0.025 19 0.009 0.067 0.084 0.004 0.026 20 0.011 0.077 0.097 0.006 0.028 21 0.021 0.061 0.089 0.009 0.018 22 0.006 0.032 0.042 0.003 0.024 23 0.005 0.073 0.086 0.005 0.021 PABLE 2. Organochlorine pesticide residues in a human milk composite, Western Australia — 1970-71 Residues in Whole Milk, ppm Sample DDE DDT DlELDRIN HCB 2- 3 0.080 0.085 0.080 0.015 0.015 0.016 0.004 0.005 0.005 0.024 0.024 0.023 Sample 1 analyzed by Government Chemical Laboratories, Perth, Western Australia. Samples 2 and 3 arc duplicates analyzed by t)ie Western Australian Institute of Technology. [Chemical Laboratories, Perth, Western Australia; the emainder was analyzed, in duplicate, at the Western Australian Institute of Technology (Table 2). Results and Discussion There is no apparent correlation between the pesticide esidue level in the milk sample (Table 1 ) and the body veight of the donor, the lipid content of the 40-ml iample, or the frequency of pesticide use around the lome (Table 3). Results of the present survey show values ranging rom 0.019 to 0.137 ppm total DDT, with an average 'alue of 0.078 ppm. This represents an average infant ntake of approximately 0.011 mg/kg/day, which is lightly in excess of the WHO maximum. DDT residues in Perth residents seem much lower han those obtained in similar surveys from other parts )f the world (Table 4), although caution should be ;xercised in making such direct comparisons. ^ofroth"s deduction that breast-fed babies in Western Australia might have a dieldrin intake as high as 30 imes the WHO level (6) is not substantiated by the iresent survey. However, this theory was based on an average dieldrin concentration of 0.67 ppm in adipose tissue from a survey performed in 1965 (7). More recent surveys have shown a decrease in this mean (S). This trend of decreasing levels is also evident in an independent survey carried out by the Public Health Department of Western Australia in 1969-70 (R. Lugg, Public Health Department, 1973: personal communica- tion). The difference in DDT and dieldrin levels in the Public Health survey and the present study highlights the danger of comparing values obtained from a small number of samples. A much larger sample is needed to obtain a reliable baseline level of DDT and dieldrin in Western Australia. However, the present survey, when viewed with earlier deductions, tends to support the thesis that organo- chlorine residue levels are decreasing in Western Aus- tralia and other parts of the world. TABLE 3. Physical and environmental factors affecting nurs- ing mothers, pesticide survey, Perth, Western Australia— 1970-71 Lipid wt (g) Use of Frequency of Donor Body Wt, OF 40-ML Pest Pesticide Use No. KG SAMPLE Strip IN Home ^." 1 61.5 1.15 yes 2 60.5 0.84 no 3 46 2.615 no 4 48 3.095 no 5 57 0.81 no 6 74 1.005 yes 7 66 0.77 yes 8 51 2.43 yes 9 53.5 1.605 no 10 51.5 1.73 yes 11 54 1.15 no 12 52.5 1.045 no 13 56 1.265 no 14 60.5 0.955 no 15 54 0.94 yes 16 60.5 1.22 no 17 53.5 1.93 no 18 47.5 1.225 no 19 52.5 1.485 no 20 59 1.42 yes 21 46 2.07 no 22 60.5 0.40 no 23 57 0.83 no ^l = frequently: once a week or more r = rarely: less than once a week -A single donor, No. 22, reported using pesticides frequently in the garden. LITERATURE CITED (/) Laug, E. P., F. M. Kunze, and C. S. Prickett. 1951. Occurrence of DDT in human fat and milk. Arch. Ind. Hyg. Occup. Med. 3(3) :245-246. (2) Quinby. G. E., J. F. Armstrong, and W. F. Durham. 1965. DDT in human milk. Nature 207(4998) : 726- 728. (i) Egan, H., R. Goulding, J. Roburn, and J. OG. Tatton. 1965. Organo-chlorine pesticide residues in human fat and human milk. Brit. Med. J. 2(5453) :66-69. (4) Tuinstra, L. G. M. Th. 1971. Organochlorine insecti- cide residues in human milk in the Leiden region. Ned. Melk-Zuiveltydschr. 25(l):24-32. (5) Food and Drug Administration. 1968. Pesticide Ana- lytical Manual. Vol. 1. Section 211. 13i (2). U.S. Department of Health, Education, and Welfare. (6) Lofroth, G. 1968. Pesticides and catastrophe. New Sci. 40(626) :567-568. /OL. 9, No. 2, September 1975 65 (7) Wassermann, M., D. H. Ciirnow, P. N. Forte, and Y. Groner. 1968. Storage of organochlorine pesticides in the body fat of people in Western Australia. Ind. Med. Surg. 37(4):295-300. (S) Springett, B. P. 1970. Biocides and man. Royal Perth Hospital J. 16:959-961. (9) Ciirlcy. A., and R. Kimbrouf;h. 1969. Chlorinated hy- drocarbon insecticides in plasma and milk of pregnant and lactating women. Arch. Environ. Health 18(2): 156-164. {10) Heyndrickx, A., and R. Maes. 1969. The excretion ol chlorinated hydrocarbon insecticides in human mothe* milk. J. Pharm. Belg. 24(9-10) :459-463. (//) Westoo, G., K. Noren, and M. Andersson. 1970. The levels of organochlorine pesticides and polychlorinateo biphenyls in margarine, vegetable oils and some food^ of animal origin on the Swedish market in 1967-1969,1 Var Foda 22(2-3) : 9-31. {12) Acker, L., and E. Schulte. 1970. The occurrence ol chlorinated biphenyls and he.xachlorobenzene in addi-i tion to chlorinated insecticides in human milk andi human fatty tissue. Naturwissenschaften 57(10):497. TABLE 4. Mean pesticide residues in human milk from seven countries Residues in Whole Milk , PPM Total COL'NTKY Year DDT DDE DDT DiELDRIN HCB Western Australia ' 1970-71 0.010 0.061 0.078 0.005 0.025 United Kingdom - 1963-64 0.045 0.073 0.127 0.006 ND United States » 1960-61 0.08 0.04 0.12 ND ND United Stales ' 1967-68 0.014 0.038 0.056 0.007 ND Western Australia = 1969-70 0.04 0.12 0.17 0.015 0.075 Netherlands" 1971 0.016 0.030 0.049 0.003 ND Belgium " 1969 0.048 0.072 0.128 0.004 ND Sweden ^ 1970 0.039 0.067 0.114 0.001 ND Germany ^ 1970 0.031 0.081 0.121 ND ND NOTE: ND = no data in the study cited. ^ See present study. - See Literature Cited, reference 3. ^ See Literature Cited, reference 2. * See Literature Cited, reference 9. ^ R. Lugg, Public Health Department. 1973: personal communication. * See Literature Cited, reference 4. "^ See Literature Cited, reference 10. ** See Literature Cited, reference 77. ^ See Literature Cited, reference 12. 66 Pesticides Monitoring Journal RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mercury Residues in Breast Muscle of Wild Ducks, 1970-71 ^ Thomas S. Baskett 2 ABSTRACT Samples of breast muscle from 327 ducks collected from October 1970 to March 1971 in the conterminous United States were analyzed for total mercury by fiameless atomic absorption spectrometry. Mercury levels for the entire collec- tion ranged from 4 mile; possible sources of Hg in- clude pulp mill, sewage, miscellaneous small industries, and out- wash from natural deposits) (B) ALABAMA: Mobile Coimiy. (Ducks collected on or within 1 mile of settling basin of chlor-alkali plant) (C) TEXAS: Lavaca Bay. (Collections within 15 miles of portion of Lavaca Bay then designated as polluted area; possible source of Hg: chlor-alkali plant) (D) CALIFORNIA: San Francisco Bay. (Northeast portion: tidal water and marshes; possible sources of Hg include chlor-alkali plant, outwash from old gold extraction areas, and outwash of natural deposits. South portion: tidal waters; sewage, paint- processing plants, chipping paint from boats and yachts, and outwash of natural deposits) Addison, Panton, and Ferrisburg, Addison County; Missisquoi Na- tional Wildlife Refuge and Missisquoi Bay, Franklin County; North Hero, Grand Isle Coimty. Chickasaw, Mobile County. Cox Bay, Mud Point, Smith Marsh, Calhoun County; Victoria Barge Canal near Bloomington, Victoria County. Northern part: Joice and Grizzly Islands, Suisun Marshes. Solano County; Napa Marshes, Napa County. Southern part: opposite South San Francisco and Palo Alto, San Mateo and Santa Clara counties. (Continued next page) 72 Pesticides Monitoring Journal TABLE 1 (cont'd.). Wild duck sampling sites, 1970-71 Area Sites Regions not known to be contaminated (E) MARYLAND: Chesapeake Bay (Bay waters and tidal inlets, middle one-lhird of Bay) (F) MARYLAND: West River. (Tidewater) (G) NORTH CAROLINA: Curolla. (Collections made in Currituck Sound, brackish water) (H) NORTH CAROLINA:. Grand>'. (Trap mortalities in Albemarle Sound: brackish water) (I) NORTH CAROLINA: Pamlico Point. (Pamlico Sound; brack- ish water) (J) ALABAMA: Baldwin County. (Tidal delta) (K) NORTH DAKOTA: Stanton. (Missouri River) (L) NORTH DAKOTA: Woodworth. (Permanent and semiperma- nent glacial marshes) (M) NORTH DAKOTA: Petiibone (Permanent glacial marsh) (N) NORTH DAKOTA: Audubon National Wildlife Refuge (Feed- lots) (O) SOUTH DAKOTA: Marshall County. (Permanent glacial lake) (P) SOUTH DAKOTA: McPherson County (Dugouts or artificial stock water excavations, plus semipermanent and permanent glacial potholes) (Q) SOUTH DAKOTA: Sand Lake National Wildli/e Refuge. (Semipermanent glacial marsh) (R) MINNESOTA; Itasca County (Large glacial lake) (S) MINNESOTA: Agassiz National Wildlife Refuge. (Large arti- ficial pool) (T) CALIFORNIA: Tule Lake and Lower Klamath National Wild- life Refuges. (Sumps on refuges, receiving drainage from agri- cultural lands) (U) UTAH: Bngham City. (Marshes on and near Bear River Na- tional Wildlife Refuge) Poplar Island, Talbot County; Cove Point, Calvert County; Fishing Bay, Dorchester County. Near junction of West and Rhodes Rivers, Anne Arundel County. Corolla, Currituck County. Grandy, Currituck County. Near Lowland, Pamlico County. Gustang Bay, Mobile Delta, near Daphne, Baldwin County. Near Stanton, Mercer County. Vicinity of Woodworth, Stutsman County. 5 miles SW of Pettibone, Kidder County. Vicinity of Coleharbor, McLean County. Piyas Lake, SE of Eden, Marshall County. Near Leola, McPherson County, and various points nearby in Mc- Pherson and adjacent Edmunds counties. Near Houghton, Brown County. Lake Winnibigoshish, Itasca County. Near Middle River, Marshall County. Near Tulelake, Siskiyou County. Near Brigham City, Box Elder County. TABLE 2. Tolal mercury in breast muscle of ducks collected in areas with high environmental mercury levels, 1970-71 (A) VERMONT: Lake Champlain vicinity Mallard Black duck M Imm F Ad F Ad F Ad F Imm F 1mm TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 0.09 0.06 0.17 0.23 0.09 0.04 11- 6-70 11-11-70 11-21-70 11-21-70 11- 8-70 11-21-70 6 0.04-0.23 0.09 Oof 6 Common goldeneye M M M F F F F F Ad Imm Imm Ad Ad Imm Imm Imm TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 0.27 0.21 0.54 0.29 0.76 0.46 0.46 0.42 11-17-70 11-17-70 11-20-70 11-17-70 11-20-70 11-12-70 11-17-70 11-29-70 g 0.21-0.76 0.44 2 of 8 (Continued next page) Vol. 9, No. 2, September 1975 73 TABLE 2 (cont'd.). Total mercury in breast muscle of ducks collected in areas with high environmental mercury levels, 1970-71 Dabbling Ducks Diving and Sea Ducks Location ' Species Sex AOE Mercury Level, ppm Date Species Sex Age Mercury Level, ppm Date (B) Gadwall M Ad 0.37 12- 9-70 Lesser M Ad 0.15 2- 2-71 ALABAMA: M Ad 0.24 12- 9-70 scaup M Ad 0.16 2- 2-71 Mobile M Ad 0.08 12- 9-70 M Imm 0.16 12- 9-70 County M Ad 0.18 2- 4-71 M Imm 0.16 2- 2-71 M Imm 3.91 2- 2-71 M Imm 0.27 2- 2-71 M Imm 0.22 2- 2-71 M Imm 0.14 2- 2-71 M Imm 0.16 2- 2-71 F Ad 2.00 12- 9-70 M Imm 1.9 2- 2-71 M Imm 0.87 2- 2-71 M Imm 0.97 2- 4-71 M Imm 1.2 2- 4-71 M Imm 0.57 2- 4-71 TOTAL DUCKS 12 TOTAL DUCKS 7 Range: Mercury levels ppm 0.08-3.9 Range: Mercury levels. ppm 0.14-2.0 Median, ppni 0.47 Median, ppm 0.16 No. at 0.5 ppm or abo ve 6 of 12 No. at 0.5 ppm or above 1 of 7 (C) Mottled M Ad 0.18 11-11-70 Lesser M Ad 0.19 11-11-70 TEXAS: duck M Ad 0.15 11-11-70 scaup M Ad 0.43 11-25-70 Port M Ad 0.09 11-11-70 M Ad 0.16 11-25-70 Lavaca M Ad 0.43 11-19-70 M Ad 1.0 11-25-70 M ND 0.43 12-26-70 M Ad 0.10 11-25-70 M ND 0.14 12-26-70 M Ad 0.30 11-25-70 M ND 0.28 12-26-70 M Ad 0.38 11-25-70 M ND 0.43 1- 4-71 M ND 0.16 12-20-70 M ND 0.35 1- 6-71 M ND 0.17 12-27-70 F Ad 0.07 11-11-70 M ND 0.32 12-29-70 F Ad 0.15 11-15-70 M ND 0.43 1-11-71 F Ad 0.25 11-15-70 M ND 0.16 1-11-71 F Ad 0.10 11-19-70 F Ad 0.40 11-20-70 F ND 0.37 12-26-70 F ND 0.06 12-29-70 F ND 0.32 12-27-70 F ND 0.09 2- 8-71 F ND 0.40 12-29-70 F ND 0.12 2- 8-71 TOTAL DUCKS 16 TOTAL DUCKS 16 Range: Mercury levels. ppm 0.070.43 Range: Mercury levels. ppm 0.06-1.0 Median, ppm >0.26 Median, ppm 0.18 No. at 0.5 ppm or abo ve 0 of 16 No. at 0.5 ppm or above 1 of 16 (D) Mallard M Ad 0.04 11- 9-70 Lesser M Ad 0.68 12-12-70 CALIFORNIA: M Ad 0.10 11- 9-70 scaup F Ad 0.22 12-12-70 San M Ad 0.03 11- 9-70 F Imm 0.13 12-12-70 Francisco M Ad 0.05 11- 9-70 F Ad 0.03 12-12-70 Bay M Ad 0.03 11- 9-70 Greater M Ad 0.68 12-12-70 M Ad 0.24 1-26-71 scaup M Imm 0.20 12-12-70 M Imm 0.04 1-26-71 F Ad 0.49 12- 7-70 M 1mm 0.10 1-26-71 F Ad 0.28 12- 7-70 M Ad 0.02 1-26-71 F Ad 0.31 12- 7-70 M Ad 1.06 1-26-71 F Imm 0.19 12- 9-70 F Ad 0.12 11- 9-70 F Imm 0.41 12-12-70 F Ad 0.06 11- 9-70 F Imm 0.44 12-12-70 F Ad 0.05 11- 9-70 F Ad 0.03 1-26-71 F Ad 0.02 1-26-71 F Imm 0.62 1-26-71 Pintail M M M F F Ad Imm Imm Ad Imm 0.09 0.05 0.06 0.08 0.15 1-26-71 1-26-71 1-26-71 1-26-71 1-26-71 TOTAL DUCKS 21 TOTAL DUCKS 12 Range: Mercury levels. ppm 0.02-1.06 Range: Mercury levels. ppm 0.03-0.75 Median, ppm 0.06 Median, ppm >0.29 No. at 0.5 ppm or abo •e 2 of 21 No. at 0.5 ppm or abov e 2 of 12 NOTE: M = male, F= female, Imm = immature. Ad = adult. ND = no data. ^ See Table 1 for complete description of collection lorations. 74 Pesticides Monitoring Journal TABLE 3. Total mercury in breast muscle of ducks collected in areas not known to be contaminated, 1970-71 Dabbling Ducks Diving and Sea Duck s Location ' Species Sex Ace Mercury Level, ppm Date Species Sex Ace Mercury Level, ppm Date (E) Mallard M Ad 0.01 1- 9-71 Common M Ad 0.20 12- 1-70 MARYLAND: M Imm 0.06 12-27-70 scoter M Ad 0.10 12- 1-70 Chesapeake M Imm 0.01 12-27-70 F Ad U.06 12- 1-70 Bay M Imm 0.03 1- 2-71 Surf scoter M Ad 0.17 12- 1-70 F Ad 0.03 1- 2-71 White- M Ad 0.08 12- 1-70 F Ad 0.06 1- 9-71 winged M Ad 0.07 12- 1-70 F 1mm 0.02 1- 2-71 scoter M Ad 0.43 12- 1-70 F Imm 0.01 1- 9-71 Canvasback ND ND ND ND ND ND ND ND ND Imm ND ND ND ND ND ND ND ND 0.61 0.09 0.16 0.05 0.22 0.11 0.24 0.15 0.10 12- 1-70 12-31-70 12-31-70 12-31-70 12-31-70 12-31-70 12-31-70 12-31-70 12-31-70 TOTAL DUCKS 8 TOTAL DUCKS 16 Range: Mercury levels, ppm 0.01-0.06 Range: Mercury levels, ppm 0.050.61 Median, ppm >0.02 Median, ppm 0.13 No. at 0.5 ppm or above Oof 8 No. at 0.5 ppm or above lof 16 (F) Canvasback ND ND 0.16 3-71 MARYLAND: No samples collected ND ND 0.08 3-71 West River ND ND ND ND ND ND ND ND ND ND ND ND 0.08 0.08 0.12 0.08 0.10 0.08 3-71 3-71 3-71 3-71 3-71 3-71 TOTAL DUCKS 8 Range: Mercurv levels, ppm 0.08-0.16 Median, ppm 0.08 No. at 0.5 ppm or above Oof 8 (G) Mallard M Ad 0.08 Lesser M Ad 0.47 NORTH M Ad 0.04 scaup M Imm 0.14 CAROLINA: M Ad 0.03 11- 8-70 M Imm 0.23 11- 8-70 Corolla M Ad 0.08 to M Imm 0.20 to M Imm 0.04 12- 5-70 M Imm 0.42 12- 5-70 F Imm 0.05 F Imm 0.10 F Imm 0.06 F Imm 0.37 F Imm 0.12 TOTAL DUCKS 8 TOTAL DUCKS 7 Range: Mercury levels, ppm 0.03-0.12 Range: Mercury levels, ppm 0.10-0.47 Median, ppm >0.0S Median, ppm 0.23 No. at 0.5 ppm or above Oof 8 No. at 0.5 ppm or above Oof? (H) Mallard M Ad 0.01 2-15-71 NORTH M Ad 0.01 2-15-71 No samples collected CAROLINA: M Imm 0.01 2-15-71 ^ Grandy M Imm 0.02 2-15-71 M Imm 0.01 2-15-71 M Imm <0.01 2-15-71 F Ad 0.16 2-15-71 F Imm 0.01 1-15-71 TOTAL DUCKS 8 Range: Mercury levels, ppm < 0.01-0.16 Median, ppm 0.01 No. at 0.5 ppm or above Oof 8 (I) Lesser M Ad 0.19 2-15-71 NORTH No samples collected scaup M Ad 0.35 2-15-71 CAROLINA: M Ad 0.70 3-29-71 PamUco Pt. M M M M F Imm Imm Imm Imm Ad 0.08 0.04 0.03 0.22 0.03 2-15-71 2-15-71 3-29-71 3-29-71 3-29-71 TOTAL DUCKS 8 Range: Mercury levels, ppm 0.03-0.70 Median, ppm >0.13 No. at 0 5 ppm or above 1 of 8 {Continued next page) Vol. 9, No. 2, September 1975 75 TABLE 3 (cont'd.). Total mercury in breast muscle of ducks collected in areas not known to be contaminated, 1970-71 Location i (J) ALABAMA: Baldwin County (K) NORTH DAKOTA: Stanton (L) NORTH DAKOTA: Woodworth (M) NORTH DAKOTA: Pettibone Dabblinci Ducks Species Gadwall Sex M M F F Age Mercury Level, ppm Imm Imm Imm Imm TOTAL DUCKS Range: Mercur>' levels, pp Median, ppm No. at 0.5 ppm or above 0.07 0.02 0.09 0.04 0.02-0.09 <0.05 Oof 4 Date 12- 9-70 Lesser 12- 9-70 scaup 12- 9-70 12- 9-70 Mallard M M M M M F ND ND ND ND ND ND 0.02 0.03 0.03 0.02 0.02 0.02 12-29-70 12-29-70 12-29-70 12-29-70 12-29-70 12-29-70 TOTAL DUCKS 6 Range: Mercury levels, ppm 0.02-0.03 Median, ppm 0.02 No. at 0.5 ppm or above 0 of 6 Mallard M Ad M Ad M Ad M Ad F Ad F Ad F Ad F Ad 0.05 0.04 0.02 0.02 0.02 0.01 0.03 0.05 10- 2-70 10- 2-70 10- 2-70 10- 3-70 10- 2-70 10- 3-70 10- 3-70 10-29-70 TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 8 0.01-0.05 >0.02 Oof 8 Mallard M Ad M Ad M Ad F Ad F Ad F Ad F Ad 0.18 0.03 0.04 0.06 0.18 0.05 0.07 1- 3-70 1- 3-70 1- 3-70 1- 3-70 1- 3-70 1- 3-70 1- 3-70 TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 7 0.03-0.18 0.06 Oof 7 Diving and Sea Ducks Species Sex Ace Mercury Level, ppm Date M Ad M Ad M Ad M Imm M Imm M Imm M Imm F Imm F Imm 0.24 0.21 0.20 0.12 0.16 0.27 0.18 0.18 0.34 11-26-70 11-26-70 2- 3-71 11-26-70 11-27-70 11-27-70 11-27-70 11-26-70 2- 3-71 TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 9 0.12-0.34 0.20 0of9 No samples collected Lesser scaup M Ad M Ad M Ad M Ad M Ad M Ad M Ad F Ad F Ad F Ad F Ad F Ad F Ad F Ad F Ad F Ad 0.70 0.11 0.53 0.21 0.36 0.12 0.70 0.43 0.18 0.12 0.22 0.04 0.22 0.37 0.26 0.43 10- 6-70 10- 6-70 10- 6-70 10- 8-70 10-29-70 10-29-70 10-29-70 10- 6-70 10- 6-70 10- 6-70 10- 7-70 10-29-70 10-29-70 10-29-70 10-29-70 10-29-70 TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 16 0.04-0.70 0.24 3 of 16 No samples collected (N) NORTH DAKOTA: Audubon NWR Mallard M Ad M Ad M Ad M Ad F Ad F Ad F Ad F Ad TOTAL DUCKS Range: Mercury levels, ppm Median, ppm No. at 0.5 ppm or above 0.04 0.04 0.03 0.03 0.07 0.01 0.10 0.03 8 0.01-0.10 >0.03 Oof 8 10-29-70 10-29-70 10-29-70 10-29-70 10-29-70 10-29-70 10-29-70 10-29-70 No samples collected (Continued next page) 76 Pesticides Monitoring Journal TABLE 3 (cont'd.). Total mercury in breast muscle of ducks collected in areas not known to be contaminated, 1970-71 Dabbling Ducks | DiviNO AND Sea Ducks Location > Species Sex Age | Mercury Level, ppm 1 Date Species Sfex Age Mercury Level, ppm Date (O) <-esser M Ad 0.28 10-27-70 SOUTH No samples collected scaup M Ad 0.20 10-27-70 DAKOTA: M Ad 0.26 10-27-70 Marshall M Ad 0.40 10-27-70 County M F F F Ad Ad Ad Ad 0.15 0.65 0.38 0.15 10-27-70 10-27-70 10-27-70 10-27-70 TOTAL DUCKS 8 Range: Mercury levels, ppm 0.15-0.65 Median, ppm 0.27 No. at 0.5 ppm or above lof 8 (P) Mallard M Ad 0.02 10- 7-70 Lesser M Ad 0.15 10-15-70 SOUTH M Ad 0.03 10- 7-70 scaup M Ad 0.19 10-15-70 DAKOTA: M Ad 0.02 10- 7-70 F Ad 0.17 10-15-70 McPherson M Ad 0.06 10- 7-70 F Ad 0.09 10-15-70 County M Ad 0.04 10- 7-70 F Ad 0.18 10-15-70 F Ad 0.02 10- 7-70 F Ad 0.18 10-15-70 F Ad 0.03 10- 7-70 F Ad 0.04 10- 7-70 TOT \l ducks 8 TOTAL DUCKS 6 Rang e: Mercury levels, ppm 002-0.06 Range: Mercury levels, ppm 0.090.19 Medi an. ppm 0.03 Median, ppm >0.17 No. It 0.5 ppm or above Oof 8 No. at 0.05 ppm or above Oof 6 (Q) Mallard M Ad 0.03 11-20-70 SOUTH M Ad 0.03 11-20-70 No samples collected DAKOTA: M Ad 0.02 11-20-70 Sand Lake M Ad 0.02 11-20-70 NWR M F F F Ad Ad Ad Ad 0.03 0.03 0.05 0.02 11-20-70 11-20-70 11-20-70 11-20-70 TOT ^L DUCKS 8 Rang e: Mercury levels, ppm 0.02.0.05 Medi an, ppm 0.03 No. it 0.5 ppm or above Oof 8 (R) Lesser M Ad 0.07 10-15-70 MINNESOTA: No samples collected scaup M Ad 0.15 10-15-70 Itasca M M M F F F Ad Ad Ad Ad Ad Ad 0.20 0.25 0.15 0.10 0.19 0.15 10-15-70 10-15-70 10-15-70 10-15-70 10-15-70 10-15-70 TOTAL DUCKS 8 Range: Mercury levels, ppm 0.07-0.25 Median, ppm 0.15 No. at 0.05 ppm or above Oof 8 (S) Mallard M Ad 0.09 10- 8-70 MINNESOTA: M Ad 0.07 10- 8-70 No samples collected Agassiz M M M M F F F F F F F F F Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad 0.07 0.04 0.03 0.10 0.04 0.18 0.08 0.13 0.17 0.24 0.04 0.10 0.12 10- 8-70 10-28-70 10-28-70 10-28-70 10- 8-70 10- 8-70 10- 8-70 10- 8-70 10- 8-70 10-28-70 10-28-70 10-28-70 10-28-70 F Ad " 0.20 10-28-70 TOT AL DUCKS 16 Rang e: Mercury levels, ppm 0.03-0.24 Med an, ppm >0.09 No. at 0.5 ppn or ab Dve Oof 16 _L {Continued next page) Vol. 9, No. 2, September 1975 77 TABLE 3 (cont'd.). Total mercury in breast m uscle of ducks collected in areas not known to be contaminated, 1970-71 Dabbling Ducks Diving and Sea Ducks | Location ' Species Sex Age Mercury Level, ppm Date Species Sex Age Mercury Level, ppm Date (T) Mallard M Ad 0.09 11-17-70 Lesser M Ad 0.06 11-17-70 CALIFORNIA: M Ad 0.03 11-17-70 scaup M Ad 0.11 11-17-70 Tule Lake M Ad 0.06 11-17-70 M Ad 0.22 11-17-70 and Lower M Ad 0.02 11-17-70 M Ad 0.10 11-17-70 Klamath M Ad 0.04 11-17-70 M Ad 0.31 2-15-71 NWR M Ad 0.17 11-17-70 M Ad 0.72 2-22-71 M Ad 0.02 1- 5-71 M Ad 0.32 2-22-71 M Ad 0.08 1- 5-71 M Ad 0.02 2-22-71 M Ad 0.06 1- 8-71 M Imm 1.77 2-22-71 F Ad 1.47 11-17-70 F Ad 0.51 11-17-70 F Ad 0.02 11-17-70 F Ad 0.16 11-17-70 F Ad 0.02 1- 1-71 F Imm 0.29 11-17-70 F Ad 0.07 1- 1-71 F Imm 0.23 11-17-70 F Ad 0.03 1- 5-71 F Ad 0.58 2-15-71 F Ad 0.05 1- 8-71 F Ad 0.02 2-22-71 F Ad 0.04 1- 8-71 F Ad 0.49 2-22-71 TOTAL DUCKS 16 TOTAL DUCKS 16 Range: Mercury levels, ppm 0.02-1.47 Range: Mercury levels, ppm 0.02-1.77 Median, ppm > 0.04 Median, ppm 0.26 No. at 0.5 ppm or above 1 of 16 No. at 0.5 ppm or above 4 of 16 (U) Mallard M Ad 0.05 10-25-70 Lesser M Ad 0.14 10-31-70 UTAH: M Ad 0.03 10-25-70 scaup F Imm 0.12 12-29-70 Brigham M Ad 0.02 10-25-70 City M M M Ad Ad Ad 0.02 0.01 0.02 10-25-70 12-14-70 12-14-70 Greater scaup F Ad 0.02 10-26-70 M Ad 0.06 12-14-70 Ring- M Ad 0.06 10-31-70 M Ad 0.02 12-15-70 necked M Imm 0.09 10-28-70 M Imm 0.19 12-19-70 duck M 1mm 0.18 10-29-70 F Ad 0.01 10-25-70 F I mm 0.03 10-25-70 F Imm 0.08 10-25-70 F Imm 0.02 10-25-70 F Ad 0.05 12-14-70 F Ad 0.06 12-14-70 F Ad 0.02 12-14-70 TOTAL DUCKS 16 TOTAL DUCKS 6 Range: Mercury levels, ppm 0.01-0.19 Range; Mercury levels, ppm 0.020.18 Median, ppm 0.02 Median, ppm 0.10 No. at 0.5 ppm or above Oof 16 No. at 0 05 ppm or above Oof 6 NOTE: M = male, F = female, Imm = immature, Ad =: adult. ND = no data. ^ See Table 1 for complete description of collection locations. 78 Pesticides Monitoring Journal Organochlorine Pesticide Residues in Small Migratory Birds, 1964-73 David W. Johnston ' ABSTRACT Chlorinated hydrocarbon pesticide burdens, especially those of DDT and its metabolites, have been determined for 19 species of small terrestrial mif^ratory birds killed chiefly at Florida television towers from 1964 to 1973. All 128 sam- ples were sorted into pools by species. All pooled samples except one contained DDE and often DDT and DDD; di- eldrin was present in 60 of the samples; but no PCB's were detected. In small subsamples, XDDT (p,p'-DDT, p,p'-DDD, and p.p'-DDE) residues sometimes differed between males and females, adults and immatures, and northbound and southbound migrants but results of these comparisons were inconclusive. IDDT burdens were highest in adipose tissue and much lower in liver and brain samples. Epecially among birds taken since 1970 have the pesticide levels in adipose tissue been at low levels, generally less than 3 ppm iDDT. These low quantities are comparable to those quoted in other reports on birds of similar trophic levels. The insecti- vorous and/or partly granivorous birds feeding on or near the ground tended to have higher "ZDDT levels than did the more arboreal species. Introduction Although the widespread occurrence and eflfects of bio- cides in natural ecosystems are matters of intense public interest, research reports on birds have concentrated on terminal members of food chains, the carnivorous and piscivorous species. These top carnivo-es are known to accumulate chlorinated hydrocarbon pesticides in fatty tissues. In species such as osprey (Pandion haliaetus), double-crested cormorant (Phalacrocorax auritus), and peregrine (Falco peregriniis), correlations have been made between pesticides, especially DDE, and popula- tion declines, mortality, and alteration of physiological processes resulting in impaired reproductive success (1-3). Particularly symptomatic of DDT burdens are decreases in eggshell thickness. In terrestrial ecosystems, however, very little attention ' Department of Zoology, University of Florida, Gainesville, Fla. 32611 Vol. 9, No. 2, September 1975 has been given to organisms of subterminal trophic levels wherein stored pesticides and pollutants could play important roles in population dynamics. For wild North American migratory birds the published litera- ture contains scattered reports of pesticide burdens, but few of these reports contain data on large numbers of species or individuals (3-17). Additional studies have concentrated on pesticide effects on small bird popula- tions (18-24) or laboratory experiments (25-29). The present investigation concerns pesticide burdens of sub- terminal members of food chains, the myriads of small insectivorous, granivorous, or frugivorous birds so vital in the metabolism of terrestrial ecosystems. Sampling Methods For at least 20 years thousands of small birds have collided with tall television towers and other person- made structures during their autumnal and vernal noc- turnal migratory flights, or have died at airport ceilome- ters in the southeastern United States (30-32). The ma- jority of the birds are insectivorous vireos and warblers that breed in eastern North America and winter in the West Indies or Central America. Alert local observers gather the dead birds in the early morning hours, usually within 6 hours after death, place them in plastic bags, and freeze them with feather coverings intact for later studies. The large sample sizes have proved valuable in migration and distributional analyses and weight and fat studies, and as scientific specimens and skeletons. For the present investigation a total of 19 species and 908 individuals were utilized. Autumnal individuals taken at the Florida sites at the beginning of p-otracted over-water flights were markedly obese: 30 percent or more of the body weight was stored subcutaneous and abdominal fat (33,34). On the other hand, the vernal migrants had completed a protracted flight from the south and were lean, having utilized much of the pre- migratory stored fat as a flight energy source (33). 79 Collection sites for birds analyzed here included the following Florida locations; television towers WJKS and WJAX, Jacksonville; WDBO tower near Orlando; WCTV tower north of Tallahassee; the Vertical Assem- bly Building, Cape Canaveral; and the Vero Beach area. mental parameters were: injection port, 210° C; col- umn, 212° C; detector, 215° C; and nitrogen flow rate, 45 ml/min. Recoveries for organochlorine compounds ranged from 75 to 95 percent. Sensitivity was greater than 0.01 mg/ml. Analytical Procedures For an accurate analysis of so many birds, single-night kills were first sorted by species, then, when possible, by sex and age. A sample size of 10 was sought for given sex and age groups, but frequently fewer than 10 were available. Pooled samples of adipose tissue were dissected from the interfurcular subcutaneous depots. In initial analyses, liver and brain samples were also taken. An attempt was made to obtain approximately the same quantity of tissue from each bird in order not to bias the pooled sample. Pooled fat samples were weighed immediately to obtain a wet weight; these averaged 1.16 g with a range of 0.58-1.95 g. Each pooled sample was thoroughly ground and mixed with sodium sulfate in a VirTis homogenizer, then extracted for 10 hours in a Soxhiet apparatus using petroleum ether as a solvent. Following solvent evaporation, the lipid residues were weighed; average weight was 0.76 g with a range of 0.14-1.56 g. Lipid residues were par- titioned with acetonitrile and hexane, and the acetoni- trile fraction was cleaned on an 8 percent water de- activated florisil column using a 3:1 hexane: benzene eluant. The resulting eluate was concentrated or diluted in hexane, as necessary, for gas chromatography. Most samples were processed on a Varian 600-D gas chromatograph containing a 6-ft-by-'/»-in. glass column of 1:1 6.4 percent OV-210:1.6 percent OV-17 on chromosorb W with an electron-capture detector. A sec- ond glass column of 1.5 percent OV-17: 1.95 percent QFI on Gas-Chrom Q of similar dimensions in a Varian model 2100 was used for confirmation. Other instru- Results SEX DIFFERENCES Because the investigations reported here for small mi- gratory birds are the first of this quantitative and com- prehensive nature, a number of variables in the sam- ples had to be evaluated and resolved at the outset. One question involved any possible differences in the pesti- cide burdens of the two sexes. Four species were se- lected at random and intraspecific samples of each sex were compared. Table 1 shows that the difference be- tween 2DDT (p,p'-DDT, p.p'-DDD, and p,p'-DDE) concentrations in each sex exceeded 50 percent in only two of the six comparisons. These variable differences suggest that, in general, attributing differences in 2DDT burdens to sex is largely unwarranted. AGE DIFFERENCES Inasmuch as autumnal samples of migratory birds killed! at television towers or ceilometers nearly always con- tain a high proportion of immature individuals, i.e., birds-of-the-year (31,32), it was deemed advisable to investigate possible differences in pesticide burdens in different intraspecific age groups. Eight species samples were used for comparisons (Table 2). In only 5 of the 12 pairings the percentage of difference in -DDT con- centrations between age groups was 50 or more; hence it is doubtful that difference in age plays a significant role in pesticide burdens of these birds. Because the immature birds were only 4-5 months old at the time of death, there is a limited number of sources which may have contributed to their 2DDT TABLE 1. Differences between ZDDT residues in adipose tissue of males and females of selected bird species, 1964-72 Sample BODV SDDT Residues, Percent Species Date LOCALFFY SlZEl Weight, g PPM wet weight Difference Dendroica striata (Blackpoll Warbler) May 1971 May 1971 WJKS WJKS ScT 5$ 12.1 11.8 0.21 0.06 71 Dendroica caernlescens (Black-throated Blue Warbler) Oct 1972 Oct 1972 Oct 1972 Oct 1972 WDBO WDBO WDBO WDBO lOAcT I0A9 91 cf 1019 — 1.19 0.66 1.10 1.55 44 29 Seiurus aurocapillus (Ovenbird) Oct 1964 Oct 1964 WJAX WJAX lOAcf 9A? 23.4 23.3 5.35 3.23 39 Setophaga ritticilla (American Redstart) Oct 1964 Oct 1964 May 1972 May 1972 WJXT WJXT VAB VAB 3Acr 12A9 109 7.2 6.7 10.25 10.42 3.27 0.97 1 70 NOTE: — = no data. ^ A = adult; I = immature. ' Difference between values expressed as a percent of the larger value. 80 Pesticides Monitoring Journal TABLE 2. Differences between TDDT residues in adipose tissue of selected bird species of various age groups Average Sample Body X DDT Residues, Percent Species Date LOCALITV Size ■ Weight, g PPM WET WEIGHT Difference = Dumetella varoUnensis Oct 1972 WCTV lOA 35,8 0.33 (Gray Catbird) Oct 1972 WCTV 41 36,6 0,27 18 Vireo olivaceus Oct 1972 WCTV lOA 25,0 0,50 (Red-eyed Vireo) Oct 1972 WCTV 101 24,1 0,18 64 Dcndroica coronata Nov 1966 WCTV 4A 10.4 7.09 ( Yellow-rumped Warbler) Nov 1966 WCTV 41 11,3 5.77 19 fall 1969 WCTV 5A 11,7 5.31 fall 1969 WCTV 71 12,7 7.56 30 Dendroica caerulescens Oct 1972 WJKS lAd 12,4 1.35 (Black-throated Blue Warbler) Oct 1972 WJKS lid 12,8 0.87 36 Oct 1972 WDBO lOA? — 0.66 Oct 1972 WDBO 101? — 1.55 57 Oct 1972 WDBO lOAd" — 1,19 Oct 1972 WDBO 9Id" — 1.10 8 Seiurus aurocapilUts Oct 1964 WJXT lOA 25,3 3.33 (Ovenbird) Oct 1954 WJXT 91 25,8 2,73 18 Oct 1968 WJXT lOA — 3,09 Oct 1968 WJXT 31 — 1,24 60 Ceothlypis Irichas Oct 1972 WJKS lOA 11.4 4,47 (Common Yellowthroat) Oct 1972 WJKS lOId' 10.9 3,28 27 Setophaga ritticilla Oct 1971 WJKS 10A9 8.9 5,62 (American Redstart) Oct 1971 WJKS 101? 9.1 12.33 54 Zonotrichia albicoUis fall 1966 WCTV 6A 2.47 (White-throated Sparrow) fall 1966 WCTV 61 — 15.09 84 NOTE: — = no data. ^ A = adult; I = immature. 3 Difference between values expressed as a percent of the larger value. burdens: transfer of a DDT metabolite from parent to offspring in the egg; contaminated food obtained from parents; and food taken by the independent immature birds. In 8 of the 12 pairings, adults had the greater SDDT burdens, possibly because the 4-to-5-month-old immatures simply had had less time to ingest DDT- laden foods than had the adults aged 1 or more years. On the other hand, some immatures had greater DDT burdens than had the adults (Table 2), It is possible that second- or third-year adults had eliminated or translocated internally a portion of a DDT metabolite when they lost stored fat supplies during at least two previous long-distance flights (35-39). It is also possible that the immatures were raised in or migrated through areas with unusually high degrees of pesticide contami- nation. ORGAN DIFFERENCES In view of the facts that chlorinated hydrocarbon pesti- cides are especially fat-soluble and that fat content of vertebrate organs differs widely, the author analyzed three tissue or organ types: adipose tissue, liver, and brain. In every species sampled (Table 3), i:DDT bur- dens progressively decreased from adipose tissue to liver to brain or from adipose tissue to brain on a wet-weight basis. Furthermore, the author found that extractable lipid also decreased from adipose tissue to liver to brain on a percentage basis. DDT burdens, expressed on a lipid-weight basis, also decreased from adipose tissue to brain. The difference in DDT burdens between adipose tissue and brain expressed on a wet-weight basis is ap- proximately 10 times that expressed on a lipid basis, partly because extractable lipids from brains represent only about 10 percent of the wet weight. In most analy- ses here only adipose tissue was sampled for pesticide burdens. INTRASAMPLE VARIATIONS Because so many individual birds were available, pooled tissue samples from sex and age groups of the same species were deemed advisable. Although the author attempted to dissect approximately the same quantity of a given tissue from each bird for the pooled sample, there is always a chance of individual variation in pesti- cide burdens among such large composites. In some instances it was possible to analyze separately a number of individuals of the same sex and age. For example, in a sample of five immature male yellow- billed cuckoos (Table 4), the mean i;DDT burden was 0.57 ppm with a range of 0.12-1.06 ppm. Deviation of minimum and maximum figures from the mean value is at least 75 percent. In seven adult male common yellowthroats the mean i)DDT burden was 3.27 ppm with a range of 1.93-5.39 ppm (Table 5). In this case the minimum deviation from the mean is approximately 40 percent. Although these sample sizes are small and the study deals with small quantities of 2DDT burdens, the average intrasample variation of 50 percent has Vol. 9, No. 2, September 1975 81 TABLE 3. Differences in pesticide residues in brain, fat, and liver of selected bird species Residues, Residues, PPM Wet Weight PPM Lipid Weight Species Tissue Date Locality Sample I Weight, o DDE SDDT DIELDRIN DDE SDDT DIELDRIN Mniolilta varia fat May 1971 VAB 6A 9.2 1.58 2.58 0 5.55 8.91 0 brain 0.02 0.03 0 0.62 0.99 0 (Black-and-white Warbler) fat May 1972 VAB lOA 9.0 0.41 1.46 0 1.05 3.76 0 brain 0.02 0.04 0 0.60 1.20 0 fat Nov 1972 GCM 9.1 1.74 2.34 0 5.60 7.53 0 brain 91 0.02 0.02 0 0.56 0.56 0 Dendroica caerulescens fat Sep 1970 WDBO 7A 11.0 1.06 1.59 0 1.45 2.17 0 brain 51 0.04 0.08 0 0.94 1.88 0 (Black-throated Blue Warbler) liver 0.03 0.09 0 10.0 31.00 0 Dendroica palmarum fat Oct 1972 WJKS 81 10.0 2.36 8.82 0.23 3.79 14.17 0.37 0.26 0.52 0 13.05 26.10 0 brain 81 9.2 0.98 0.98 0 5.04 5.04 0 (Palm Warbler) fat brain Nov 1972 GCM lA 1? 0 0.02 0 0.29 0.29 0 SeiuTus aurocapillus tat Oct 1972 WJKS lOA 23.2 1.76 2.78 0 2.12 3.54 0 brain 0.02 0.02 0 0.62 0.62 0 (Ovenbird) fat Nov 1972 GCM 2A 20.1 0.48 0.69 0 1.23 1.78 0 brain 41 0 0 0 0 0 0 Seiurus noveboracensis fat May 1971 VAB 11 15.0 2.05 11.49 0 10.80 24.27 0 brain 0.23 0.29 0 8.93 11.37 0 (Northern Waterthrush) fat Oct 1972 WJKS 61 18.2 4.07 9.68 0.79 7.04 17.25 1.44 brain 0.07 0.12 0 2.67 4.80 0 fat Nov 1972 GCM 91 17.3 4.80 5.01 0 12.38 12.92 0 brain 0.06 0.06 0 1.87 1.87 0 Geothlypis trichas fat liver brain Oct 1964 WJXT 61 rf 12.0 3.53 1.01 0.04 6.53 1.39 0.10 0.03 0.01 0.01 (Common Yellowthroat) fat liver Oct 1964 WJXT 6A9 9.5 3.11 0.35 3.63 0.43 0 0 brain Oct 1964 WJXT 6A9 9.5 0.04 0.04 0 fat May 1972 VAB lOAcf 8.9 4.11 4.43 0 9.50 10.23 0 brain 0.02 0.02 0 0.75 0.75 0 fat Nov 1972 GCM 61 cT 9.5 1.01 1.01 0 3.51 3.51 0 brain 419 0.07 0.07 0 2.03 2.03 0 fat Oct 1972 WJKS lOIcT 10.9 2.15 3.28 O.Il 3.81 5.83 0.19 Setophaga rtiticilla fat Oct 1969 VAB 6A9 8.2 2.01 4.65 0.51 2.57 5.94 0.65 liver 0.52 0.91 1.93 6.01 10.50 1.93 brain 0.08 0.24 0.02 0.68 2.04 0.20 (American Redstart) fat Oct 1972 WCTV 719 — 2.29 6.02 0 3.20 8.42 0 brain 0 0 0 0 0 0 fat May 1972 VAB 109 6.7 0.97 0.07 0 brain 0.02 0.02 0 0.80 0.80 0 fat May 1972 VAB Sd' 7.2 3.03 3.27 0 19.51 21.05 0 brain 0.51 0.51 0 1.36 1.36 0 fat Nov 1972 GCM 10? «.8 2.92 2.92 0 14.3 14.3 0 brain 0.10 0.10 0 2.89 2.89 0 adult; I = immature. TABLE 4. Pesticide burdens in adipose tissue, yellowbillcd cuckoo (Coccyzus americanus) Date Age' Sex Body Weight, g Residues , PPM Wet Weight DDT DDD DDE SDDT DIELDRIN Autumn Oct 21, 1971 Arf 77.3 1.01 0.26 1.10 2.37 0.06 Sept 29, 1970 A9 66.2 0.15 0.04 0.18 0.37 0.21 Sept 30, 1970 A? 72.5 0.27 0.07 0.25 0.59 0.01 X 72.0 0.48 0.12 0.51 1.11 0.09 Oct 2, 1972 Id 70.3 0.06 0 0.06 0.12 0.03 Oct 11, 1971 Id 78.3 0.20 0 0.28 0.48 0 Oct 11, 1971 Id 96.1 0.68 0 0.24 0.92 0 Oct 11, 1971 Id 79.7 0.50 0 0.55 1.06 0.01 Oct 11, 1971 Id 70.4 0.19 0 0.10 0.29 0 X 78.9 0.33 0 0.25 0.57 <0.01 SPRING May 10, 1972 d 52.3 0 0 0.04 0.04 0 Apr 9, 1973 d 70.2 0 0 0.13 0.13 0.02 May 10, 1972 9 64.8 0 0 0 0 0 Apr 10, 1973 9 50.5 0 0 0.41 0.41 0 X 59.5 0 0 0.15 0.15 <0.01 adult; 82 Pesticides Monitoring Journal TABLE 5. Pesticide burdens in adipose tissue, adult male common yellowthroats (Geothlypis trichas) — October 6, 1964 Specimen Residues, ppm Wet Weight Number Body Weight, g DDT DDD DDE SDDT : 9.7 0.71 0.25 2.25 3.21 2 11.3 0.71 0.25 2.24 3.20 3 10.5 0.56 0.07 1.71 2.33 9 11.2 0.81 0.18 3.35 4.34 10 10.5 0.57 0.12 4.70 5.39 11 12.0 0.14 0 1.79 1.93 12 9.8 0.25 0 2.21 2,46 X 10.7 0.54 0.12 2.61 3.27 been helpful in assessing possible differences in sex or age samples as discussed above. INTRASPECIFIC, INTERSPECIFIC, AND ANNUAL VARIATIONS As demonstrated recently by Johnston {17), most of the migratory species studied here experienced a dramatic decrease in -DDT burdens between 1964 and 1973; this trend was believed to correlate with decreased DDT usage in the United States. Recognizing these intraspe- cific temporal declines and the additional variables pointed out above, one must exercise caution in assess- ing the voluminous data on the 18 species itemized in Table 6. TABLE 6. Pesticide burdens in adipose tissue of migratory birds, Florida — 1964-73 Average Residues, Residues, Body PPM Wet Weight PPM Lipid Weight Species Date Locality Sample ' Weight, g DDE SDDT DIELDRIN DDE SDDT DIELDRIN Chordeiles minor Aug 1970 Vero Beach 6A 78.6 0.35 0.47 0.12 0.48 0.64 0.16 (Common Nighthawk) Sept 1970 WDBO 2A — 1.13 2.25 0 2.32 4.61 0 Ditnietella carotinensis Oct 1972 WCTV lOA 35.8 0.21 0.33 0 0.62 0.97 0 (Gray Catbird) Oct 1972 WCTV 41 36.6 0.09 0.27 0 0.28 0.84 0 FaU 1973 WCTV 51 36.9 0.88 1.16 0 1.28 1.68 0 Catharus ustulata Oct 1969 WCTV 8A 34.7 1.27 1.67 0 1.64 2.15 0 (Swainson's Thrush) May 1971 WCTV 7A 27.0 0.45 0.51 0 0.64 0.72 0 Oct 1972 WCTV 7A 38.0 1.27 1.60 0.10 1.68 2.12 0.13 Catharus fiiscescens Sept- (Veery) Oct 1969 WCTV 4A 37.0 0.21 0.67 0.01 0.29 0.93 0.02 May 1971 WCTV IDA 29.1 0.05 0.05 0 0.08 0.08 0 Vireo griseus Sept 1970 WDBO 8A 3.56 3.94 0.03 9.93 11.01 0.07 (White-eyed Vireo) Sept 1971 VAB 9A — 1.92 3.01 0.01 3.17 4.96 0.02 Oct 1972 WJKS 9A 14.5 2.11 4.26 0.05 2.57 5.18 0.06 Vireo olivaceits Sept 1966 WCTV lOA 15.6 4.80 8.62 1.10 6.70 12.02 1.50 (Red-eyed Vireo) March- Apr 1970 WCTV 7 16.2 0.50 0.81 0 0.42 0.68 0 Oct 1972 WJKS 101 18.6 3.00 3.22 0.17 4.00 6.82 0.22 Oct 1972 WCTV lOA 25.00 0.08 0.50 0 0.16 0.95 0 Oct 1972 WCTV 101 24.1 0.02 0.18 0 0.04 0.31 0 Fall 1973 WCTV lOA — 0.36 0.61 0 0.47 0.79 0 Mniolilta varia Fall 1969 WCTV 4,3- 12.7 3.37 3.55 0 4.94 5.81 0 (Black-and-white Warbler) Aug 1970 WCTV 4A 14.3 4.22 8.96 0.07 6.86 14.56 o.u Apr 1971 VAB 7A 9.1 6.16 8.93 0 21.54 31.24 0 May 1971 VAB 6A 9.2 1.58 2.58 0 5.55 8.91 0 May 1972 VAB lOA 9.0 0.41 1.46 0 1.05 3.76 0 Oct 1972 WCTV 41 13.4 2.70 5.41 0.12 5.66 11.33 0.25 Nov 1972 GCM mixed 9.1 1.74 2.34 0 5.60 7.53 0 Fall 1973 WCTV 41 11.5 0.29 0.50 0.05 0.36 0.63 0.06 Dendroica coronata Nov 1966 WCTV 4A 10.4 3.33 7.09 0.13 9.73 20.72 0.38 (Yellow-rumped Warbler) Nov 1966 WCTV 41 11.3 2.97 5.77 0.11 6.88 13.37 0.26 Fall 1969 WCTV 5A 11.7 3.17 5.31 0 16.18 27.08 0 Fall 1969 WCTV 71 12.7 5.23 7.56 0.05 18.98 27.41 0.19 Fall 1970 WCTV 8A 10.9 1.42 2.55 0.12 1.49 2.69 0.13 Fall 1971 WCTV 4A 12.4 1.43 3.29 0 2.02 4.65 0 Fall 1973 WCTV 41 5A — 2.12 2.47 0.07 4.24 4.95 0.14 Dendroica striata May 1971 WJKS 5,^ 12.1 0.14 0.21 0 0.29 0.43 0 (BlackpoU Warbler) May 1971 WJKS 59 11.8 0.06 0.06 0 0,12 0.12 0 May 1972 VAB 11.4 0.28 0.37 0 0.49 0.65 0 Dendroica caerulescens Sept 1970 WDBO 7A 11.0 1.06 1.59 0 1.45 2.17 0 (Black-throated Blue Warbler) 51 Oct 1972 WJKS 7Acr 12.4 0.55 1.35 0 0.70 1.72 0 Oct 1972 WJKS 7icr 12.8 0.14 0.87 0 0.19 1.17 0 Oct 1972 WDBO lOAtf — 0.28 1.19 0 0.39 1.64 0 Oct 1972 WDBO 91 c^ — 0.66 1.10 0 0.87 1.45 0 Oct 1972 WDBO lOA? — 0.22 0.66 0 0.36 1.04 0 Oct 1972 WDBO 101? — 0.78 1.55 0 1.08 2.14 0 Oct 1972 Jax lOAcT — 2.44 3.83 0.06 4.03 6.33 0.10 Oct 1972 Jax lOIcT — 1.57 2.60 0 2.73 4.53 0 Fall 1973 WJKS 6Ad" 13.1 0.28 0.41 0.04 0.35 0.51 0.05 (Continued next page) Vol. 9, No. 2, September 1975 83 TABLE 6 (cont'd.). Pesticide burdens in adipose tissue of migratory birds, Florida — 1964-73 Average Residues, Residues, Body PPM Wet Weight PPM Lipid Weight Species Date Locality Sample ^ Weight, g DDE SDDT DIELDRIN DDE XDDT DIELDRIN Dendroica palmarum Oct 1969 WCTV 5A 9.8 12.34 25.07 0.85 15.38 31.24 1.06 (Palm Warbler) Oct 1970 WCTV 8A 11.0 3.06 4.41 0.13 7.81 11.27 0.32 Oct 1971 Jax lOA 10.9 2.64 5.05 0.29 3.81 7.29 0.41 Oct 1972 WJKS 81 81 lA 10.0 2.36 8.82 0.23 3.79 14.17 0.37 Nov 1972 GCM 9.2 0.98 0.98 0 5.04 5.04 0 Oct 1971 Jax 1? 101 lOA 11.5 3.50 6.63 0.38 4.83 9.19 0.53 Fall 1973 WCTV — 0.61 0.70 0.21 1.28 1.47 0.44 Seiurus aurocapiUus Oct 1964 WJXT lOA 25.3 1.71 3.33 0 2.76 5.39 0 (Ovenbird) Oct 1964 WJXT 91 25.8 1.40 2.73 0 2.15 4.19 0 Oct 1964 WJAX 10A,:r 23.4 4.04 5.35 0.06 7.39 10.35 0.10 Oct 1964 WJAX 9A? 23.3 2.05 3.23 0.03 3.55 5.58 0.05 Sept 1967 WJXT 5A — 5.21 8.59 0.03 10.45 17.24 0.06 Oct 1968 WJXT lOA — . 1.81 3.09 0.02 2.74 4.67 0.02 Oct 1968 WJXT 31 — 0.40 1.24 0 0.60 1.87 0 Apr 1969 WJXT 8A 18.9 14.39 40.80 33.77 95.74 Sept 1969 WCTV 5A 23.5 1.93 2.37 0.02 3.31 4.05 0.33 Sept 1969 WCTV 51 23.0 2.65 3.09 0.02 4.90 5.78 0.03 Sept 1970 WDBO 3A — 2.13 2.74 0.03 2.68 3.44 0.04 Sept 1970 WDBO 41 — 2.15 2.97 0 2.67 3.68 0 May 1971 VAB lOA 17.7 1.69 2.27 0.03 3.40 4.57 0.21 Oct 1971 WJKS 2A — 1.29 1.89 0 1.57 2.30 0 Oct 1971 WJKS 81 — 1.09 2.37 0 1.37 2.97 0 Oct 1972 WJKS lOA 23.2 1.76 2.78 0 2.12 3.54 0 Nov 1972 GCM mixed 20.1 0.48 0.69 0 1.23 1.78 0 Sept 1973 WJXT 9A 23.7 0.32 0.38 0.02 0.41 0.49 0.02 Seiurus noveboracensis May 1971 VAB 11 15.0 5.11 11.49 0 10.80 24.27 0 (Northern Waterthrush) Oct 1972 WJKS 61 18.2 4.07 9.68 0.79 7.04 17.25 1.44 Nov 1972 GCM 91 17.3 4.80 5.01 0 12.38 12.92 0 Geothlypis trichas Oct 1964 WJXT 6A9 9.5 3.11 3.63 0 (Common Yellowthroat) Oct 1964 WJXT 61 rf 12.0 3.53 6.53 0.03 Apr 1969 WJXT id 29 9.2 7.08 7.99 0 23.42 26.45 0 Oct 1969 WCTV 5A3- — 3.59 5.54 0 12.60 18.74 0 Oct 1971 WJKS 9Ad" 9.8 4.57 6.17 0 9.84 13.31 0 May 1972 VAB lOAcT 8.9 4.11 4.43 0 9.50 10.23 0 Geothlypis trichas Oct 1972 WCTV 4Acf 11.0 3.56 4.22 0 10.86 12.91 0 (Common Yellowthroat) Oct 1972 WJKS 101 cT 10.9 2.15 3.28 0.11 3.81 5.83 0.19 Oct 1972 WJKS lOAcT 11.4 3.40 4.47 0.11 5.80 7.65 0.18 Nov 1972 GCM lOIcf 9.5 1.01 1.01 0 3.51 3.51 0 Fall 1973 WCTV — 1.53 1.87 0.11 2.26 2.76 0.16 Setopliaga ruticilla Oct 1964 WJXT 3Acr 6.72 10.25 0.27 10.30 15.69 0.41 (American Redstart) Oct 1964 WJXT 12A? 6.14 10.42 0.46 13.1 22.30 0.46 Oct 1969 VAB 6A9 8.2 2.01 4.65 0.51 2.57 5.94 0.65 Oct 1971 WJKS 10A9 8.9 3.05 5.62 0.37 4.13 7.61 0.50 Oct 1971 WJKS 1019 9.1 5.29 12.33 — 7.01 16.34 — May 1972 VAB 8<^ 7.2 3.03 3.27 0 19.51 21.05 0 May 1972 VAB 10? 6.7 0.97 0.97 0 Oct 1972 WJKS lOAcf 9.6 1.45 2.62 0.08 2.49 4.50 0.14 Oct 1972 WCTV 719 — 2.29 6.02 0 3.20 8.42 0 Nov 1972 GCM 109 6.8 2.92 2.92 0 14.3 14.3 0 DoUchonyx oryzivorus Spr 1971 WCTV lOcT 33.9 0.50 0.90 0.08 0.83 1.47 1.0 (Bobolink) Passerculus sandwichensis Oct 1966 WCTV 61 14.4 15.48 18.68 0.18 31.93 38.53 0.38 (Savannah Sparrow) Zonotrichia albicolUs Fall 1966 WCTV 6A 2.33 2.47 0 4.52 4.79 0 (White-throated Sparrow) Fall 1966 WCTV 61 — 7.67 15.09 0 20 02 39.39 0 NOTE: — = no data. ' A = adult, 1 = immature. Some of the interspecific burdens are related to specific feeding habits. Chordeiles minor (common nighthawk), for example, captures flying insects which apparently contain minute quantities of DDT. Only a single year's sample of this bird was available; hence results are not conclusive. Species in Table 6 known to feed on insects at or near ground level include Dendroica palmarum, Seiurus aurocapiUus, S. noveboracensis, Geothlypis trichas, DoUchonyx oryzivorus, Passerculus sandwichen- sis, and Zonotrichia albicolUs. In the late 1960's and early 1970's when residue burdens in these species were relatively high (17), five of these species had the high- est residues found in the present study, ranging from 11.5 to 40.8 ppm. Although annual samples are some- times few, these data sugges,t that ground-feeding species may be more susceptible to DDT-contaminated foods 84 Pesticides Monitoring Journal than are birds feeding at higher levels. The gray catbird (Duinetella carolinensis) and Catharus spp. thrushes consume significant quantities of fruits and some in- sects. Table 6 shows that these species had relatively low DDT burdens, 0.27-2.25 ppm. Tables 4-6 illustrate the frequency of DDT or metabo- lites and dieldrin detection in the total samples. Of 128 samples involving 19 species and 908 individuals, only one sample, an individual Coccyzus americanus, lacked DDT or a metabolite. Dieldrin, however, occurred less frequently (absent in 68 samples) and in smaller quan- tities (n^45, mean=0.17 ppm) than the -DDT bur- den (n = 100, mean =4.31 ppm). No PCB's were found in any species studied here despite the widespread occurrence of these pollutants in worldwide ecosystems. SEASONAL VARIATIONS The small birds studied here migrate annually from breeding grounds in the eastern United States to winter- ing quarters in the West Indies or Central or South America. Birds taken from the television tower kills in autumn represent southbound migrants en route to win- tering quarters, whereas those collected in the spring are northbound to the breeding grounds. Several factors are important in determining the pesticide burdens of the two seasonal samples; the obese autumnal migrants had not yet expended much energy from their fat stores and therefore still retained large pesticide burdens, as- suming that pesticides are subsequently lost or trans- located from dwindling fat stores; the spring migrants collected in Florida had already lost much of the pre- migratory fat stores; an undetermined amount of pesti- cides had been excreted earlier by the birds; and en- vironmental pesticide loads in the wintering grounds may differ from those of the birds' breeding habitat. There is no way to accurately assess all these factors, but data in Table 7 demonstrate that in 5 of 1 1 com- parisons the spring (northbound) samples differed more than 50 percent from the autumnal (southbound) sam- ples. Of the four species in Table 7, approximately one- half had higher autumnal DDT burdens. Coupled wdth these data are the seasonal burdens in yellow-billed cuckoos (Table 4) whose autumnal burdens were much higher than their spring burdens. Persson (40) reported a much higher DDT content in spring than in autumn for the migratory whitethroats (Sylvia communis) breeding in Sweden. She stated, "This suggests that the birds were subjected to a con- siderably higher contamination by chlorinated hydro- carbons during the spring migration through North Africa and Europe than during the late summer in Sweden, where the use of DDT has been prohibited since 1970." Discussion Literature on DDT levels in passerine birds of similar trophic levels in the ecosystem suggests that the values reported here (Table 6) for migrants are reasonably comparable. Prey of peregrines in Alaska included mi- grant seed-eating passerines with i;DDT burdens of 0.23-0.66 ppm and migrant insectivorous passerines with burdens of 0.45-1.51 ppm (3). Temple (14) re- ported that DDE levels in brains of five prey species of merlin (Falco columbarius) ranged from 0.18 to 3.17 ppm dry weight. Data on brain burdens in Table 3 are not strictly comparable to those of Temple because the present values are reported on a wet- or lipid-weight basis. For the latter, 15 samples averaged only 1.47 ppm, although 2 samples had high levels, 11.37 ppm TABLE 7. Pesticide burdens in adipose tissue of spring (northbound) vs. autumn (southbound) samples of selected bird species Average Residues, Body PPM Wet Weight Percent Species Date Location Sample i Weight, o SDDT Difference = Mniotilta varia May 1971 VAB 6A 9,2 2.58 (Black-and-white Warbler) Aug 1970 WCTV 4A 14.3 8.96 71 May 1972 VAB lOA 9.0 1.46 Oct 1972 WCTV 41 13.4 5.41 73 Seinrus aiirocapillus Apr 1969 WJXT 8A 18.9 40.80 (Ovenbird) Sept 1969 WCTV 5A 23.5 2.37 94 May 1971 VAB lOA 17.7 2.27 Oct 1971 WJKS 2A — 1.89 17 Geolhlypis Irichas (Common Yellowthroat) Apr 1969 WJXT 4cr 2? 9.2 7.99 Oct 1969 WCTV SAcf — 5.54 31 May 1972 VAB lOA 8.9 4.43 Oct 1972 WJKS lOAd" 11.4 4.47 I Setophaga ruticilla May 1972 VAB SJ 7.2 3.27 (American Redstart) Oct 1972 WCTV 71? — 6.02 46 NOTE: — = no data. ^ A = adult; I = immature. ^ Difference between values expressed as a percent of the larger value. Vol. 9, No. 2, September 1975 85 and 26.10 ppm. Healthy mockingbirds (Mimus poly- glottos) and blue jays (Cyanocitta cristata) in southern Florida had a mean DDE level of 1.23 ppm in brain tissue (7). A variety of passerine birds (whole bodies) analyzed by Crabtree (6) and DeWitt et ai. (5) re- vealed DDE levels usually less than 0.9 ppm and DDT concentrations ranging from 0 to 26 ppm. DDE levels in muscle of a few passerines in Texas were mostly less than 0.1 ppm (W). In his nationwide survey of star- lings (Sturnus vulgaris), Martin (8) stated, "Most of the average residues found for DDT and metabolites occurred in the range of <0. 1-3.0 ppm; and for di- eldrin, in the range of <0. 1-0.3 ppm" (whole body, wet weight). His report revealed several geographic varia- tions, including the fact that the southern United States generally had the highest concentration of 2DDT, up to 5 ppm. On the other hand, in Idaho, starling adipose tissue had a mean value of 19.23 ppm for DDE with an extreme of 66.97 ppm (9). Despite the facts that thousands of small migrants are killed annually by colliding with towers and buildings and that the present study reveals a high incidence of pesticide burdens in many of these birds, the author finds no concrete evidence that such burdens caused them to fly into towers. Numerous instances in the preceding paragraph involved noncolliding feral song- birds with pesticide burdens of approximately the same magnitude as those of colliding birds. Some 2DDT burdens in Table 6 appear to be excep- tionally high for certain species in recent years: 25.07 ppm for Dendroica palmanim in 1969; 40.80 ppm for Seiunis aurocapilhts in 1969; 11.49 ppm for Seiiirus noveboracensis in 1971; 12.33 ppm for Setophaga ruti- cilla in 1971; 18.68 ppm for Passerculus sandwichensis in 1966; and 15.09 ppm for Zonotrichia albicollis in 1966. Whether these relatively high burdens had any effects on the species at that time is unknown, but certainly if birds having such high burdens subsequently became prey, pesticide concentrations in the predators would be magnified and the consequences would likely be serious (3). By 1973 these relatively high concentra- tions in most of the small migratory birds cited above had significantly decreased to a mean SDDT burden of approximately 1.0 ppm (17). Even such low burdens can be magnified by predators (41). Keith and Gruchy (12), writing about shorebirds as prey of peregrines, stated, ". . . it is not necessary to look for residue levels higher than 2 ppm in birds taken as food by raptors to account for the DDE levels in those raptors now associated with population damage." As early as 1963 Bernard (4) suggested relationships among fat depots, DDT burdens, their lethal levels, and starvation. He stated, ". . . when the fat reserves are utilized (as in starvation), the DDT may be released to more sensitive areas (such as the brain) resulting in tremors followed by death. Some birds might retain sublethal amounts of DDT in fat all summer and perish in winter or during migration when fats are utilized.' For migratory birds, especially those that experience excessive premigratory fat deposits such as the 19 species of the present study, Bernard's thesis might be correct, although there is as yet no first-hand evidence that obese, pesticide-laden birds ". . . perish . . . during migration when fats are utilized." Indeed there exists at least laboratory evidence that birds and some other vertebrates dispose of some pesticide quantities by a variety of mechanisms including kidney excretions {42-45) and oil secreted from uropygial glands (45). On the other hand, starved birds may experience redis- tribution of pesticides from diminished fat depots to skeletal muscles (37) or the central nervous system (36,38). By analyzing adipose tissue and brain of obese premigratory and lean postmigratory birds, the author concluded in an earlier report (16) that the lean post- migrants had not concentrated the DDT burdens in the remaining fat depots nor translocated them to the brain. DDT burdens of the postmigrants could have been partly excreted or translocated to tissues other than the brain. The extent to which any DDT burdens reported here affected the bird populations is unknown. Certainly songbird breeding populations are known to decrease in areas heavily sprayed with DDT (4,11,18-20,22,23). Sublethal effects in feral birds are more difficult to de- tect; cases of eggshell thinning in songbirds have not been positively attributed to pesticides. Yet Jefferies (27,29) showed that Bengalese finches (Lonchiira striata) fed DDT experienced a reduction in fertility, hatchability of eggs, and fledging success. When starved, some captive cowbirds (Molothrus ater) previously dosed on DDT mobilized the DDT to the point of death (26,46). A cknowledgments Since 1964 the following persons assisted in the collec- tion of birds at television towers: at WCTV tower, per- sonnel at the Tall Timbers Research Station including H. L. Stoddard, Sr. (deceased), R. A. Norris, W. W. Baker, and R. L. Crawford; at Jacksonville towers, T. T. Allen and many assistants; at WDBO tower and the Vertical Assembly Building, W. K. Taylor and assist- ants; and from the Vero Beach area, H. W. Kale II. Advice and counsel on analytical procedures were ob- tained from N. P. Thompson and P. W. Rankin at the Pesticide Research Laboratory, University of Florida. R. Bull, B. Gadkar, and D. R. J. Grocki were all in- valuable assistants in the numerous laboratory analyses. Some specimens were made available through the kind- ness of P. Brodkorb, University of Florida, and O. L. Austin, Jr., Florida State Museum. Financial support of the 3-year investigation was made possible by grants 86 Pesticides Monitoring Journal from the National Science Foundation (GB 25872), the American Philosophical Society (No. 1065, Johnson Fund, 1972), and the Bradley Fisk Fund. The author is deeply grateful for the assistance and support of all these individuals and agencies. LITERATURE CITED (7) Anderson, D. W., J. J. Hickey, R. W. Risebrough, D. F. Hughes, and R. E. Christensen. 1969. Signifi- cance of chlorinated hydrocarbon residues to breeding pelicans and cormorants. Can. Field Nat. 83(2): 91-112. (2) Ames, P. L. 1966. DDT residues in the eggs of the osprey in the northeastern United States and their relation to nesting success. J. Appl. Ecol. 3(suppl.): 87-97. (J) Cade, T. J., C. M. White, and J. R. Haugh. 1968. Peregrines and pesticides in Alaska. Condor 70(2): 170-178. (4) Bernard, R. F. 1963. Studies on the effects of DDT on birds. Publ. Museum, Mich. State Univ., Biol. Serv. 2(3):155-192. (J) DeWitt, J. B., W. H. Stickel. and P. F. Springer. 1963. Wildlife studies, Patuxent Wildlife Research Center. In Pesticide-Wildlife Studies, U.S. Dept. Interior Cir. 167:74-96. (6) Crabtree, D. G. 1964. Wildlife studies, Denver Wild- life Research Center. In Pesticide-Wildlife Studies, 1963, Fish Wildl. Circ. 199:44-76. (7) Lehner, P. N., T. O. Boswell, and F. Copeland. 1967. An evaluation of the effects of the Aedes aegypti eradi- cation program on wildlife in south Florida. Pestic. Monit. J. l(2):29-34. (5) Martin, W. E. 1969. Organochlorine insecticide resi- dues in starlings. Pestic. Monit. J. 3(2) :102-114. (9) Benson, W. W., and J. Gabica. 1970. Insecticide resi- dues in starlings in Idaho. Bull. Environ. Contam. Toxicol. 5(3):243-246. (10) Applegate, H. G. 1970. Insecticides in the Big Bend National Park. Pestic. Monit. J. 4(l):2-7. (11) Pimentet, D. 1971. Ecological Effects of Pesticides on Non-target Species. Office of Science and Technology, Washington, D.C. 220 pp. (12) Keith, J. A., and I. M. Griichy. 1972. Residue levels of chemical pollutants in North American wildlife. Proc. XV Int. Ornithol. Congr. Pp. 437-454. (13) Martin, W. £., and P. R. Nickerson. 1972. Organo- chlorine residues in starlings — 1970. Pestic. Monit. J. 6(l):33-40. (14) Temple, S. A. 1972. Chlorinated hydrocarbon residues and reproductive success in eastern North American merlins. Condor 74( 1) :105-106. (15) Grocki, D. R. J., and D. W. Johnston. 1974. Chlori- nated hydrocarbon pesticides in North American cuc- koos. Auk 91(1):186-188. (16) Johnston, D. W. 1974. Persistent pesticides in post- migratory birds from Grand Cayman Island. Year Book, 1973. Amer. Philosophical Soc. Pp. 316-318. (17) John.iton, D. W. 1974. Decline of DDT residues in migratory songbirds. Science. 186(4166) :841-842. (18) Adams, L., M. G. Hanavan, N. W. Hosiey, and D. W. Johnston. 1949. The effects on fish, birds and mam- mals of DDT used in the control of forest insects in Idaho and Wyoming. J. Wildl. Manage. 13(3): 245-254. (19) Benton, A. H. 1951. Effects on wildlife of DDT used for control of Dutch elm disease. J. Wildl. Manage. 15(l):20-27. (20) Robbins, C. S., P. F. Springer, and C. G. Webster. 1951. Effects of five-year DDT application on breed- ing bird population. J. Wildl. Manage. 15(2) :2I3-216. (21) Mitchell, R. T., H. P. Blagbrough, and R. C. VanEtten. 1953. The effects of DDT upon the survival and growth of nestling songbirds. J. Wildl. Manage. 17(1): 45-54. (22) Montgomery, A. E. 1956. Bird mortality in Elmhurst, 111. Audubon Bull. No. 99. Pp. 1-3. (23) Hunt, L. B. 1960. Songbird breeding populations in DDT-sprayed Dutch elm disease communities. J. Wildl. Manage. 24(2) : 139-146. (24) Stickel, L. F., and R. G. Heath. 1965. Wildlife studies, Patuxent Wildlife Research Center. In Effects of Pesti- cides on Fish and Wildlife. Fish Wildl. Serv. Circ. 226:3-30. (25) Bernard, R. F. 1966. DDT residues in avian tissues. J. Appl. Ecol. 3(suppl.):193-198. (26) Stickel, L. F., W. H. Stickel, and R. Christensen. 1966. Residues of DDT in brains and bodies of birds that died on dosage and in survivors. Science 151(3717): 1549-1551. (27) Jefferies, D. J. 1967. The delay in ovulation produced by p, p'-DDT and its possible significance in the field. Ibis 109(1967):266-272. (28) Hill, E. F., W. E. Dale, and J. W. Miles. 1971. DDT intoxication in birds: subchronic effects and brain resi- dues. Toxicol. Appl. Pharmacol. 20(4) :502-514. (29) Jefferies, D. J. 1971. Some sublethal effects of pp'- DDT and its metabolite pp'-DDE on breeding pas- serine birds. Mededelingen Fakulteit Landbouwweten- schappen Gent 36(l):34-42. (30) Johnston. D. W., and T. P. Haines. 1957. Analysis of mass bird mortality in October, 1954. Auk 74(4): 447-458. (31) Stoddard, H. L., Sr. 1962. Bird casualties at a Leon County, Florida, TV tower, 1955-1961. Bull. No. 1, Tall Timbers Res. Sta. Pp. 1-94. (32) Stoddard, H. L., Sr., and R. A. Norris. 1967. Bird casualties at a Leon County, Florida, TV tower: an eleven-year study. Bull. No. 8, Tall Timbers Res. Sta. Pp. 1-104. (33) Odum, E. P., C. E. Connell, and H. L. Stoddard. 1961. Flight energy and estimated flight ranges of some mi- gratory birds. Auk 78(4) :515-527. (34) Caldwell, L. D., E. P. Odum, and S. G. Marshall. 1964. Comparison of fat levels in migrating birds killed at a Central Michigan and a Florida Gulf Coast television tower. Wilson Bull. 75(4):428-434. Vol. 9, No. 2, September 1975 87 (35) Harvey, J. M. 1967. Excretion of DDT by migratory birds. Can. J. Zool. 45(5) :629-633. (36) Ecobichon, D. J., and P. W. Saschenbrecker. 1969. The redistribution of stored DDT in cockerels under the influence of food deprivation. Toxicol. Appl. Phar- macol. 15(3):420-432. (37) Findlay, G. M., and A. S. W. DeFreitas. 1971. DDT movement from adipocyte to muscle cell during lipid utilization. Nature 229(5279) : 63-65. (38) Sodergren, A., and S. Ulfstrand. 1972. DDT and PCB relocate when caged robins use fat reserves. Ambio l(l):36-40. (39) Parstow, J. L. F., and D. J. Jefferies. 1973. Relation- ship between organochlorine residues in livers and whole bodies of guillemots. Environ. Pollut. 5(2): 87-101. (40) Persson, B. 1972. DDT content of whitethroats lower after summer stay in Sweden. Ambio l(l):34-35. (41) Woodwell, G. M. 1967. Toxic substances and ecologi- cal cycles. Sci. Amer. 216(3) :24-31. (42) Dale, W. E., T. B. Gaines, and W. J. Hayes. 1962. Storage and excretion of DDT in starved rats. Toxicol. Appl. Pharmacol. 4(1):89-106. (43) Richardson, A., M. K. Baldwin, and J. Robinson. 1968. Metabolites of dieldrin (HEOD) in the urine and faeces of rats. Chem. Ind. Pp. 588-589. (44) Robinson, J., and M. Roberts. 1968. Accumulation, distribution and elimination of organochlorine insecti- cides by vertebrates. Soc. Chem. Ind. Monog. No. 29:106-119. - (45) Dindal, D. L. 1970. Accumulation and excretion of Cr DDT in Mallard and Lesser Scaup Ducks. J. Wildl. Manage. 34(l):74-92. (46) VanVelzen, A. C, W. B. Sliles, and L. F. Slickel. 1972. Lethal mobilization of DDT by cowbirds. J. Wildl. Manage. 36(3):733-739. 88 Pesticides Monitoring Journal Insecticide Residues in the Tuttle Creek Reservoir Ecosystem, Kansas — 1970-71 ^ Harold E. Klaassen " and Ahmed M. Kadoum ' ABSTRACT Various components of the aquatic ecosystem of Tuttle Creek Reservoir on the Big Blue River in northeastern Kansas were examined for organochlorine insecticide resi- dues in 1970-71. Components examined were water, sedi- ments, periphylon, zooplankton, insects, and whole-body samples of 10 common fish species. Only dieldrin and ZDDT residues were detected. Dieldrin was found in part of tlie nonfish samples at levels ranging up to 0.01 ppm and in 97 percent of the fish samples with a high level of 0.17 ppm. ZDDT residues were also de- tected in part of the nonfish samples at levels ranging up to 0.42 ppm, and in 98 percent of the fish samples at levels as high as 0.57 ppm. Authors' findings are roughly similar to those of other surveys of Kansas fishes. All levels are relatively low compared with those reported in surveys from other parts of the Nation. Introduction The use of agricultural chemicals has become an ac- cepted practice during the last few decades but the safety of many of these compounds has been challenged in the renewed awareness of environmental responsibility. Many people are concerned about the ecological effects of persistent residues and their potential hazard to hu- mans who may be consuming them. Of special concern are effects of long-lived insecticides on fish and wildlife. Sport enthusiasts often are unsure whether the fish they catch are safe to eat. This paper deals with residues of organochlorine insecti- cides in water, sediments, periphyton, zooplankton, in- sects, and fishes of Tuttle Creek Reservoir, a popular ' Contribution No. 1244, Division of Biology; Contribution No. 1124, Department of Entomology. Kansas Agricultural Experiment Station, Kansas State University, Manhattan, Kans. Supported in part by North Central Regionai Project NC-96. Environmental Impiications of Pesticide Usage. '■ Division of Biology, Kansas State University, Manhattan, Kans. 66506. * Department of Entomology, Kansas State University, Manhattan, Kans. sport-fishing reservoir in Kansas. It is based on an ex- tensive survey of residues in the reservoir ecosystem with emphasis on fish in a wide range of trophic levels. Methods STUDY AREA Samples were collected from Tuttle Creek Reservoir, a flood control lake on the Big Blue River. The reservoir, which was completed in 1962, is about 8 km north of Manhattan in northeastern Kansas. At conservation level its surface area is about 6,400 ha. and it extends ap- proximately 35 km northward into the river valley. The reservoir is long and narrow with a few short coves (Fig. 1). The deepest part over the flood plain (about 15 m) is near the dam; mean depth is about 8 m. Water conditions are typical of plains reservoirs in that thermal stratification rarely occurs and the water is faiily turbid. The area which drains into the reservoir extends ap- proximately 240 km northward into southeastern Ne- braska (Fig. 1). The watershed above the dam is 2,591,000 ha. (6,400,000 acres), a large proportion of which is under agricultural cultivation. Major crops are grain sorghum, corn, and wheat. COLLECTION OF SAMPLES Fish samples were collected at two sites, one at the north end of the reservoir just north of Randolph Bridge and one near the southeast corner at Mclntire cove (Fig. 1). At the north site, the central reservoir area was 2-3 m deep and could be sampled readily. Samples from the south side were collected from the cove because fish were scarce and difficult to sample in the deep open water. Samples from both sites were taken at various places from near shore to the middle of flood plain. Fishes were usually collected for 2 or 3 weeks during three seasons: summer 1970, fall 1970, and spring 1971. Vol. 9, No. 2, September 1975 89 D KEY = AREA SAMPLED (SEE ENLARGEMENT) ■DRAINAGE BASIN TUTTLE CREEK RESERVOIR KILOMETERS KEY ®=SAMPLING SITES FIGURE 1. Map of Kansas and Nebraska showing sampling siles of Tutlle Creek Reservoir drainage basin. Water samples were taken from the surface of the open water; sediment samples were taken with an Ekman dredge in open water and the surface inch was retained for analyses. Zooplankton was collected with a No. 20 mesh plankton net. Bottom insects were collected with an Ekman dredge and periphyton was scraped off rocks or trees on the edge of the reservoir. Fish were collected with bottom-fishing gill nets with eight mesh sizes rang- ing from ^4 to 4 in. square. The ten species of fish collected for residue analysis included popular game fishes, the main forage fish, and the most common rough fish. These species, in increas- ing order of trophic position, included gizzard shad {Dorosoma cepedicinum) , river carpsucker (Carpiodcs carpio), smallmouth buffalo (Ictiobus bubalus) , carp (Cyprinus carpio), channel catfish (Ictalurus pimctatus), freshwater drum (Aplodinotiis grtinniens) , white crappie {Poinoxis annularis), white bass (Morone chrysops), walleye (Stizostedion vitreum), and longnose gar (Lepi- sosteus osseus) . Fish were grouped into three size cate- gories, small, medium, and large, because the degree of maturity may influence residue content. Immature young that were 1 year old or less were classified as small. Medium-size fishes were those starting to mature and to interest persons fishing in the reservoir. Large fishes were definitely mature and would be considered accept- able catch by sports enthusiasts. Samples included up to 10 fish of one size of the same species. In most cases there were fewer but in several instances small fish that had hatched in the year of collection were taken in larger numbers to get enough i biomass for analysis. Samples were frozen until analysis. SAMPLE PROCESSING The entire body of each fish was ground in a meat grinder. The ground material was mixed and a 100-g subsample was taken from each ground fish in order that larger fish did not bias the sample. Subsamples were pooled and homogenized in a blendor. A specific amount of distilled water was added to facilitate homogenizing. A sample of the homogenate was then taken and frozen in an aluminum foil package until residue was extracted. The only exception to this procedure was the treatment of small fish less than 1 year old when the individuals were very similar in size. After their entire bodies were ground, they were run through the blendor without subsampling. Nonfish samples including unfiltered water were ex- tracted directly for residue analysis. RESIDUE EXTRACTION AND ANALYSIS Subsamples measuring 10 g were placed in an omnimixer with 50 ml redistilled hexane and enough anhydrous sodium sulfate to absorb the water. The mixture was blended at high speed for 1-2 minutes, and was then decanted through No. 43 Whatman filter paper into a 100-ml suction flask. The residue was extracted with two additional portions of hexane as described above; extracts were filtered and combined in a suction flask. The container, filter paper, and contents were washed with a final 10-ml portion of hexane. The total hexane 90 Pesticides Monitoring Journal extract was transferred to a round-bottom flask for con- centration under vacuum at 35°-40° C to 2-3 ml hexane. The concentration was transferred quantitatively to a 15-mi centrifuge tube using small portions of hexane totaling 5 ml. An aliquot was used for cleanup and gas chromatographic (GC) analysis. For the cleanup procedure a silica gel chromatographic microcolumn was prepared by loosely packing a plug of glass wool about 4 cm from the tip of a disposable pipette and then adding 1 g of high-purity silica gel (No. 950, 60-200 mesh). Prior to column chromatog- raphy, solvent extract was evaporated to 1 ml. For partial deactivation of silica gel, the 1 ml concentrated extract used for charging the column was saturated with 5 /il distilled water and transferred quantitatively to the column. It was permitted to percolate through the column at 1-2 ml/min. Column walls were rinsed with small hexane portions. When the solvent reached the top of the silica gel, elution with the desired solvent was begun. Eluting solvents were 2, 7, and 70 percent benzene in hexane, 100 percent benzene, and 8 percent ethyl acetate in benzene. The eluate was collected in a 15-mI gradu- ated centrifuge lube. Eluates were concentrated sepa- rately to 1 ml by a nitrogen stream just before GC (1,2). Analyses were performed with a Barber-Coleman GC equipped with an electron-capture detector. Operating conditions were as follows: Column: Temperature; Carrier Gas; Volume injected; 6 ft-glass packed with 3 percent DC-11 on 60-80 mesh silanized Gas-Chrom P Column 200° C Detector 220° C Injector 240° C Nitrogen at a flow rate of 37 ml/min 4 /il extract in hexane Each sample was analyzed for endrin, aldrin, dieldrin, heptachlor, heptachlor epoxide, o,p'-DDT, p,p'-DDT, DDE, and p,p'-DDD. The sensitivity was 0.01 ppm. Residue levels were not corrected because recovery f.om fortified samples was essentially 100 percent. Results and Discussion FISH POPULATION Table 1 lists the species of fishes collected in Tuttle Creek Reservoir during various studies {3-5), their rela- tive abundance, trophic relation, and sport category. Species sampled are among the most common and, therefore, ecologically important. They include the major sport species and represent a wide range of trophic positions. PESTICIDE RESIDUES Results of pesticide residue analyses are given in Tables 2 and 3. Values other than trace residues were rounded to the nearest 0.01 ppm. No residues of endrin, aldrin, heptachlor, or heptachlor epoxide were detected in any sample. Dieldrin and ZDDT residues were the only compounds detected. Dieldrin was detected at 0.01 ppm in one of six water samples. It was not detected in any sediment samples but was detected in three of four periphyton samples at levels ranging up to 0.01 ppm. Five of six zooplankton samples had dieldrin levels as high as 0.01 ppm. Of the five insect samples, four contained dieldrin levels that ranged up to 0.01 ppm. Of the 102 fish samples, 97 percent contained dieldrin residues ranging from a trace to 0.17 ppm. Most residue values were less than 0.10 ppm. The few which were higher occurred in gizzard shad, river carpsucker, smallmouth buffalo, and fresh- water drum, all nongame species. 2DDT residues were found in one of six water samples at a level of 0.02 ppm but not in any bottom sediment sample. It was detected in two of four periphyton samples; the highest level was 0.42 ppm. Four of the six zooplankton samples had traces of DDT compounds. SDDT residues were detected in four of five samples samples at levels up to 0.05 ppm. Of the fish samples tested, 98 percent contained detectable 2DDT residues ranging from a trace to 0.57 ppm; most of these residues were less than 0.10 ppm. Higher amounts were found at least once in each species except carp and white TABLE 1 . Fishes collected from Tuttle Creek Reservoir Relative Trophic Use Species ' ABUNDANCE - POSITION ' CATEGORY Longnose Gar * + + high rough Gizzard Shad ' + + + low forage Northern Pike + high sport StoneroUer + low forage Goldfish + low rough Carp« + + + low and med rough Golden Shiner + + med forage Suckermouth Minnow + low forage Minnows {Nolropis sp.) + + low forage Minnows (Pimepfiates sp. ) + low forage River Carpsucker « + + -f low rough White Sucker + + + low rough Smallmouth Buffalo « + + + low rough Bigmouth Buffalo + low and med rough Black Buffalo -1- low rough Shorthead Redhorse -i- low rough Blue Catfish + med sport Black Bullhead 4- med sport Yellow Bullhead + med sport Channel Catfish « + + + med sport Flathead Catfish + + high sport White Bass « + + + med and high sport Green Sunfish + med forage Orangespotted Sunfish + med forage Bluegill + + med forage and sport Largemouth Bass + + med and high sport White Crappie « + + -I- med and high sport Black Crappie -t- med and high sport Walleye ' + + high sport Freshwater Drum * + + + med rough * Accepted common names of fishes established by American Fisheries Society (See Literature Cited, reference 11). 3 + = sparse, + + =: moderately abundant, -f -f -f = abundant. 3 Low = omnivorous diet of algae, detritus, microcrustacea; medium = diet of microcrustacea, insects, and occasional small fish; high = diet mainly of other fishes. * Analyzed in this study. Vol. 9, No. 2, September 1975 91 crappie. Highest levels in fishes were found in a fresh- water drum sample (0.57 ppm) and a smallmouth buffalo sample (0.43 ppm). No residue pattern was discernible in regard to time of year or end of reservoir sampled. Classical biological magnification was not noticeable in the fishes. Species at the lowest trophic level had residues as high or higher than those at the highest trophic positions. Comparing these results with those of the National Pes- ticides Monitoring Program shows that levels in Tuttle Creek Reservoir are relatively low. Henderson et al. (6, 7) found that 75 percent of the whole-body fish samples taken nationally in 1967-68 contained dieldrin levels of nearly 2 ppm. In 1969 they found dieldrin in 93 percent of the samples with levels up to 1.59 ppm. In the present study dieldrin was detected in a higher percentage (97 percent) of samples but at considerably lower levels: the highest was 0.17 ppm. Henderson et al. (6, 7) showed ZDDT levels as high as 45 ppm in 99 percent of the 1967 samples and as high as 57.8 ppm in 100 percent of the samples taken in 1969. The present study reports 2DDT residues in almost all samples (98 percent), but the highest level detected was 0.57 ppm. Results of other pesticide residue surveys in Kansas are similar to those of the current study. Klaassen and Kadoum (8) found dieldrin in 15 percent of the samples. The highest whole-body residue was 0.08 ppm in fish of the Smoky Hill River of western Kansas during 1967-69. -DDT residues were detected in 75 percent of these samples; the highest whole-body level was 0.10 ppm. The use of different species in other surveys makes the accuracy of direct comparisons questionable. The Kansas Forestry, Fish and Game Commission (9, 10) found organochlorine insecticides in 98 percent of the fish samples in 1971. 2DDT residues were detected in 89-96 percent of all samples collected; mean levels ranged from 0.19 to 0.21 ppm. Dieldrin was in 61-76 percent of the samples in amounts slightly higher than those detected in this survey. In 1972 the Commission found organochlorine insecticides in 91 percent of the fish samples. 2DDT residues were detected in 89-90 percent of the samples with levels ranging from 0.03 to 0.27 ppm. Dieldrin levels ranging from 0.03 to 0.42 ppm were found in 40 percent of the samples. TABLE 2. Pesticide residues in aquatic ecosystem, north end of Tuttle Creek Reservoir — 1970-71 Summer 1970 ' Fall 1970 = Spring 1971 = a w 5 0 o m 0 a a 0 a D H ■a a 0 H D m r s o 0 tn D s o a b 0 r o » Z 0 D m o o 0 o ■a 6 3 13 a Sample Size* SlZE« Size' Lake water ND ND ND ND ND ND ND ND ND ND 0.01 ND 0.01 0.01 ND Bottom sediment ND ND ND ND ND ND ND ND ND ND Periphyton 0.01 0.18 ND 0.06 0.18 T ND ND ND ND Zooplankton T T ND ND ND ND T ND ND ND 0.01 ND ND ND ND Diptera larvae ND 0.02 ND ND ND Mayfly (Hexagenia) nymphs 0.01 0.01 ND 0.01 0.03 Gizzard shad S(2) 0.05 0.01 ND ND ND S(3) 0.08 0.04 0.06 0.04 0.17 M<2) 0.04 0.02 0.02 0.01 0.05 L(4) 0.07 0.02 ND ND ND M(6) L(4) 007 0.09 0.04 0.07 0.02 0.04 0.04 0.05 0.16 0.20 L(6) 0.02 0.01 0.02 ND 0.02 River carpsucker L(IO) 0.16 0.06 ND ND ND S(l) L(10) 0.01 0.16 O.OI 0.07 T 0.03 0.01 0.01 0.03 0.25 L(10) 0.05 0.05 0.03 0.03 0.10 Smallmouth buffalo L(10) 0.14 0.07 ND ND ND L(3) 0.12 0.08 0.06 0.02 0.27 L(10) 0.08 0.06 0.08 0.04 0.09 Carp L(10) 0.01 0.03 ND ND ND L(l) 0.02 0.04 0.01 0.01 0.03 L(10) 0.01 0.01 0.01 ND ND Channel catfish S(4) 0.01 0.01 ND ND ND S(3) 0.02 0.01 ND ND 0.05 M(IO) 0.03 0.01 0.02 ND ND U9) 0.04 0.04 ND ND ND L(10) 0.04 0.05 0.02 ND 0.06 L(8) 0.03 0.03 0.02 ND ND Freshwater drum S(10) 0.01 0.01 ND ND ND S(4) 0.02 0.01 0.01 ND 0.03 S(2) 0.02 0.01 T 0.01 0.03 L(10) 0.13 0.06 ND ND ND L(3) 0.08 0.12 0.02 0.02 0.23 L(5) 0.03 0.02 0.01 0.01 0.53 White crappie S(IO) 0.01 0.01 ND ND ND S(7) 0.01 0.01 ND ND ND S(IO) ND T ND ND ND L(IO) T ND ND ND ND M(IO) T T ND ND 0.03 M(10) ND ND ND ND ND L(IO) 0.01 0.02 0.01 0.01 0.04 L(4) 0.02 0.01 0.01 ND ND White bass S(l) 0.01 0.01 ND ND ND L(10) 0.03 0.02 0.02 0.01 0.05 S(2) L(10) 0.02 0.03 0.01 0.01 0.02 0.02 ND ND 0.01 O.OI WaUeye S(l) 0.05 0.02 0.02 0.01 0.08 S(l) L(2) 0.04 0.08 0.02 0.03 0.01 0.03 0.01 ND 0.02 0.02 Longnose gar M(4) 003 0.05 0.04 0.01 0.03 M(l) 0.07 0.02 0.01 ND ND NOTE: ND = not detected. T = trace. ^ Samples collected August 3-5. - Samples collected October 30-November 5. => Samples collected April 7-May 20. * S, M. L = small, medium, large. Number of individuals in each sample reported in parentheses. Pesticides Monitoring Journal TABLE 3. Pesticide residues in aquatic ecosystem, south end of Tuttle Creek Reservoir — 1970-71 Summer 1970 ' Fail 1970 ' Spring 1971 » a P s 3 o D m D 0 a b 3 6 o H D fa z D a m o a D 0 6 ■a 6 0 S a » Z 0 o 6 ■a Sample SlZE« Size' Size* Lake water ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND Bottom sediment ND ND ND ND ND ND ND ND ND ND Periphyton ND 0.03 ND ND ND T ND ND ND ND Zooplankton T T ND ND ND 0.01 T ND ND ND 0.01 ND ND ND ND Mayfly (Hexagenia) nymphs adults T O.OI T ND ND ND ND ND ND ND nymphs 0.01 0.01 ND O.OI 0.02 Gizzard shad S(SO) M(10) L(IO) 0.02 0.07 0.17 0.01 0.01 0.03 0.01 0.03 0.06 0.01 T T 0.02 0.02 0.01 S(37) M(I0) L(IO) 0.01 0.02 0.03 ND ND 0.02 0.01 O.OI 0.03 ND ND ND ND ND ND S(IO) M(10) L(IO) 0.03 0.02 0.04 O.OI O.OI 0.02 0.02 0.02 0.03 ND ND ND ND ND ND River carpsucker S(12) L(IO) 0.01 0.05 T 0.02 0.01 0.02 T 0.01 0.01 0.02 S(9) L(IO) T 0.03 0.01 0.03 ND 0.02 ND ND ND ND S(4) L(4) 0.01 0.03 O.OI 0.02 T 0.02 ND ND ND ND Smallmoutli buffalo L(10) 0.10 0.05 0.05 0.03 0.04 L(10) 0.03 0.04 0.02 0.02 0.07 L(3) 0.03 0.03 0.02 ND ND Carp M(IO) 0.02 0.03 0.02 0.01 T L(5) 0.01 0.01 ND ND ND L(IO) 0.01 0.04 0.02 ND ND Channel catfish S(IO) L(IO) 0.01 0.07 0.01 0.07 T 0.06 0.01 0.01 0.01 0.05 S(IO) L(10) 0.01 0.02 0.01 0.02 T 0.02 O.OI O.OI 0.04 0.03 S(4) M(7) L(10) 0.01 0.02 0.03 T 0.03 0.06 ND O.OI 0.01 ND ND ND ND 0.01 0.06 Freshwater drum S(12) L(8) 0.02 0.01 0.01 0.01 0.01 ND T ND 0.01 T S(IO) L(3) 0.02 0.04 0.01 0.02 O.OI O.OI 001 0.01 0.04 0.04 S(3) L(4) 0.01 0.04 T 0.02 T 0.02 ND ND ND ND White crappie S(IO) L(10) T 0.01 T 0.01 ND O.OI ND T ND 0.01 S(3) M(10) L(2) 0.02 ND T 0.01 T 0.01 0.01 ND ND ND ND ND ND ND ND S(8) M(I0) O.OI T 0.01 T T ND ND ND ND ND White bass S(4) L(2) 0.01 0.02 0.01 0.02 T 0.01 T T 0.01 0.01 S(4) L(IO) 0.01 0.01 0.01 0.01 0.01 0.01 ND ND ND ND S(IO) M(10) 0.03 0.05 0.01 0.02 0.01 0.02 ND ND ND 0.02 Walleye S(5) L(6) 0.01 0.07 0.19 0.04 0.01 0.04 0.01 0.01 0.01 0.03 S(!0) L(10) O.OI 0.02 0.01 0.03 0.01 O.OI ND 0.01 ND 0.02 S(9) L(6) 0.04 0.09 0.02 0.03 0.02 0.04 ND ND ND ND Longnose gar M(IO) 0.02 0.04 0.05 T 0.02 L(I) 0.05 0.08 0.08 0.02 0.06 NOTE: ND = not detected. T =: trace. • Samples collected August 7-18. ' Samples collected October 20-November 1. ' Samples collected March 30-May 20. * S, M, L = small, medium, large. Number of individuals in each sample reported in parentheses. LITERATURE CITED (7) Kadoum, A. M. 1967. A rapid micromethod of sample cleanup for gas chromatographic analysis of insecti- cidal residues in plant, animal, soil, and surface and ground water extracts. Bull. Environ. Contam. Toxicol. 2(5):264-273. (2) Kadoum, A. M. 1968. Application of the rapid micro- method of sample cleanup for gas chromatographic analysis of common organic pesticides in ground water, soil, plant and animal extract. Bull. Environ. Contam. Toxicol. 3(2):65-70. (i) Klaassen, Harold E. 1974. Unpublished data from 7 years of sampling Tuttle Creek Reservoir. Kansas State University, Manhattan, Kans. (4) Klaassen, H. E., and G. R. Marzolf. 1971. Relation- ships between distributions of benthic insects and bot- tom-feeding fishes in Tuttle Creek Reservoir. In Reser- voir Fisheries and Limnology, Amer. Fish. Soc. Special Publ. No. 8. Pp. 385-395. (5) Perry, Kenneth R. 1970. The distribution and food habits of bottom fishes in Tuttle Creek Reservoir. Mas- ter of Science Thesis, Kansas State University. Man- hattan, Kans. 85 pp. (6) Henderson, D., A. Inglis, and W. L. Johnson. 1971. Organochlorine insecticide residues in fish — fall 1969: National Pesticide Monitoring Program. Pestic. Monit. J. 5(1):1-I1. (7) Henderson, D., W. L. Johnson, and A. Inglis. 1969. Organochlorine insecticide residues in fish: National Pesticides Monitoring Program. Pestic. Monit. J. 3(3): 145-171. (8) Klaassen, H. E., and A. M. Kadoum. 1973. Pesticide residues in natural fish populations of the Smoky Hill River of western Kansas — 1967-69. Pestic. Monit. J. 7(1):53-61. (9) Capcl, Stephen. 1972. Pesticide residues in Kansas streams. Dingell-Johnson Project Report F-15-R-7, Job No. K-1-1, Kansas Forestry, Fish and Game Commis- sion, Pratt, Kans. 37 pp. (10) Lillie, Joe. 1973. Pesticide residues in Kansas streams. Dingell-Johnson Project Report F-15-R-2, Job No. K-1-2, Kansas Forestry, Fish and Game Commission, Pratt, Kans. 38 pp. (//) Bailey, R. M., J. E. Fitch. E. S. Herald, E. A. Lachner, C. C. Lindsey, C. R. Robins, and W. B. Scott. 1970. A List of Common and Scientific Names of Fishes from the United States and Canada. 3rd ed. Amer. Fish. Soc. Special Publ. No. 6. 149 pp. Vol. 9, No. 2, September 1975 93 RESIDUES IN FOOD AND FEED Pesticide Residues in Total Diet Samples (VIII) D. D. Manske and R. D. Johnson ^ ABSTRACT During the eighth year of the Total Diet Study, residues remained at the relatively low levels reported previously. A total of 35 market baskets were collected in 32 cities which ranged in population from less than 50,000 to 1,000,000 or more. Averages and ranges of residues found are reported for the period June 1971 through July 1972 by region and food class. Results of recovery studies within various classes of residues are also presented. Introduction This report presents results obtained in the Total Diet Program (/) of the Food and Drug Administration (FDA), U.S. Department of Health, Education, and Welfare, for the period June 1971 through July 1972. The amounts and types of residues found from June 1964 through April 1971 have been described in earlier reports (,2-8). Seven samples were collected in each of the five regions at 35 different grocery markets. These markets were located in 32 different cities. Unless other- wise stated, the conditions, procedures, methodology, and limits of quantitation were the same as those de- scribed in the last report (7, 9-13. Also: H. K. Hundley and J. C. Underwood, Food and Drug Administration, 1970: personal communication; and J. Okrasinski, Food and Drug Administration, 1970: personal communica- tion). Results A total of 1,003 residues of 35 different materials were found in samples in the current reporting period, which covered 35 market baskets. In the previous reporting period, 1,081 residues of 33 different chemicals were found in 30 market baskets. Because of the procedural changes made during the previous reporting period, it is difficult to assess the significance of the overall values for frequency of occurrence. An example of one of these changes was the discontinuance of the bromide analysis in the middle of the previous reporting period. The 35 different residues found are listed in decreasing order of frequency in Table 1. 'Kansas City Field Office Laboratory, Food and Drug Administration, U.S. Department of Health, Education, and Welfare, Kansas City, Mo. 54106. TABLE 1. Pesticide residues in food composites. June 1971 - July 1972 Pesticide No. Composites With Residues No. Positive Composites With Residues Reported As Trace ' Range, ppm CADMIUM 256 0 0.01-0.14 DIELDRIN Not less than 85% of l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a- oclahydro-I,4-enrfo-exo-5,8-dimethanonaphthalene 110 41 0.001-0.016 DDE l,l-dichloro-2,2-bis (p-chlorophenyl) ethylene (isomers other than p,p' also included in reporlings) 104 64 0.002-0.048 MALATHION diethyl mercaptosuccinate, j-ester with o,o-dimethyl phosphorodithioate 70 10 0.004-0.492 DDT l,I,l-trichloro-2,2-bis (p-chlorophenyl) ethane (isomers other than p,p' also included in reportings) 64 47 0.004-0.045 (Continued next page) 94 Pesticides Monitoring Journal TABLE 1 (cont'd.). Pesticide residues in food composites, June 1971 - July 1972 Pesticide No. CoMPosrrES With Residues No. Positive Composites With Residues Reported As Trace i Range, ppm TDE l,l-dichloro-2,2-bis (p-chlorophenyl) ethane (isomers other than p,p' also included in reportings) 57 41 0.005-0.043 PCB's (polychlorinated biphenyls). Calculated as Aroclor ® with varied chlorine content— 54% and 60% reported this period 51 46 0.035-0.15 DIAZINON o,o-diethyl o-(2-isopropyl-6-methyl-4-pyrimidinyI) phosphorothioate 51 32 0.002-0.016 BHC 1,2,3,4, 5, 6-hexachlorocyclohexane, mixed isomers except gamma 47 32 0.01-0.013 HEPTACHLOR EPOXIDE l,4,5,6,7,8,8-heptachloro-2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindan 33 27 0.003-0.020 MERCURY 23 0 0.02-0.08 ENDOSULFAN 6,7,8,9,10,10hexachloro-l,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide (reportings include isomers I, II, and the sulfate) 20 16 0.003-0.010 LINDANE 1,2,3,4,5,6-hexachlorocyclohexane, 99% or more gamma isomer 17 11 0.001-0.005 PARATHION o,o-diethyl o-p-nitrophenyl phosphorothioate 13 9 0.005-0.006 CIPC isopropyl n-(3-chlorophenyn carbamate 10 0 0.008-1.40 ETHION o,o,o',o'-tetraethyl i,i'-methylene bisphosphorodithioate 9 3 0.007-0.027 ARSENIC (As,0,) 8 0 0.1-0.7 DICOFOL (KELTHANE®) 4,4'-dichloro-a-(trichloromethyl) benzhydrol 8 2 0.005-0.77 METHYL PARATHION o,o-dimethyI o-p-nitrophenyl phosphorothioate 7 5 0.007-0.010 ORTHOPHENYLPHENOL 2-hydroxydiphenyl 7 3 0.1-0.4 CARBARYL 1-napthyl methyl carbamate 6 5 0.02 BOTRAN ® 2,6-dichloro-4-nitroaniline 5 1 0.006-0.069 HCB hexachlorobenzene 4 0 0.002-0.011 ENDRIN l,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l,4- endo-cndo-S, 8-dimethanonaphthalene 4 3 0.006 PERTHANE l,l-dichloro-2,2-bis (p-ethyl phenyl) ethane 4 0 0.013-0.215 PCA pentachloroaniline 3 0 0.005-0.023 CAPTAN n-trichloromethylthio-4-cyclohexane-l,2-dicarboximide 2 1 0.007 PHOSALONE o,o-diethyl i-(6-chloro-2-oxobenzoxazdin-3-yl) methyl phosphorodithioate 2 0 0.034-0.089 METHOXYCHLOR l,l,l-trichIoro-2,2-bis (p-methoxyphenyl) ethane 2 1 0.015 TOXAPHENE chlorinated camphene containing 67% to 69% chlorine 1 0 0.10 CHLORDANE (Technical). Cis and trans isomers of 1.2,4,5,6,7,8,8-octachloro- 3a,4,7,7a-tetrahydro.4,7-methanoindane plus approximate 50% related compounds 1 0 0.59 RONNEL o.o-dimethyl o-2,4,5-trichlorophenyl phosphorothioate 1 1 T PCNB pentachloronitrobenzene 1 1 T 2,4-D 2,4-dichlorophenoxyacetic acid 1 0 0.01 ALDRIN Not less than 95% of l,2,3.4,10,I0-hexachloro-l,4,4a,5,8,8a- hexahydro-1 ,4-ent/o-exo-5,8-dimethano naphthalene 1 1 1 T ^ Trace implies residues detected and qualitatively confirmed at too low a level to be quantified. See reference (7^ for further explanation. Vol. 9, No. 2, September 1975 95 TABLE 2a. Levels of pesticide residues commonly found — by food class and region, June 1971 - July 1972 Chemical Boston I Kansas Crry Los Angeles Residues, ppm Minneapolis (Continued next page) 96 I. Dairy Products DIELDRIN Average 0.001 T 0.001 T T Positive Composites Number 6 3 7 7 4 Range T-0.002 T-O.OOl T-0.005 T-O.OOl T-O.OOl DDE Average T T T 0.007 T Positive Composites Number 4 2 2 6 2 Range T T T T-0.015 T BHC Average 0 T T T T Positive Composites Number 0 4 2 2 5 Range 0 T T T T HEPTACHLOR EPOXIDE Average T T 0.001 T T Positive Composites Number 2 1 5 1 3 Range T T T-0.004 T T CADMIUM Average T T 0.01 T T Positive Composites Number 2 1 5 1 1 Range 0.01 O.OI 0.01-0.03 0.01 0.01 II. Meat, Fish, and Poin.TRY DIELDRIN Average Positive Composites Number Range 0.003 7 T-fl.007 0.002 7 T-0.003 0.002 5 T-0.006 0.003 7 T-0.009 0.002 6 T-0.005 DDE Average Positive Composites Number Range 0.01 7 T-0.03 0.004 7 T-0.009 0.004 5 T-O.0I2 0.032 7 0.015-0.048 0.002 7 T-0.006 DDT Average Positive Composites Number Range o.on 6 T-0.045 0.002 5 T-0.008 0.005 6 T-0.015 0.003 6 T-0.023 T 4 T PCB's Average Positive Composites Number Range 0.012 3 T-0.081 T 2 T T 3 T T 6 T T 2 T TDE Average Positive Composites Number Range 0.003 5 T-0.013 T 2 T 0.001 3 T-0.006 0.001 3 T-0.008 T 3 T CADMIUM Average Positive Composites Number Range 0.01 2 0.02-0.03 0.01 4 0.01-0.04 0.01 5 0.01-0.03 0.02 3 0.01-0.07 0.01 5 0.01-0.02 MERCURY Average Positive Composites Number Range 0.01 4 0.02-0.03 0.02 6 0.02-0.03 0.01 2 0.03 0.01 3 0.02 0.01 4 0.02 ARSENIC Average Positive Composites Number Range T 2 0.1 T 2 0.1-0.2 T 1 0.1 0.1 1 0.7 T 2 0.1-0.2 III. Grain and Cereal PCB's Average 0.014 T T 0.005 T Positive Composites Number 4 4 5 4 3 Range T-0.101 T T T-0.035 T Pesticides Monitoring Journal TABLE 2a (cont'd.). Levels of pesticide residues commonly found- June 1971 - July 1972 -by food class and region, Chemical Baltimore Boston Kansas City Los Angeles Minneapolis MALATHION Average Positive Composites Number 0.017 7 0.017 7 0.019 7 0.019 7 0.018 7 Range T-0.033 T-0.038 T-0.029 0.008-0.025 0.011-0.031 DIAZINON Average Positive Composites Number 0.001 4 T 3 0.001 5 T 2 0.001 6 Range T-0.006 T T-0.006 T-0.003 T-0.005 CADMIUM Average Positive Composites Number 0.03 7 0.04 7 0.03 7 0.02 7 0.03 7 Range 0.01-0.05 0.02-0.05 0.02-0.05 0.01-0.04 0.02-0.03 IV. Potatoes CIPC Average Positive Composites Number Range 0.105 3 0.0800.504 0 0.291 4 0.012-1.40 0.001 1 0.008 0.039 2 0.102-0.170 DIELDRIN Average Positive Composites Number Range T 2 T-0.002 T 2 T-O.OOl 0.003 4 T-0.016 T 2 0.001-0.002 0.001 2 T-0.004 CADMIUM Average Positive Composites Number Range 0.02 7 0.02-0.04 0.06 6 0.03-0.14 0.05 7 0.02-0.10 0.06 7 0.02-0.09 0.05 7 0.03-0.10 V. Leafy Vegetables DIAZINON Average Positive Composites Number Range 0.003 2 0.011 0.003 3 T-0.015 0.001 1 0.008 0.002 1 0016 T 2 T-0.002 PARATHION Average Positive Composites Number Range 0.002 5 T-0.006 T 1 T T 1 T 0 T 1 T CADMIUM Average Positive Composites Number Range 0.08 6 0.01-0.4 0.03 6 0.02-0.05 0.05 7 0.02-0.09 0.06 7 0.03-0.11 0.05 7 0.02-0.08 VI. Legume Vegetables :admium Average Positive Composites Number Range 0.01 2 0.02-0.03 0.01 2 0.02-0.05 0.01 3 0.02 <0.01 2 0.01-0.02 <0.01 1 0.02 VII. Root Vegetables :admium Average Positive Composites Number Range 0.03 6 0.02-0.07 0.02 0.02-0.04 0.02 7 0.01-0.04 0.02 6 0.01-0.05 0.02 0.01-0.03 VIII. Garden Fruits DIELDRIN Average Positive Composites Number Range 0.002 6 T-0.004 0.002 4 T-0.006 0.001 4 T-0.003 T 3 T-0.002 0.001 2 T-0.004 rOE Average Positive Composites Number Range 0.012 5 TO 043 0.001 4 TO 006 0.006 5 T-0 034 T 1 T 0 Continued next page) /OL. 9, No. 2, September 1975 97 TABLE 2a (cont'd.)- Levels of pesticide residues commonly found- June 1971-July 1972 ■by food class and region, Chemical Baltimore Boston Kansas City Los Anoeies Minneapolis CADMIUM Average Positive Composites Number Range 0.02 6 0,01-0.06 0.02 0.01-0.08 0.02 7 0.01-0.05 0.01 5 0.01-0.02 0.03 7 0.02-0.06 IX. Fruits KELTHANE Average Positive Composites Number Range ETHION Average Positive Composites Number Range ENDOSULFAN (I, II, and the Sulfate) Average Positive Composites Number Range 1 T 0.001 2 T-0.006 0.003 1 0.019 0.003 3 T-0.011 0.006 0.013-0.027 0.003 2 T-0.020 0.007 2 T-0.046 0.001 3 T-0.007 0.014 0.009-0.077 0.002 1 0.014 X. Oils, Fats, and Shortening MALATHION Average Positive Composites Number Range DDE Average Positive Composites Number Range DDT Average Positive Composites Number Range CADMIUM Average Positive Composites Number Range TDE Average Positive Composites Number Range DIELDRIN Average Positive Composites Number Range BHC Average Positive Composites Number Range CADMIUM Average Positive Composites Number Range 6 T-0.19 0.001 4 T-0.005 0.001 3 T-0.009 0.02 6 0.01-0.04 0.002 4 T-0.015 2 T-O.OOl 0.098 0.02-0.492 4 T-0.003 0.002 4 T-0.007 0.01 0.01-0.06 0.002 3 T-0.006 3 T 0.039 0.01-0.131 6 T-0.002 0 02 6 0.01-0.04 0.002 0.003-0.015 0.005 2 T-0.028 0.001 3 T-0.006 0.03 6 0.02-0.04 1 T XI. Sugars and Adjuncts 0.002 <0.01 1 0.02 0.001 3 0.001-0.003 <0.01 1 0.02 0.002-0.003 0.01 3 0.01-0.03 2 T 0.01 3 0.01-0.05 0.015 6 T.0.029 0.001 3 T-0.007 0.001 2 T-0.01 0.02 7 0.01-0.05 2 T-0.009 1 0.002 4 T-O.OOl 0.01-0.02 NOTE: Seven composites examined from each of five regions: Baltimore, Boston, Kansas City, averages of the seven composites from each site. — denotes not applicable. T = trace; see definition, Table 1. Los Angeles, and Minneapolis. Residues listed at 98 Pesticides Monitoring Journa TABLE 2b. Pesticides found infrequently — by food class and region, June 1971 - July 1972 Pesticide Region No. Composites Residues, ppm I. Dair^ Products Vlercury Boston 1 0.02 TDE Kansas City Baltimore 1 1 T T DDT Baltimore Los Angeles 1 2 T T.T Vlethoxychlor Baltimore 1 T 'CB's Boston Los Angeles 1 1 T T II. Meat, Fish, and Poultry fleptachlor Epoxide Kansas City Baltimore Boston Los Angeles Minneapolis T, T, 0.003 T, T, T, T, 0.003 T, T T T.T.T Lindane Kansas City Baltimore Boston Los Angeles T 0.001 T,T T BHC Kansas City Baltimore Boston Los Angeles Minneapolis T, T, T, O.OOI T.T T.T.T T T Diazinon Baltimore Minneapolis T T III. Grain and Cereal Vlercury Boston 0.02 Parathion Baltimore 0.006 Dieldrin Kansas City Minneapolis 0.002 0.002 Lindane Los Angeles T, 0.002, 0.002 DDT Baltimore Boston Los Angeles T T.T T DDE Kansas City Boston Los Angeles T T T TDE Boston Los Angeles Minneapolis T T T donnel Kansas City T ^eptachlor Epoxide Los Angeles T 3HC Los Angeles 2 0.002, 0.004 rhlordane Boston 1 0.059 IV. Potatoes 3HC Baltimore 1 0.005 Endrin Baltimore Boston 2 1 T.T t 'Heptachlor Epoxide Boston Minneapolis 1 2 T T, 0.020 vlercury Los Angeles 1 0.03 DDT Baltimore Boston Los Angeles Minneapolis 2 1 1 1 T, 0.006 T T T DDE Kansas City Baltimore Boston Los Angeles Miimeapolis 2 2 2 2 2 T.T T.T T,T T, 0.007 T.T roE Boston 1 T 'CBs Baltimore 1 T Diazinon Baltimore Minneapolis 1 1 T 0.004 indosulfan I, II, and the Sulfate) Baltimore 1 T Continued next page) /OL. 9, No. 2, September 19' 75 99 TABLE 2b (cont'd.). Pesticides found infrequently— by food class and region June 1971 - July 1972 Pesticide Region 1 No. Composites Residues, ppm V. Leafy Vegetables Methyl Parathion Carbaryl HCB Botran BHC Perthane Endosulfan a, II, and the Sulfate) DDE DDT TDE Malathion 2,4-D KeUhane Dieldrin Toxaphene Kansas City Baltimore Boston MinneapoUs Kansas City Baltimore Baltimore Baltimore Baltimore Baltimore Boston Boston Los Angeles Minneapolis Kansas City Baltimore Boston Los Angeles Boston Los Angeles Boston Boston Los Angeles Boston Los Angeles Minneapolis Los Angeles 1 T.T T T T, 0.010 0.02 T 0.002 0.013 0.005 0.215 0.03 T,T,T T, 0.028, 0.017 T T T.T T T, 0.011 T 0.007 T 0.020 0.01 0.041 T T 0.1 VI. Legume Vegetables DDE DDT Dieldrin PCB's TDE Parathion Kansas City Los Angeles Kansas City Baltimore Boston Los Angeles Minneapolis Kansas City Baltimore Los Angeles Minneapolis 1 T T T T 0.014 T T T T T T VII. Root Vegetabi Es DDE Parathion DDT Dieldrin PCB's Lindane Mercury Baltimore Los Angeles Baltimore Baltimore Boston Los Angeles Los Angeles Boston Kansas City T, T, 0.010 T 0.005 0.004 T T T T 0.08 VIII. Garden Fruits Carbaryl BHC Diazinon PCBs Kansas City Minneapolis Kansas City Los Angeles Minneapolis Kansas City Baltimore Boston Minneapolis Boston 1 1 2 2 1 1 1 1 1 1 T T 0.009, 0.009 T, 0.013 T T T T T T (Continued next page) 100 Pes TiciDEs Monitoring Journal TABLE 2b (cont'd.). Pesticides found infrequently — by food class and region, June 1971 - July 1972 Pesticide DDE Endrin Parathion Lindane Endosulfan (I, II, and the Sulfate) DDT Heptachlor Epoxide Perthane Dieldrin Phosalone Captan Botran Orthophenylphenol BHC Aldrin Methoxychlor Malathion DDT Lindane Cadmium Diazinon Methyl Parathion Carbaryl DDE TDE Region Boston Los Angeles Los Angeles Los Angeles Los Angeles Kansas City Baltimore Boston Baltimore Boston Los Angeles Los Angeles Minneapolis No. Composites IX. Fruits Baltimore Boston Boston Los Angeles Baltimore Los Angeles Kansas City Minneapolis Kansas City Baltimore Boston Minneapolis Kansas City Baltimore Los Angeles Minneapolis Kansas City Kansas City Baltimore Boston Minneapolis Boston Baltimore Kansas City Baltimore Boston Los Angeles Minneapolis Kansas City Baltimore Los Angeles Minneapolis Boston Los Angeles Minneapolis Boston Los Angeles Los Angeles X. Oils, Fats, and Shortening Residues, ppm T T, T, T 0.006 T T T T,T, T T, T T T T,T T T 0.4 0.013 0.027 T 0.001 0.089 0.034 0.007 T T 0.069 0.006 0.043 0 3,0.1 T T T, 0.1 T T 0.015 T, 0.004, 0.053 T, 0.012, 0.006 T T 0.01,0.01,0.02 0.01 0.02 0.02 0.01,0.02 T T, 0.002 T, T 0.002 0.007 T T T T,T PCBs Kansas City Baltimore Los Angeles Minneapolis T, T, 0.05 0.15 T T Pentachloroaniline Baltimore Boston Minneapolis COOS 0.023 0.022 HCB Bahimore Boston Minneapolis 0.004 0.004 0.011 Parathion Kansas City T BHC Boston T (Continued next page) Vol. 9, No. 2, September 1975 101 TABLE 2b (cont'd.)- Pesticides found infrequently — by food class and region, June 1971 - July 1972 Pesticide Region No. COMPOSIIES Residues, ppm PCNB Heptachlor Epoxide Diazinon Boston Boston Los Angeles 1 1 1 T T T XI. Sugars and Adjuncts Dieldrin Kansas City 2 T,T Lindane Kansas City Baltimore Boston Los Angeles Minneapolis 1 2 0.003 T, T 0.005 0.007 T Malathion Kansas City Baltimore T 0.01,0.005 PCBs Kansas City Minneapolis T T Diazinon Kansas City Boston Los Angeles Minneapolis T, T.T T, T T T DDE Kansas City Los Angeles Minneapolis T T T DDT Kansas City Minneapolis T T TDE Kansas City Minneapolis T T Xn. Beverages Cadmium Kansas City Boston Minneapolis 0.01,0.02 0.05, 0.01 0.01 NOTE: Seven composites examined from each of five regions: Baltimore, Boston, Kansas City, Los Angeles, and Miimeapolis. Residues listed are averages of the seven composites from each site. T = trace; see definition, Table 1. The most common residues, maximum levels of those residues, and residues reported less frequently are dis- cussed below for each of the 12 food composites. Find- ings are reported in more detail in Tables 2a and 2b. Averages were calculated by dividing the sums of the residues found by the total number of composites exam- ined from each region (seven in all cases). None of the reported findings have been corrected for recovery. Table 3 summarizes recovery studies. DAIRY PRODUCTS Of 35 composites examined, 32 contained residues. Organochlorine residues were the most prevalent, ap- pearing in 32 composites. The most common and their maximum concentrations were dieldrin, 0.005 ppm; DDE, 0.015 ppm; BHC, trace; and heptachlor epoxide, 0.004 ppm. Also found were DDT, polychlorinated bi- phenyls (PCB's), methoxychlor, and TDE. Cadmium appeared in 10 of 35 composites at levels of 0.01-0.03 ppm. Mercury was found in 1 of 35 composites at 0.02 ppm. MEAT, FISH. AND POULTRY Eight organochlorine compounds were found in varying combinations in all 35 composites. Most common or- ganochlorine residues and their maximum concentra- tions were DDE, 0.048 ppm; dieldrin, 0.009 ppm; DDT, 0.045 ppm; TDE, 0.013 ppm; and PCB's, 0.081 ppm. Heptachlor epoxide, BHC, and lindane were also found. Trace levels of diazinon were found in 2 of 35 com- posites. Arsenic was found in 8 composites: 0.1-0.7 ppm; mercury in 19 composites: 0.02-0.03 ppm; and cadmium in 19 composites: 0.01-0.07 ppm. GRAIN AND CEREAL PRODUCTS Organophosphorus residues were the most common in this commodity class. Malathion was found in all 35 composites at a maximum level of 0.038 ppm; diazinon was found in 20 composites at a maximum level of 0.006 ppm. Ten organochlorine compounds occurred in various combinations in 27 composites. The most com- mon of these were PCB's at a maximum level of 0.101 ppm. Other residues detected were DDT, DDE, TDE, dieldrin, BHC, lindane, ronnel, chlordane, heptachlor epoxide, and parathion. Cadmium appeared in all 35 composites ranging from 0.01 to 0.05 ppm and mercury appeared in 1 composite at 0.02 ppm. POTATOES Ten organochlorine compounds were detected in 27 of the 35 composites. The most common of these com- 102 Pesticides Monitoring Journal TABLE 3. Recovery experiments on pesticides found in total diet samples, June 1971 - July 1972 Pesticide Type of Food Composite Spike Level, PPM Range of Blank Levels, PPM Range of Total Recovered, PPM No. Recovery Experiments CARBARYL ARSENIC CADMIUM MERCURY CHLORDANE PARATHION 2,4-DB MCP MALATHION DIELDRIN DIAZINON RONNEL ETHION Ncifatty Fatty Nonfatty Fatty Nonfatty Fatty Nonfatty Fatty Nonfatty Fatty Nonfatty Fatty Nonfatty Nonfatty Fatty Nonfatty Fatty Nonfatty Fatty 0.05 Nonfatty 0.02 Nonfatty 0.05 Fatty 0.01 Nonfatty 0.01 Fatty 0.02 Nonfatty 0.02 Fatty 0.01 Nonfatty 0.01 Nonfatty 0.02 Fatty 0.02 Nonfatty 0.02 Nonfatty 0.01 0.2 0.2 0.2 0.10 0.10 0.05 0.05 0.06 0.06 0.2 0.2 0.02 0.02 0.01 0.03 0.03 0.02 0.02 Nonfatty 0.01 ALDRIN Fatty 0.005 Nonfatty 0.005 BHC Fatty 0.003 Nonfatty 0.003 PCBs Fatty 0.05 Nonfatty 0.05 0-T 0-0.10 (0.00) 0-0.040 (0.00) 0-0.020 (0.006) 0-0.020 (0.004) 0-0.010 (0.003) 0-0.010 (0.002) 0-0.025 (0.006) 0-0.008 (0.001) 0-0.006 (0.001) 0-0.005 (0.001) 0 0 0-0.018 (0.006) 0 0-0.019 (0.003) 0-0.007 (0.003) 0-0.006 (0.001) 0-0.002 0 0 0 0 0 0 0 0 0-0.0010 (0.0002) 0 0.05-0.20 (0.19) 0.04-0.31 (0.15) 0.01-0.33 (0.15) 0.078-0.122 (0.100) 0.070-0.131 (0.103) 0.038-0.220 (0.061) 0.040-0.072 (0.051) 0.041-0.095 (0.061) 0.038-0.077 (0.060) 0.098-0.167 (0.145) 0.136-0.231 (0.179) 0.013-0.018 (0.015) 0.013-0.027 (0.019) 0.0058-0.013 (0.0087) 0-0.039 (0.019) 0-0.042 (0.022) 0.003-0.015 (0009) 0.007-0.24 (0.014) 0.029-0.060 (0.047) 0.0160.026 (0.020) 0.035-0.063 (0.048) 0.010-0.015 (0.013) 0.009-0.018 (0.012) 0.012-0.018 (0.015) 0.014-0.024 (0.018) 0.004-0.01 1 (0.007) 0.008-0.011 (0.010) 0.011-0.022 (0.016) 0.014-0.017 (0.016) 0.015-0.019 (0.016) 0.007-0.011 (0.009) 0.0025-0.0028 (0.0027) 0.00300.0056 (0.0042) 0-0.0034 (0.0020) 0-0.0048 (0.0027) 0.021-0.078 (0.042) 0.023-0.056 (0 045) 69 33 66 12 17 15 20 35 70 5 10 10 10 10 19 38 3 5 6 3 6 11 21 4 6 4 4 5 5 3 6 5 10 NOTE: Numbers in parentheses represent average residue levels. Vol. 9, No. 2, September 1975 103 pounds and their maximum levels were dieldrin, 0.016 ppm; CIPC (chlorpropham), 1.40 ppm; DDE, 0.007 ppm; and DDT, 0.006 ppm. Also detected were hepta- chlor epoxide, endrin, PCB's, BHC, TDE, endosulfan, and diazinon. Cadmium was found in 34 composites ranging from 0.02 to 0.14 ppm and mercury was found in 1 composite at 0.03 ppm. LEAFY VEGETABLES Residues of 12 organochlorines were discovered in vary- ing combinations in 16 composites. Organophosphorus residues appeared in 17 composites. The most common of these compounds and their maximum levels were diazinon, 0.016 ppm; parathion, 0.006 ppm; endosul- fan, 0.028 ppm; methyl parathion, 0.010 ppm; and DDE, 0.011 ppm. Cadmium was found in 33 of 35 composites ranging from 0.01 to 0.40 ppm. Other resi- dues were DDT, perthane, toxaphene, kelthane (Dico- fol), botran, hexachiorobenzene (HCB), BHC, dieldrin, TDE, 2,4-D, malathion, and carbaryl. LEGUME VEGETABLES Five organochlorine residues were observed in 6 of 35 composites. These included trace levels of PCB's, DDT, TDE, and DDE; 0.014 ppm dieldrin was detected. A trace level of parathion was discovered in one compo- site. Cadmium was observed in 10 composites ranging from 0.0 1 to 0.05 ppm. ROOT VEGETABLES Five organochlorine residues were found in 7 of 35 composites. The most common and their maximum levels were DDE, 0.010 ppm; and dieldrin, which ap- peared in trace amounts. Mercury was observed in 1 composite at 0.08 ppm and cadmium was found in 31 composites ranging from 0.01 to 0.07 ppm. Other residues were PCB's, lindane, DDT, and parathion. GARDEN FRUITS Various combinations of 10 organochlorine residues were detected in 29 of 35 composites. The most com- mon of these and their maximum levels were dieldrin, 0.006 ppm; TDE, 0.043 ppm; BHC, 0.013 ppm; and endosulfan, which appeared in trace amounts. Cadmium was found in 30 composites ranging from 0.01 to 0.08 ppm. Other residues were DDE, DDT, heptachlor epox- ide, PCB's, lindane, endrin, diazinon, parathion, and carbaryl. FRUITS Residues of 13 organochlorines were discovered in 19 of 35 composites. The most common of these and their maximum levels were kelthane, 0.077 ppm; endosulfan, 0.020 ppm; botran, 0.069 ppm; and DDE, which ap- peared in trace quantities. Five organophosphorus resi- dues were observed in varying combinations in 20 of 35 composites. The most common and their highest levels were ethion, 0.027 ppm; malathion, 0.053 ppm; and diazinon, 0.002 ppm. Cadmium appeared in eight composites ranging from 0.01 to 0.02 ppm. Other resi- dues were captan, perthane, dieldrin, TDE, DDT, BHC, methoxychlor, lindane, aldrin, methyl parathion, phosa- lone, carbaryl, and o-phenylphenol. OILS, FATS, AND SHORTENING Of 35 composites, 26 showed residues of 10 organo- chlorines. The most common and their maximum levels ; were DDE, 0.007 ppm; DDT, 0.010 ppm; TDE, 0.015 ppm; dieldrin, 0.015 ppm; and PCB's, 0.15 ppm. Mala- thion was detected in 25 composites; maximum level was 0.492 ppm. Cadmium was found in 30 composites ranging from 0.01 to 0.06 ppm. HCB, PCA, heptachlor epoxide, BHC, PCNB, parathion, and diazinon were also discovered. SUGARS AND ADJUNCTS Varying combinations of seven organochlorines occurred in 18 of 35 composites. The most common and their maximum levels were BHC, 0.003 ppm; and lindane, 0.007 ppm. Trace levels of diazinon appeared in seven composites. Cadmium was found in 1 1 composites. DDE, TDE, DDT, dieldrin, PCB's, and malathion were also observed. BEVERAGES Cadmium appeared in 5 of the 35 composites ranging from 0.01 to 0.05 ppm. No other residues occurred in these composites. Discussion Of the 420 composites examined, organochlorine resi- dues were found in 226, or 54 percent. Organophos- phorus residues were found in 117 composites, or 27.8 percent. Corresponding quantities of organochlorines in previous years were 61.4 percent, 1970-71; 74.2 per- cent, 1969-70; and 64.7 percent, 1968-69. For organo- phosphorus residues during the same years, correspond- ing amounts were 21.4, 20.6, and 16.4 percent. Carbaryl occurred in six composites during the present reporting period; five of these were at trace levels. This appears nearer normal than in the previous reporting period, during which a high of 20 composites contained carbaryl residues. All eight findings of arsenic occurred in Group II: Meat, Fish, and Poultry. Levels ranged from 0.1 to 0.7 ppm. Cadmium residues appeared in all 12 composites; maxi- mum level was 0.40 ppm. Of the 420 composites examined, 256 contained cadmium. Only one composite with a chlorophenoxy acid herbi- cide was found during this reporting period; no penta- chlorophenol (PCP), which is detected by the chloro- phenoxy acid method, was found. Mercury residues were discovered in 23 of 420 com- posites; 19 appeared in Group II: Meat, Fish, and Poul- try. Current analyses of individual commodities within 104 Pesticides Monitoring Journal this composite corroborate the previous Total Diet re- port (7) showing seafood to be the main source of mercury in the diet. Recovery studies were conducted for all classes of chemicals sought throughout the entire year (Table 3). Each recovery experiment consisted of a single determi- nation for the unfortified food composite and a single determination for the fortified sample. These were per- formed simultaneously; hence the fortification level was occasionally below the level present in the sample. In other cases, not enough recoveries were run to permit statistical evaluation; such recovery data are not re- ported. At very low fortification levels recoveries may range from 0 to 200 percent. As the fortification level is raised however, the recovery improves. Recovery data demon- strate that individual, low-level residues reported may vary from the so-called true value but the overall find- ings are useful in appraising the national residue picture. LITERATURE CITED (1) Duggan, R. E., and F. J. McFarland. 1967. Assess- ments include raw food and feed commodities, market basket items prepared for consumption, meat samples taken at slaughter. Pestic. Monit. J. 1(1): 1-5. (2) Corneliussen, P. E. 1969. Pesticide residues in total diet samples (IV). Pestic. Monit. J. 2(4) : 140-152. (J) Corneliussen, P. E. 1970. Pesticide residues in total diet samples (V). Pestic. Monit. J. 4(3):89-105. (4) Corneliussen, P. E. 1972. Pesticide residues in total diet samples (VI). Pestic. Monit. J. 5(4) :3 13-330. (5) Duggan, R. E., H. C. Barry, and L. Y. Johnson. 1966. Pesticide residues in total diet samples. Science 151 (3706): 101-104. (6) Duggan, R. E., H. C. Barry, and L. Y. Johnson. 1967. Pesticide residues in total diet samples (II). Pestic. Monit. I. 1(2):2-12. (7) Manske, D. D., and P. E. Corneliussen. 1974. Pesticide residues in total diet samples (VII). Pestic. Monit. J. 8(2):110-124. (5) Martin, R. J., and R. E. Duggan. 1968. Pesticide resi- dues in total diet samples (III). Pestic. Monit. I. 1(4): 11-20. (9) Food and Drug Administration. 1970. Pesticide Ana- lytical Manual, Vol. I and II. U.S. Department of Health, Education, and Welfare. (10) Association of Official Analytical Chemists. 1970. Offi- cial Methods of Analysis, 11th ed. Washington, D.C. Section 25.016. (//) Munns, R. K., and D. C. Holland. 1971. Determination of mercury in fish by flameless atomic absorption. J. Ass. Offic. Anal. Chem. 54(1 ) :202-205. (12) Porter, M. L., R. J. Gajan, and J. A. Burke. 1969. Acetonitrile extraction and determination of carbaryl in fruits and vegetables. J. Ass. Offic. Anal. Chem. 52(1):177-181. (13) Finocchiaro, J. M., and W. R. Benson. 1965. Thin- layer chromatographic determination of carbaryl (Sevin®) in some foods. J. Ass. Offic. Agr. Chem. 48(4):736-738. Vol. 9, No. 2, September 1975 105 GENERAL Occurrence of Chlorinated Hydrocarbon Insecticides, Southern Florida— 1968-72 ' Harold C. Mattraw, Jr. ABSTRACT The frequency with which chlorinated hydrocarbon insecti- cides appear in samples of southern Florida surface waters decreased sharply between 1968 and 1972. Sediment analyses attest to the earlier widespread use of chlordane, DDT, and dieldrin. Insecticide residues are more frequently detected in southern Florida than in other U.S. cropland soils. Trans- port of DDT, DDD, and DDE from the Everglades agri- cultural area into water conservation areas and undeveloped parts of the Everglades of southeastern Florida is facilitated by a system of water-management canals. Canal sediments within the urban area of southern Florida have high DDD, DDE, and dieldrin residue concentrations which may reflect local use of insecticides rather than their transport from adjacent agricultural areas. Introduction The flat terrain, abundant water, and subtropical climate of southern Florida have encouraged an extensive agri- cultural economy. Chlorinated hydrocarbon insecticides were heavily applied to ensure high agricultural pro- ductivity between 1940 and 1965 but recent restrictions have reduced use to a few specific crops. The persistence of several of the restricted insecticides and the potential of the hydrologic system to disperse them throughout the area have resulted in the initiation of several pro- grams by the Geological Survey, U.S. Department of Interior, to analyze water and sediment from much of southern Florida {I). LAND USE The division of southern Florida into general land-use categories is shown in Figure 1. Urban development, previously restricted to the elevated coastal ridge, is now moving into adjacent areas. Agriculture has occupied two areas: the Everglades agricultural area, muck lands south of Lake Okeechobee, and the eastern agricultural 1 Geological Survey, U.S. Department of Interior, 901 S. Miami Ave- nue, Miami, Fla. 33130. area, parts of the rocky glades and sandy flatlands adja-i cent to the urban area. The Everglades is primarily saw grass marsh. The northern part has been converted to ai water conservation area with an extensive system ofn canals and levees; the southern part includes most of I the Everglades National Park, which receives regulated I water discharge from the water conservation areas. The' western part of the Big Cypress watershed has been partly drained to facilitate development, but the eastern part is still largely swamp. WATER-MANAGEMENT SYSTEM The Kissimmee River basin forms the northern end of the regional water-management system. Most of the surface flow (2) that enters Lake Okeechobee from the Kissimmee and from several streams is diverted west- ward through the Caloosahatchee River to the Gulf ofl Mexico or eastward through the St. Lucie Canal to thai Atlantic Ocean (Fig. 1). A system of levees, canals, control structures, pumping stations, and water-storage' areas permits the management of the freshwater re- sources of Palm Beach, Broward, and Dade Counties. Levees impound water in Lake Okeechobee and the water conservation areas and protect the eastern and I Everglades agricultural areas and urban area from flood- ing during the rainy season, June through October. Large pumping stations protect the Everglades agricul- tural area and flood-prone areas immediately east of the' conservation areas by pumping surplus surface runofl into Lake Okeechobee or the conservation areas. Watei can be transferred from conservation areas into Ever- glades National Park, agricultural areas, or to the cities as demand dictates. INSECTICIDE SOURCES AND DISPERSION MECHANISMS Chlorinated hydrocarbon insecticides applied to crop- lands persist in the soil (i). Inadvertent spraying ol waterways adjacent to croplands facilitates insecticide dispersion by the hydrologic system. Volatilization intc 106 PESTICIDES Monitoring Journal FIGURE 1. Major canals and land-use areas, southern Florida the atmosphere also disperses insecticides when the vola- tile fraction remains in the vapor phase or is adsorbed to particulate matter in the atmosphere. The sorbed frac- tion returns to the ground surface as dry fallout or in rainfall. Erosion of treated soils provides a third mecha- nism for introduction of insecticides into the hydrologic system. The urban area provides additional pathways for insecticides through the discharge of industrial efflu- ents, treated sewage, and storm water runoff. Analytical Techniques Data were not collected within any strict statistical de- sign. Water samples were taken several inches below Vol. 9, No. 2, September 1975 107 the surface in hexane-rinsed 1 -liter glass or teflon bottles. This sampling method has been used because most southern Florida water bodies are very shallow. Samples collected in the canal system were obtained in the same manner so results would not be influenced greatly by the highly variable suspended loads characteristic of these regulated canals (4). In Geological Survey studies, ana- lyses for 1 1 chlorinated hydrocarbon insecticides were run using dual-column electron-capture gas chroma- tography according to procedures outlined by Goerlitz and Brown (5). Identifications were confirmed by mass spectrometry when sufficient sample remained. Interfer- ences from PCB concentrations were corrected in 1970 (6). All earlier chromatograms were reviewed and cor- rected if necessary. The detection limit is about 0.005 /ig/ liter for water. Values between 0.005 and 0.01 /ug/ liter are reported as 0.01 /ig/liter and values greater than 0.10 /ig/liter are rounded to two significant figures. The top 2 inches of bottom sediment was collected in wide-mouth hexane-rinsed glass jars using the jar as a sampling device. Sediments from canals too deep to sample directly were collected using an Ekman dredge. If sufficient material was collected, the subsample ana- lyzed was taken from the middle of the collected sample. Insecticides were extracted from sediment samples with an acetone/ hexane solvent. The extract was washed with distilled water, dried over NajSOj, and concentrated and cleaned on alumina (7). Sediment samples were also analyzed for moisture content and insecticide con- centrations are reported on a dry-weight basis. Sample recovery of chlorinated hydrocarbon insecticides in bot- tom materials averaged 97.9 percent (8). The detection limit was 0.05 /ig/kg; values between 0.05 and 0.1 are reported as O.l^^g/kg. Values greater than 1.0 /^g/kg are rounded to two significant figures. Results WATER The number of surface water samples analyzed from southern Florida and the percentage containing detect- able insecticide concentrations are shown in Figure 2. The limit of detection was 0.005 /ig/liter. Of the 11 compounds for which technicians tested, only 5, DDT, DDD, DDE, dieldrin, and lindane, were detected in water samples. The majority of the identifications were at the lower detection limit of 0.005 ^g/ liter. These detections may be caused by insecticides adsorbed on suspended organic matter. tn CO UJ UJ _j o ^o < I- w o UJ oc in UJ z o< UJ o o liJ < I- I- UJ Z Q Ul O I Q: I- uj - Q- * 12 II 10 9 8 7 6 5 4 3 2 365 188 365 366 362 367 (NOTE: No. samples analyzed reported above chemical name.) 368 366 157 367 146 Q Ul z < o o Q O O O O O O OC o UJ o o UJ o _l I o < Q. UJ X q: CL Q- UJ UJ X Ul z < UJ z UJ I Q. < X o FIGURE 2. Chlorinated hydrocarbon detections in surface waters, southern Florida — 1968-72 108 Pesticides Monitoring Journal TABLE 1. Detection of insecticides in surface waters, southern Florida — 1968-72 Insecticide 1968 1969 1970 1971 1972 No. POSITIVE No. POSITIVE No. POSITIVE No. POSITIVE No. POSITIVE SAMPLES Positive SAMPLES, SAMPLES Positive SAMPLES, samples PosrrrvE SAMPLES, SAMPLES Positive SAMPLES, SAMPLES PosmvE No. SAMPLES No. SAMPLES No samples No. SAMPLES No. SAMPLES SAMPLES, ANALYZED % ANALYZED % ANALYZED % ANALYZED % ANALYZED % DDT 17 21 81 7 26 27 11 47 23 4 109 3.7 2 166 1.2 ODD 9 22 41 4 26 15 6 49 12 7 122 5.7 6 163 3.8 DDE 5 22 23 3 26 12 1 45 2.2 6 122 4.9 5 163 3.1 Dieldrin 5 23 22 0 26 0 0 48 0 11 110 10 24 161 15 The frequency of chlorinated hydrocarbon detection in southern Florida water samples declined between 1968 and 1972 (Table 1). Rainfall samples collected in southern Florida during the same period have shown a concomitant decrease (A. L. Higer, Geological Survey, USDI, Miami, Fla., 1973: written communication). The decrease in the frequency of detectable insecticide resi- dues in southern Florida probably reflects restrictions on agricultural applications of these chemical compounds. Annual synoptic surveys of U.S. surface waters indicate a peak occurrence of chlorinated hydrocarbon insecti- cides in 1966 (9). SEDIMENT The number of southern Florida sediment samples and the percentage containing detectable insecticide concen- trations (0.05 /ig/kg) are shown in Figure 3. Most fre- quently detected were chlordane, DDT, DDD, DDE, and dieldrin. Less than 5 percent of the samples ana- lyzed contained aldrin, lindane, or toxaphene. Chlor- dane, dieldrin, DDT, DDD, and DDE were detected in a higher percentage of sediment samples from this study than in soil samples collected for the National Soils Monitoring Program (10). Aldrin was detected less frequently (Table 2), probably indicating a differ- ent insecticide-use pattern in southern Florida than in the rest of the Nation. Concentrations of DDD in southern Florida sediments are illustrated by land-use areas in Figure 4. Sedi- ment samples from the Everglades agricultural area, where DDT and DDD were directly applied to soils, showed the highest percentage of samples containing DDD and the highest concentrations. DDD concentra- tions occurred in decreasing order in the urban area, Everglades area, eastern agricultural area, and the un- developed Big Cypress watershed. The Big Cypress is remote from areas of DDT and DDD application and probably receives most of its insecticides from atmos- pheric transport mechanisms. The highest DDD con- centration reported in the undeveloped Big Cypress was 6 ^g/kg. Specific pesticide concentrations were compared to the percent of samples containing that amount or less to obtain cumulative frequencies of detection. The rela- tion between DDE concentrations and the cumulative frequencies of detection is illustrated in Figure 5. Distri- bution of DDE residues in sediment by land-use area is similar to that of DDD (Fig. 4). The slopes of the semilogarithmic plots for DDE and DDD are nearly equal. This similarity indicates that the occurrence of various concentrations of these two pesticides within any one land-use area is essentially the same. The similarity of concentrations and cumulative frequencies of DDD and DDE detection (Fig. 4,5) indicate that their dispersion with distance from source areas and persistence with time are comparable. A comparison of DDD and DDE concentrations in canal and marsh sediments of the Everglades area is shown in Figure 6. The slopes of the lines representing concentrations of these two pesticides versus cumulative frequencies of detection are similar. The general slope of the lines showing concentrations versus cumulative TABLE 2. Frequency of insecticide residue detection in cropland soil and sediment, southern Florida — 1969-72 Cropland soil Sediment positive SAMPLES, positive samples. Insecticide %, 1969 %, 1969-72 Dieldrin 27.8 53.3 DDE 24.8 80.5 DDT 22.2 37.3 DDD 15.3 80.3 Aldrin 10.9 2.2 Chlordane 8.7 32.7 Heptachlor Epoxide 8.0 ND Toxaphene 4.2 3.2 Heptachlor 3.9 ND Endrin 2.3 ND Lindane 0.9 0.7 NOTE: ND = not detected Vol. 9, No. 2, September 1975 109 PERCENTAGE OF SEDIMENT SAMPLES WITH DETECTABLE INSECTICIDES 80 70 60 50 40 30 20 10 277 279 277 283 (NOTE: No. samples analyzed reported above _ chemical name.) --_ 126 280 132 2^^, |— I 287 279 214 0 z (X o _l < CHLORDANE DDT DDD DDE DIELDRIN z cc Q z UJ HEPTACHLOR HEPTACHLOR EPOXIDE LINDANE TOXAPHENE FIGURE 3. Chlorinated hydrocarbon detections in sediment, southern Florida — 1968-72 frequencies of detection for these compounds in the canal environment is steeper than the slope for marsh sediments. The higher DDD and DDE concentrations in some canal sediment samples indicate higher intro- duction rates from the Everglades agricultural area. The less frequent occurrence of DDD and DDE in sediments from the Everglades canal system appears to indicate active transport of sediment within the canals. The fine-grained, organically rich sediments have high residue levels and are apparently accumulating in a few areas where channel geometry and low velocity of flow encourage settling. Thus relatively few areas with high concentrations of insecticide-rich sediments would be expected in the canal system. The low slope of the graph of DDD and DDE con- centrations versus cumulative frequencies of detection for marsh areas (Fig. 6) is probably indicative of the uniform aerial introduction of insecticides. Because the sluggish surface water flow within marsh areas is less efficient in redistributing these insecticide loads, sedi- ment concentrations display less variability. The high frequency with which DDD and DDE are detected in sediment samples from marsh areas is caused by tht proximity of the two primary areas of insecticide use the Everglades agricultural area and the eastern agrr cultural area. Time does not appear to be a significani variable in controlling the slope of the concentratio) versus the cumulative frequency of detection plot. The concentration of dieldrin in sediments amon the various land-use areas is illustrated in Figure Dieldrin in sediments is more frequently detected an^ has higher concentrations in the urban area than in an other land-use region. The use of dieldrin for eradica tion of domestic termites would account for its mor frequent occurrence in urban area sediments. Low ovei all dieldrin concentrations in all land-use areas indicat a lower use rate than that of DDT (//). The undeveloped Big Cypress watershed has the low est dieldrin concentrations and the lowest frequency o dieldrin detection. Because dieldrin moves from solutio to the atmosphere more slowly than do other chlorinate hydrocarbons {12), it is usually retained more readil in the aqueous phase than are the more volatile DDT DDD, and DDE. This behavior would explain its ver 110 Pesticides Monitoring Journa ow occurrence in sediments from the Big Cypress watershed, which receives most of its input from the itmosphere. The generally low frequency of detectable lieldrin suggests a lower application rate. Summary Restrictions on insecticide use have resulted in less requent detection of several chlorinated hydrocarbons n southern Florida surface waters between 1968 and 1972. Occurrence of these insecticides is expected to ;ontinue to decrease. The tendency for insecticides to be adsorbed by par- ticulate matter is well illustrated by the higher fre- quency of detectable residues in sediment samples than in water samples. The prior widespread application of chlorinated hydrocarbons in southern Florida and the ability of sediment to retain insecticides and residues are indicated by a frequency of occurrence which is higher than that determined in the National Soils Moni- toring Program. An extensive canal system transports sediment and adsorbed chlorinated hydrocarbon insecti- cides from a high application area, the Everglades agri- lOOO IOO-- 05 a. uS 19 I< m o o o Q Q O IO-- I.O — O.I — ▲ A ♦ EVERGLADES AGRICULTURAL AREA URBAN AREA EVERGLADES AREA EASTERN AGRICULTURAL AREA UNDEVELOPED BIG CYPRESS A WATERSHED ^AAA ♦ ♦ Ji^ AA A^ A^ ---•^ A^' •••^ AA^^ ^* ^ ^A^ ♦♦♦♦♦ , • •- . i^ ♦♦♦♦ • • • •MM ▲ .^i ♦ • MM* m, ^ ♦♦♦♦♦ « • A^ • • ♦♦♦♦*. . • • ♦♦ • • • • t O.OI lO 20 30 4-0 50 60 70 80 90 lOO PERCENTAGE OF SAMPLES THAT EQUAL OR ARE LESS THAN THE VALUE INDICATED FIGURE 4. DDD concentrations in sediment, southern Florida — 1968-72 'OL. 9, No. 2, September 1975 111 lOOO IOO-- a. < cc z UJ o z o o LU Q O IO-- I.O-- O.l — O.OI A EVERGLADES AGRICULTURAL AREA • URBAN AREA i EVERGLADES AREA • EASTERN AGRICULTURAL AREA ^ UNDEVELOPED BIG CYPRESS • WATERSHED .••• ^ A A -• .^''' *ti* »/i''' tii^ ij ♦♦♦♦ • • t t • ♦ ♦ ♦ ♦♦ • • t lO 20 30 -40 PERCENTAGE OF OR ARE LESS THAN 50 60 70 SO 90 SAMPLES THAT EQUAL THE VALUE INDICATED 100 FIGURE 5. DDE concentrations in sediment, southern Florida — 1968-72 cultural area, into the Everglades. The adjacent unde- veloped Big Cypress watershed receives little channelized runoff from agricultural areas and has lower concen- trations of DDD, DDE, and dieldrin than do the Ever- glades. Concentrations of DDD, DDE, and dieldrin in sedi- ments reflect land use. The complex interplay between proximity to high application areas, canals transporting surface water flow, and the various transport mecha- nisms indicates that numerous sediment analyses are required to establish the general pattern of insecticide distribution. The variability of concentrations within ar^ one area indicates a need to sample numerous locatioi s before establishing rigid reference standards. Maximu 3 concentrations of sediments in natural areas of southei n Florida appear to be 6 iig/^^g for DDD, 9 /ig/kg f(» DDE, and less than 1 /^g/kg for dieldrin. Acknowledgments Water and sediment samples were gathered by Ge- logical Survey personnel in Miami through cooperati-e programs with numerous city, county. State, and Fe' ■ 112 Pesticides Monitoring Journ/i. ral agencies. Noteworthy are the programs with Bro- ard County, the National Park Service, the U.S. Army orps of Engineers, and the Central and Southern lorida Flood Control District. Analytical work was one by the Geological Survey Organics Laboratory, /ashington, D.C. 0 LITERATURE CITED Kolipinski, M. C, and A. L. Higer. 1971. Organo- chlorine insecticide residues in Everglades National Park and Loxahatchee National Wildlife Refuge, Flori- da. Pestic. Monit. J. 5(3) :281-288. Leach, S. D., H. Klein, and E. R. Hampton. 1972. Hydrologic Effects of Water Control and Management of Southeastern Florida. Bureau of Geology, Florida Department of Natural Resources, Report of Investi- gation 60. 115 pp. (3) Kearney, P. C, R. G. Nash, and A. R. hensee. 1969. Persistence of pesticide residues in soils. In Chemical Fallout: Current Research on Persistent Pesticides. Proceedings Publication of Rochester University Con- ferences on Toxicology. Charles C. Thomas. Spring- field, 111. Pp. 54-67. (4) Pitt. W. A., Jr. 1972. Sediment Loads in Canals 18, 23, and 24 in Southeastern Florida. U.S. Geol. Surv. Open-File Rep. 72013. 48 pp. (5) Goerliiz, D. F., and E. Brown. 1972. Methods for anal- ysis of organic substances in water. U.S. Geol. Surv. Techniques, Book 5, chapter A-3. 40 pp. lOOO i k lOO- ( ^ 1 1 1 ai • » in A z # * • o 1- A * ..••♦ > < DC lO- ♦ ♦♦♦♦ - 1- Z LU o z ♦♦J ••• o o • . • "^^ LU Q .♦♦^^••* Q Q Z < I.O- Q Q Q A O.l - - SEDIMENT A DDD CANAL • DDE CANAL ♦ DDE MARSH t DDD MARSH O.OI c 5 lO 20 30 40 50 60 70 80 90 lOO PERCENTAGE OF SAMPLES THAT EQUAL OR ARE LESS THAN THE VALUE INDICATED FIGURE 6. DDD and DDE concentrations in sediment, Everglades marsh and canal — 1968-72 DL. 9, No. 2, September 1975 113 lOOO IOO-- a. < O o CJ DC Q I.O-- O.l — O.OI A ♦ EVERGLADES AGRICULTURAL AREA URBAN AREA EVERGLADES AREA EASTERN AGRICULTURAL AREA UNDEVELOPED BIG CYPRESS WATERSHED • 4 y A ♦ ♦ .♦;*"' ♦ ♦♦i ♦ ♦ i t ▲ ♦♦♦ dA t ♦♦♦♦«iJi lO 20 30 AO 50 60 70 SO 90 PERCENTAGE OF SAMPLES THAT EQUAL OR ARE LESS THAN THE VALUE INDICATED 100 FIGURE 7. Dieldrin concentrations in sediment, southern Florida — 1968-72 (6) Criimp-Wiesner. H. ]., H. R. Fellz, and M. L. Yates. 1973. A study of the distribution of polychlorinated biphenyls in the aquatic environment. J. Res. U.S. Geol. Surv. 1(5) :603-607. (7) Law, L. M., and D. F. Goerlilz. 1970. Microcolumn chromatographic cleanup for the analysis of pesticides in water. J. Ass. OfRc. Anal. Chem. 53(6) ; 1276-1286. {8) Goerlitz, D. F., and L. M. Law. 1974. Determination of chlorinated insecticides in suspended sediment and bottom material. J. Ass. Offic. Anal. Chem. 57(1): 176-181. (9) Lichlenberg, J. J., J. W. Eichelberger, R. C. Dressman, and J. E. Longbollom. 1970. Pesticides in surface waters of the United States — a 5-year summary, 1964 68. Pestic. Monit. J. 4(2):71-86. (70) Wiersma. G. B.. H. Tai, and P. F. Sand. 1972. Pesti cide residue levels in soils, FY 1969 — National Soil Monitoring Program. Pestic. Monit. J. 6(3) : 194-228. (11) Higer, A. L., and M. C. Kolipinski. 1970. Sources o Pesticides in Florida Waters. U.S. Geol. Surv. Open File Rep. 70005. 20 pp. (12) MacKay, D., and A. W. Wolkoff. 1973. Rate of evapo ration of low-solubility contaminants from water bodie to atmosphere. Environ. Sci. Technol. 7(7) :61 1-614. 114 Pesticides Monitoring Journa APPENDIX Chemical Names of Compounds Discussed in This Issue LDRIN HLORDANE DD DE DT lELDRIN SJDRIN CB EPTACHLOR EPTACHLOR EPOXIDE NDANE :bs (polychlorinated biphenyls) JE 3XAPHENE Not less than 95% of l,2,3,4,10,I0-Hexachloro-l,4,4a,5,8,8a-hexahydro-l,4-?Mdo-«xo-5,8-dimethanonaphthalene l,2,3,5,6,7,8,8-Octachloro-2,3,3a,4,7,7a-hexahydro-4,7-methanoindene. The technical product is a mixture of several compounds, including heptachlor, chlordene, and two isomeric forms of chlordane. See TDE. Dichlorodiphenyl dichloro-ethylene (degradation product of DDT) Main component (p,p'-DDE): l,l-Dichloro-2,2-bis(p-chlorophenyl)ethylene o,p'-DDE: l,l-Dichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl) ethylene oc-Bis (p-chlorophenyl) ;3,g,0-trichloroethane. Numerous isomers in addition to p,p'-DDT are possible, and some are present in the commercial product. o,p'-DDT ll,l,l-Trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)cthanel Not less than 85% of l,2,3,4,I0,10-Hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-I,4-?ndo-?j:o-5,8-dimethano- naphthalene 1,2,3,4, 10, 10-Hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l,4-cndo-endo-5,8-dimethanonaphthalene Hexachlorobenzene l,4,5,6,7,8,8-Heptachloro-3a,4,7,7a-tetrahydro-4,7-cndo-methanoindene 1,4,5,6,7,8,8-Heptachloro 2,3-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindane Gamma isomer of benzene hexachloride 1,2,3,4,5,6-hexachlorocyclohexane of 99+% purity Mixtures of chlorinated biphenyl compounds having various percentages of chloride 2, 2-Bis (p-chlorophenyl ) -1 , 1 -dichloroethane Chlorinated camphene (67-69% chlorine). Product is a mixture of polychlorinated bicyclic terpenes with chlorinated camphenes predominating. 3L. 9, No. 2, September 1975 115 Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretive information which contribute to the understanding and evaluation of pesticides and their residues in relation to man and his environment. The publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries; medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. Accuracy, reliability, and limitations of the sam- pling and analytical methods employed must be clearly demonstrated through the use of appropriate procedures, such as recovery experiments at appropriate levels, confirmatory tests, internal standards, and inter-labora- tory checks. The procedure employed should be ref- erenced or outlined in brief form, and crucial points or modifications should be noted. Check or control samples should be employed where possible, and the sensitivity of the method should be given, particularly when very low levels of pesticides are being reported. Specific note should be made regarding correction of data for percent recoveries. Preparation of manuscripts should be in con- formance to the CBE Style Manual, 3d ed. Coun- cil of Biological Editors. Committee on Form and Style, American Institute of Biological Sciences, Washington, D. C, and/or the Style Manual of The United States Government Printing Office. An abstract (not to exceed 200 words) should accompany each manuscript submitted. All material should be submitted in duplicate (original and one carbon) and sent by first-class mail in flat form — not folded or rolled. Manuscripts should be typed on 8'/2 x II inch paper with generous margins on all sides, and each page should end with a completed paragraph. All copy, including tables and references, should be double spaced, and all pages should be num- bered. The first page of the manuscript must con- tain authors' full names listed under the title, with affiliations, and addresses footnoted below. Charts, illustrations, and tables, properly titled, should be appended at the end of the article with a notation in text to show where they should be inserted. -Charts should be drawn so the numbers and text I will be legible when considerably reduced foi publication. All drawings should be done in blacl ink on plain white paper. -Photographs should be made on glossy papeil Details should be clear, but size is not important I -The "number system" should be used for literal ture citations in the text. List references in thi order in which they are cited in the text, givin, name of author/ s/, year, full title of article, exac name of periodical, volume, and inclusive pages. The Journal also welcomes "brief" papers reportin; monitoring data of a preliminary nature or studies o limited scope. A section entitled Briefs will be included I as necessary, to provide space for papers of this typ" to present timely and informative data. These paper must be limited in length to two journal pages (85t words) and should conform to the format for regula papers accepted by the Journal. Pesticides ordinarily should be identified by common or generic names approved by national scientific soi cieties. The first reference to a particular pesticidi should be followed by the chemical or scientific nam' in parentheses — assigned in accordance with Chemicaii Abstracts nomenclature. Structural chemical formula should be used when appropriate. Published data an( information require prior approval by the Editoria Advisory Board; however, endorsement of published ini formation by any specific Federal agency is not intended or to be implied. Authors of accepted manuscripts wil' receive edited typescripts for approval before type is sel After publication, senior authors will be provided witl 100 reprints. Manuscripts are received and reviewed with the unden standing that they previously have not been accepted fo( technical publication elsewhere. If a paper has beei given or is intended for presentation at a meeting, or ii a significant portion of its contents has been publishei or submitted for publication elsewhere, notations of sue) should be provided. Correspondence on editorial matters or circulation mat ters relating to official subscriptions should be addressei to; Paul Fuschini, Editorial Manager, PESTICIDE MONITORING JOURNAL, Technical Services Divi sion. Office of Pesticides Programs, U. S. Environments Protection Agency, Room B49 East, Waterside Mall 401 M Street, S.W., Washington, D. C. 20460. ■ft- U.S. GOVERNMENT PRINTING OFFICE: 197S G21-BS2/1 116 Pesticides Monitoring Journai 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 man and his environment. The WORKING GROUP is comprised of representatives of the U.S. Departments of Agricul- ture; Commerce; Defense; the Interior; Health, Education, and Welfare; State; Transportation; and Labor; and the U.S. Environmental Protection Agency. The pesticide MONITORING PANEL consists of representatives of the Agricultural Research Service, Animal and Plant Health Inspection Service, Extension Service, Forest Service, Depart- ment of Defense, Fish and Wildlife Service, Geological Survey, Food and Drug Administration, Environmental Protection Agency, National Marine Fisheries Service, National Science Founda- tion, and Tennessee Valley Authority. Publication of the Pesticides Monitoring Journal is carried out by the Technical Services Divi- sion, Office of Pesticides Programs of the Environmental Protection Agency. Pesticide monitoring activities of the Federal Government, particularly in those agencies repre- sented on the pesticide MONITORING PANEL which participate in operation of the national pesticides monitoring network, are expected to be the principal sources of data and interpretive articles. However, pertinent data in summarized jorm, together with interpretive discussions, are invited from both Federal and non-Federal sources, including those associated with State and community monitoring programs, universities, hospitals, and nongovernmental research institu- tions, both domestic and foreign. Results of studies in which monitoring data play a major or minor role or serve as support for research investigation also are welcome; however, the Journal is not intended as a primary medium for the publication of basic research. Manuscripts received for publication are reviewed by an Editorial Advisory Board established by the MONITORING PANEL. Authors are given the benefit of review comments prior to publication. Editorial Advisory Board members are: John R. Wessel, Food and Drug Administration, Chairman Paul F. Sand, Agricultural Research Service, Vice Chairman Anne R. Yobs, Center for Disease Control William F. Durham, Environmental Protection Agency Thomas W. Duke, 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 Mention of trade names or commercial sources in the Pesticides Monitoring Journal is for identification only and does not represent endorsement by any Federal agency. Address correspondence to : Paul Fuschini Editorial Manager PESTICIDES MONITORING JOURNAL U.S. Environmental Protection Agency Room B49 East, Waterside Mall 401 M Street, S.W. Washington, D. C. 20460 Martha Finan Joanne Sanders Editors CONTENTS Volume 9 December 1975 Number 3 Page RESIDUES IN WATER Analysis of various Iowa waters for selected pesticides: atrazine, DDE, and dicldrin—1974 117 John J. Richard, Gregor A. Junk, Michael J. Avery, Nancy L. Nehring, James S. Fritz, and Harry J. Svec RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mirex residues in nontarget organisms after application of experimental baits for fire ant control, southwest Georgia — 1971-72 124 Daniel P. Wojcik, W. A. Banks, W. B. Wheeler, D. P. Jouvenaz, C. H. Van Middelem, and C. S. Lofgren GENERAL Chlorinated hydrocarbon residues in fish, crabs, and shellfish of the lower Fraser River, its estuary, and selected locations in Georgia Strait, British Columbia— 1972-73 1 34 L. J. Albright, T. G. Northcote, P. C. Oloffs, and S. Y. Szeto Mirex residues in wildlife and soils, Hawaiian pineapple-growing areas— 1972-74 141 Arthur Bevenue, James N. Ogata, Lester S. Tengan, and John W. Hylin Exposure and contamination of the air and employees of a pentachlorophenol plant, Idaho — 1972 150 Joseph A. Wyllie, Joe Gabica, W. W. Benson, and Julie Yoder APPENDIX Chemical names of compounds discussed in this issue 154 Information for contributors 155 RESIDUES IN WATER Analysis of Various Iowa Waters for Selected Pesticides: Atrazine, DDE, and Dieldrin — 1974 '■' John J. Richard, Gregor A. Junk, Michael J. Avery, Nancy L. Nehring, James S. Fritz, and Harry J. Svec ABSTRACT Atrazine, DDE, and dieldrin were extracted and concen- trated from various surface, subsurface, and finished waters using the macroreticular resin method. Organic components in the concentrates from these waters were separated by gas chromatography: the amounts of the three pesticides in the waters ranged from 0.5 to 42,000 parts per trillion by weight. Every major watershed in the State of Iowa revealed some degree of pesticide contamination and seasonal varia- tions were consistent with agricultural runoff models. Atra- zine concentrations were highest of the three pesticides, a symptom of its widespread use in the corn belt. DDE also appeared in substantial quantities, providing further evidence of the persistence of DDT and its metabolites. Water from several shallow wells and finished water from many water treatment plants were also contaminated. Current treatment processes do not effectively remove these pesticides. Introduction The present study was undertaken during the 1974 growing season to ascertain the degree and extent of contamination by dissolved pesticides of surface, sub- surface, and finished drinking waters in the State of Iowa. All major watersheds and several smaller ones were included m the survey of surface waters. During periods of heavy runoff, appreciable sediment was present but no attempt was made to measure pesticides sorbed in the suspended particles; thus pesticide content of surface waters quoted here represents only part of the total burden. For the subsurface and finished waters, quoted values accurately reflect the total pesticide burden be- cause sediment was not a factor. The survey of subsurface waters included both shallow- and deep-well systems within and outside the alluvial ' Supported in part by National Science Foundation Contract GP 3352ftX. - Ames Laboratory, U.S. Atomic Energy Commission, and the Energy and Mineral Resources Research Institute, Iowa State University, Ames, Iowa 50010. plains of contaminated rivers. The survey of finished water covered most of the major cities in the State including those which obtain their raw water from subsurface supplies. Three pesticides were selected for monitoring: atrazine, DDE, and dieldrin. They are readily separated from interferences using gas chromatography (GC) and were present in amounts sufficient for quantification using electron-capture gas chromatography (EC/GC). These three pesticides were found in most of the water samples. Atrazine is used in large amounts for weed control in cornfields and has appeared in runoff from small test plots of soil treated with atrazine (1-7). Aldrin and DDT have been used extensively in previous years and several investigators have found their metabolites, diel- drin and DDE, in Iowa rivers (8-11). The most convenient method for isolating dissolved organic materials from the water prior to separation, identification, and quantification was by sorption on XAD-2 resin (12-14). The resin absorption method has two major advantages over solvent extraction: large sample volumes are possible without elaborate equip- ment, and the ratio of solvent used to amount of water sampled is very small. Materials and Methods Petroleum ether (30°-60°C) and acetonitrile were pes- ticide quality. Diethyl ether was redistilled. Organic-free water was obtained by passing distilled water through a column containing XAD-2 resin and fresh activated charcoal. Organic-free sodium sulfate was obtained by heating anhydrous sodium sulfate at 400°C in a muffle furnace for 2 hours. The XAD-2 macroreticular resin received from Rohm and Haas in Philadelphia was pre- pared for column packing by slurrying in methanol and decanting to remove the fines and purifying by sequen- VoL. 9, No. 3, December 1975 117 tial Soxhlet extraction with methanol and acetonitriie (72). The purified resin was stored in a glass-stopf)ered bottle under methanol. A Beckman GC-5 gas chromatograph equipped with a helium-dicharge EC detector was used for the gas chro- matography. A 1.5 percent OV-17/1.95 percent QF-1 column was used for separating and quantifying the biocides. When large amounts of DDE were present, the dieldrin was quantified using a 5 percent OV-210 column. The pesticide identifications were verified by comparing retention times using a 5 percent OV-210 column and a 10 percent DC-200 column. Additional confirmations were made using a Du Pont 21-490-1 gas chromato- graph / mass spectrometer. When interference peaks on the EC gas chromatograms precluded accurate quanti- fication of atrazine, samples were chromatographed on a 5 percent OV-1 column and mass fragmentography was employed to quantify the amount of atrazine present. GRAB SAMPLES Grab samples of surface waters were collected in 4-liter amber reagent bottles. No velocity or depth integration was attempted to determine exact pesticide suspension. However, the sampling procedure was duplicated for each surface water supply. The sampling site for the three small streams, Skunk River, Indian Creek, and Fernald Drainage Ditch, was a single transverse posi- tion located at the centroid of flow halfway between the surface and the bottom. Water from sites 6, 7, 8, and 9 were analyzed in triplicate from various sampling sites and results varied by less than 1 percent. All other grab samples of surface waters were taken 6 inches below the surface. The collected water samples were allowed to settle overnight before extraction with the XAD-2 resin. The apparatus used for extracting the pesticides is shown in Figure 1. The settled water sample was de- canted into the 5-liter reservoir and passed through the resin by gravity flow at a rate of 25-50 ml/min. When the water level reached the upper glass wool plug sedi- ment from the bottle was transferred to the reservoir using several rinses with organic-free water. After all the water had passed through the resin, the stopcock was closed, the reservoir was removed, and 15 ml diethyl ether was added to the resin. About 5 ml was allowed to flow through the resin and collect in a 60-ml separatory funnel. The stopcock was then closed for 15-.^0 minutes after which the remaining 10 ml ether was collected in the separatory funnel. This elution procedure was repeated with a second 15-ml portion of ether which was combined with the first. The water layer was drained from the separatory funnel and final traces of water were removed from the eluate by adding 10-15 ml petroleum ether and 2-3 g anhydrous sodium sulfate. The mixture was shaken approximately 30 sec- KEY A- 5-iiter reservoir B— glass wool plugs C- 24/40 ground glass joint with Teflon sleeve D- glass tube. 8 bv 140 mm, packed with — 5 ml 40-60-mesh XAD-2 resin E— Teflon plug stopcock FIGURE 1. Apparatus for extracting organic solutes from water onds and the liquid extract was transferred quantitative- ly to a concentration flask. The extract was concentrated to 1 ml using the micro-distillation procedures described previously (12). A l-5-/jl aliquot of the concentrated sample was gas-chromatographed without further treat- ment. This grab sampling procedure was also used for finished water samples unless low contamination was suspected or found in preliminary assays; in those cases an 8- to 16-liter water sample was used. An earlier study re- ported recoveries of atrazine, DDE, and dieldrin from water spiked at 20 parts per trillion (ppt) as 83, 81, and 93 percent, respectively, for the XAD-2 resin sorp- tion procedure (72). In this study additional tests of the recovery of atrazine at the amounts reported here revealed values between 77 and 84 percent. COMPOSITE SAMPLES The composite sampling procedure described below represents the average amount of pesticides present in the water over a 24-hour sampling period. The appara- tus used is shown in Figure 2. Sampling was accom- 118 Pesticides Monitoring Journal ^ KEY A— standard garden hose coupling B- Teflon washer C— Va-lnch-ID Teflon tubing D— glass wool plugs E— glass tube, ^^ inch OD by 4 inches long, packed with ^ 5 ml 40-60-mesh XAD.2 resin FIGURE 2. Apparatus for extracting organic solutes from finished drinking water plished by attaching the standard garden hose coupling to a water faucet adjusted to deliver a flow of approxi- mately 50 ml/min. After about 70 liters of water had been sampled during the 24-hour period, the XAD-2 column was removed from the coupling. Teflon sleeves were used to attach a reservoir and Teflon plug stop- cocks to appropriate ends of the column. The column was then eluted with diethyl ether and the eluate was treated as described above for grab water samples. To insure that the capacity of the resin was not exceeded, tests were made using flows up to 150 ml/min and both longer and shorter sampling periods. All tests produced identical results which agreed with grab sample volumes of 8 liters. Either sampling procedure may be used for surface, subsurface, or finished waters, although grab sampling was used exclusively for all surface waters. Results and Discussion Surface water samples were collected from rivers, reser- voirs, and tributaries in major watersheds in the State of Iowa (Fig. 3). A small river, a creek, and a drainage ditch near Ames, Iowa, were sampled weekly and after each major rainfall. Des Moines and Raccoon Rivers and Rathbun and Redrock Reservoirs were sampled periodically throughout summer 1974. The Des Moines city finished water was sampled several times through- out spring and summer 1974. Finished waters from each of the other major cities in the State were sampled at least once during 1974. Atrazine had been found pre- viously in many of these finished waters during a 1972 survey. In general, pesticide contamination existed in all waters which originated from shallow wells in the alluvial plains of contaminated rivers and in all finished waters that originated from either surface waters or shallow wells. Amounts of the three pesticides present in the various waters are presented and discussed in separate sections. SURFACE WATER Concentrations of atrazine, DDE, and dieldrin in water collected from the South Skunk River near Ames appear in Table 1. The first general rainfall in the river basin TABLE 1. Pesticide concentrations in Sonlli Skunk River near Ames, Iowa — 1974 Residues, ng/liter Sampling Atrazine DDE Dieldrin Date 6/9 12,000 1,820 33 6/n 3.900 475 6 6/16 420 45 3 6/19 2.300 688 36 6/22 2,000 688 76 6/27 1.575 87 10 7/2 540 16 13 7/9 230 10 10 7/16 260 14 6 7/22 250 6 5 7/30 500 62 15 8/8 170 4 4 8/11 300 9 5 8/19 160 5 4 8/25 190 2 4 9/12 250 3 3 9/22 < 100 3 3 10/13 <100 3 2 NOTE: Samples taken at site No. 1; see inap. Figure 3. after corn planting in 1974 occurred June 8. That 3- inch rainfall was so intense that significant runoff and erosion occurred in the watershed upstream from the sampling point. Pesticide levels in the South Skunk River during the week immediately following the heavy rainfall correlate with discharge data for the river from the Geological Survey. U.S. Department of Interior. Residues decreased with time following the June 8 rain- fall. A similar pattern was established previously in studies of much smaller watersheds (2-4) and very small test plots (/, 6) where factors influencing pesticide loss were more closely controlled. The same pattern of pesticide loss after a single rainfall is evident for Indian Creek data in Table 2 and drainage ditch data in Table 3. However, no discharge data were available for those streams so no exact correlations between runoff and amount of pesticide in the water is possible. Table 4 gives the concentration of atrazine, DDE, and dieldrin in Des Moines and Raccoon Rivers and Red- rock and Rathbun Reservoirs. Values for the various Vol. 9, No. 3. December 1975 119 FIGURE 3. Sites in Iowa watersheds sampled for selected pesticides, 1974 TABLE 2. Pesticide concentrations in east branch of Indian Creek near Fernald, Iowa — 1974 TABLE 3. Pesticide concentrations in drainage ditch near Fernald, Iowa — 1974 Residues, ng/liter Sampling Residues, nc/iiter Sampling Atrazine DDE DlELDRlN Atrazine DDE Dieldrin Daie Date 6/9 42,000 3,920 25 6/9 9,000 1,150 20 6/11 3,400 600 7 6/11 1,800 244 10 6/16 870 80 4 6/16 440 76 3 6/19 2,000 910 30 6/19 1,500 407 23 6/22 2,400 435 71 6/22 700 200 72 6/27 1,075 100 17 6/27 625 235 8 7/2 510 6 9 7/2 190 32 11 7/9 255 6 8 7/9 132 10 10 7/16 210 8 7 7/16 170 12 9 7/22 285 4 6 7/22 250 10 6 7/30 880 34 24 7/30 220 20 10 8/8 163 6 8 8/8 176 17 4 8/11 225 5 6 8/11 353 18 7 8/19 300 4 4 8/19 290 19 7 8/25 300 2 4 8/25 260 4 8 NOTE: Samples taken at site No. 2; see map. Figure 3. 120 NOTE: Samples taken at site No. 3; see map. Figure 3. Pesticides Monitoring Journal TABLE 4. Pesticide concentrations in surface water from Iowa sites sampled on several occasions — 1974 Residues, ng/liter - Location Sampling Site ' No. Dates Sampled Period Atrazine DDE DlELDRIN Des Moines River Boone Raccoon River Van Meter Red Rock Reservoir •^ 10 mi. upstream from dam Red Rock Reservoir dam site Rathbun Reservoir '*' 10 mi. upstream from dam Rathbun Reservoir dam site 5 7 6 6 7 12 8 5 9 10 5/21-7/25 211(50-800) 68(1-248) 7(2-14) 5/30-7/25 814(120-3300) 59(2-250) 7(1-12) 5/19-7/25 813(60-2500) 131(1-373) 11(3-21) 5/21-9/12 921(100-1900) 212(8-350) 18(5-36) 4/21-6/25 4094(207-9400) 420(5-1121) 9(3-22) 4/23-9/22 1285(165-3750) 92(7-325) 3(2-6) ^ See map. Figure 3. 2 Figures in parentheses represent ranges. periods correspond roughly with those in Tables 1-3 in that the concentrations are highest in the spring and decrease gradually during the growing season. This observation agrees with pesticide runoff concepts (15) and patterns observed for small watersheds (3-6). Table 5 gives the values obtained for single samples collected at various times from rivers representing other major watersheds of the State; sampling was not coinci- dent with rainfall. These random samples demonstrate the extent of pesticide contamination. That the biocide contamination is not a problem unique to areas adjacent to midwestern agricultural land is attested by results of analyses of water from the Mississippi River at New Orleans (Table 5). TABLE 5. Pesticide concciitralions in surface water from Iowa and Louisiana sites sampled on one occasion, 1974 Residue, ng/liter Location Sampi-INg Sampling Atrazine Site > Date DDE DlELDRIN Cedar River 10 Cedar Rapids, Iowa Iowa River 1 1 Iowa City, Iowa Skunk River 12 Oskaloosa, Iowa Mississippi River 13 McGregor. Iowa Gremore Lake 14 McGregor, Iowa Mississippi River 15 Davenport. Iowa Mississippi River New Orleans, La. Missouri River 16 Council Bluffs, Iowa Farm Pond 17 southern Iowa Des Moines River 18 Ottumwa, Iowa 6/24 6/24 7/29 8/12 8/12 7/30 7/30 8/15 7/1 7/29 6,350 50 100 331 80 368 480 42 2 Atrazine detected in 1972 survey at all three locations. - See map, Figure 3. monitoring biocides in raw water and in water which had passed through the carbon filter bed. Raw river water contained 331, < 0.5, and < 0.5 ppt atrazine, DDE, and dieldrin, respectively. Corresponding residues in carbon-filtered water collected the same day were 469, 2, and 1 ppt. This increase in amounts of pesticides after carbon filtration agrees with findings by the U.S. Environmental Protection Agency (EPA) in 1973 (16). After monitoring the Davenport activated carbon bed, EPA officials concluded that occa- sionally the activated carbon treatment may add certain organic chemicals to the water depending upon the history of the activated carbon beds. Experience indi- cates, however, that odor and taste are removed by activated carbon beds long after they have apparently lost the capacity to remove other organic contaminants. Des Moines obtains approximately 40 percent of its raw water directly from the Raccoon River and approxi- mately 60 percent from an infiltration gallery that paral- lels the river for several miles. The amounts of the pesticides in water samples from the Raccoon River, the infiltration gallery, a mixture of the two, and the finished water are given in Table 8. All phases were TABLE 8. Pesticide concentrations in Des Moines, Iowa, water supply, raw and finished — 1974 Date Resid UES. NG/LITER Source ' Atrazine DDE D ELDRIN Raccoon River 7/29 25 6 2 Infiltration Gallery 7/29 82 5 0.5 Prefilter 7/29 47 4 0.5 Finished Water 7/29 29 2 0.4 Finished Water - 8/1 60 2 Finished Water ■' 8/1 71 2 2 ■ Sampling sites 5 and 30; see map. Figure 3. - 60-liter composite sample ■■' 16-liter grab sample sampled the same day and the finished water was sampled again 3 days later. Exact comparisons of fin- ished and raw water are not valid because of uncon- trolled mixing which occurs in a large water plant and its distribution system. However, average values over a period of time for finished and raw water should be a valid indicator of the relative purities. For this reason samnle.s of finished water from Des Moines were taken 122 from June I to July 25, 1974. Average values for atra; zine, DDE, and dieldrin were 515, 21, and 3 pp| respectively. For approximately the same samplini period, average values of the three biocides in raw wata from the Raccoon River were 814, 59, and 7 ppt. Thesi results strongly suggest that current treatment processe do not significantly reduce pesticide contamination. Conclusions The pesticides atrazine, DDE, and dieldrin were founi in most of the water samples tested. Atrazine concera trations were highest of the three pesticides monitored which is not surprising; atrazine is used widely on corn a major product of Iowa, and has relatively high wate solubility, 33 ppm. The substantial concentrations o DDE found provide additional evidence of the grea persistence of DDT and its mstabolites. Water treatment plants are not removing substantia amounts of pesticides from raw water. Even filtratioi through activated carbon beds, as employed by om modern treatment plant in this study, is ineffective. A cknowledgments Atithors wish to acknowledge Ann Konermann, Lewin Naylor, and Larry Wing for their help in collectin) samples, and the water plant supervisors and superin tendents who generously cooperated in the study. Spe« cial thanks are due Harris Seidel of the city of Ames for his cooperation and good offices. LITERATURE CITED (/ ) Bailey. G. W., A. P. Barnett. W. R. Payne, and C. N* Smith. 1974. Herbicide Runoff from Four Coastali Plain Soil Types. EPA Report No. 660/2-74-017. (2) Hall, ]. A'., M. Pawlus, and E. R. Higf;ins. 1972.. Losses of atrazine in runoff water and soil sedimentj J. Environ. Quality 1 (2 ): 172-176. (jf) Hall, J. K. 1974. Erosional losses of s-triazine herbw cide. J. Environ. Quality 3(2 ): 174-180. (4) Ritter. 11'. F., H. P. Johnson, W. G. Lovely, and M.l Molnau. 1967. Atrazine, propachlor and diazinon resi- dues on small agricultural watersheds — runoff losses persistence, and movement. Environ. Sci. Technol.- 8(l):38-42. (5) Trichell, D. W., H. L. Morton, and M. G. Merkel. 1968. Loss of herbicides in runoff water. Weed Sci. 16(4)1447-449. (6) White, A. W., A. P. Barnett, B. G. Wrinht, and 1. H.I Holladay. 1967. Atrazine losses from fallow land caused by runoff and erosion. Environ. Sci. Technol. l(9):740-744. (7) Ritter. W. F. 1967. Environmental Factors Affecting the Movement of Atrazine, Propachlor and Diazinon in Ida Silt Loam. Unpublished Ph.D. thesis, Iowa State University library, Ames, Iowa. (5) Johnson. L. G., and R. L. Morris. 1971. Chlorinated hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J. 4(4):216-219. Pesticides Monitoring Journali (9) Liclilcnbcrv. J. J.. J. W. Eichelhciffer. R. C. Dress- man, anil J. E. Lon,i;hoii(»ii. 1970. Pesticides in surface waters of the United States — a 5-year summary, 1964- 68. Pestic. Monit. J. 4(2):71-86. (10) Ricluinl. J. J., and 1. S. Fritz. 1974. Adsorption of chlorinated pesticides from river water with XAD-2 resin. Talanta 21(l):9l-93. (//) Kclhi;,!,', R. L. 1974. Dieldrin Contamination of Chan- nel Catfish, Invertebrates and Minnows from the Des Moines River. Unpublished M.S. thesis, Iowa State University library, Ames, Iowa. (/2) Junk. G. A.. J. J. Richard. M. D. Gric.scr, D. Witiak. J. L. Witiak. M. D. Artmclh. R. Vick. H. J. Svec, J. S. Fritz, and G. V. Colder. 1974. The use of macro- reticular resins in the analysis of water for trace or- ganic contaminants. J. Chromatogr. 99( 1 ) :745-762. (13) Harvey. G. R. 1972. Adsorption of Chlorinated Hydro- carbons from Seawater by a Crosslinked Polymer. Re- port No. WH()l-72-86. Woods Hole Oceanographic Institution. Woods Hole, Mass. Unpublished manu- script. (14) Atiisly. F. R.. and G. Nieklc.'is. 1974. Use of amberlite XAD-4 for extraction and recovery of chlorinated in- secticides and polychlorinated biphenyls from water. J. Chromatogr. 89(2) : 185-190. (15) Bailey. G. W., R. R. Swank, and H. P. Nicholson. 1974. Predicting pesticide runoff from agricultural land: a conceptual model. J. Environ. Quality 3(2)- 95-102. (16) Carswell. J. A'., R. W. Biielow, and M. Symons. 1973. Removing organic matter from drinking water — moni- toring treatment processes. News of environmental re- search in Cincinnati — water supply research. News Release, U.S. Environmental Protection Agency. 'oL. 9, No. 3, December 197.5 123 RESIDUES IN FISH, WILDLIFE, AND ESTUARIES Mirex Residues in Nontarget Organisms after Application of Experimental Baits for Fire Ant Control, Southwest Georgia — 1971-72 Daniel P. Wojcik,i W. A. Banks,' W. B. Wheeler,^ D. P. Jouvenaz,' C. H. Van Middelem,-^ and C. S. Lofgren i ABSTRACT Mirex, llie only compound approved for control of the red imported fire ant (Solenopsis invicta) and the black im- ported fire ant (Solenopsis richteri). is normally applied at a rate of 1.40 kg/ha. (1.25 Ih/acre). Influenced by recent .studie."; .allowing that low /cif/.v of mirex are toxic to certain nontarf;et or/^ani.'im.^, particularly estuarine spccie.t, authors report liere on a monitorinf; study of mirex in three large treatment areas of southwest Georgia. Four formulations of bait were applied aerially in 1971-72. Low-level residues were observed in small terrestrial vertebrates and inverte- brates and in fresh-water inhabitants. Levels detected were about the .same for all baits. Maximum residues were de- tected 1-3 months after treatment and gradually declined to low levels of 0.02-1 .16 ppm 1 year after treatment. Introduction The chlorinated hydrocarbon insecticide mirex is the only compound approved for control of the red import- ed fire ant, Solenopsis invicta. and the black imported fire ant, S. richteri. The insecticide, formulated at a con- centration of 0.3 percent in a corncob grit/soybean oil bait, is normally applied at a rate of 1.40 kg/ ha. (1.25 lb/acre) . Initially, residues were not considered to be a problem because of the very small quantities of mirex used and its low mammalian toxicity (/). However, recent lab- oratory studies have shown that low levels of mirex are toxic to certain nontarget organisms, particularly estu- arine species {2-4), demonstrating the need for thorough monitoring of mirex residues in nontarget organisms following mirex bait applications. Several studies have been conducted on birds, other large terrestrial verte- 1 Insects Affecting Man Research Laboratory, Agricultural Research Service, U.S. Department of Agriculture, Gainesville. Fla. 32604. - University of Florida, Department of Food Sciences, Pesticide Re- search Laboratory, Gainesville. Fla. ■"' Present address: Division of Chemistry, Florida Department of Agri- culture and Consumer Services. Tallahassee, Fla. 124 brates, and aquatic and estuarine organisms (5-12), buJi very little work has focused on small terrestrial verte-i brates and invertebrates or on fresh-water inhabitants. The present paper reports the results of a monitoring study of mirex in three large treatment areas in south-l west Georgia in 1971-72 following applications of 8 standard bait formulation and of three experimental! formulations. Methods and Procedures SAMPLE AREAS Two experimental test sites were selected within eact of three larger treatment blocks in Tift, Turner, anc< Worth Counties in southwest Georgia. APPLICATION OF MIREX Baits used in this study were formulated by Alliec Chemical Corporation according to the procedures ol Banks et al. {13). Four formulations of bait (Table 1) TABLE 1. Components of mirex bait applied for fire aiif control, Georgia — 1971-72 FORMUIATION Components or Bait, % log weight Mirex SOVBEAN Oil Corncob Grits Late X COATINI A 0.3 14.7 85.0 NA B 0.15 14.85 85.0 NA C 0.15 18,85 71.0 10.0 D 0.10 18.9 71.0 10.0 NOTE; Treatments A and B represent standard proportions of mirex« 0.3 percent and 0.15 percent. Treatments C and D were latefl coated. were applied in a series of three treatments (Table 2) Baits were dispersed from an altitude of 700 feet b) multi-engine commercial aircraft under the supervisior of personnel of the Plant Protection Division, Agricul* Pesticides Monitoring Journad TABLE 2. Application patterns of mirex bait in three Georgia counties, 1971-72 Date County Formulation; Mirex, % Area Treated Bulk Rate i Spring 71 Turner 0.3 25,369 ha. 1.40 kg/ha. (standard) (62,640 acres) (1.25 lb/ acre) 0.!5 12,685 ha. 1.40 kg/ha. (standard) (31,390 acres) (1.25 lb/ acre) Spring 71 Tift 0.15 12,150 ha. 1.12 kg/ha. (latex coated) (30.000 acres) (1.0 lb/acre) O.IO 14,783 ha. 1.12 kg/ ha. (latex coated) (36,500 acres) (1.0 lb/ acre) Fall 71 Worth 0.10 40.500 ha. 1.12 kg/ha. (latex coated) (100.000 acres) (1.0 lb/ acre) 0.3 40.500 ha. 1.40 kg/ha. (standard) (100.000 acres) (1.25 lb/acre) Each of the Worth County test areas contained two collection pon(Js. The pretreatment samples from Tift and Turner County and the 7-day posttreatment samples from Turner County were collected in 70 percent isopropanol as described by Markin et al. (9). However, authors found that isopropanol leached mirex from trapped specimens and thus distorted the values for mirex residues (16); therefore these samples were discarded. Subsequently, TABLE 3. Invertebrates and small vertebrates analyzed for mirex residues, Georgia — 1971-72 Scientific Name Common Name 1 Numbers in parentheses show amount of actual toxicant, i.e.. mirex, applied to each hectare. tural Research Service, U.S. Department of Agriculture (USDA), (now a part of Animal and Plant Health Inspection Service, USDA). All aircraft operated under an electronic guidance system (14) and were equipped with auger-fed dispersal systems mounted within the wings of the aircraft. TREATMENT AND SAMPLING SCHEDULE Dates of bait application and sample collection were as follows: Turner County Pretreatment samples: May 24-28, 1971 Baits applied: May 28 7-day posttreatment samples: May 31-June 4 1-month posttreatment samples: June 21-25 3-month posttreatment samples: August 23-26 Tift County Pretreatment samples: May 17-21, 1971 Baits applied: May 25-June 2 7-day posttreatment samples: June 14-18 1-monlh posttreatment samples: July 6-9 3-month posttreatment samples: September 13-16 Worth County Pretreatment samples: September 28-October 5, 1971 Bails applied: October 5-12 I-month posttreatment samples: November 8-12 6-monlh posttreatment samples: April 10-14, 1972 1-year posttreatment samples: September 1-8 SAMPLE COLLECTION Twenty pitfall traps for the collection of invertebrates and small vertebrates {15) were placed at sites which had been established randomly in each treatment area. Turner, Tift, and Worth Counties contained 5, 4, and 7 such trap sites, respectively. Hand collections were used to supplement pitfall collections whenever possible. Scientific and common names of species selected appear in Table 3. Aquatic vertebrates were collected by hand and by sein- ing from farm ponds located in each test area. The areas in Tift County treated with standard 0.15 percent and 0.3 percent baits contained two and one such ponds, respectively; the areas in Turner County treated with latex-coated 0.15 percent and 0.1 percent baits contained four and five collection ponds, respectively. P ic tone mob ius amhitiosus Neonentobius near mormonius Subfamily Neombinae Gryllus ruhens Gryilus firmus Gryllus fultoni M iogrylhis verlicalis Scapleriscus aclelus Scapterisctis viciniiM Gryllolalpa hexadactyla Ceiilhophiliis spp. Parcoblatla spp. Carihlatta litiea Chorisoneura texensis Jchnoptera deropelliformis Lahidura riparia Euborellia immilipes Prosapia bicincta Ground cricket Ground cricket Immature ground crickets Southern field cricket Sand cricket Southern wood cricket Stripe-headed cricket Southern mole cricket Changa Northern mole cricket Camel crickets Wood cockroaches Small yellow cockroach Small yellow Texas cockroach Dark wood cockroach Riparian earwig Ringk'gged earwig Twolined spittlebug Spiders Lalrodeclus mactans Black widow spider ISOPODS ArmadilUdium yulnare Pillbug Worms (Mixed unidentified earthworms) M4MMAIS Cryptotis parva Least shrew Reptiles Cnemidophoriis sexlinealus Scincella laterale Eiimeces laticeps Coluber constricior priapus Nalris sipedon fasciaia Sixlined racerunner Brown skink Greater fivelined skink Southern black snake Banded water snake Amphibians Rana sphenocephalo Rana calesbeiana Gasirophyryne carolinensis Bujo lerrestris Bufo quercicus Acris gryllus Pseudoacris ornata Leopard frog Bull frog Narrow-mouth toad Southern toad Oak load Cricket frog Ornate chorus frog Gambusia affinis Lepomis macrochirus Lepomis cyanellus Lepomis marginaius Fundulus liueolaius Notemigoniis crysoleucas Microplerus salmoides Mosquito fish Bluegill Green sunfish Dollar sunfish Lined topminnow Golden shiner Largemoulh bass Vol. 9, No. 3, December 1975 125 technical crystals of chlorpyrifos were used in small open glass jars as the killing agent for specimens from pitfall traps. The pitfall traps were checked everyday or every other day during each sampling period. During each collection period the contents of the 20 traps at each site were combined into one glass jar and quick-frozen in the field with dry ice. Aquatic vertebrates were wrapped in aluminum foil and frozen in the same manner. In the laboratory, all samples from a given treatment area and a single collection period were pooled into one com- posite. The pooled samples were separated by species and delivered to the Pesticide Research Laboratory, University of Florida, for analysis. Species were selected to represent a cross-sectional sample of the food web. No pitfall or pond samples were collected within a half-mile of the boundaries of the treatment areas, in order to reduce the chance of contamination by other baits or by movement of ani- mals. The limited widths of the treated areas precluded sampling of birds and larger mammals. Analytical Procedures EXTRACTION Samples dried in air to remove surface moisture, con- densate, were weighed and then blended in at least 4 ml acetone per gram of sample at high speed for 4 minutes. The extract was filtered through a Buchner funnel, rinsed with fresh solvent, and transferred to a Kuderna-Danish concentrator. The acetone was partly evaporated on a steam bath, and /(-hexane was added to the concentrator. The evaporation continued until the volume of hexane was reduced substantially. This procedure essentially removed all the acetone. The hex- ane was then concentrated to a known volume before cleanup. CLEANUP The extract, now in hexane, was cleaned by using florisil column chromatography. Three g of 60/100 mesh PR grade florisil was placed in I -cm-ID glass columns fitted with a fritted glass disk. The florisil was topped with 2-3 cm anhydrous sodium SLilfate and placed in a 150°C oven for at least 3 hours. Then the columns were pre- washed with 50 nil hexane, and the washings were dis- carded. The extract, representing up to 1 g of sample, was placed on the column, and the mirex was eluted with 20 ml hexane. The hexane eluate was concentrated to 1.0 ml before gas chromatographic analysis. QUANTIFICATION The gas chromatograph used for analysis was a Packard model 7610 equipped with an electron-capture detector. The glass column, 6 ft by '4 in., was packed with 2 percent OV-IOI on 100/120 mesh Gas-Chrom Q and had a nitrogen carrier gas flow rate of 100 cc/min. Injection port, column, and detector temperatures were 215°, 190°, and 208°C, respectively. The method can detect 0.01 ppm mirex in a 1.0-g sample. and to fat, I of 0.01-l.oJ Mirex, which had been added to insects brain, liver, and muscle of birds at levels ppm, was recovered at a rate of 90-100 percent. Thei identity of mirex was confirmed occasionally by deter- mining a p-value. Results and Discussion \ Mirex residues were found in 10 of the 28 species represented by the 49 pretreatment samples taken in Worth County. One year after treatment, residues in six of these same species were equal to or lower than those in pretreatment samples. In the other samples residues were relatively low 1 year after treatment; 62 percent had less than 0.05 ppm mirex and 92 percent had less than 0.5 ppm. Residues in the pretreatment samples probably resulted from treatment of fire ant mounds by landowners, since this area had not received any large-scale treatments. As noted, pretreatment sam- ples from the Turner and Tift County test areas were cross-contaminated by isopropanol collection and were discarded. The pooled findings did not lend themselves to statistical analysis, and none was attempted. The majority of the 248 post-treatment samples, 71.77 per- cent, contained mirex residues. As shown in Tables 4-11, maximum levels of mirex i were reached 1 month after treatment, though in a fewt small vertebrates they were noted 3-6 months after r treatment. Among the invertebrates, nymphal ground crickets had the highest residues (Table 4). Two speci- mens of Pictoncmohius anihitiosus had residues of 13.20 ppm and 10.20 ppm 7 days after treatment and another cricket nymph in the subfamily Nemobinae had residues of 12.87 ppm 3 months after treatment. Residues were generally higher in crickets than in the other arthropods; wood cockroaches had the second-highest residues. Most i arthropods analyzed are omnivorous feeders. Crickets i and other arthropods were often found in the old I mounds after the ants had died; they probably had fed on the dead ants or the remnants of the bait still in the mound. The Neonemobius near monnonius (Table 4) and GryUits riihens (Table 5) crickets have at least two ' generations of young each year in southwest Georgia. Thus the specimens of these two species taken 1 year ■ after treatment almost certainly had not yet hatched at 1 the time of treatment, and the Nemobinae cricket 1 nymph (Table 4) taken 3 months after treatment prob- ably hatched after the bait applications. It seems likely that the residues noted in these cases were acquired by crickets inhabiting the old mounds as previously de- scribed. Lahidiini n'ptiria has been found to transfer food by trophallaxis to the nymphs {17). Such transfer could 1 126 Pesticides Monitoring Journal TABLE 4. Mirex residues in crickets of subfamily Nemobinae according to test site, Georgia — 1971-72 County Month of Application, 1971 Mirex Applied. g/ha. Residues, ppm POSTTREATMENT Pretreatment 7 Days Mo 3 Mos 6 Mos Yr PiCTONEMOBIUS AMBITIOSUS (ADULT GROUND CRICKETS) Tift May Tift Mav Turner May- Turner June Worth October Worth October 1.12 1.68 2.10 4.20 1.12 4.20 D D 1.76(1) ND (4) 0.36(1) 0.15 (3) 1.92 (1) 5.40 (1) ND(1) 5.73 (1) 3.40(1) 0,15 (10) 0.91 (2) 2.06 (2) ND (1) PiCTONEMOBIUS AMBITIOSUS (NYMPHAL GROUND CRICKETS) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 13.20 (1) 1.68 10.20 (1) 2.10 1.26 (6) 4.20 6.08 (5) ND(1) 1.12 ND(5) ND(I) 4.20 ND (4) ND (1) ND (3) 0.01 (3) NEONEMOBIUS NEAR MORMONIUS (ADULT GROUND CRICKETS) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 D ND (1) 1.68 D 2.08 (1) 3.11 (1) 0.59 (2) 1.43 (1) 3.90 (2) 2.26(1) 2.10 D D ND (6) ND (4) 4.20 D D 1.12 ND(5) 1.01 (1) 4.20 ND(1) ND (5) 0.63 (2) 0.98 (1) ND (1) Crickets of subfamily Nemboniae (nymphal ground crickets) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 1.68 2.10 4.20 1.12 4.20 D D D D ND (7) ND (45) 1.06(1) ND (1) ND (1) ND (4) 0.84 (29) 12.87 (1) 0.86 (9) 1.81 (4) 1.28 (14) ND (30 1.84 (7) ND(5) ND (3) ND (12) ND (3) NOTE: D = discarded cross-contaminated samples. ND — no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimens in pooled sample. account for the residues of mirex found in samples of earwigs (Table 8) 1 year after treatment. The presence of relatively high residues, 21.50 ppm, in shrews (Table 10) was not surprising, since these mammals are insec- tivores and would be expected to exhibit some biological concentration of mirex. Authors do not know whether the lower levels noted 3 months and 6 months after treatment are an indication of metabolism and excretion or of population turnover. The residues found in terrestrial and semiterrestrial reptiles and amphibians (Table 10) probably resulted from biological concentration following consumption of animals that contained lower residues. The highest levels in these organisms were noted in cricket frogs (Table 10); slightly lower levels were found in narrow-mouth toads. Residues in all these animals 1 year after treat- ment were below 0.5 ppm except in one black snake which had 1.16 ppm mirex. The semiaquatic and aquatic vertebrates (Table 11) generally contained low levels of residues. The highest levels were detected in mosquito fish (Table 11). The only other aquatic animal that contained more than 0.5 ppm mirex was a single specimen of leopard frog which had 1.08 ppm (Table 11)3 months after treat- ment. Residues in all aquatic animals 1 year after treat- ment were 0.09 ppm or less. Mirex residues appeared relatively quickly in all levels of the ecosystem studied. However, maximum levels appeared in the various organisms at different intervals after treatment, depending to a large extent on the niche occupied by the organism in the food chain. The levels of mirex detected in the organisms 1 year after treat- ment were comparable to those found by Baetcke et al. (5) and Collins et al. (7). All specimens analyzed were taken alive or entered pitfall traps alive, and demonstrated no obvious effects Vol. 9, No. 3. December 1975 127 from mirex residues present. Authors observed no mass mortality of nontarget organisms in the tield after treat- ments nor received reports of such mortality. No sub- stantial differences were noted in the population size of any given species when it was tested before treatment and again 1 year after treatment. No appreciable differences were noted in the residues in nontarget organisms as a result of applications of the various bait formulations. Indeed, amounts detected in the organisms from the area that received the latex- coated 0. 1 percent mirex bait were comparable to those detected in organisms from the area that received the standard 0.3 percent mirex bait. This appears to sub- stantiate the observations of Banks et al. (13) that less mirex is bound up in the corncob grits and thus more mirex is available to the ants in the latex-coated baits. Even though residue levels were comparable, it seems logical to assume that the 75 percent reduction in toxi- cant load afforded by the 0.1 percent mirex bait must result in less environmental contamination. Since the 0.1 percent mirex bait provides excellent control of the ants (/i), it should be an environmentally acceptable substitute for the standard mirex formulation. A cknowledgments Authors are indebted to D. M. Hicks, J. K. Plumley, J. W. Summerlin, and K. H. Schroeder for their in- valuable aid in the collection of samples; all are em- ployed by the Insects Affecting Man Research Labora- tory, Agricultural Research Service, USDA, Gainesville, Fla. Gratitude is also expressed to the many landowners who permitted authors to collect samples on their property. LITERATURE CITED (/) Gaines. T. D., and R. D. Kimbrniisb. 1970. Oral tox- icity of mirex in adult and suckling rats. Arch. En- viron. Health 21 :7-14. (2) Lowe. J. I.. P. R. Panish. A. J. Wilson. Jr.. P. D. Wilson, and T. W. Duke. 1971. Effects of mirex on selected estuarine organisms. 36th N. Amer. Wildl. Natur. Resour. Conf. Trans. Pp. 171-186. (.3) Ludke. J. L., M T. Finley. and C. Lii.sk. 1971. Tox- icity of mirex to crayfish, Procamharus blandini;i. Bull. Environ. Contam. Toxicol. 6(l):89-95. (4) Van Valin. C. C, A. K. Austin, and T. L. Eller. 1968. Some effects of mirex on two warm-water fishes. Trans. Am. Fish Soc. 97(2) : 185-196. (5) Baetcke, K. P.. J. D. Cain, and W. E. Poe. 1972. Mirex and DDT residues in wildlife and miscellaneous samples in Mississippi — 1970. Pestic. Monit. J. 6(1): 14-22. (6) Borthwick. P. W.. T. W. Duke. A. J. Wilson. Jr.. J. /. Lowe. J. M. Patrick, Jr., and J. C. Oherheu. 1973. Accumulation and movement of mirex in selected estuaries of South Carolina, 1969-71. Pestic. Monit. J. 7(l):6-26. (7) Collins, H. L., J. R. Davis, and G. P. Markin. 1973. Residues of mirex in channel catfish and other aquatic organisms. Bull. Environ. Contam. Toxicol. 10(2): 73-77. (S) Markin. G. P.. J. H. Ford, and J. C. Hawthorne. 1972. Mirex residues in wild populations of the edible red crawfish (Procuinbarus clarki). Bull. Environ. Con- tam. Toxicol. 8(6):369-374. (9) Markin. G. P., J. H. Ford. J. C. Hawthorne, J. H. Spence, J. Davis, H. L. Collins, and C. D. Loftis. 1972. The insecticide mirex and techniques for its monitoring. USDA, APHIS, 81-83. 19 pp. (10) Naqvi. S. M.. and A. A. de la Cruz. 1973. Mirex in- corporation in the environment: residues in nontarget i organisms— 1972. Pestic. Monit. J. 7(2) : 104-1 1 1. (//) Oherheu, J. C. 1972. The occurrence of mirex in star- lings collected in seven southeastern states — 1970. Pestic. Monit. J. 6(l):41-42. [12) Wolfe. S. L.. and B. R. Norment. 1973. Accumulation ' of mirex residues in selected organisms after an aerial treatment, Mississippi — 1971-72. Pestic. Monit. J. 7(2):112-116. (/.?) Banks. W. A., C. S. Lofgren, D. P. Jouvenaz, D. P. Wojcik. and J. W. Summerlin. 1973. An improved mirex bait formulation for control of imported fire ants. Environ. Entomol. 2(2 ): 1 82-185. Wf) Pagei-Clarke, C. D. 1971. Electronic guidance system used in fire ant eradication programmes. Agri. Aviat. 13(3):89-90. (.15) Wojcik, D. P., W. A. Banks, D. M. Hicks, and J. K. Plumley. 1972. A simple inexpensive pitfall trap for collecting arthropods. Fl. Entomol. 55.(2) : 115-1 16. (16) Carlson, D. A., W. A. Banks, and D. P. Wojcik. 1973. Distortion of mirex residues in insects owing to the use of isopropyl alcohol as a collection solvent. Bull. Environ. Contam. Toxicol. 9(6) :365-369. (17) Shcpard. M.. V. Waddill. and W. Klofl. 1973. Biology of the predaceous earwig Lahidura riparia (Dermap- tera: Labiduridae). Ann. Entomol. Soc. Amer. 66(4): 837-841. 128 Pesticides Monitoring Journal TABLE 5. Mirex residues in crickets of subfamily Gryllinae according to test site, Georgia — 1971-72 County Month of AppI ICATION, 1971 Mirex - Applied. g/ha. Residues, ppm POSITHEATMENT Pretreatment 7 Days 1 Mo 3 Mos 6 Mos 1 Yr GRYLLUS RUBENS (ADULT SOUTHERN FIELD CRICKETS) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 D 1.68 D 2.10 D 4.20 D 1.12 0.02(12) 4.20 ND (8) 0.23 (4) 0.27 (1) O.OI (15) 001 (26) 0.03 (4) ND (17) 0.05 (29) ND (22) ND (39) GRYLLUS FULTONl (ADULT SOUTHERN FIELD CRICKETS) Tift Worth Worth May October October 1.12 1.12 ND (22) 4.20 ND(1) 1 .04 ( 1 ) ND (1) ND (1) Gryllus firmus (adult sand crickets) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 1.68 2.10 D 4.20 D 1.12 ND(15) 4.20 ND (32) ND (3) 0.06 (4) 0.02 (36) 0.18 (16) 0.41 (2) 0.27 (7) 0.05 (2) 0,04 (10) ND (1) 0.03 (21) MiOGRYLLUS VERTICALIS (STRIPE-HEADED CRICKETS) Worth Worth October October 1.12 4.20 ND (2) (adults) ND (8) (nymphs) ND (6) (nymphs) NOTE : D = discarded cross-contaminated samples. ND = no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimens in pooled sample. TABLE 6. Mirex residues in mole crickets according to lest site, Georgia — 1971-72 County .Month of Application. 1971 MiREX - Applied, g/ha. Residues, ppm Posttreatment Prefreatment 7 Days 1 Mo 3 Mos 6 Mos 1 Yr Scapteriscus acletus (adult and nymphal southern mole crickets) Tift Turner Turner Worth Worth May May- June October October 1.68 D 0.18 (4) 2.10 D D 0.53 (19) 0,04 (6) 4.20 D D 0.08 (4) 1.12 0.10 (13) 0.91 (2) 0.23 (2) 4.20 ND (32) ND (3) 0.14 (9) 0.09 (8) Scapteriscus vicinus (adult and nymphal changas) Tift Turner Turner Worth May May- June October 1.68 2.10 4.20 4.20 D D ND ID 0.05 ( 1 ) 0.58 (1) 1.15 (2) 0.14 (1) 0.34 (2) ND(3) 0.06 (9) ND (2) Gryllotalpa hexadactyla (adult northern mole crickets) Worth Worth October October 1.12 4.20 0.10 (6) ND (1) 0.13 (3) ND (1) NOTE: D — discarded cross-contaminated samples. ND = no residues detected at 0.01 ppm level. Figures in parentheses represent number of snecimens in pooled sample. Vol. 9, No. 3, December 1975 129 TABLE 7. Mircx residues in cockroaches according: to lest site, Georgia — 1971-72 Month of Application, 1971 Residues, PPM Applied. Posttreatment County g/ha. Pretreatment 7 Days 1 Mo 3 Mos 6 Mos 1 Yr Parcoblatta spp. (adult and nymphal wood cockroaches) Tift Tift Turner Worth Worth May May May-June October October 1.12 D 3.98(1) 0.78(8) 1.68 D 1.50(2) 3.74(7) 6.18 (2) 4.20 D 1.12 ND(3) 4,39(2) 4.20 ND (3) ND(1) 0.12(2) 1.41 (2) 0.19(6) 0.22 (1) 0.60(5) ND (2) ND (2) Cariblatta lutea (adult small yellow cockroaches) Tift Worth May October 1.12 D ND(1) 4.20 ND(3) Chorisoneura texensis (adult small yellow TEXAS cockroaches) Tift May 1.68 ND(1) Ichnoptera deropeltiformis (4DULT dark wood cockroaches) Worth October 4.20 0.18 (1) NOTE: D = discarded cross-contaminated samples. ND = no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimens in pooled sample. TABLE 8. Mirex residues in earwigs according to test site, Georgia — 1971-72 Residues, ppm Month of Application, 1971 Applied, g/ha. Pretreatment Posttreatment County 7 Days 1 Mo 3 Mos 6 Mos 1 Yr Labidura riparia (adult and nymphal riparian EARWIGS) Tift May 1.12 0.19 (29) Tift May 1.68 O.ll (4) Turner May- 2.10 D ND (1) 0.23 (8) Turner June 4.20 D 0.63 (3) 0.08 (11) Worth October 1,12 0.02 (48) ND(1) 0.03 (33) Worth October 4,20 ND (214) ND (4) 0.85 (4) 0.04 (168) EUBORELLIA ANNULIPES (ADULT AND NYMPHAL RINCl BOOED EARWIGS) Tift May 1.12 D 0.43 (15) 0.14 (7) Tift May 1.68 D 2.25(1) 0 06 (49) Turner May- 2.10 D D ND (27) Turner June 4.20 D D ND (1) 0.37(2) 0.61 (4) Worth October 1.12 0.06 (93) 0.13 (12) ND (18) Worth October 4.20 ND (11) 0.51 (3) ND (3) 0.04 (27) D = discarded cross-contaminated samples. ND — no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimens in pooled sample. 130 Pesticides Monitoring Journal TABLE 9. Mirex residues in miscelhineoiis invcrlebralcs according to lest site, Georgia — 197 1-72 Month of Application, 1971 Mirex Applied, c/ha. Pretreatment Residues, ppm PO.SITRE\TMENT 7 Days CeUTHOPHILUS SPP. (NYMPHAL camel CRICKETS) 6 Mos 1 Yr May May- June October October 1.68 D 1.75 (1) 3.60(1) 2.10 D D 0.40 ( 1 ) 4.20 D D 0.66(1) 2.88 (2) 1.12 ND (17) 4.20 ND (3) 0.12 (21) 0.01 (7) ND (3) ND (2) PROSAPIA BICINCTA (ADULT TWO-LINED SPITTLE BUGS) May May-June October October 1.12 4.20 1.12 ND (8) 4.20 ND (25) ND (22) ND (7) 3.23 (1) ND(1) 0.58 (1) Armadillidium vulgare (adult and immature pillbugs) May May May-June October 1.12 D 1.68 D 2.10 1.12 ND 0.04 (16) 0.03 (10) ND (1) 0.01 (10) 0.02 (5) ND (1) Earthworms May May May- June October October 1.12 0.02(10) 0.49 (20) 0.04 (25) 1.68 ND (26) 0.03 (10) 2.10 D 0.10 (20) 4.20 D 0.49 (10) 1.12 ND (50) ND(1) 0.02 (10) ND (18) 4.20 ND(1) ND(1) 0.03 (10) Latrodectus mactans (black widow spider) October 1.12 0.28 (3) NOTE: D = discarded cross-contaminated samples. ND = no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimetis in pooled sample. 9, No. 3, December 1975 131 TABLE 10. Mircx residues in terrestrial and semilerrestrial vertebrates accordinf> to test site, Georgia — 1971-72 Tift Tift Worth Worth May May October October Month of Application, 1971 MlPFX Residues, ppm Applied. Posttreatment COUN 1 Y g/ha. Pretreatment 7 Days 1 Mo 3 Mos 6Mos 1 Yr CR'tPTOTIS PARVA (LEAST SHREWS) 1.12 1.68 D 1.12 ND (1) 4.20 ND (2) 21.50 (1) 5.16(1) 1.15 (1) 0.78 (1) CNEMIDOPHORUS SEXLINEATUS (6-LINED RACERUNNERS ) Turner Turner Worth Worth May- June October October 2.10 D D 4.20 D 1.12 ND (1) 4.20 ND(1) 0.63 (I) 0.93 ( 1 ) 0.07 (1) 0.40 (I) SCINCELLA LATERALE (BROWN SKINKS) Tift Worth Worth Turner Turner Worth Worth May October October May-June May-June October October 1.12 D 1.12 ND (2) 4.20 ND(3) 0.34 (1) 2.10 D 4.20 D 1.12 ND(3) 4.20 0.94 (5) 0.10 (1) 0.24 (5) 0.39 (1) 0.22 (4) 0.66 (1) 0.02 (2) ND (1) ND(1) EUMECES LATICEPS (GREATER 5-LlNED SKINK) Worth October 1.12 ND(1) Coluber constrictor (black snake) Worth October 1.12 1.16(1) Natris sipedon fasciata (banded water snake) Turner May-June 4.20 D 0.04 { 1 ) BuFo terrestris (southern toads) Gastrophyryne carolinensis (narrow-mouth toads) Tift Tift Turner Turner Worth Worth May May May- June October October 1.12 D 1.68 D 2.10 D 4.20 1.12 ND (16) 4.20 0.12(5) 0.47 (2) 3.46 (3) 2.02 (9) 0.41 (14) 0.33 (1) 1.06(2) NOTE: D — discarded cross-contaminated samples. ND = no residues detected at 0.01 ppm level. Figures in parentheses represent number of specimens in pooled sample. 0.17 (4) 0.04 (1) PSEUDOACRIS ORNATA (ORNATE CHORUS FROG) Worth October 1.12 0.10 (1) AcRis gryli us (cricket frogs) Worth Worth October October 1.12 9.27 (2) 4.20 3.01 (9) 0.14 (3) BUPO QUERCICUS (OAK TOADS) Worth Worth October October 1.12 4.70 ND (5) 0.08 (2) 132 Pesticides Monitoring Journal TABLE 1 1. Mirex residues in semiaquatic and aquatic vertebrates according to test site, Georgia — 197 1-72 May May- June October October Month of Application, 1971 Residles, PPM Applied. Posttreatment County g/ha. Pretreatment 7 Days 1 Mo 3 Mos 6 Mos I Yr Rana sphenocephala (Leopard frogs) 1.68 2.10 4.20 1.12 4.20 ND (1) 0.08 (I) 1.08 (I) 0.24 ( 1 ) 0.56 (1) 0.34 (1) Rana catesbeiana (bullfrogs) May May May-June October October 1.12 1.68 2.10 1.12 4.20 D ND (4) 0.05 ( 1 ) 0.43 (1) 0.08 (12) 0.25 (3) 0.15 (4) 0.03 (6) 0.09 (1) GAMBUSIA AFFINIS (MOSQUITO FISH) May May May- Jitne October October 1.12 1.68 2.10 4.20 1.12 4.20 D D D D ND (25) 0.15 (15) ND (10) 0.06(25) 0.02 (20) 0.08 (25) 0.08 (20) 0.25 (3) 2.25 (10) O.n (18) ND (150) 0.24 (24) 2.93 (125) ND (1) 1.75(105) ND (6) 0.03 (30) LEPOMIS MACROCHIRtIS (BLUEGILLS) Tift Tift Turner Worth Worth May May May-June October October 1.68 D 2.10 D 1.12 4.20 0.03 ND (69) 0.23 (10) ND (5) ND (12) ND (14) 0.02 (16) 0.05 (4) ND (1) 0.03 (2) 0.03 (5) Fundulus lineolatus (lined topminnows) Tift Tift Turner Turner Worth May May May- June October 1.12 1.68 2.10 4.20 4.20 D 0.03 (2) 0.05 (9) 0.21 (5) 0.17 (10) 0.03 (2) 0.04 (10) Lepomis cyanellus (green sunfish) Tift Worth May October 1.12 4.20 0.05 ( I ) 0.05 (I) Lepomis MARGINATL'S (DOLLAR SUNFISH) Turner May-June 4.20 0.15 (6) NOTEMIGONUS CRYSOLEUCAS (GOLDEN SHINERS) Worth Worlh October October 1.12 4.20 ND (7) ND (1) 0.09 (11) ND (8) 0.02 (21) MiCROPTERUS SALMOIDES Worth October 4.20 ND (5) NOTE: D — discarded cross-contaminated sample. ND = no residues detected at O.OI ppm level. Figures in parentheses represent number of specimens in pooled sample. Vol. 9, No. 3, December 1975 133 GENERAL Chlorinated Hydrocarbon Residues in Fish, Crabs, and Shellfish of the Lower Fraser River, Its Estuary, and Selected Locations in Georgia Strait, British Columbia — 1972-73 L. J. Albright,' T. G. Northcote," P. C. Oloffs,' and S. Y. Szeto ' ABSTRACT Between Aiitiii^t 1972 ami September 1973. fi'.h. crabs, and shellfish were collected from the lower Fraser River, its estuary, and selected areas of Georf,'ia Strait in British Co- lumbia. Samples were analyzed for aldrin, dieldrin, a- and y-chlordane, p,p' -DDT, p.p'-DPE, p.p'-DDD, heplachlor. heptachlor epoxide, lindane, and polychlorinated biphenyls (PCBsi. Of these, p.p'-DDT. p.p'-DDE. p.p'-DDD. hepta- chlor epoxide, and one PCB. Aroclor 1254, were detected in samples of many fish, crabs, and shellfish from the lower Fraser River and its estuary. Generally, compounds found in decreasini; order of ma;jililude in samples from the Fraser River and its estuary were: PCB's, p.p'-DDE, heptachlor epoxide, p.p'-DDT, and p.p'-DDD. Greatest concentrations of these compounds occurred in biota from the waters adja- cent to the City of I'aiieouver. With one exception, animals from Georf;ia Strait and those away from the immediate influence of Fraser River water contained no detectable levels of chlorinated hydrocarbons. Inlroduclion Numerous investigators have found chlorinated hydro- carbon insecticides and their metabolites as well as poly- chlorinated biphenyls (PCB"s) in a variety of aquatic organisms including freshwater and marine fish (1.2), birds (.3.4), plankton {4.5}, mammals (4,6), and various invertebrates (7, 8). Some of these studies have shown that biological matter concentrates chlorinated hydrocarbon residues from the aquatic milieu and mag- nifies them through the various trophic levels (4-6). The presence and persistence of chlorinated hydrocar- bons in various river systems, including their watersheds and estuaries, of the United States (1.2.7), and to a lesser extent Europe {9.10). have also been dcmon- ^ Depanment of Biological Sciences. Simon Fraser University, Burna- by. British Colunihia, Canada V'5A IS6. - Westwattr Research Centre. University of British Coiumbia, Van- couver. British Ci>himbia. Canada. 134 strated. However, except for several studies of Ontario Rivers (//, 12), such data are generally lacking for many of the watersheds, rivers, and estuaries of Canada, particularly rivers which drain relatively uninhabited I areas. Such a river system is the Fraser, which originates i in the Rocky Mountains and flows for much of its length through forested or range land. However, this • river passes through areas of intense agricultural and industrial use as well as human habitation immediately before terminating in Georgia Strait (Fig. 1). This estuary is adjacent to greater Vancouver, a metropolitan area of approximately one million inhabitants, and re- ceives most of that city's domestic and industrial effluents. Thus, by studying this river system, one may determine I chlorinated hydrocarbon residue levels in water, sedi- ment, and biota in areas adjacent to low habitation, in- J tensive agricultural production, and an urban popula- ' tion. Such data are essential for evaluating the signifi- cance of chlorinated hydrocarbons to the aquatic flora and fauna and are relevant in determining the suitability of this water for various uses. Methods and Materials Fish were taken from the Fraser River with gill nets and seines and from Georgia Strait with bottom trawls. Most river fish were captured in gill nets set during the day near the river margin at each station (Fig. 1), although some were taken in seine hauls made near the same location. Within a few hours of capture, all fish were frozen. After a specimen selected for analysis was thawed, measured, and weighed, its dorsolateral surface was scraped clean to remove any debris or slime. Then an area of epaxial white muscle tissue was exposed with a new scalpel which was cleaned with acetone. A block Pesticides Monitoring Journal - 50° 1 _/ / 1 \ V \ — V 1 1 \ V \jll. , BRITISH "(vl){ , COLUMBIA ■ C\\ ^ C-:-:>^ \ ALBERTA \Vv' 'irp::.-- \ / \ \ N^ J\ ^'^^^K. ^ ^ i;:ft:l^:::::r. ■'y \ \ \ F\ PACIFIC Arv^^^'^'^S^H'^-- \ k OCEAN ^^o^X ^i::):l' --'^ rf N 1 V \ ^ V:^T"" "^' ^-•^ ' \ / .^ \ l-L ^\ V > m '! ' .i \ i f" ^^ V. /J ^ m -^ ! ^ I'V § K \ ^ ^^"' ''"^ J^ ; V J y¥ , J^M, "-X. ^ /f^^''^ ' -"■'-T^ r '^^ - / A // m> jf ^ Hu ^'-- ) %^-_ —' ^^ s ^:==L/ a ^^ y^-'-U^ { f2 "^/ 1^ %=^ ^<^^^ 13 / 1 •,tj3 "Y^ i' ^^§*r^^*==n~ / / w-^-^ 10 \ ^H r r-' v-~N. 1 /** ^ \ I 49°- - t\? - - ^^ JL. . .-490 k --- / ■'^_ — - \ S 0 MILES 10 ^\ -'' 11.^ N 1 "~ — -* V. y 123° -\ tz \____ ' 121° ^ ° kI. 20 'v./ '2,2" FIGURE 1. Fraser River with sampling stations of approximately 25 g tissue was removed, placed in an externally labeled glass jar, and refrozen. Other animals, including shellfish and crabs, were obtained by scuba divers. Tissue samples were placed into glass jars and frozen. In some cases, entire animals were frozen for future analysis (Table 1). All glass contain- ers were cleaned with redistilled hexane and acetone, then heated to 135°C for 12 hours prior to use. Tissues were extracted with 50 ml of a 1:1 v/v hexane: acetone mixture for every 25 g sample tissue in a Lourdes homogenizer for 30 minutes. After 15 minutes, 25 g anhydrous Na^.SO, was added. Each extract was then filtered through glass wool into a 250-ml separa- tory funnel and washed twice with 50 ml of an aqueous solution of 2 percent Na.SO,. Aliquots of each extract equivalent to 1 g tissue were then cleaned by a combination of sweep codistillation and column chromatography as described in detail for human adipose tissue extracts by Oloffs et al. {13). Finally, PCB's were separated from the other organo- chlorines according to the method of Armour and Burke (14). The clean extracts were picked up with 2 ml hexane for every 1 g tissue extracted. Gas-liquid chromato- graphic (GLC) analyses were performed with a Tracor MT 220 and a Tracor 550 equipped with two and one "'Ni electron-capture detectors, respectively. A 183-cm- by-0.64-cm column packed with 2 percent OV-1 and 6 percent OV-210 in 80/100 mesh chromosorb W HP was used. Nitrogen, the carrier gas, had a flow rate of 80 ml/min. The temperatures of the injector, column oven, and detector were 220°, 190°, and 300°C, re- spectively. Standard curves were prepared daily before and after sample analyses with reference-grade chemicals in hex- ane. Residues wjrc quantified to the following concen- trations: heptachlor epoxide. 2 ppb; dieldrin, DDD, and DDE, 4 ppb; and DDT, 10 ppb. Aroclor 1254, the only PCB found in these samples, was quantified to 20 ppb standard Aroclor 1254 on the basis of four selected peaks as described and critically discussed by Iwata et al. (15). If an injection of 8 fi\ of the 2 ml hexane : 1 g tissue extract gave a response for one of the compounds which Vol. 9, No. 3, December 1975 135 TABLE 1. Chlorinntcd hycirocarhon concenliations in muscle lissue of fish, Fraser River, British Cohtmbia — 1972-73 6 Z 1 SPECtES ' Fork Length, m m Heptachlor Epoxide DDE PCB's r. < -; Mean Range Mean Range, N = N' N« Mean, Range, N- N' N' Mean, Range, N = N3 N< o crt PPB PPB PPB PPB PPB PPB _z 14 SQUAW 337.5 262-440 ND 0 0 17 56.2 T - 164.3 16 1 0 32.7 ND- 234.7 5 5 7 14 LSS ■■ 389.1 346-453 4.1 ND- 26.5 5 0 11 10.7 ND- 55.3 8 1 7 138.0 ND- 589.7 9 0 7 14 RT 279.0 256-302 ND 0 0 5.9 ND- 11.7 1 0 1 37.2 T - 72.4 I 1 0 14 CTT 308 ND 0 0 ND 0 0 1 T 0 1 0 14 MW 275.3 245-297 ND 0 0 56.3 7.0-100.3 4 0 0 ND 0 0 4 14 CHUB 255.5 254-257 ND 0 0 106.0 57.5- 154.4 2 0 0 ND 0 0 2 14 ST 434.0 363-475 ND 0 0 37.6 31.9- 40.0 4 0 0 41.7 ND- 164.7 1 1 2 13 SQUAW 301.0 264-359 1.7 ND-5.0 1 0 9.9 T - 17.6 2 1 0 204.2 ND- 526.7 2 0 1 13 LSS 335 ND 0 0 9.6 1 0 0 349,8 1 0 0 13 BBH 246 ND 0 0 3.5 1 0 0 235.3 I 0 0 13 CARP 492 ND 0 0 53.5 1 0 0 ND 0 0 1 13 RT' 316.5 245-394 ND 0 0 20.3 ND- 48.8 6 0 2 58.9 ND- 229.2 3 4 1 13 CHUB 260.3 242-277 ND 0 0 44.4 26.7- 62.8 3 0 0 ND 0 0 3 12 SQUAW 286.3 261-355 ND 0 0 48.2 ND-144.7 5 0 1 0,3 ND-T 0 1 5 12 LSS 320 ND 0 0 ND 0 0 1 ND 0 0 1 12 MW 258.5 252-265 ND 0 0 28.9 27.5- 30.3 2 ft 0 ND 0 0 2 12 CHUB 258 ND 0 0 49.6 1 0 0 ND 0 0 1 12 ST 400.7 356-464 ND 0 0 18.1 15.0- 22.9 3 0 0 13 ND-T 0 2 1 11 LSS 330 ND 0 0 ND 0 0 1 ND 0 0 1 11 SQUAW 325.0 286-364 ND 0 0 37.2 4.9- 59.4 2 0 0 ND 0 0 2 11 RT 356.5 276-442 ND 0 0 32.1 6.9- 59.5 4 0 0 0,5 ND-T 0 1 3 11 CTT 311 ND 0 0 14.4 1 0 0 ND 0 0 1 11 MW 253 ND 0 0 20.3 1 0 0 ND 0 0 1 11 CHUB 257.5 249-266 ND 0 0 32.1 22.1- 42.1 2 0 0 ND 0 0 2 10 SQUAW 320.5 313-328 ND 0 0 36.4 11.5- 61.3 2 0 0 83,8 ND- 167.5 1 0 1 10 RT" 293.3 253-418 2.3 ND-10.7 3 0 7.3 ND- 29.4 8 2 2 61.7 ND- 106.2 9 0 3 10 ST 438 ND 0 0 ND 0 0 1 ND 0 0 1 10 LSS 317.5 275-360 4.6 ND- 9.1 1 0 7.5 ND- 14.9 1 0 1 147 ND- 294.0 1 0 1 10 DV 337 ND 0 0 19.5 0 0 1 164.3 1 0 0 9 RT 283.3 275-288 ND 0 0 8.9 ND- 14.5 2 0 1 ND 0 0 3 9 LSS 368 ND 0 0 ND 0 0 1 3694.9 I 0 0 9 CHUB 263 ND 0 0 37.3 1 0 0 ND 0 0 1 8 MW 192 ND 0 0 T 0 1 0 ND 0 0 1 8 ST 355 ND 0 0 21.8 1 0 0 ND 0 0 1 8 LSS 364 ND 0 0 ND 0 0 I 623.4 1 0 0 8 SQUAW 288 ND 0 0 329.3 1 0 0 ND 0 0 1 8 CHUB 233 ND 0 0 34.7 1 0 0 ND 0 0 1 7 ST 455 ND 0 0 10.6 1 0 0 ND 0 0 1 7 CHUB 247 ND 0 0 33.4 1 0 0 ND 0 0 1 7 RT» 344.4 273-400 12.4 ND-44.9 3 0 34.9 ND- 50.1 4 0 1 143.2 58.2- 192.8 5 0 0 7 CTT "■ 423.7 319-565 4.7 Nn-13.7 2 0 19.8 ND- 43.5 3 0 1 128.2 77.1- 208.5 4 0 0 fi LSS 308.7 302-314 ND 0 0 ND 0 0 3 171.2 ND- 259,4 -> 0 1 6 SQUAW - 279.8 IS3-340 ND 0 0 85.0 8.8- 151.7 5 0 0 748.4 204,1-1894,4 5 0 0 6 ST 413.0 390-436 ND 0 0 11.8 ND 23.5 1 0 1 143.4 ND- 286,7 I 0 1 5 LSS 417.8 374-453 ND 0 0 7.2 T - 16.9 3 1 0 90.6 T - 198.7 2 1 1 5 DV 422 ND 0 0 17.5 1 0 0 ND 0 0 1 5 ST 438.5 419-458 4.2 ND- 8,3 1 0 22.9 3.4- 42.3 2 0 0 167.4 136.9- 197.8 2 0 0 5 RT" 282.5 282-283 3 3 ND- 6,5 1 0 7.4 6.8- 8.0 2 0 0 128 9 64.8- 192.9 2 0 0 5 SQUAW '= 351 5 344-359 4.3 ND- 8.6 1 0 238.3 39.5-437.1 2 0 0 1039,8 426.7-1652.9 2 0 0 5 CARP" 557 ND 0 0 1739.6 1 0 0 933,9 1 0 0 4 RT 283 ND 0 0 20.0 1 0 0 1388 1 0 0 4 SQUAW 217.8 153-367 ND 0 0 36.4 3.8- 99.9 4 0 0 121.8 ND- 483.2 1 2 1 3 SOCK- EYE 595.8 561-633 ND 0 0 ND 0 0 5 ND 0 0 5 3 CTT" 362.5 344-381 4.5 ND- 9.0 1 0 253 21,1- 29,4 2 0 0 118.6 101.7- 135.4 2 0 0 3 CHUB 225.3 211-253 ND 0 0 43.4 T - 69.9 ■» 1 0 90.8 ND- 272.4 1 0 2 3 CHI- NOOK 394.5 389-400 2 2 ND- 4.3 1 0 12.3 9.0- 15.5 2 0 0 86.8 83.5- 90.1 2 0 0 2 3 SQUAW 359.5 325-394 47.0 7. 4-86. 6 2 0 73.3 51.4- 95.2 2 0 0 755.4 607.6- 903.2 n 0 0 2 3 LSS 331.7 302-370 ND 0 0 12.2 ND- 36.5 1 0 2 153.9 ND- 250.6 2 0 1 3 3 ST'" 510,9 391-635 3.9 ND- 7.1 3 0 149 ND- 47.4 7 0 2 165,4 ND- 317.7 1 0 2 9 2 RT 303.0 267-345 4,2 ND- 12.6 1 0 34.5 T - 54.9 2 1 0 116,5 T - 314.1 2 1 0 3 1 CHUB 237 ND 0 0 85.9 1 0 0 527,3 I 0 0 1 NOTE: ND = not detectable; T = trace. ^ SQUAW = northern squawfish; LSS = large scale sucker; RT = rainbow trout; CTT = cutthroat trout; MW = mountain whitefish: CHUB peamouth chub; ST = sturgeon; BBH = bullhead; DV = dolly varden. ^ No. samples with concentrations >4 ppb (> 20 ppb for Aroclor 1254). ■■' No, samples with a trace of residue. * No. samnlcs with no detectable residue. ^ Similar to Aroclor 1254. '■■ One sample had a trace of DDT, four had a trace of DDD, and one had a trace of dieldrin. " One sample had a trace of DDT. ■^ Three samples had a trace of DDT; five had a trace of DDD. " Two samples had a trace of DDT, two had a trace of DDD, and one had traces of DDT and DDD. '"Three samples had a trace of DDT, three had a trace of DDD, and two had a trace of dieldrin. '1 One sample had a trace of DDD. '-Two samples had a trace of DDT; one sample had a trace of DDD. '" One sample had traces of DDT and DDD. " Three .samples had a trace of DDT, three had a trace of DDD, and one had 9.7 ppb dieldrin. 136 Pesticides Monitoring Journal was below the lowest amount of standard injected, ap- proximately 5 percent chart deflection, it was designated a trace amount. If no response was observed, it was considered to be not detectable. For quantification of compounds with higher concentrations, hexane extracts were appropriately diluted to yield responses within the range of the injected standards. Samples containing sufficiently high concentrations of DDE and Aroclor 1254 were checked by mass spec- trometry. These spectra resembled those of the corres- ponding reference-grade compounds. The instrument was a Varian gas chromatograph series 1400 with an attached Hitachi Pcrkin-Elmer RMV-6E spectrometer. The column and packing remained the same for this study. A 183-cm-by-0.64-cm column packed with 2 percent OV-1 and 6 percent OV-210 was employed for confirmation. Recoveries and the efficiency of separating Aroclor 1254 from the other compounds were checked periodically with tissue samples spiked with standards at concentra- tions near the lower limits of quantification. Average percentages of recovery were Aroclor 1254, 85.2; DDD, 89.2; dieldrin, 91.3; DDT, 91.4; DDE, 92.8; heptachlor epoxide, 93.9; aldrin, 94.3; lindane, 97.5; and hepta- chlor, 99.0. Recovery studies were occasionally done so that the person analyzing the samples did not know they were spiked. Results and Discussion Eichelberger and Lichtenberg (16) have shown that of 28 common pesticides including 12 organochlorines, 9 organophosphates, and 7 carbamates placed in raw river water for up to 8 weeks, all were degraded except chlorinated hydrocarbons BHC, heptachlor epoxide, dieldrin, p.p'-DDT, p.p'-DDE, p.p'-DDD, and endrin, as well as the organophosphate monocrotophos. In ad- dition to their greater resistance to degradation, these compounds also tend to accumulate in both plant and animal biota (5). Data in Tables 1 and 2 indicate this as well. Although chlorinated hydrocarbons were not detected in waters or sediments of the lower Eraser River, its estuary, or Georgia Strait (17-19), dieldrin, p.p'-DDT. p,p'-DDD, p,p'-DDE, heptachlor epoxide, and PCB's were found in many fish and benthic animal samples of the Eraser River and its estuary (Tables 1,2). Howevc, except for a very low mean level of p.p'-DDE in three of seven Cancer magisler samples from station C (mean of 2.1 ppb), no chlorinated hydrocarbons were found in fish and crab samples from Georgia Strait and in an area away from the immediate influence of Eraser River water (Eig. 2, stations A, B, and C). Table 3 lists the fish and crabs analyzed. Chlordane, lindane, endrin, and aldrin were not detected in any of these samples. GEORGIA STRAIT FIGURE 2. Georgia Strait with sampling stations Analysis of the data in Table 1 indicates that several chlorinated hydrocarbons were present to a greater ex- tent than others in fish. Compounds in Eraser River estuary fish were found in the following order of de- creasing concentrations: PCB's, p.p -DDE, heptachlor epoxide, p,p'-DDD, and p,p'-DDT (stations 1-7, Fig. 1, Table 1). Analysis of the relative concentrations of chlorinated hydrocarbons in other fauna of this estuary indicates a similar pattern (Fig. 3, Table 2). The order of decreasing concentrations of compounds in fish from the upper reaches (stations 13, 14, Fig. 1, Table 1) was PCB's, p.p'-DDE, heptachlor epoxide, p,p'-DDD, p.p'-DHJ, and dieldrin. A similar pattern was noted for fish from the middle reaches (stations 8-12, Eig. 1, Table 1). Clearly, PCB's and /j.p'-DDE are the chlorinated hydro- carbons of major importance in the biota sampled with- in this aquatic system. Further analysis of the data in Table 1 indicates that the average PCB and p.p'-DDT residues in fish species from the estuary (stations 1-7) were significantly greater than those from the upper portion (stations 13, 14) of the Eraser River. These patterns of concentrations may reflect the uses of land adjacent to the river at each station. Most of the upper and middle reaches are adjacent to agricultural regions whereas the estuary is next to the urban and industrial region of greater Vancouver as well as agricultural land. Hence the relatively greater concentrations of chlori- VoL. 9, No. 3, December 1975 137 ■S S ^ Z (rt o OQ z U ,, a. z O 0. Z 3 ^ 5 O ri S UJ 5 hJ LU oa - < J H w 1°- ^ EQ Z o. X O — ' ^ i/^ '-" o o o o o o o o o Q D C Q z z z z "ON NOIIVIS o o a z z z ^ r^ Ml ■— o o o o o o o o o o o o a 0 a o o o z z z z z z o — ^ o ^ -- o o o -" o ^ o — o o o in w-i o Q Q 2 2 Z H Z rn o H — ^ tn m o o o o o o O O O (N r-1 O O Q z z Q Q C z z z u O S S u u o u u o S S o: a J o o u S o u o II o u u II II u S J J O O on i« o . II (=^ wT t« 3 f y i/i J QH QD 99 Q, ii . ^ ^ f^ ^ ^ W-. Tt ■a i> 3 5 £ £ £ o o J .— .t; - - u o : ? s s 2 e (« < < D O O ij 6 d UZZ « rt jj « lT O C U ID ■ E C - C C « ^ « cd L_ fc x: O pj -* . £ — ii ggE d I E z « « uj I02 - -O O a; c o * c »5(0(- O 138 Pesticides Monitoring Journa FIGURE 3. Fraser River estuary with scimpliiii; slutioiis nated hydrocarbons in estuarine fish may reflect in- creased residue levels in estuarine water compared to water from the upper reaches of the Fraser River. Chlorinated hydrocarbons are believed to enter water bodies, including rivers, via rainfall, surface runoff, aerial sprays, ground water, direct application for insect control, and domestic and industrial effluents. However, the most probable pathways by which PCB's enter the Fraser River and its estuary are by surface runoff and domestic and industrial effluents from the Vancouver region. The storm and sewage lines of the city of Van- couver combine and terminate in an outfall near station L (Fig. 3). PCB residues in fauna were highest in animals from this estuary; their concentration appears to be proportional to the distance of the sampled benthic animals from the outfall. Exemplary are levels of C inagister at stations O, Q, S, and R, and CaUinanassa TABLE 3. Fish and crahs sampled from Georgia Strait ami areas away from the immediate influence of Fraser River water, British Columbia — 1972-73 Fork Length OR No. Individuals Species Station Shell Width. CM Analyzed Red snapper A 36 Sole A 24 Ralfisti A 37 Tomcod A 36 Skate A 62 Rock fish A 37.5 2 Coho salmon B 46 3 Ratfisti C 30.6 5 Rockfish c 23.5 2 Cancer niagi.ster c n.2 7 califoiniensis at stations L and M (Table 2). It is thus possible that one major route through which PCB's, and possibly other chlorinated hydrocarbons, enter this water and are taken up by fish and other biota, is the lona Island sewage outfall adjacent to station L. The two species of salmon adults sampled from the Fraser River estuary contained either low chlorinated hydrocarbon levels (chinook salmon) or none at all (sockeye salmon. Table 1). Because chinook are only in the river as juvenile migrants and are only tempo- rarily near the estuary and sockeye are present only as juvenile migrants before they return as adults, the general low levels in these species seem reasonable. Henderson et al. (/) have shown that of 147 fish removed from 50 sampling locations on various rivers across the United States, all contained p.p'-DDT and its metabolite p.p'-DDE. Dieldrin was present in 137 of these 147 samples whereas BHC was reported in fish from 15 stations only. Heptachlor epoxide residues were present in six samples at three stations whereas chlordane was present in samples from six stations. A calculation of mean p.p'-DDE, p,p'-DDT, and PCB concentrations in fish from levels reported by these authors revealed values of 692.9, 289.6, and 1,254.8 ppb, respectively. Mean values of p.p'-DDE, p.p'-DDT, and PCB's reported in this investigation of Fraser River fish were very much lower at 40.5, 0.3, and 140.8 ppb, respectively. Henderson et al. (/) have further shown that p.p'-DDT levels in fish vary widely, depending upon the river in question. However, reported values for p.p'-DDT and p.p'-DDE in the 50 United States rivers sampled were all greater than values in fish from the Fraser River. Studies of Long Island estuaries (7) and several Cali- fornia estuaries (2) revealed that shellfish and fish sampled from these waters also tended to concentrate chlorinated hydrocarbons in their tissues. In both areas levels of p.p'-DDT, p,p'-DDD, p.p'-DDE, and dieldrin were determined in animal tissue. In addition, many fish and shellfish removed from the California marine estuaries contained endrin (2). Authors' analyses indicated the presence of only p.p'- DDE, heptachlor epoxide, and PCB's in fish and other benthic animals from the Fraser River estuary although several samples contained trace residues of p.p'-DDT, p,p'-DDD, and dieldrin. However, concentrations of p.p'-DDE were approximately equivalent to those re- ported by Modin (2) for C. inagister removed from the California coast in the vicinity of San Francisco. Miles and Harris (12), working with agricultural, ur- ban-agricultural, and resort rivers in Ontario, found a more extensive pattern of chlorinated hydrocarbon in- secticides than authors have noted for the lower Fraser River system. In addition to p.p'-DDE, heptachlor Vol. 9, No. 3, December 1975 139 epoxide. p.p'-DDT, o.p'-DDE. and p.p'-TDE, they de- tected o,p'-DDT, o.p'-'TDE, p.p'-TDE. a-chlordane, and endrin in sampled fish whereas the authors of the present study did not. The one river in which they detected PCB's in fish was the Thames River, which is urban-agricultural as is the lower part of the Fraser River. PCB contamination of water, and hence fish and other aquatic fauna, appears to be more closely asso- ciated with rivers adjacent to urban areas than with agricultural or forested land. A cknowledgments Authors acknowledge the financial support of the Water Resources Research Program, Canada Department of the Environment; the National Research Council of Canada; and Westwater Research Centre, University of British Columbia. Authors thank T. Parsons, Institute of Oceanography, University of British Columbia, for collecting many animals from the Fraser River estuary, and the captain, officers, and crew of Canadian Forces Auxiliary Vessel Endeavour for aid in obtaining fish and crab samples from Georgia Strait. The aid of Gwen Brown in preparing this manuscript is appreciated. LITERATURE CITED (/) Henderson, C. A. Inslis, and W. L. Johnson. 197 1. Organochlorine insecticide residues in fish — fall 1969: National Pesticide Monitoring Program. Pestic. Monit. J. 5(n:I-ll. (2) htodin, ]. C. 1969. Chlorinated hydrocarbon pesticides in California bays and estuaries. Pestic. Monit. J. 3(l):l-7. U) Riscbroui;h. R. W., J. D. Davis, and D. W. Anderson. 1970. Effects of various chlorinated hydrocarbons on birds. In J. Gillette (ed.). The Biological Impact of Pesticides in the Environment. Environ. Health Sci. Series 1. Oregon State University, Corvallis, Oreg. Pp. 40-53. (4) Robinson. ]., A. Richard.son, A. N. Crabtree, J. C. Coiilson. and C. R, Ports. 1967. Organochlorine resi- dues in marine organisms. Nature 214( 13) : 1307-131 I. (5) National Academy of Sciences. 1971. Chlorinated hy- drocarbons in the marine environment. Washington. DC. (6) Jensen, S., A. G. Jolincis, M. Olsson, and G. Otterlind. 1969. DDT and PCB in marine animals from Swedish waters. Nature 224(5216) :247-250. (7) Foelirenbacli, J., G. Maliinood, and D. Sullivan. 1971. Chlorinated hydrocarbon residues in shellfish (Pele- cypoda) from estuaries of Long Island, New York. Pestic. Monit. I. 5(3) :242-247. (8) Duke. T. W.. J. I. Lowe, and A. J. Wilson, Jr. 1970. A polychlorinated biphenyl (Aroclor 1254 ®) in the water, sediment and biota of Escambia Bay, Florida. Bull. Environ. Contam. To.xicol. 5(3 ): 171-180. (9) Croll, B. T. 1969. Organochlorine insecticides in water. Part I. Water Treatment and Examination 18(3): 255-274. {10) Lowden, G. F., C. L. Saunders, and R. W. Edwards. 1969. Organochlorine insecticides in water. Part II. Water Treatment and Examination 18(3) :275-294. (//) Miles. J. R. W., and C. R. Harris. 1971. Insecticide residues in a stream and a controlled drainage system in agricultural afeas of southwestern Ontario, 1970. Pestic. Monit. I. 5(3) :289-294. (12) Miles. J. R. W., and C. R. Harris. 1973. Organochlor- ine insecticide residues in streams draining agricul- tural, urban-agricultural, and resort areas of Ontario, Canada— 1971. Pestic. Monit. I. 6(4 ) :363-368. (/i) Oloffs. P. C, D. F. Hardwick. S. Y. Szeto, and D. G. Moerman. 1974. DDT, dieklrin, and heptachlor epox- ide in humans with liver cirrhosis. Clin. Biochem. 7(3):297-306. {14) Armour. J. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. I. Ass. Offic. Anal. Chem. 53(4) :761-768. (15) Iwata, Y., F. A. Gunther. and W . E. Westlake. 1974. Uptake of a PCB (Aroclor 1254) from soil by carrots under field conditions. Bull. Environ. Contam. Toxicol. ll(6):523-528. {16) Eichelberiicr. J. W ., and J. J. Lichtenberi-. 1971. Per- sistence of pesticides in raw river water. Environ. Sci. Technol. 5( 6 ) :54l-544. {17) Hall. K. J.. J. A. Koch, and I. Ye.wki. 1974. Further investigations into water quality conditions in the lower Fraser River system. Technical Report No. 4, West- water Research Centre, University of British Colum- bia. 104 pp. {IS) Oloffs. P. C, L. J. Albright, and S. Y. Szeto. 1972. Fate and behavior of five chlorinated hydrocarbons in three natural waters. Can. I. Microbiol. 18(9) : 1393- 1398. {19) Oloffs, P. C, L. J. Albrii-hl. S. Y. Szeto. and J. Lau. 1973. Factors affecting the behavior of five chlorinated hydrocarbons in two natural waters and their sedi- ments. J. Fish. Res. Bd. Can. 30( 1 1) : 1619-1623. 140 Pesticides Monitoring Journal Mirex Residues in Wildlife and Soils, Hawaiian Pineapple-Growing Areas — 1972-74 '■" Arthur Bevenue, James N. Ogata, Lester S. Tengan, and John W. Hylin ABSTRACT A monitoring prosiani was conduclcd in the pineapple- growing areas of Hawaii from 1972 to 1974 to survey mirex residues in sediments, soils, and aquatic and terrestrial wild- life. Residues in pineapple field soils ranged from 3 to 18 pph 9 months after mirex had been applied. No residues were found in the .sediments. Only 8 fish of 110 aquatic animals .sampled contained mirex; lhe.se levels were low and ranged from 3 to 7 ppb. Mirex residues in birds ranged from undetectable to 10 ppm: residues in rodents were quite variable, but in terms of the geometric mean, the amounts in the Polynesian rat decreased with time from 1,270 to 56 ppb. Similarly, values for the roof rat ranged from 666 to 17 ppb. The geometric mean for residues in mongooses decreased from 2,200 ppb immediately after ap- plication to 238 ppb 39 weeks later. Aerial application of mirex to the pineapple fields did not contaminate the marine environment of Hawaii and no evidence of mirex residue buildup in the aquatic food chain was apparent. Mirex accumulation in terrestrial biota was temporary: there was no definitive indication of permanent accumulation in the wildlife of the areas studied. Introduction Successful pineapple production requires the control of several insect-transmitted diseases, the most serious of which is mealybug wilt caused by the pineapple mealy- bug (Dysinicocciis brevipes). Direct control of this organism is not feasible, but because it is transported and protected by the bigheaded ant {Pheidolc megace- phala), the disease can be controlled by reducing the ant population in pineapple fields. Mirex has been suc- cessfully used for ant control in pineapple production in Hawaii since 1970. It was used on about 30,000 acres in 1972 when about 76,000 lb bait containing 220 lb mirex (0.29 percent active ingredient) was applied. The ' Presented in part at the Third Inlernalional Congress of Pesticide Cheinislry. Helsinki, Finland. July 3-9, 1974. Journal Series No. 1858. Hawaii Agricultural Experiment Station. 'University of Hawaii, Honolulu, Hawaii 96822. use of mirex in Hawaii was temporarily suspended in 1972 when the U.S. Environmental Protection Agency (EPA) permitted an exception to their Notice of Can- cellation of registrations of pesticides containing mirex (March 18, 1971, and amended by two Determination and Orders on May 3, 1972, and June 30, 1972), pro- vided that aerial application of mirex in the Hawaiian pineapple fields would be subjected to EPA approval. Monitoring procedures used for the 1972-74 pineapple- growing seasons and the analytical results of mirex residues in environmental specimens obtained from pineapple-growing areas are described in this report. Sampling State areas pertinent to mirex monitoring are indicated in Figures 1-3. The 1972-73 samples included aquatic specimens, sediments, and soils; sampling was confined to two coastal areas on the island of Maui and one each on the islands of Molokai and Oahu. Samples were taken quarterly for 1 year. The 1973-74 samples were primarily terrestrial verte- brates with some additional aquatic and soil samples. The second-year sampling program for soil and terres- trial biota was confined to the Maliko watershed area on the island of Maui, an area which contained 4,962 acres under pineapple production. Aquatic specimens were collected at both the Maliko and Honokohau areas. vSoil and sediment samples were selected from sites where mirex would most likely be transported by streams from the fields to coastal areas. Sediment sam- ples were taken near the shoreline areas at an approxi- mate depth of 1 cm and placed in 1 -quart cans which had been baked at 200°C. Topsoil samples were re- moved to a depth of about I cm from 9-ft- areas and were also stored in heat-treated cans. At least two samples were taken during each round of monitoring from two pineapple fields in an area where surface water runoff converged after exiting each field. Most Vol. 9, No. 3. December 1975 141 Honokohau Ba Napill Bay Pauwela Pt. Kaanapali Lahaina KEY -Major highways Mirex application areas FIGURE 1. Pineapple-growing areas treated with mirex, Maui, Hawaii — 1972-74 Ilio Pt. Kahiu Pt. Kaiehu „ , > \ -. Kalaupapa ( \ 1*. ^--^3:^ ^"""^ V<§25(^°^Pelekunu^ — ■ ^ Papohaku f ^Hh^^ 1 %L.m^-my^ ^wa Beach r f^fUmi Palaau Area M^ Laau / / ''*• HaTe~o~rotT(r'~"'1^/ ^aialua Wharf Kama 10 KEY iVyiajnr highwyayc ^^Mi.xapp„cat,on FIGURE 2. Pineapple-growing areas treated with mirex, Molokai, Hawaii — 1972-73 142 Pesticides Monitoring Journal of the fish, shrimp, and crabs were caught by either throw or scoop nets. Occasionally, spearfishing was sub- stituted for netting. Algae and oy.sters were gathered by hand; birds were shot; and rodents and mongooses were obtained with snap and live traps, respectively. All animals were taken within the confines of a mirex- treated field. Specimens were obtained 1 week before and 1-2 weeks after mirex application. Additional samples were taken at approximately 1 -month intervals for a period of 9 months. All specimens were labelled and packaged separately, packed in ice in chilled insulated containers, and transporte'd to the analytical laboratory within 24 hours of collection. Upon arrival, samples were imme- diately prepared for analysis. A total of 27 sediment, 4 soil, and 89 aquatic biota samples were analyzed for the 1972-73 period. In 1973- 74, 10 soil and 23 aquatic biota samples were collected; other samples include 20 birds, 6 mice, 41 rats, and 22 mongooses. Table 1 lists all species collected. Analytical Procedures The analytical method used for mirex residues was essentially the same as the method recommended by Wilson (/). In the present study the method was ap- plied to certain types of biological species not hereto- fore examined by this procedure. Equipment included a Waring blendor; a Sorvall Omni- mixer; a Buchi rotary vacuum evaporator; a Soxhiet apparatus, size 23; 400-mm-by-20-mm-ID chromato- graphic columns with 200-ml reservoir fitted with teflon ultramax valves; and glass wool rinsed with acetone and hexane, air-dried, and heated at 200°C for 16 hours before use. All glassware was soaked in a sulfuric acid: Laie Bay Kaena Pt. KEY -Major highways Mirex application areas Barbers Pt. FIGURE 3. Pineapple-.qrowing areas treated with mirex, Oaliii. Hawaii — 1972-73 Vol. 9, No. 3. December 1975 143 TABLE 1. Species sampled for mircx residues, Hawaiian pineapplc-i^rowitii,' areas — 1972-74 Common Name Scientific Name Alg^e Chnospora sp. Acanthophora specifera Sargassion sp. Crus:aceae Crab Crab Crenate swimming crab Long eyed swimming crab Shrimp Poriunus sanguinolentus Grapsus firapsus TJuihimita crenata Podophthalmus \igil Palaemon debilis ECHINODERM Sea cucumber Sea urchin Flat sea urchin Holothiiria atra Tripneustes grafilla Colobocentrotus afratus Fish Aholehole Great barracuda Largcmoulh bass Daniselfish Goalfish Goathsh Halibut Molhc Striped mullet False nuilk't Parrotfish Pompano Surgeonfish Mozambique tibpia Wrasse Wrasse Wrasse Kiihlia sandvicensis Sphiaena barracuda Microplenis salmoides Abudejduf abdominalis Pariipeneus muliifasciadts Pcinipeneus porphyreits Boihiis pantherinits MolUenisia lalipiuna Muf^il cephalus Neomyxus chaplalii Scams dubius Caranx i^nobilis Acanthiinis ciindvicensis Tilopia mossambica Aniimp\es f^odeffroyi Thalussoma duperreyi Thalaswma juscum Clam Mussel Oyster Limpet Limpet Rough reriwinkie Open dye shell Ncrila (pitchy sea snail) Qitadrnns palatam Iso^-nnmon califorutcitni Cra\sostrea virtiinica Celhina calcosa CeUuna exerota Litiorina scabra Purpura aperla Nerila picea Birds Golden Pacific plover Barred dove Spotted dove Mynah Ruddy turnstone Pluvialis dominica fulva Geopelia striata Streptopelia chinensis Acridotheres iristis Arenaria interpres Mammals Mouse Polynesian rat Roof rat Small Indian mongoose Mus musculus Raltus exulans Rattus rattus Herpestus auropunctalus potassium dichromate solution, rinsed thoroughly with distilled water and then with acetone and hexane. The dry glassware was heated at 200°C for 16 hours prior to use. Operating conditions for the gas chromatograph were; Instrument: Hewlett-Packard model 5750 Columns: Glass. i/4 in. by 4 ft OD, packed with 2 percent OV-101 on 100/120 mesh Gas Chrom Q For confirmation: Temperatures: Carrier Gas: Glass. Vi in. by 4 ft OD. packed with 0.73 percent OV-17 and 0.97 percent OV-210 on 100/120 mesh Gas Chrom Q Electron-capture, with 200 mCi tri- tium as ionizing source Column Injector Detector 196^C 212 C 207°C Argon:methane (90:10) flowing at 60 ml/min The following reagents were employed: Sodium sulfate: anhydrous powder, J. T. Baker No. 3898 QUSO-G30: precipitated silica (Philadelphia Quartz Co.. Philadelphia, Pa.) Desiccant mix: 10 percent QUSO, 90 percent anhydrous sodium sulfate Acetone, acetonitrile. hexane, petroleum ether: all redis- tilled Ethyl ether: Mallinckrodt No. 0844 Florisil: Regular grade (Floridin Co.. Berkeley Springs, W, Va.), heated 5 hours at BO^C Fluting solvents A; 100 ml distilled water made to 1000 ml volume wiih acetonitrile B: 60 ml ethyl ether made to 1000 ml volume with petroleum ether SAMPLE PREPARATION Soil and Sediments: Samples were air-dried at room temperature, 20''-25X, for 72 hours, then mixed for 1 minute in a Waring blendor and stored in pint-size Mason jars for subsequent analysis. A separate 10-g portion of each soil or sediment sample was weighed in a tared aluminum dish. The sample was dried for 16 hours at room temperature and then for 16 hours at 1 lO^'C in an air oven. After cooling in a desiccator, samples were reweighcd and the percent solids was i calculated. Aquatic Biota: Initially, all samples were blotted dry < and weighed. Shells were removed and discarded from i all mollusk samples except the Nerita specimens. The: operculum of the snails and tiie carapace of the crabs ' were also removed and discarded. The remainder of' each of these species was homogenized in a Waring >; blendor. Sea cucumbers, sea urchins, shrimp, algae, and small fish less than 4 cm were prepared for whole-body analysis by homogenization in a blendor. Larger fish weighing less than 150 g were scaled; the head. tail, and , viscera were removed and discarded; and the remainder ' of each fish was homogenized. Fish weighing more i than 150 g were scaled and fillet samples were homo- genized. Birds: Breast and wing muscles of the dressed birds, were composited and homogenized. | Mice and Rafs: The head, feet, skin, and viscera, in- cluding kidney, heart, and lungs, were removed from each specimen and discarded. The remainder of the 144 Pesticides Monitoring Journal mice was homogenized for analysis. Samples of tissue were removed from the back and legs of the rats and homogenized for analysis. Mongooses: Samples of tissue from the two hind legs and lower back were removed from each skinned mon- goose and homogenized for analysis. A 30-g sample of each homogenized specimen was weighed into a pint-size Mason jar and chilled at -10°C for 30 minutes. A quantity of the desiccant mix was added to the chilled sample and mixed thoroughly with a spatula. The amount of desiccant mix added to each sample varied from two to four times the weight of the speci- men and was governed by the wetness of the sample. The mixture was frozen and then pulverized in a Sor- vall Omni-mixer. It was necessary to refreeze and re- grind the samples several times to obtain a free-flowing powdery mixture. Prepared samples were stored in the freezer until analysis. SAMPLE EXTRACTION The biota sample was packed between two 1-inch layers of glass wool and Soxhlet-extracted for 4 hours with petroleum ether at a solvent cycle rate of 6-7 minutes. The extraction procedure for sediment and soil was similar except that the extract mixture was composed of acetone : petroleum ether (1:9). SAMPLE CLEANUP Extracts were concentrated to approximately 10 ml in a rotary evaporator. The biota concentrates were trans- ferred with petroleum ether in 3-4-ml portions to chromatographic columns containing 3 inches of un- heated florisil. A gentle vacuum was applied to the columns after the addition of each portion to evaporate the solvent from the column. Residues were then eluted from the columns with 70 ml eluting solvent A and the eluate was evaporated to dryness in a rotary evaporator. Biota residues obtained from this cleanup procedure were dissolved in petroleum ether and the sediment and soil concentrated extracts were transferred to chroma- tographic columns containing 4 inches of heat-treated florisil and topped with '2 inch anhydrous sodium sul- fate. Columns had been previously washed with pe- troleum ether. Residues were eluted from the columns with 200 ml eluting solvent B. Eluates were evaporated to approximately 1 ml in a rotary evaporator, trans- ferred to volumetric flasks, and made to volume with hexane. Suitable aliquots of the sample extracts and standardized solutions of mirex were applied to the gas chromatograph. Peak heights were compared and mirex residues were calculated and recorded. Samples of sediment, soil, and aquatic and terrestrial biota were fortified with mirex at the 0.1-0.5 ppm level to substan- tiate the efficiency and reliability of the analytical pro- cedure (Table 2). Residue data reported have not been corrected for recovery. Analytical specificity was con- firmed by examination of mirex residues found in mon- TABLE 2. Percent recovery of mirex from soils and biota, Hawaiian pineapple-growing areas — 1972-74 ' „ Percent ^"■"■'^^ RECOVERY Sediment Soil Barracuda Goatfish Mollie Wrasse Crenaie crab Limpet Nerita Sea cucumber Sea urchin Flat sea urchin Rat 96 91 75 87 94 80 91 90 86 90 98 94 90 98 92 91 76 96 92 93 77 ' All samples were spiked with 0.1 ppm mirex except the Nerita which received 0.5 ppm. gooses and rats by mass spectrometry/gas chromatogra- phy with the utilization of a Finnigan Model 3000 GC Quadropole Mass Spectrometer Peak Identifier. Results Mirex bait is aerially applied once each year at the rate of 2.5 lb (1,134 g)/acre in the pineapple fields. The active insecticide ingredient in this amount is 3.29 g. To comprehend the significance of this small amount of insecticide per acre in terms of potential environ- mental contamination, several physical properties of the bait were measured in the laboratory (Table 3). TABLE 3. Properties of mirex bait formulation applied, Hawaiian pineapple-growing areas — 1972-74 Mirex content, % Average mass of individual bait grains, mg Range Settling rate of bait grains in water, cm/sec ' Majority of grains Fastest rate Solubility of mirex in water at 25 'C: 3 trials, ppm - Average solubility, ppm 0.29 0.783 0.1-3.0 5.9 11.8 0.048 0.093 0.073 0.071 1 Less than 1% of the bait floats. - One bait was agitated gently in tap water for 2 hr, then allowed to soak overnight or 22 hr. The filtrate, passed through Whatman No. 42 analytical grade paper, was analyzed for mirex. Only 5 fish and 3 soil samples of the 120 samples collected for the 1972-73 season contained mirex resi- dues and all residues were near the level of analytical detectability (Table 4). The five fish samples originated from the Maui estuaries. The limit of detection for mirex ranged from 3 to 6 ppb. Fish species similar to Vol. 9, No. 3, December 1975 145 TABLE 4. Mirer residues in environmental samples, Hawaiian pineapple-growing areas — 1972-74 Specimen ' Collection Site MlREX residue, fLGl KG from the same field 6-8 months later contained no detectable mirex residues. Samples obtained from field No. 234 during the same period of time contained mirex residues in the range of 5-9 ppb (Table 5). Goatfish (I) Wrasse (I) Aholehole (I) Maliko Bay, Maui Maliko Bay, Maui Honokohau Bay, Maui Maliko Bay, Maui Honokohau Bay, Maui Palaau Field, Molokai September 8, 1972 December 8, 1972 March 15, 1973 June 15, 1973 Makua, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu 3 3 3 4 7 ND 18 10 15 ND ND ND TABLE 5. Mirex residues in soil and fish samples, Hawaiian pineapple-growing areas — 1973-74 Aholehole (2) Sample ',= Date Mirex residue, mc/ko Aholehole (18) Soil- Control Series, Fish Goatlish (2) Goalfish (2) Aholehole (1) Soil, Maui field 233 Soil, Maui field 234 Fish Wrasse fl) Aholehole (1) Aholehole ( 1 ) October 6, 1973 » November 3, 1973 January 19, 1974 April 21, 1974 July 13, 1974 October 6, 1973 November 2, 1973 January 19, 1974 April 21, 1974 July 13, 1974 October 6, 1973 October 6, 1973 April 21, 1974 ND 3 4 ND ND ND 9 5 9 9 NOTE: ND = not detected. 1 Number in parentheses indicates number of samples; reported on fresh-tissue basis. residues in fish 3 3 3 residues reported on air-dried basis. - Specimens obtained in areas remote from mirex usage. the specimens which contained residues were obtained far from mirex usage areas and were analyzed for mirex residue to make certain that the residue observed in the fish had indeed been contributed by mirex and not by an inherent gas-chromatographic-sensitive com- ponent characteristic of these species. These samples did not positively show mirex residues. It is possible for a fish to have randomly ingested one bait particle which would contribute a residue in the fish and it would be commensurate with the amounts of mirex in Table 3. Analytical residue results for the first season's monitoring program did not indicate any environmental problem resulting from the use of mirex in the pine- apple fields, at least not in terms of aquatic biota and sediment contamination. However, the random finding of very low amounts of residue in the aforementioned fish and the apparent small but persistent residue found in the soil of one field (Table 4) prompted a second sample collection which was confined to the island of Maui and included a terrestrial vertebrate sampling program. EPA permitted aerial application of mirex to the Hawaiian pineapple fields during the 1973-74 season provided that a monitoring program be continued as set forth in the Agency's Determination and Order dated August 31, 1973. In the second season, top soil samples were obtained from two treated fields at a point where surface runoff would converge after leaving the fields. Areas from which the samples were taken consisted of well-drained soils with gentle to moderate slopes. Two samples from field No. 233 obtained within 3 months after mirex application contained 3-4 ppb mirex. San.ples obtained NOTE: ND = not detected. ' Soil samples taken adjacent to fields where surface runoff converged after exiting the field. Soil residues reported on dry-weight basis. - Analyses of only 3 fish of 23 aquatic biota indicated the presence of a low level of mirex residue. Number in parentheses indicates num- ber of samples; residues in fish rertorted on fresh-tissue basis. ^ October 6, 1973, was 1 week before mirex application. A total of 1 1 marine fish, 5 mollusk, 3 echinoderm, and 2 seaweed samples were collected from the Maliko and Honokohau areas. Only three of the marine fish contained mirex residues (Table 5); each residue was at the minimum detectable level. Freshwater fauna sampled near the end of the second collection to de- termine whether mirex was accumulating in this area of the local environment contained no mirex residues. Discussion Markin et al. (2) published data from an island near i Gulfport, Miss., which had been treated with mirex i three times in 1 year. Residues appeared in practically ' all marine life examined in the area 3 weeks after the ' third mirex treatment. Residues decreased to either un- detectable or trace amounts in the subsequent 3-year period. Bretcke et al. (3) found residues in most of I the fish examined in certain areas of Mississippi where mirex had been used extensively for at least 5 years before the sampling program. Borthwick et al. (4) I examined estuarine wildlife in an area of South Carolina i 24 months after treatment of the area with mirex and I found residues greater than 0.01 ppm in only 10 percent of the specimens examined. In a study of a crawfish-growing area of Louisiana Markin et al. (5) found, in most instances, no mirex I residues in crawfish, some of which had been obtained ' from areas treated five times during the year prior to the sampling program. The absence of mirex residues in the aquatic areas of Hawaii may be attributed to 146 Pesticides Monitoring Journal several factors: in some areas reservoirs and irrigation canals receive all runoff water because there are no large rivers or streams in the pineapple-producing areas of the State: normal rainfall is quickly absorbed by the volcanic soils; and soil and water conservation measures, including contour plowing, diking, and grassing of water courses, are constantly practiced to contain the soil and water within the pineapple fields so that runoff is limited to roadways and newly planted fields. Bird samples were predominantly from golden Pacific plover. This bird and the ruddy turnstone are migra- tory and reside in Hawaii from September to May. Both species feed principally on insects and larvae, preferably in newly plowed and planted fields. Mirex residues in plovers varied considerably between samples from 80 to 10,400 ppb (Table 6); no definitive cumu- lative or diminutive trend of residues with time was apparent. It is reasonable to assume that the plover which weighed 127 g and contained 10.4 ppm mirex in its body tissue could have randomly acquired these residues from less than 0.5 g bait (Table 3) or from insects which had ingested the bait (2). Yet plover data (Table 6) indicate that these levels were excep- tionally high. Furthermore, bait deteriorates rapidly in the field, becoming unacceptable to the birds as a feed- stuff. Similarly, residue data obtained from a limited number of samples of the ruddy turnstone and the mynah were inconclusive. Difficulty in acquiring definite time-related data on a migratory species over a period of 7 months is readily TABLE 6. Mirex residiiex in birds, Hawaiian pineapple- firowini,' areas — 1973-74 MiRF.x Residue, 0 0 Range of Total Recovered, PPM 0-0.048 (0.020) 0.014-0.047 (0.032) No. op Recovery Experiments 15 26 DDT Fatly Nonfatty 0.01 0.01 0-0.0095 (0.0037) 0-0.0031 (0.0004) 0.0064-0.0182 (0.0130) 0.0069-0.0181 (0.0118) 5 8 2, 4-D Fatty Nonfatty 0.02 0.02 0 0 0-0.017 (0.010) 0-0.024 (0.015) 4 15 Dieldrin Fatty Nonfatty 0.005 0.005 0-0.0105 (0.0042) 0-0.0024 (0.0007) 00035-0.0162 (0.0084) 0.0042-0.0081 (0.0058) 5 10 MCP Fatty Nonfatty 0.04 0.04 0 0 0-0.042 (0.025) 0.008-0.048 (0.034) 9 14 Strobane Fatty Nonfatty 0.20 0.20 0 0 0.108-0.263 (0.176) 0.169-0.280 (0.186) 6 9 2, 4-DB Fatty Nonfatty 0.02 0.02 0 0 0-0.017 (0.011) 0-0.022 (0.016) 6 19 Ronnel Fatty Nonfatty Fatty Nonfatty 0.005 0.005 0.005 0,005 0 0 0-0.0016 (0.0003) 0 0.0035-0.0045 (0.0039) 0.0036-0.0046 (0.0042) 0.0034-0.0061 (0.0045) 0.0036-0.0058 (0.0047) 5 10 5 10 Carbaryl Nonfatty 0.20 0 T-0.20 (0.18) 60 Endrin Orthophenyl- phenol Nonfatty 0.4 0 0-0.40 (0.30) 59 Cadmium Fatty Nonfatty 0.1 0.1 0-0.037 (0.010) 0-0.152 (0.045) 0.077-0.127 (0.108) 0.080-0.221 (0.119) 30 Kellhane Fatty Nonfatty 0.02 0.02 0 0 0.010-0.023 (0.018) 0.015-0.025 (0.018) 4 10 60 Lead Fatty Nonfatty 0.2 0.2 0-0.090 (0.034) 0-0.336 (0.082) 0.080-0.300 (0.182) 0.060-0.880 (0.262) 36 Methyl Fatty Nonfatty 0.01 0.01 0 0 0.0062-0.0133 (0.0099) 0.0064-0.0150 (0.0097) 5 10 Mercury Fatty Nonfatty 0.064 0.064 0-0.036 (0.006) 0-0.009 (0.001) 0.034-0.1 oil (0.067) 0.035-0 090 (0.063) 29 60 Fatty Nonfatty 0.005 0.005 0 0 0.0041-0.0055 (0.0046) 0.0026-0.0076 (0.0050) 5 10 Arsenic Fatty Nonfatty 0.2 0.2 0-0.160 (0.030) 0-0.072 (0.016) 0.090-0.310 (0.169) 0.035-0.240 (0.172) 28 60 Eho Fatty Nonfatty 0.005 0.005 0 0 0.0037-0.0050 (0.0045) 0-0.0058 (0.0040) 5 10 Selenium Fatty Nonfatty Nonfatty 0.2 0.1 0.2 0-0.340 (0.093) 00.220 (0.020) 0-0.405 (0.034) 0.120-0.850 (0.299) 0.040-0.390 (0.299) 0.100-0.575 (0.206) 32 30 1 Numbers in parentheses represent average residue levels. 37 Vol. 9, No. 4, March 1976 167 TABLE 5. Pesticide residues in individual commodities of dairy composite of four market basket samples Pesticide Commodity '.2 Whole Fluid Evaporated Ice Cottage Processed Natural Margarine Ice Milk (4) Milk (4) Cream (4) Cheese (4) Cheese (4) Cheese (4) Butter (4) (4) Milk (3) 1 DDE No. occurrences Range, ppm DIELDRIN No. occurrences Range, ppm HCB No. occurrences Range, ppm BHC No. occurrences Range, ppm HEPTACHLOR EPOXIDE No. occurrences Range, ppm METHOXYCHLOR No. occurrences Range, ppm LINDANE No. occurrences Range, ppm p,p'-DDT No. occurrences Range, ppm TDE No. occurrences Range, ppm PCB's No. occurrences Range, ppm MALATHION No. occurrences Range, ppm 2 2 3 2 4 0.001-0.003 0.013-0.016 T-0.019 0.012-0.015 T-0.008 3 4 0.003-0.008 0.005-0.154 1 T 1 T 3 0.002-0.003 3 T-0.007 3 T 1 T 2 T-O.OOI 3 T-O.OOl 1 T 2 T 2 T-0.002 I T 1 T 1 0.001 2 T 2 T 4 4 4 0.005-0.010 0005-0.014 0.014-0.056 4 3 3 0.004-0.011 0.002-0.005 0.009-0.018 4 T-0.004 2 0.0O3-0.012 3 0.005-0.007 t 0.031 2 0.029-0.040 1 0.001 1 0090 2 T 3 T-0.006 3 T-O.OU 3 T 3 T-0.005 3 T 2 T 2 T-0.009 2 T 1 T 1 0.013 ^ Buttermilk, skim milk, and nonfat dry milk not shown because no residues were found. ■ Figures in parentheses represent number of replicates. 168 Pesticides MoNiTokiNc Journah ■a o S 5 8 "3 s ^3 s a n < o: p S:r OS 9 3 ^ d nJ VO 1 Vi m ^ a: o 5S? o B-e •* o ■* d oo ±s o 15 g ;d u ■JS o t d li? 00 s :} < H« 2 ■*H ,^ lA rf 8 9 s ^ d 8 QZBi 0 "H g S o o i 9 8 "to '^ d N© 9 8 9 -h -H r4 H ^ d ^ o !^ - uj y w z Z d S OZBi B5 3 H O u II 9, No. 4, March 1976 169 RESIDUES IN FISH, WILDLIFE, AND ESTUARIESJ Chlorinated Hydrocarbon Pesticides and Mercury in Coastal Y oung-of-the-Y ear Finfish, South Carolina and Georgia — 1972-74 Robert J. Reimold = and Malcolm H. Shealy, Jr.' ABSTRACT Pesticides and heavy metals were monitored in fish collected from 11 estuaries representing all the Atlantic drainage basins in Georgia and South Carolina. Part of the U.S. Environmental Protection Agency National Esluarine Moni- toring Program, the semiannual survey of young-of-lhe-year fishes, was conducted from 1972 to 1974. Data are intended to provide an initial base line for residue levels in the fish studied in these waters. Dieldrin was found in 2 percent of the samples, DDT and metabolites were in 33 percent, poly- chlorinated biplwnyls were in 4 percent, and mercury was in 47 percent. Noticeably absent were any measureable residues of loxaphene even though there is a toxaphene manufacturing plant in Brunswick, Ga. Introduction The presence of chlorinated hydrocarbons in continental United States marine and estuarine molluscs was moni- tored from 1965 to 1972 by the U.S. Environmental Protection Agency (EPA) (1,2). Nevertheless there is a paucity of data concerning the concentrations of these compounds and total mercury in estuarine finfish from coastal Georgia and South Carolina. As part of the EPA National Estuarine Monitoring Program, a semiannual survey of selected Georgia and South Carolina estuaries was initiated in October 1972. This paper reports base line chlorinated hydrocarbon and total mercury concentrations, including negative results, in young-of-the-year finfish from the Georgia and South Carolina estuaries of the Atlantic coast from fall 1972 through spring 1974. > Contribution No. 517, University of Georgia Marine Resources Ex- tension Center, Contribution No. 46, South Carolina Marine Resour- ces Center. ^ University of Georgia Marine Resources Extension Center, P.O. Box 517, Brunswick. Ga. 31520. ' Marine Resources Research Institute. P.O. Box 12559, South Caro- lina Wildlife and Marine Resources Department, Charleston, S.C. Methods The study area included coastal Georgia and South i Carolina. Collection sites in six South Carolina estuaries and five Georgia estuaries are depicted in Figures 1 and I 2. At each location, samples were collected during fall ' 1972, spring 1973, fall 1973, and spring 1974. Speci- mens for residue analysis were restricted to young-of- the-year fish. Consequently, residues reflect the accumu- lation over a period of not more than 1 year preceding sample collection. Each sample consisted of a 25-g aliquot from a composite sample of at least 25 fish. South Carolina fish were collected with a 6-m semi- balloon otter trawl described by Shealy {3). Georgia specimens were collected with an otter trawl described by Reimold and Durant {4). Georgia samples were placed on ice and were processed for analysis within 4 hours of collection according to techniques of Reimold and Durant {4) and Durant and Reimold (5). South Carolina samples were frozen immediately upon collec- tion and were processed later for analysis by the tech- niques noted above. All samples were analyzed by the EPA Pesticide Moni- toring Laboratory, Bay St. Louis, Miss., using the tech- niques of Butler (2) for pesticides and of Uthe et al. {6) and Brandenberger and Bader (7.H) for total mer- cury. Specific chlorinated hydrocarbons for which analyses were conducted were: DDT, DDE, TDE, dieldrin, endrin, polychlorinated hiphenyls (PCB's), toxaphene, mirex, and chlordane. Phenoxy-herbicides, and carbamate and organophosphorus pesticides were also monitored but are not discussed in this report because their residues were not detected. PCB's were quantified by matching residues with an Aroclor 1254 standard. Recovery of pesticides was between 85 and 90 percent; data have not been corrected. Concentra- tions of all pesticides and mercury are reported on a whole-body, wet-weight basis. Pesticide concentrations 170 Pesticides Monitoring Journal Winyoh Bay South Sontee River ♦. Charleston Horbor Scole 10 20 H I Kilometers South Edisto River Saint Helena Sound Port Royal Sound FIGURE 1. Estuarine collection sites in coastal South Carolina, 1972-74 less than 10 /ig/kg and mercury concentrations less than 20.0 fig/ kg are not reported. Results Table 1 lists scientific names and collection locations of dl fishes analyzed. Scientific and common names are those accepted by the American Fisheries Society (9). Quantifiable concentrations of chlorinated hydrocarbons and mercury in coastal sites of South Carolina and Georgia are summarized in Table 2. Dieldrin was detected only in Atlantic croaker collected in the Savannah River, Ga., in spring 1973, and in star drum from St. Andrews Sound, Ga., in fall 1972. DDT was detected in star drum (33 /ng/kg) collected from Port Royal Sound, S.C, in spring 1973. All other samples containing detectable concentrations of DDT were collected during the fall of 1972. DDE was found in ichthyofauna from all collection sites. The maximum concentration (40 ;ig/kg) was measured in spot from the Savannah River, Ga., in fall 1972. TDE was found at all collection locations except the south Edisto River, S.C; St. Helena Sound, Ga., and St. Catherines Sound, Ga. TTie maximum concentration of 43 /ng/kg TDE was in star drum collected in fall 1972 from St. Andrews Sound. PCB's equivalent to Aroclor 1254 were detected in silver perch from Port Royal Sound (182 /tg/kg, fall 1972), star drum from the Savannah River (137 /ig/kg, spring 1974), and star drum from St. Andrews Sound (508 ^g/kg, fall 1972). No other pesticides were detected in any samples during the monitoring period. Mercury was detected at all geographic locations with highest values in Winy ah Bay, S.C. (797 Mg/kg in At- Savannah River St. Catherines Sound Altannaha Sound St. Sinnons Sound St. Andrews Sound Scole 6 0 6 12 18 I I I L_J Kilometers FIGURE 2. Estuarine collection sites in coastal Georgia, 1972-74 V'oL. 9, No. 4, March 1976 171 TABLE 1. List of coastal youn,q-of-the-year fishes sampled from fall 1972 through spring 1974, South Carolina and Georgia ScffiNTiFic Name South Carolina Georgia Common Name SS CH SE SHS PRS SR SCS SSS SAS Anchoa mitchilU Bay anchovy Arius felis Sea catfish Bairdiella chrysura Silver perch Brevoortia tyrannus Atlantic menhaden Cynoscion regalis Weak fish Etropus crossotus Fringed flounder Leiostomus xanthurus Spot Menticirrhus americanus Southern kingfish Micropogon undulalus Atlantic croaker X Peprilus alepidolus Harvestfish Rissola marginala Striped cusk-eel Stellifer lanceolatiis Star drum X Symphurus plagiusa Blackcheek tonguefish X XX XXX X X X X X X X X XXX X X X X X XXX X X NOTE: WB = Winyah Bay, SS = South Sanlee River, CH = Charleston Harbor, SE = South Edisto River. SHS = St. Helena Sound, PRS = Port Royal Sound, SR = Savannah River, SCS = St. Catherines Sound, AS = Altamaha Sound, SSS = St. Simons Sound, and SAS = St. Andrews Sound. lantic croaker, spring 1973), and the South Santee River, S.C. (3,059 /xg/kg in silver perch, spring 1973). Discussion When combined, levels in ichthyofauna in the two States represent an array of indicator finfish species and chlorinated hydrocarbon and mercury residues in a large number of fishes common to estuaries of the southeastern United States. Thirteen species, represent- ing eight families from five orders, are included. The five fish species reported for the South Carolina coast, all in the family .Sciaenidae, were selected be- cause they are among the most abundant and ubiquitous bottom fishes in these estuaries (70). The eight Georgia species reported represent various diets and several ad- ditional important families, including the Engraulidae, Clupeidae, Ariidae, Bothidae, Cynoglossidae, Ophidiidae, and Stromateidae. Eleven estuaries representing all the Atlantic drainage basins in the two States were monitored, allowing com- parison of contaminant residue levels between various locations over much of the portion of the southeastern Atlantic coast known as the Georgia Embayment. Total mercury values listed do not differentiate between inorganic mercury and the much more harmful organo- mercurials. For further information on organic mercury, the reader is referred to DTtri (11) and Lepple (12). During spring 1973, the 797 yxg/kg mercury in Atlantic croaker from Winyah Bay, S.C, represented a level slightly above the 500 lig/kg legal maximum concentra- tion of mercury in food set by the Food and Drug Administration, U.S. Department of Health, Education, and Welfare (12). The 3,059 /.'g/'^g 'n silver perch from South Santee, S.C. is six times above this level. In both estuaries, mercury levels were considerably lower both before and after spring 1973. The cause of the singularly high total mercury values in the two 172 estuaries during this sampling period has not been ascertained. The data establish base line conditions by which future comparisons of chlorinated hydrocarbon and total mer- cury residue levels can be made for selected ichthyo- I fauna of coastal South Carolina and Georgia. During this study detectable concentrations were measured and reported for dieldrin, DDT, DDE. TDE. PCBs, and i total mercury (i.e., concentrations greater than or equal ; to 10 /ng/kg for chlorinated hydrocarbons and 20 /^g/kg for mercury). Dieldrin was never detected after spring 1973. Similarly, DDT was found only prior to spring 1973, which may reflect the 1972 ban by EPA. The metabolites of DDT, namely DDE and TDE, were seasonally and spatially ubiquitous throughout the monitoring period. The PCB detected may represent isolated instances associated with industrial activities adjacent to Beaufort and Port Royal Sound in South Carolina, the Savannah River in Savannah, Ga., and St. Andrews Sound. The chlorinated hydrocarbons toxa- phene, chlordane, endrin, and mirex, and phenoxy- ■ herbicides, carbamates, and organophosphorus pesticides i were never detected in concentrations greater than or ■ equal to 10 ftg/kg. The absence of toxaphene is extremely interesting be- < cause a toxaphene manufacturing plant at Brunswick, Ga., was in operation throughout the monitoring pro-' gram and agricultural use of toxaphene has continued il in the watersheds of South Carolina and Georgia. . Earlier studies (13) evaluated effluents from a toxa-i phene manufacturing plant in Georgia and found de-f tectable quantities of toxaphene in estuarine biota dur-|i ing 1971-72, including salt marsh cordgrass. Spartinat alterniflora; white shrimp, Penalus setiferus; American t oyster, Crassostrea virginica; spot, Leiostomus xan-* thurus; mummichog, Fundulus heteroclitus; striped mul-' let, Mugil ceplialus; lesser scaup, Aythya affinis; and' p>ed-billed grebe, Podilymbus podiceps. This discrepancy | between toxaphene residues in the two studies, and the I fact that analytical precision of the studies was similar. Pesticides Monitoring Journal i suggest that a pollution abatement program initiated by the toxaphene manufacturing plant effectively removed toxaphene during the present study. Residues of dieldrin, DDT, DDE, and TDE were found in 2, 10, 33, and 16 percent of the samples, respectively. The PCB equivalent to Aroclor 1254 was found in only 4 percent of the samples; mercury was found in 47 percent. The distribution of DDT and its metabolites and mercury was similar in coastal areas of both Geor- gia and South Carolina. Aroclor 1254 was found more frequently in the Caribbean sites than in those along the southeastern coastline of the United States. Concen- tration ranges were also generally lower in samples from the southeastern United States; maximum residue levels were: dieldrin, 98 i^g/kg; DDT, 33 Mg/kg; DDE, 40 /xg/kg; PCB's (Aroclor 1254), 508 /ig/kg; and mercury, 3,059 /oig/kg. Future monitoring activities should include sampling of different trophic levels in each geographic location where significant concentrations are detected. Finfish moni- toring should be continued and compared periodically to the base line residue levels of the current study to determine whether these pollutants are increasing, de- creasing, or maintaining a steady state in these estuaries and indicator finfish species. A cknowledgments Authors sincerely thank Philip Butler and the U.S. En- vironmental Protection Agency National Estuarine Monitoring Program (Contract No. P5-01-1380J and 68-02-1254) for supporting this research. In addition authors acknowledge Paul A. Sandifer. V. G. Burrell, Jr., T. D. Mathews, and David W. Menzel for review- ing the manuscript; Patrick C. Adams, Jeannette E. Durant, and Tracy Walker for assisting with field col- lections and preparing Georgia samples; John V. Mig- larese, Charles R. Richter, and Yvonne Bobo for assist- ance with field collections and preparation of South Carolina samples; and Coastal Plains Regional Com- mission (Contract No. 10340031) for partial support of the South Carolina portion of the research. LITERATURE CITED (/) Butler, P. A. 1969. Monitoring pesticide pollution. Bio- Science 19(10);889-891. (2) Butler, P. A. 1973. Organochlorine residues in estu- arine moUusks, 1965-72 — National Pesticide Monitor- ing Program. Pestic. Monit. J. 6(4) :238-362. (i) Shealy, M. H., Jr. 1974. Bottom Trawl Data from South Carolina Estuarine Survey Cruises, 1973. S.C. Wildl. Mar. Res. Dept. Data Rep. No. 1. 113 pp. (4) Reimold, R. J., and C. J. Durant. 1974. Toxaphene content of estuarine fauna and flora before, during, and after dredging toxaphene-contaminated sediments. Pestic. Monit. J. 8(l):44-49. (5) Durant, C. J., and R. J. Reimold. 1972. Effects of estuarine dredging of toxaphene-contaminated sedi- ments in Terry Creek, Brunswick, Ga. — 1971. Pestic. Monit. J. 6(2):94-96. (6) Ulhe, J. F., F. A. J. Armstrong, and M. P. Stainton. 1970. Mercury determination of fish samples by wet digestion and flameless atomic absorption spectro- photometry. J. Fish. Res. Bd. Can. 27(4):805-811. (7) Brandenberger, H., and H. Bader. 1967. The determi- nation of nanogram levels of mercury in solution by a flameless atomic absorption technique. At. Absorp. Newsl. 6:101. (S) Brandenberger, H., and H. Bader. 1968. The determi- nation of mercury by flameless atomic absorption II: A static vapor method. At. Absorp. Newsl. 7:53. (9) Bailey, R. M., J. E. Fitch, E. S. Herald, E. A. Lachner, C. C. Lindsey, C. R. Robins, and W. B. Scott. 1970. A List of Common and Scientific Names of Fishes from the United States and Canada. Third ed. Amer. Fish. Soc. Spec. Pub. No. 6, Washington, D.C. 150 pp. (10) Shealy, M. H., Jr., J. V. Miglarese, and E. B. Joseph. 1974. Bottom Fishes of South Carolina Estuaries — Relative Abundance, Seasonal Distribution, and Length-frequency Relationships. S.C. Marine Resources Center Tech. Rep. No. 6. 189 pp. (//) D'ltrie, F. M. 1972. The Environmental Mercury Problem. CRC Press, Cleveland, Ohio. 124 pp. (12) Lepple, F. K. 1973. Mercury in the Environment. Univ. Del. Sea Grant Pub. Del-SG-8-73. 75 pp. (13) Reimold, R. J. 1974. Toxaphene Interactions in Estu- arine Ecosystems. Georgia Marine Science Center, University of Georgia, Skidaway Island, Ga. Tech. Rep. No. 74-76. 80 pp. Fall 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 TABLE 2. Chlorinated hydrocarbon and mercury concentrations in young-of-the-year ichthyofauna. South Carolina and Georgia — 1972-74 Atlantic croaker Star drum Atlantic croaker Star drum Atlantic croaker Star drum Atlantic croaker Star drum Common Name WHOLE-BODY WET WEIGHT, /lO/KO D.4TE Dieldrin DDT DDE TDE PCB's Mercury WiNYAH Bay, S.C. 18 10 17 10 16 10 13 17 10 797 286 64 80 <20 <20 (Continued next page) Vol. 9, No. 4, March 1976 173 Date TABLE 2 (cont'd). Chlorinated hydrocarbon and mercury concentrations in young-of-the-year ichthyofauna, South Carolina and Georgia — 1972-74 Common Name WHOLE-BODY WET WEIGHT. flO/KC DiELDRIN DDT DDE TOE PCB's South Santee River, S.C. Fall 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 Spot Silver perch Spot Silver perch Spot Silver perch Spot Silver perch 16 21 17 14 23 17 — — — — 12 — — 19 11 — 13 — 19 10 67 114 3059 48 50 Charleston Harbor, S.C. Fall 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 Silver perch Star drum Silver perch Star drum Silver perch Star drum Silver perch Star drum 19 21 20 sample not available 14 — 12 — sample not available 13 10 22 157 <20 32 South Edisto River, S.C. Fall 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 Star drum Silver perch Star drum Silver perch Star drum Silver perch Star drum Silver perch 16 10 111 111 140 200 32 138 St. Helena Sound, S.C. FaU 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 Star drum Weakfish Star drum Weakfish Star drum Weakfish Star drum Weakfish 11 15 13 429 286 <20 <20 Port Royal Sound, S.C. Fall 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 FaU 1973 Spring 1974 Spring 1974 Silver perch Star drum Silver perch Star drum Silver perch Star drum Silver perch Star drum 1821 33 15 18 10 629 143 48 <20 (Continued next page) 174 Pesticides Monitoring Journal Dafe TABLE 2 (cont'd). Chlorinated hydrocarbon and mercury concentrations in youna-of-the-ycar ichthyofauna, South Carolina and Georgia — 1972-74 WHOLE-BODY WET WEIGHT, ;iG/KG Common Name DlELDRIN DDT DDE TDF PCB's Mercury Savannah River, Ga. Spot Sea catfish Blackcheek tonguefish Atlantic croaker Southern kingfish Blackcheek tonguefish Star drum Atlantic croaker 22 40 10 10 194 19 I37I St. Catherines Sound, Ga. Weakfish Sea catfish Spot Fringed flounder Southern kingfish Bay anchovy Weakfish 13 13 48 65 Altamaha Sound, Ga. Sea catfish Star drum Atlantic croaker Star drum Blackcheek tonguefish Southern kingfish Atlantic menhaden Atlantic croaker 136 227 18 St. Simons Sound, Ga. Star drum Silver perch Bay anchovy Striped cusk-eel sample not available sample not available sample not available sample not available 130 St. Andrews Sound, Ga. FaU 1972 Fall 1972 Spring 1973 Spring 1973 Fall 1973 Fall 1973 Spring 1974 Spring 1974 Star drum Blackcheek tonguefish Star drum Atlantic menhaden Star drum Fringed flounder Harvestfish Bay anchovy 98 22 43 5081 16 210 161 70 NOTE: — 1 Compound = not detectable, equivalent to Aroclor 1254. Vol. 9, No. 4, March 1976 175 Nationwide Residues of Organochlohnes in Wings of Adult Mallards and Black Ducks, 1972-73 Donald H. White i and Robert G. Heath = ABSTRACT Organochtorine residues in winps of adult mallards and black ducks were monitored during the 1972-73 hunting season. DDE. DDT, DDD, dieldrin, and polychlorinaled biphenyls (PCB's) were present in all samples. Mallard wings from Alabama contained the highest mean levels of DDE, DDT, DDD, dieldrin, and PCB's. Mallards and black ducks from the Atlantic Flyway and mallards from the Pacific Flyway contained significantly lower DDE residues than in 1969-70. Black ducks from the Atlantic Flyway contained significantly less dieldrin than in 1969-70, and mallards in the Central and Pacific Flyways contained sig- nificantly lower levels of PCB's. As in 1969-70, DDE resi- dues were lowest in the Central Flyway and highest in the Atlantic Flyway. The average PCB level remained un- changed in the Atlantic Flyway but was higher in the Mississippi Flyway than in 1969-70, probably because of the unusually high levels in Alabama samples. All organo- chlorine residues in black ducks from the Atlantic Flyway significantly correlated. DDE concentrations in mallards from the Atlantic Flyway significantly correlated with those of DDT. DDD. and PCB's. Introduction Use of technical DDT as a control agent for insect pests in the United States began in the 1940's. Domestic use exceeded 55 million pounds in 1950 and reached a maximum of more than 75 million pounds in 1959. Usage gradually declined to a low of 13 million pounds in 1971, but increased in 1972 to 23.5 million pounds (1.2). In the environment, DDT breaks down to many different metabolites. DDE is by far the most persistent of these and occurs most frequently in nature (i). It is conceivable, then, that a decline in usage of technical DDT would be reflected in a decline of residues of DDT and its metabolites in waterfowl tissues. Longcore ' Fish and Wildlife Service, US. Department of Interior, Patuxent Wildlife Research Center, L.iurel, Md. 20811. ^Technical Services Division, Office of Pesticide Programs, U.S. En- vironmental Protection Agency, Washington, D.C. and Mulhern {4) found lowered levels of DDE in i black ducks eggs between 1964 and 1971. The Fish and Wildlife Service, U.S. Department of ' Interior, began nationwide monitoring of organochlorine pesticides in waterfowl wings in 1965-66 as part of the National Pesticides Monitoring Program. Samples were taken again in 1966-67 and were scheduled for every third year thereafter to detect trends in residue levels. . Wings of adult mallards (Anas platyrhynchos) and black ducks (Anas rubripes) are sampled because their combined range covers the continental United States. Overall objectives and procedures have been discussed in earlier papers (5-8). This paper presents results for the 1972-73 hunting season. Authors have included mean residue levels for each State, a comparison of State residues in the four sampling periods since 1965, a comparison of flyway residues in 1969-70 and 1972-73, and correlations of residues in mallards and black ducks in the Atlantic Flyway. Collection Methods Cooperating hunters mailed wings of approximately 5,400 adult mallards and black ducks to a collection station within each flyway where wings were classified according to age and sex, and grouped according to State. Wings from each State were then sorted system- atically into pools of 25 wings. Pools from each State were selected randomly for chemical analysis; the num- ber taken was roughly proportional to each State's harvest. Pools were given a code number, placed in individually tagged plastic bags, and shipped in dry ice to WARE Institute, Inc., Madison, Wis. Wings were kept frozen in storage until chemical analyses were per- formed. A total of 237 pools were analyzed for organo- chlorine residues. 176 Pesticides Monitoring Journal A nalytical Procedures Prior to analysis, feathers were trimmed and the wings from each pool were ground together by hand in a meat grinder. A 40-g aliquot was weighed into a 260-ml beaker and placed in a 40°C oven for 190 hours. After drying, the sample was reweighed and the dry weight was recorded. The sample was ground with approxi- mately 30 g Na.SO,, placed in a 43-by-123-mm What- man extraction thimble, and extracted for 8 hours in a Soxhlet with 105 ml ethyl ether and 255 ml petroleum ether. The solvent was evaporated to 5-10 ml on a steam bath and diluted to 50 ml with petroleum ether. A 10-ml aliquot of the sample was placed on a pre- viously standardized florisil column and eluted with 260 ml of 20 percent ethyl ether in petroleum ether. This solution was evaporated to 5-10 ml, placed on florisil, and eluted with 150 ml of 3 percent ethyl ether in petroleum ether, followed by 260 ml of 15 percent ethyl ether in petroleum ether. After florisil cleanup the resulting eluates were evaporated separately on a steam bath to 5-10 ml and each was diluted to 25 ml with hexane. The first elution from the florisil was injected into the gas chromatograph to identify BHC, HCB, and lindane, and to approximate the amount of polychlorinated bi- phenyl (PCB) intereference present. An aliquot of this solution containing up to 5 jxg DDE and 20 fig PCB's was run through a silicic acid/celite column according to the method of Armour and Burke for separating PCB's from DDT and its analogs (9). Each resulting solution was chromatographed and residues were quantified. Identifications were made by injecting up to 10 /A of the sample solutions into a Barber-Coleman model 5360 pesticide analyzer. The column was glass, 1219 mm by 4 inm, and packed with 5 percent DC-200 80/100 mesh Gas-Chrom Q. Temperatures were: column, 205°C; in- jector, 225 °C; and detector, 245 °C. The carrier gas was nitrogen at a flow rate of 80 ml/min. Residues in 5 percent of the samples were confirmed by mass spectrometry. All residues are expressed as ppm wet weight. They may be converted to approximate dry or lipid weight by dividing by 0.60 or 0.13, the mean proportions of dry and lipid material in the samples, respectively. Limits of sensitivity were 0.005 ppm for organochlorine pesticides and 0.01 ppm for PCB's. Recovery percent- ages from spiked samples were: DDE, 80; DDT, 94; DDD, 88; dieldrin, 82; and PCB's, 78. Analytical re- sults have not been corrected for recovery. Results and Discussion Table 1 lists the means, standard errors, and ranges of organochlorine residues in wing pools from the 1972-73 and 1969-70 hunting seasons, and the combined residues for the 1965-66 and 1966-67 hunting seasons. Data are arranged by State and major flyway. Waterfowl are highly mobile species and may cover a wide range of habitats in many States. Therefore, interpretations should not be made on strictly statewide bases. Residue levels are not indicative of year-round levels because collections were made only in the fall and winter months. DDT and DDD residues were not reported for the 1965 and 1966 seasons because of possible PCB interference. DDE, DDT, and PCB's were present in all wing pools at levels equal to or exceeding limits of analytical sensi- tivity. DDD and dieldrin were present in at least trace amounts in all samples. DDE residues in individual pools of mallard wings ranged from a low of 0.04 ppm in eastern Wyoming to a high of 4.12 ppm in Alabama; DDE residues in pools of black duck wings ranged from a low of 0.07 ppm in New Hampshire to a high of 1.60 ppm in New Jersey. The State with the lowest mean value for DDE was Wyoming (0.06 ppm); Ala- bama had the highest (1.85 ppm). Levels of PCB's ranged from 0.02 ppm in a pool from Texas to 7.73 ppm in a pool from Alabama. The lowest rnean value for PCB's was 0.04 ppm in Nebraska and western Wyoming; the highest was 6.34 ppm in Alabama. Resi- dues of DDD and dieldrin seldom exceeded 0.05 ppm in individual pools. State means for these two com- pounds averaged 0.01-0.02 ppm. Heptachlor epoxide, HCB, and BHC were present in all samples in at least trace amounts. Because residues of these three chemicals rarely exceeded 0.02 ppm, they were excluded from the tables. Lindane was present in trace amounts in approximately 75 percent of the samples. A few samples contained traces of alpha- and gamma-chlordane. Table 2 lists the mean residues and standard errors of samples of mallards and black ducks from the major flyways (Atlantic, Mississippi, Central, and Pacific) in the 1972 and 1969 hunting seasons. Statistical com- parisons were made to detect residue trends. Residues of DDE declined in both mallards and black ducks. The changes were highly significant statistically: p<0.01 or p<0.001. Residues of DDE declined by 57 percent in mallards and 73 percent in black ducks in the Atlantic Flyway, and by 52 percent in mallards in the Pacific Flyway (Table 2). DDE residues in mallards from the Mississippi Flyway remained relatively un- changed during the sampling period. Residues appeared to be lower in the Central Flyway, but not significantly so. Flyway means for DDT and DDD showed no change over the 3-year period. The only exception was in the Pacific Flyway where DDT residues decreased by 73 percent, a significant change (p<0.01). Diel- drin residues declined in black ducks in the Atlantic Flyway by 86 percent, a significant change (p<0.01), but remained unchanged in mallards from all flyways. Vol. 9, No. 4, March 1976 177 0\ a I <3 o n. :§ PQ < m u a. Q Q Q Q 1° H D Q Q Q < u O m CO o ON o in r- On m ■* O ^ CT-' d d ^ d d d d d d d d d ^ in li-i m — rj O n d d d d d d d d as 5£ d — **? T — — ^s SS 2S 3 On M v|i rJ — ' ^ -^ (N O "*, o d d d 8 OOP o o o »/^ o o S o d O ir. d "^ 'T On 00 ^ ■^ m S?12 oo ON fn O r) TT On On -]- on CT. 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T ^ "t* m — (-1 ri odd ddd ddd ddd d d 0 d — — ■ ddd ■ rJ On »/^ Ji r- ^ ^ i« ON ON On ri o^ >r> _ ri o- iri ■ r- ^ no o r- so \d 5*OnOnOn XIOsOnOn . ri On «ri — r- o NO C OS Ov O- o "" n (?« lA ri oi Vi . r^ sc ^o ^ t^ >o ^ O^^CT'0^ — ^ O- O^ rl 0\ w-i [^ vO >c =0 o 182 Pesticides Monitoring Journal z < UJ i55 UJ bj Q O D Z < d d rj r- OS Sro — o o odd O <*1 'C a •-'■'-■ O O ^ T- 00 Wl p O O d d <^ o o d d o Tt d d 5S d d O (N 99 "^'2 I o o d d n oo — o d d o o d d m ^ ci 'd g" S8 99 o o d d m 00 ^ m ■— "* ^ Tt — d> dd d dt'Z. oo 00 ■-' m v£) f*! Sod vO w n : r- so s£) ; Ov Qv o^ °^ ^ (N 0^ w-> . ^ r-- sD sD .N 2 OS Os Os t: j= Era o ■;; si II '^ ° 5 > o £ c S n — ca C (« u ■5 c!5 X o - o= c a c 3 o S o ■" o. — (u rt c 5 4^ QJ ^ : S <» S3 K ■§SS II £ « IIQ oi: a> O E c H I Vol. 9, No. 4, March 1976 183 TABLE 2. Mean residues of organochlorines in wing pools by major flyway, 1969 and 1972 Flywav Year No. Poois Residues, ppm wet weight DDE DDT DDD Dieldrin PCB'S Species Mean Standard Error Mean Standard Error Standard Mean Error Mean Standard Error Mean Standard Error Black Duck Allantic 1972 1969 44 42 0.35" 1.32 0.043 0.149 0.07 0.12 0.009 0.011 0.02 0.03 0.003 0.019 0.02 = 0.14 0.004 0.057 1.36 1.37 0.149 0.161 Mallard Atlantic 1972 1969 21 19 0.44 = 1.03 0.069 0.173 0.08 0.09 0.011 0.014 0.06 0.02 0050 0.002 0.02 0.05 0.003 0.025 1.24 1.29 0.230 0.457 Mallard Mississippi 1972 1969 61 51 0.37 0.40 0.072 0.058 0.18 0.08 0.057 0.012 (0.06) (0.05) — 0.02 0.04 0.001 0.003 0.66 0.44 0.303 0.061 Mallard Central 1972 J 969 56 49 0.15 0.30 0.012 0.098 0.02 0.03 0.001 0.009 T T — (0.02) 0.02 0.006 0.103 0.20 0.013 0.039 Mallard Pacific 1972 1969 55 51 0.34' 0.71 0.043 0.054 0.031 0.11 0.0O3 0.012 (0.01) T - (0.01) 0.02 0.005 0.11' 0.20 0.009 0.014 NOTE: T = mean residue below limit of quantification t = trace residue below limit of quantification — — not applicable Parenthesized values are approximations involving trace residues. ' Flyway means for the 2 years significantly different: p <0.flOI. = Flyway means for the 2 years significantly different: p < 0.01. 'Flyway means for the 2 years significantly different: p < 0.05. As reportecJ in the 1969 survey (S), PCB resicJues showed pronounced geographical differences: levels were highest in the Atlantic Flyway and diminished westward. PCB levels in mallards declined by 50 percent in the Central Flyway and by 45 percent in the Pacific Flyway (p <0.01 ) but not in the Atlantic or Mississippi Flyways. In fact, PCB levels in the Mississippi Flyway increased somcuhat, but the increase was insignificant, probably because of the high variability in 1972 results. Correlation of organochlorine residues among wild bird tissues, already well documented (10. 1 1), is further illus- trated by data in the present study. Regression analyses indicate highly significant correlations (p <0.01) among all residues in Atlantic Flyway black ducks (Table 3). In Atlantic Flyway mallards, however, DDE correlated significantly with residues of all pesticides except diel- TABLE 3. Correlation amonf; residues in Atlaniic FIvwuv black ducks and mallards, 1972-73' Product- Moment C'jkrelation Coe FFICIENTS DDE DDT DDD Dieldrin PCB's Black Ducks DDE DDT DDD Dieldrin PCB's 1 0,7710- 0.6890-' 1 0.8019-' 1 0.4140- 0.2895- 0.3803 -' 1 0.5094 = 0.4295 = 0.6352 ■■ 0.5103 = 1 Mali ards DDE DDT DDD Dieldrin PCB's 1 0.6502- 0.7129- 1 0.3558 1 0.0265 0.1273 0.3752 1 0.5274 = 0.3236 0.3064 0.1778 1 ' Residues were power transformed by the equation y regression analysis. = p <0.01 ax'i before drin. None of the other residues significantly correlated (Table 3). Conclusions Residues of DDE, DDT, dieldrin, and PCB's in mallards and black ducks have declined since 1969 in certain flyways, showing that duck wings can serve as indicators of environmental levels of organochlorines and thus provide information on residue trends over time. Geo- graphical differences in levels of contamination also were detected. Acknowledgments Authors wish to acknowledge the assistance of person- nel of the Fish and Wildlife Service for their help in sample collections. Special thanks are extended to the following: Donald Rusch, Department of Wildlife Ecol- ogy, University of Wisconsin; Jack Gross, Colorado Co- operative Wildlife Research Unit; the late Howard M. Wight, Oregon Cooperative Wildlife Research Unit; and Sam Carney, Office of Migratory Bird Management. Helen Young performed many of the statistical compu- tations and Deborah Snyder compiled the tables. LITERATURE CITED (/) U.S. Department of Agriculture. 1953-66. The Pesticide Situation for 1952-53 (and for succeeding years through 1965). (2) U.S. Department of Agriculture. 1966-74. The Pesti- cide Review, 1966 (and succeeding years through 1973). (5) White. D. H.. and L. F. Stickel. 1975. Impacts of chemicals on waterfowl reproduction and survival. Trans. First Int. Waterfowl Symp. St. Louis. Pp. 132- 142. 184 Pesticides Monitoring Journal (4) Longcorc, J. R., and B. M. Mulhern. 1973. Organo- chlorine pesticides and polychlorinated biphenyls in black duck eggs from the United States and Canada — 1971. Pestic. Monit. J. 7(l):62-66. (5) Heath, R. G., and R M. Proiity. 1967. Trial monitor- ing of pesticides in wings of mallards and black ducks. Bull. Environ. Contam. Toxicol. 2(2) : 101-1 10. (6) Heath, R. G. 1969. Nationwide residues of organo- chlorine pesticides in wings of mallards and black ducks. Pestic. Monit. J. 3(2) : 1 15-123. (7) Dustman, E. H.. W. E. Martin, R. G. Heath, and W. L. Rcichel. 1971. Monitoring pesticides in wildlife. Pestic. Monit. J. 5(l):50-52. (S) Heath. R. G., and S. A. Hill. 1974. Nationwide organo- chlorine and mercury residues in wings of adult mal- lards and black ducks during the 1969-70 hunting season. Pestic. Monit. J. 7(3/4): 153-164. (9) Armour. J. A., and J. A. Burke. 1970. Method for separating polychlorinated biphenyls from DDT and its analogs. J. Ass. Offic. Anal. Chem. 53(4) :761-768. (10) Bhis. L. ]., A. A. Belisle, and R. M. Prouty. 1974. Relations of the brown pelican to certain environ- mental pollutants. Pestic. Monit. J. 7(3/4) :181-194. (11) Clark, D. R.. and M. A. R. McLane. 1974. Chlorinated hydrocarbon and mercury residues in woodcock in the United States, 1970-71. Pestic. Monit. J. 8(l):15-22. Voi,. 9, No. 4, March 1976 185 GENERAL Seasonal Concentrations of Dieldrin in Water, Channel Catfish, and Catfish-Food Organisms, Des Moines River, Iowa — 1971-73 ' R. L. Kellogg = and R. V. Bulkley - ABSTRACT Conccniialions of dieldrin in aquatic insects, crayfish, min- nows, and small carpsuckers, and muscle tissue of channel catfish (Ictalurus punctatus) were compared with the diel- drin content of Des Moines River water in 1971-73. Monthly mean concentrations of dieldrin in river water and most aquatic organisms were highest in June and July, soon after aldrin had been applied to corn land in the watershed. Several groups of aquatic organisms also exhibited high dieldrin levels in the fall when the dieldrin content of river water wa^ seasonally low. The influence of temperature on metabolic rate and enzyme activity and the differences in body fat content were suggested as probable causes of varia- tions observed in the dieldrin content of aquatic organisms. Introduction Chlorinated hydrocarbon insecticides have been used on midwestern farmland for many years. Most uses of these substances including DDT and clordane were discon- tinued in the late 1960's but aldrin was used widely against soil insects as late as 1974. Between 1961 and 1965, aldrin was applied in Iowa at the rate of 5-6.5 million pounds/year for control of western corn root- worm. As rootwornis became more resistant to aldrin, usage against rootworms and other soil insects decreased to 2 million pounds annually between 1968 and 1973 (Harold Stockdale, 1973, Extension Entomologist, De- partment of Entomology, Iowa .State University, Ames, Iowa: personal communication). Use of aldrin and other pesticides has contributed sig- nificantly to the production of record corn crops. Morris ' Journal Paper No. J-S215. Project No. 1928. Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Financed by grant from Office of Water Resources Research. U.S. Department of In- terior (Agreements 14-31-0001-3515. -3815, -4015) under Public Law 88-379. Made available through Iowa State Water Resources Research Institute to the Iowa Cooperative Fishery Research Unit, which is sponsored by the Iowa State Conservation Commission, Iowa State University of Science and Technology, and the Fish and Wildlife Service, U.S. Department of Interior. ■ Iowa Cooperative Fishery Research Unit, Iowa State University, Ames, Iowa 5001 1. and Ebert (/). however, reported that aldrin applied to row crops in Iowa was appearing in the form of high concentrations of dieldrin, the initial oxidation product of aldrin, in edible tissue of channel catfish {Ictalurus punctatus) in rivers draining cropland. Morris and Johnson (2) found that dieldrin concentrations in some large catfish collected from several Iowa rivers exceeded 300 ppb, the level in human food permitted by the Food and Drug Administration, U.S. Department of Health, Education, and Welfare. Concentrations were as high as 1,600 ppb in muscle tissue: this represents more than five times the allowable level. Inasmuch as the channel catfish is an important game fish in Iowa, contamination of this species with dieldrin could serious- ly affect the sport and commercial fisheries of the State. From 1971 to 1973, authors attempted to obtain more information on dieldrin concentrations in channel cat- fish. The portion of the study reported here covers seasonal variations of dieldrin levels in river water, cat- fish muscle tissue, and organisms important in the cat- fish diet. The Des Moines River above Boone, Iowa, was selected as the study site because of its importance as a catfish angling stream, its similarity to many other Iowa rivers, and the extensive row-crop farmland in its watershed. The Des Moines, the largest river flowing through Iowa, arises in a glacial moraine in southwestern Minnesota and flows southeasterly across Iowa to the Mississippi River. The collection site in Boone County is about 426 km upstream from the mouth of the river. At this point the river drains about 1.4 million ha. or 38 percent of the total drainage area of the basin (i). Nearly 80 percent of the Des Moines River watershed is cropland, 10-15 percent is permanent pasture, and 5 percent is urban (4). The river basin has a temperate climate. The average yearly temperature of the Iowa portion of the basin 186 Pesticides Monitoring Journal ranges from about 8° to 10°C from north to south (3). Annual precipitation over the dainage area aver- ages about 70 cm, ranging from 63 cm in the north to 79 cm in the south. Precipitation is usually heaviest in May and June, a period when the river reaches its high levels each year. Frequently an early spring flood fol- lows thawing and fast runoff. Cloudbursts and heavy rains occasionally cause temporary flooding in summer and even in early fall. The river bottom is composed chiefly of sand and gravel but includes sand-silt, rubble, and boulders in limited areas. During times of low water levels many sand bars appear. Deep holes are present below the bars and at bends. The river has few connecting sloughs and back- waters except during high water. Methods SAMPLE COLLECTION AND ANALYSIS Authors collected 1 -liter water samples monthly from May through October in 1971 and duplicate I -liter water samples weekly from April 24 through June and twice monthly from July to October 15. 1972. A clean glass container was submerged about 300 mm below the surface of the water in a rapidly flowing section of the river to obtain the sample. The containers were then sealed with screw caps lined with Teflon or aluminum foil. Samples were shaken thoroughly and 750 ml was decanted off for single extraction with 60 ml of 15 percent ethyl ether : hexane in 1971. A second extrac- tion with 60 ml hexane was performed on water samples in 1972 (5). Extracts were concentrated to I ml for quantitation. In 1973, triplicate 2-liter samples were collected twice weekly from April 21 through July and usually weekly from August I to November 16. Samples were filtered through pre-extracted No. 40 Whatman filter paper to separate dissolved fractions from suspended fractions. The dissolved fraction was extracted twice with 120 ml of 15 percent ethyl ether and hexane, followed by a third extraction with 150 ml hexane. Collection vessels were rinsed with a portion of the initial extraction solvent to remove pesticides adhering to the container walls. Extracts were combined and concentrated to 1 ml for quantitation. Florisil cleanup (5) was employed when necessary. The suspended fraction retained on the filter paper was extracted with 300 ml acetonitrile in a Soxhiet extrac- tion assembly for 18 hours. The pesticide residues were partitioned into petroleum ether by adding 200 ml dis- tilled water to the acetonitrile and extracting three 60- ml portions of petroleum ether. The final extraction was followed by the addition of 1,200 ml distilled water. Petroleum ether extracts were combined and washed with distilled water to remove the remaining acetonitrile. Further cleanup on florisil columns was necessary. Samples were concentrated to 1 ml for quantitation. Results were expressed as parts per trillion (pptr) for both dissolved and suspended fractions. Bottom sediment samples were collected monthly from July to November 1973. The top 15 mm of sediment was scooped from shallow, silty areas of the river bottom in an attempt to collect newly deposited mate- rial. Samples were passed through a No. 230 standard sieve with 63-;u openings and allowed to dry thoroughly at room temperature. Three 100-g aliquots were Soxhlet- extracted with 300 ml chloroform for 18 hours. Ex- tracts were concentrated to 2-3 ml and introduced onto a 6-by-90 mm Fisher coconut charcoal column with 15 ml of 25 percent acetone and ethyl ether to remove polychlorinated biphenyl (PCB) interferences (6). Pesticide residues were elated from the charcoal column with 90 ml of 25 percent acetone and ethyl ether leaving the PCB's absorbed on the charcoal. This eluate was concentrated to 2-3 ml, introduced onto a florisil column, and eluted with 200 ml of 20 percent ethyl ether and petroleum ether. Samples were concentrated to 10 ml for quantitation. In 1972 authors collected mayfly naiads (Potamanthus sp. ) from April 23 to July 10. and crayfish (Orconectes nisticus) from April 23 to October 15, by moving rocks in riffle areas and capturing the dislodged or- ganisms with a dip net. Potamanihus collections were pooled into three subsamples for each collection date. Individual analyses were run on O. nisticus. In 1973. aquatic insects, crayfish, minnows, and small carpsuckers (Carpiodes sp.) were collected from June to November. Early spring collections could not be taken because the river was flooded. Aquatic insects were collected in basket substrate samplers suspended from floats and by dislodging rocks in riffle areas. In- sects collected and grouped by taxon for pesticide analysis were: Acroneuria, Pteronarcys, Potamanthus, Isonychia, Ephoron. Corydalus, Heptageniidae, Chiro- nomidae, and Tricoptera. Because the faunal assemblage varied throughout the sampling period, it was not pos- sible to collect representatives from more than four of the groups at any one time in sufficient numbers for pesticide analysis. Orconectes rusticus, O. virilis, spot- fin shiners {Notropis spilopterus), sand shiners (N. stramineus) , bluntnose minnows (Pimephales notatus), and young-of-the-year and yearling carpsuckers were collected regularly throughout the sampling period by seining. Collections were pooled by taxonomic groups, blotted dry, and weighed. Sample size of most aquatic insects ranged from 0.3 to 8.0 g. Samples ranged from 4 to 50 g for Corydalus and Orconectes, and from 12 to 82 g for minnows. Replicate samples were run when sample size was adequate. Tissue samples were analyzed according to the procedures in the Pesticide Analytical Manual of the U.S. Department of Health, Education, and Welfare (7). The extraction procedure was slightly Vol. 9, No. 4, March 1976 187 modified when a double petroleum ether extraction was made during the partitioning phase. Extracts were concentrated and eluted in the same man- ner as the sediment extracts. Samples were concentrated to 1-10 ml for quantitation. In 1971, authors collected channel catfish monthly from April through October in hoop nets and by electro- shocking. Total length was measured at capture. Fish were then wrapped in aluminum foil and frozen until analysis. Dorsal muscle tissue of catfish 300-399 mm long and of all catfish taken in June was analyzed indi- vidually (7). Catfish 200-299 mm long, which were collected during months other than June, were pooled on each collection date for a single analysis. In 1973, channel catfish were collected monthly from June to September. Spring and fall flooding prevented further sampling. Specimens were grouped for pesticide analysis in four lengths: 150-199 mm, 200-299 mm, 300-399 mm, and 450-550 mm. Muscle tissue from 4 to 15 catfish in each length group was pooled into three subsamples for each collection day. Small numbers of 450-550-mm catfish occasionally were analyzed indi- vidually. Samples were extracted and cleaned on char- coal and florisil columns as previously described for crayfish and small fish. QUANTITATION A Beckman GC-5 gas chromatograph equipped with a discharge electron-capture detector was employed for the quantitation of all samples. Quantitation was accom- plished on a 5 percent OV-210 column at 180°C and a 1.5 percent OV-17/QF-1 column at 200°C. Helium flow was about 100 mm/min and attenuation was 2X10-'. A 4 percent SE-3/6/QF-1 column with a gas flow rate of 120 mm/min, a temperature of 200°C, and an attenuation of 2X10*' was used as a qualitative check. Confirmation was made by comparing retention time of the samples to that of a dieldrin standard filtered through two chromatographic columns of difl'erent polarity. Background levels of 8.4 ng (standard deviation: 0.8 ng) of what seemed to be dieldrin were measured from a series of blanks in 1973. This contamination was usually less than 1 percent for crayfish and fish samples weighing more than 10 g. Background dieldrin levels for aquatic insect samples, however, varied from 2 to 27 percent because very little tissue was available for analysis. The reported dieldrin concentrations in aquatic insects were corrected for this contamination. Pesticides in all organisms were expressed on a wet-weight basis. RECOVERY Channel catfish were exposed to 10 ppb "C-dieldrin in 360 liters of water for 6 hours. A 519 ppb (standard deviation: 31 ppb) stock mesh and a 53.6 ppb (stand- ard deviation: 2.8 ppb) stock mesh were prepared by homogenizing muscle tissue of the exposed catfish with portions of cold tissue in a Waring blendor. Stock mesh dieldrin levels were determined by directly counting tissue samples. Three replicates of four dieldrin levels (5190.0, 1072.0, 107.0, and 53.6 ng) were prepared by varying sample sizes from the two stock meshes in order to cover the range of dieldrin levels encountered in the survey. These samples were extracted and cleaned according to the method of analysis employed through- out the investigation. Aliquots of these extracts were removed to scintillation vials with 15 ml BBOT scin- tillation cocktail for counting on a Packard Tri-Carb scintillation counter. Quenching was corrected by in- ternal standardization. Recovery of dieldrin from cat- fish muscle tissue averaged 86 percent and ranged from 78 to 99 percent. Results were not corrected for percent recovery. Results Dieldrin concentrations in Des Moines River water and suspended sediment ranged from 10 to 50 pptr in 1971, from less than 10 to 40 pptr in 1972, and from 1 to 31 pptr in 1973. Variation within and among years was significant (Fig. 1). Average dieldrin concentrations from May to September decreased from 32 pptr in 1971 to less than 15 pptr in 1972 and to 8 pptr in 1973 (Table 1). Wide variations in stream flow and suspend- ed sediment load also occurred during the 3-year period. Flow during the study period was about normal in 1971, higher in 1972, and at record highs in 1973. Because concentrations might vary directly or inversely with flow, authors calculated the actual amount of dieldrin being transported past the study site. Comparisons of dieldrin concentrations were most reliable on an annual basis for 1971 and 1973 and for June and July of all 3 years. The average amount of dieldrin transported downstream per day was 174 g in 1971 but only 89 g in 1973. Concentrations and amounts of dieldrin trans- ported downstream decreased in June and July each year. Seasonal trends in dieldrin concentrations were also consistent from year to year: the dieldrin content was low in early spring, increased rapidly thereafter, and decreased in late summer (Fig. 1). Average concentra- tions were highest in June and July. When mean monthly concentrations for the 3 years combined were plotted to reveal general trends more clearly, the rela- tively high concentrations during June and July were very evident (Fig. 2). This seasonal trend in dieldrin levels was evaluated in light of occurrences in the watershed. Most Iowa farm- land is plowed in late fall so that the land is clear of vegetation in early spring when final preparations, in- cluding the application of aldrin, are made for planting. Heavy rains during the spring sometimes deposit huge quantities of soil in the streams. For example, a storm 188 Pesticides Monitoring Journal CO C3 C3 50- 40 30 20- 10 c^l971 ^1972 A^ -below 10 pptr •-1973 APRIL MAY JUNE JULY AUG. SEPT. OCT. NOV. FIGURE 1. Total dicldrin concentration, nnftltcred Dcs Moines River water, Iowa — 1971-73 on the watershed caused increased river flow and heavy sediment discharge from May 30 to June 2, 1973. On May 31. 19.233 metric tons of suspended sediment were carried downriver past the Saylorville. Iowa, gaging station located below the study site {8). On June 2, when water samples were collected for analysis, stream flow was 320 mVsec; sediment load was 12,973 metric tons. A total of 858 g of dieldrin was transported downstream that day. This calculation was based on an average of 19 pptr (61 percent) sorbed on the sus- pended sediment and 12 pptr dieldrin in filtered water samples. The source of this sediment was unknown, but Glymph (9), who examined data on small watersheds in four Iowa counties, reported that 56-100 percent of the sediment in streams came from sheet erosion off the land. Huang and Liao (10) and Huang (11.12) illus- trated the high affinity of different types of clay particles for dieldrin. Thus, the sorbed pesticide can be carried TABLE I. Mean monthly concentrations of dissolved and suspended dieldrin, mean daily stream flow, and calculated dieldrin transport, Des Moines River, Iowa — May-September, 1971-73 No. SAMPLING DAYS Mean dieldrin concentration, pptu Mean daily STREAM flow, M™/ SEC ^ Calculated dieldrin TRANSPORT. G/DAY Month 1971 1972 1973 1971 1972 1973 1971 1972 1973 1971 1972 1973 May 1 4 7 10 <10 8 66.1 137.9 244.6 57-' <119 169 June 1 5 8 50 24 10 110.9 116.4 175.1 479 242 151 July 1 2 7 40 23 12 97.9 83.6 92.5 .338 166 96 August 1 2 6 30 <10 6 14.7 114.9 26.4 38 <99 14 September 1 1 4 30 <10 4 5.7 42.3 44.2 15 <36 15 MEAN 32 <15 8 59.1 99.0 116.6 174 <132 89 ' See Literature Cited, references 8, 19, and 20. = 10 pptr X 10-'= X 66.1 m' X 10" X 86,400 sec = 57 g/day. Vol . 9, No. 4. March 1976 189 ' CORN • DIELDRIN 40 — — 40 i= a. o. s5 /^. t/» O^* / , UJ 30 - 30 1 H- / / ^ ^c oc ^f / ^ / ►— ^j ^c ^^ / 1/ LiJ « 20 - 20 i ^3 O Cd / / 2 10 / I / 1 / 1 II 1 1 1 ^ " 10 1 APRIL MAY JUNE JULY AUG. SEPT. OCT. FIGURE 2. Timing of corn planting and aldrin application in relation to monthly mean dieldrin concentrations, Des Moines River water, Iowa — 1971-73 with the soil into river systems by storm runoff. The amount of pesticide transported during any one storm depends on variables such as duration of storm runoff, antecedent soil/ moisture conditions, rainfall intensity, and the source of runoff in the watershed (13). Corn was planted progressively later in each of the 3 study years because of adverse weather and heavy rain- fall in the spring of 1?72 and 1973. About 95 percent of the corn was planted by May 24 in 1971, and by May 28 in 1972, but not until after June 4 in 1973 (14,15). For 3 years corn planting and aldrin applica- tion were essentially completed by the first week in June. In June and July mean dieldrin concentrations in river water were at their peak. Although authors did not determine the source of the dieldrin in river water, these relations support the premise of Johnson and Morris (16) that dieldrin in Iowa rivers and streams originates mainly from agricultural application of aldrin through surface runoff from cultivated areas. Authors examined the relative amounts of dieldrin in the suspended dissolved fractions of water samples col- lected in 1973. Suspended dieldrin, extracted primarily from soil particles and secondarily from plankton, ranged from less than 1 pptr to 19 pptr, which was 3-67 percent of the total dieldrin measured in water samples on a given day (Fig. 3). An average of about two- thirds the total dieldrin measured was dissolved; con- centrations ranged from 1 to 16 pptr. A significant correlation between amounts of suspended and dissolved dieldrin was evident (r = 0.47; p = 0.01), which indi- cated that both values followed the same seasonal trend. Volume of stream fiow and concentration of dissolved dieldrin significantly correlated (r = 0.55; p = 0.01), but stream flow and concentration of suspended dieldrin did not correlate. Levels of suspended dieldrin were highest in late May and early June, when sediment was most likely coming from agricultural land rather than from sloughing of the stream bank. Dieldrin concentrations in bottom-sediment samples averaged 4 ppb in July, 2.4 ppb in August, and less than 0.1 ppb in September and November. September and November samples may have been comprised largely of material scoured from the banks, resulting in the low dieldrin levels. Dieldrin content in mayflies of the genus Potamanthus exhibited marked seasonal trends in 1972. Concentra- tions increased from 44 ppb in April and May to 115 ppb in June, and decreased to 48 ppb in July (Fig. 4). Emergence of the adult mayflies in late July prevented further sampling. This spring trend of dieldrin content 190 Pesticides Monitoring Journal 30 CO 20 10- I • TOTAL o SUSPENDED APRIL MAY JUNE JULY AUG. SEPT. OCT. NOV. FIGURE 3. Mean concentrations of total and suspended dieldiin, Des Moines River water, Iowa — 1973 of PoKimanihus in 1972 was not observed in 1973 because collecting did not begin until June. Neverthe- less, sharp decreases in dieldrin residues in this genus were noted from June to July in both years. A decrease in June levels from 115 ppb in 1972 and 61 ppb in 1973 also corresponded to the drop in dieldrin concen- trations in June water samples between the 2 years. In 1973, dieldrin concentrations in aquatic insects ranged from 10 to 98 ppb and were similar among the insect groups in any single month (Table 2). The mean dieldrin concentration in all insects for the 6- month period was 35 ppb. A significant seasonal trend was observed; concentrations decreased from 66 ppb in June to 15 ppb in September and then increased sharply to 63 ppb in late October. Dieldrin content of crayfish in both 1972 and 1973 was much lower than that of aquatic insects; the mean con- centration was 9 ppb in 1972 and 6 ppb in 1973 (Table 3). In 1972 no seasonal trend was evident but in 1973 there was a marked seasonal decrease from 13 ppb in June to 4 ppb in July and 2 ppb in September. TABLE 2. Mean dieldrin concentrations in aquatic insect f,'roiips, Des Moines River, Iowa — 1973 CONCENTR ATION. PPB Organism June 17 JuLV July 8 25 Aug. 15 Sept, 22 Oct. 27 Acroneiiria Small Large - 25 14 44 11 27 19 15 62 Pleronarcys - - 15 13 — — Polamanthiis 61 24 — — — 76 Isonychia 70 .18 - — — — Ephoorn - - 14 — — — Heptagcniidae 44 — — — — — Tricoptera — — — 18 18 52 Corvdalux 35-55 mm 65-75 mm - — — 12 20 12 14 - Chironomidae — — — — 14 — MEAN 66 29 22 17 15 63 NOTE: — = no sample taken Vol. 9, No. 4, March 1976 191 120 - POTAMANTHUS ^ 100 o o K- C9 80 - / °\ / °\ \ -J LU 40 0 O 00 1 1 1 o 1 APRIL MAY JUNE JULY FIGURE 4. Mean dicldrin concentrations in mayflies of ficniis Potamimthus Dc^ Moines River, Iowa — 1972 TABLE 3. Monthly mean clieldrin concentrations in crayfish (Orconectes), Des Moines River. Iowa — 1972-73 1972 1973 Month ' No. SPECIMENS DlEL DRIN, PPB No. SPECIMENS DiELDRIN, PPB April 14 6 — — June 12 12 2 13 July 4 10 4 4 August 2 23 12 3 September 8 2 17 2 October 6 3 — — MEAN 9 6 NOTE: — — no samples taken 1 No samples were collected in May. Dicldrin concentration in minnows and small carpsuck- ers collected in 1973 averaged 48 ppb for all samples combined: the range in individual samples was 5-160 ppb. Seasonal trends were similar to trends observed in aquatic insects (Fig. 5). Dicldrin concentrations and seasonal trends differed significantly, however, among the four groups of forage fish (F = 22.4 and 4.9; p = O.OI). The spotfin shiner contained the highest dicldrin residues throughout the entire sampling period except August; mean dicldrin concentrations in this species were 156 ppb in June, 25 ppb in August, and 61 ppb in November. The sand shiner and bluntnose minnow contained somewhat lower dicldrin concentrations; averages in June were 101 ppb and 66 ppb, respectively. Seasonal trends in the two species were similar to those in the spotfin shiner. However, the decrease in concen- tration from June to August was much less in the bluntnose minnow than in the spotfin and sand shiners. Small carpsuckers contained the lowest dicldrin con- centrations among the forage fish collected; the mean June level was 16 ppb. The seasonal trend of concen- trations differed from that in the minnows: concentra- tions decreased slightly from June to July and then increased steadily to a high of 42 ppb in November. In 1971. authors investigated seasonal trends in dicldrin content of muscle tissue of channel catfish collected from April to October. In June, the average dieldrin content of 32 fish 155-602 mm long was 89 ppb (range: 2-940 ppb). The mean concentration in 105 fish col- lected from April to October was 60 ppb. Among fish 200-299 mm long (Table 4), mean monthly concentra- tions were higher in July (61 ppb) than in any month except October (74 ppb). Monthly means in fish 300- 399 mm long ranged from 109 ppb in July to 5 ppb in October. Differences in monthly means were sta- tistically significant in this length group (p = 0.05). Concentrations in individual fish ranged from 0 to 207 ppb. Differences between monthly samples in the 200- 299-mm group could not be tested statistically because fish were pooled for chemical analysis rather than analyzed individually. Mean concentrations in this length group could be compared on a monthly basis with concentrations in the 300-399-mm group. Mean monthly concentrations in the smaller fish fell within 160 140 " n o Spotfin shiner N, •Sand shiner \ j^ Bluntnose minnow A ACarpsucker 120 \ 100 - 'I \ 80 - \ \ 60 - \V \ ^^^ 40 20 1 1 1 1 1 JUNE JULY AUG. SEPT. OCT. NOV. FIGURE 5. Mean dieldrin concentrations in four groups of small fish, Des Moines River, Iowa — 1973 192 Pesticides Monitoring Journal TABLE 4. Dieldrin content of channel catfish, Des Moines River, Iowa— 1971 Month No. FISH Concentration, PPB » Fish Length 200-299 MM April 15 29 May 7 26 June 9 33 July 6 61 August 4 35 September 3 44 October 3 74 Total/ MEAN 47 43 Fish Length; 300-399 MM April 9 71 (18) May 8 27(9) June 6 39 (13) July 7 109 (19) August 3 9 (4) September 4 70 (24) October 4 5(1) Total/ MEAN 41 47 ' Standard errors for fish analyzed individually are in parentheses. the 95 percent confidence limits for the 300-399-mm group in May, June, and September and outside these limits in the other months (Table 4). Confidence limits greater than twice the monthly mean indicated the large variation in dieldrin content in muscle tissue of catfish of similar size. In 1973, muscle of channel catfish collected from June to September contained 10-172 ppb dieldrin; the mean for all fish analyzed was 45 ppb (Table 5). Although TABLE 5. Monthly mean dieldrin concentration in muscle tissue of channel catfish, Des Moines River, Iowa — 1973 Length DiEr DRiN concentration, ppb MM June July August September Mean 150-199 15(9) 14(12) 13(12) 12(15) 13 200-299 22(12) 75(12) 133(12) 113(12) 86 300-399 25(9) 72(4) 40(9) 26(12) 41 450-550 20(9) 60(4) 49(5) 36(4) 41 Mean 20(39) 54(32) 58(38) 48(43) 45 NOTE: Values in parentheses represent number of fish sampled. dieldrin concentrations among length groups were not significantly different in the June sample, they were significantly different over the full sampling period (F = 4.2; p = 0.01 ) (Fig. 6). Dieldrin content was lowest in the 150-199-mm length group (mean: 13 ppb). This group had the lowest dieldrin levels from June through September. Dieldrin concentrations were highest in LENGTH OF FISH, mm /\ * 150-199 / \ 120 " o 200-299 / \ . 300-399 / ^ • 450-550 / 100 / ■a a. Q. / t/> 80 / CATFISH C9 60 - A UJ 40 - / ^^ 20 * — A • — * — A 1 1 1 JUNE JULY AUG. SEPT. FIGURE 6. Mean dieldrin concentrations in dorsal muscle of channel catfish, Des Moines River, Iowa — 1973 muscle of 200-299-mm fish, which contained an average of 86 ppb. Monthly mean values increased from 22 ppb in June to 133 ppb in August, and then decreased slightly in September. The 300-399-mm and 450-550- mm length groups contained maximum concentrations of 72 ppb and 60 ppb in July; concentrations then decreased in August and September. Seasonal trends of dieldrin concentrations in muscle of 200-299-mm and 300-399-mm catfish observed in 1973 differed markedly from trends in 1971 (Tables 4, 5). Statistical evaluation of the differences in seasonal trends between the 2 years was not possible because of differ- ences in pooling samples, but some general comparisons could be made. Mean dieldrin concentrations increased from June to July in both length groups in 1971 and 1973. Trends in dieldrin content during late summer and early fall varied considerably between the 2 years. Mean concentrations of dieldrin in catfish muscle from June to September 1971 were not significantly different from those of all other samples during the same months in 1973 nor from concentrations in the 200-299- and 300-399-mm length groups, considered separately. Hence, even though dieldrin concentrations seemed to decrease in river water from 1971 to 1973, this de- Voi. 9. No. 4, March 1976 193 Crease could not be detected in muscle tissue of channel catfish. Discussion Dieldrin concentrations varied seasonally in river water, aquatic invertebrates, minnows, and small carpsuckers, and in muscle tissue of all but one length group of channel catfish. Dieldrin content of water was highest immediately after aldrin application to the watershed. Mean dieldrin concentration in most aquatic organisms was highest in June and July, coincidental with high dieldrin levels in river water, although much variation and some exceptions were evident. In late summer and fall, increases in dieldrin content in insects, small fish, and some length groups of catfish coincided with re- duced concentrations in water. This absence of a con- sistent correlation throughout the season between diel- drin concentrations in the water and residues in aquatic organisms is not unexpected since several environmental and physiological factors are involved in pesticide up- take and retention by animals (17). Authors believe that seasonal changes in fat content (18) and metabolic rate, caused by factors such as water temperature and reproductive activity, can alter the amount of certain pesticides stored in the body. Activity of detoxifying enzymes that degrade pesticides and thereby allow their elimination is also temperature-dependent, and thus could vary seasonally in eflfectiveness. This study demonstrated clearly the absence of a con- sistent relation throughout the season between dieldrin concentrations in catfish of different lengths. Contrary to common expectations, concentrations were not always greater in large catfish than in small ones. Physio- logical diflferences noted above may explain this phe- nomenon. A cknowledgments Authors thank John' Richard and Larry Shannon, Iowa State University, for conducting the 1971 chemical analyses on catfish tissue. LITERATURE CITED (/) Morris, R. L., cmd D. W. Eberl. 1972. Pesticides and heavy metals in the aquatic environment. Health Lab. Sci. 9(2):145-151. (2) Morri.s. R. L.. and L. G. Johnson. 1971. Dieldrin levels in fish from Iowa streams. Pestic. Monit. J. 5(1): 12-1 6. (3) Sclnvob, H. H. 1970. Floods in the Upper Des Moines River Basin, Iowa. Geological Survey, U.S. Depart- ment of Interior, Iowa City, Iowa. 49 pp. (4) U.S. Department of Agriculture. 1970. Upper Missis- sippi River Comprehensive Basin Study. Appendix N: Agriculture. U.S. Department of Interior, Washington, D.C. 210 pp. (J) U.S. Environmental Protection Agency. 1971. Methods for Organic Pesticides in Water and Wastewater. Na- tional Environmental Research Center, Cincinnati, Ohio. 38 pp. (6) Berg, O. W., P. L. Dio.mdy, and G. A. V. Rees. 1972. Column chromatographic separation of polychlorinated biphenyls from chlorinated hydrocarbon pesticides, and their subsequent gas chromatographic quantitation in terms of derivatives. Bull. Environ. Contam. Toxi- col. 7(6):338-347. (7) Food and Drug Administration. 1970. Pesticide Analy- tical Manual. Vol. 1, Sec. 212.1. U.S. Department of Health, Education, and Welfare. (8) Geological Survey. 1973. 1972 Water Resources Data for Iowa. U.S. Department of Interior, Iowa City, Iowa. 303 pp. (9) Glyinph, L. A/., Jr. 1957. Importance of sheet erosion as a source of sediment. Trans. Am. Geophys. Union 38(6):903-907. (10) Huang, Ju-Chang, and Chen-Sun Liao. 1970. Adsorp- tion of pesticides by clay minerals. J. Sanit. Eng., Div. Proc. Am. Soc. Civ. Eng. 96(SA5) : 1057-1078. (//) Huang, Ju-Chang. 1971. Effect of selected factors on pesticide sorption and desorption in the aquatic sys- tem. I. water PoUut. Control Fed. 43(8) : 1739-1748. (12) Huang, Ju-Chang. 1971. Organic pesticides in the i aquatic environment. Water Sewage Works 118(5): 139-144. (13) Caro. J. H., and A. W. Taylor. 1971. Pathways of loss " of dieldrin from soils under field conditions. J. Agric. Food Chem. 19(2) :379-384. (14) U.S. Department of Commerce and U.S. Department of Agriculture. 1971. Weekly Weather and Crop Bulle- tin. Lucius W. Dye (Ed.). 58(17-23). (15) U.S. Department of Commerce, U.S. Department of Agriculture, and Iowa Department of Agriculture. 1973. Iowa Weekly Weather and Crop Report. 73 I (4-10). (16) Johnson, L. G., and R. L. Morris. 1971. Chlorinated I hydrocarbon pesticides in Iowa rivers. Pestic. Monit. J. 4(4):216-219. (17) Cope, O. B. 1966. Contamination of the fresh-water r eco-system by pesticides. J. Appl. Ecol. 3(Suppl): 33-34. (18)Bulkley, R. I'.. L. R. Shannon, and R. L. Kellogg. 1974. Contamination of Channel Catfish from Agri- cultural Runoff. Iowa State Water Resour. Res. Inst. Completion Rep. 62. Project No. A-042-IA. 144 pp. (19) Geological Survey. 1972. 1971 Water Resources Data, for Iowa. U.S. Department of Interior, Iowa City, Iowa. 349 pp. (20) Geological Survey. 1974. 1973 Water Resources Data for Iowa. U.S. Department of Interior, Iowa City, Iowa. 335 pp. 194 Pesticides Monitoring Journ.\l APPENDIX Chemical Names of Compounds Discussed in This Issue ' ALDRIN BUC (BENZENE HFXACHLORIDE) CHLORDANE DDD DDE DDT niELDRIN ENDRIN HCB HEPTACHLOR EPOXIDE LINDANE MIREX PCB'S (POLYCHLORINATED BIPHENYLS TDE TOXAPHENE Not less than 95% of I,2,3.4.10.10-Hexachloro-I,4,4a,5,8,8a-hexahydro-l,4c«rfo-Mo-5,8-dimclhan,inarhthalene 1,2,3,4,5, 6-Hexachlorocyclohexane (mixture of isomers). Commercial product contains several isomers of which gamma is most active as an insecticide. l,2,3,5,6,7,8,8-Octachloro-2,3,3a,4,7,7a-hexahydro-4.7-methanoindene. The technical product is a mixture of several compounds including heptachlor, chlordcne, and two isomeric forms of chlordane. See TDE. Dichlorodiphenyl dichloro-ethylene (degradation product of DDT) r.P'-DDE: l,l-Dichloro-2,2-bis(p-chlororhenyl) ethylene o.p'-DDE: l,l-Dichloro-2-(o-chlorophenyl)-2.(p-chlorophenyllt;thylene Main component (p.p--DDT): a-Bis(p-chlorophenyl) /3,/3,^-trichloroethane Other isomers are possible and some are present in the commercial product. o.p'-DDT : 11,1,1 -Trichloro-2- ( o-chlorophenyl ) -2-(p-chlorophenyl ) ethancl Not less than 85% of l,2,3,4,10,10-Hexachloro-6,7-epoxy-l,4,4a, 5,6,7,8, 8a-octahydro-l,4-fndo-fvo-5.8-dimethano- naphthalene l,2,3,4.10,10-Hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a octahydro-l,4-endo-p»ido-5,8-dimelhanonaphthalene Hexachlorobenzene 1,4,5,6,7,8,8-Heptachloro 2,3-epoxy-3a,4,7.7a-tetrahydro.4,7-metIianoindane Gamma isomer of benzene hexachloride 1,2.3,4,5,6-hexachlorocyclohexane of 99+% purity Dodecachlorooctahydro-l,3,4-metheno-2H-cyclobutalcdlpentalene Mixtures of chlorinated biphenyl compounds having various percentages of chlorine 2,2-Bis(p-chlorophenyl)-l,l-dichloroethane Chlorinated camphene (67-69% chlorine). Product is a mixture of polychlor bicyclic terpenes with chlorinated camphenes predominating ' Does not include chemicals listed only in tables of paper by Johnson.'Manske. Vol. 9, No. 4, March 1976 195 A cknowledgment The Editorial Advisory Board wishes to thank the following persons for their valuable assistance in reviewing papers submitted for publication in Volume 9 of the Pesticides Monitoring Journal: U.S. DEPARTMENT OF AGRICULTURE George F. Fries Kenneth R. Hill J. V. Lagerwerff U.S. ENVIRONMENTAL PROTECTION AGENCY Jack I. Lowe G. Bruce Wiersma Alfred J. Wilson U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE Stephen G. Capar Paul E. Corneliussen William J. Trotter Sidney Williams U.S. DEPARTMENT OF INTERIOR Lawrence J. Blus Donald F. Goerlitz 196 Pesticides Monitoring Journai SUBJECT AND AUTHOR INDEXES Volume 9, June 1975— March 1976 Preface Primary headings in the subject index consist of pesti- cide compounds listed alphabetically by common name or trade name when there is no common name, the media in which residues are monitored, and several concept headings, as follows: Media and Concept Headings Air Degradation Factors Influencing Residues Food and Feed Humans Plants (other than those used for food and feed) Sediment Soil Water Wildlife Compound headings are used as secondary headings under the primary media and concept headings and vice versa. When a particular paper discusses five or more organochlorines, the compounds are grouped by class under the media or concept headings; in the pri- mary headings, however, all compounds are listed indi- vidually. In the author index, the names of both senior and junior authors appear alphabetically. Full citation is given only under the senior author, with a reference to the senior author appearing under junior authors. Vol. 9, No. 4, March 1976 197 SUBJECT INDEX Air Industrial PCP 9{3):150-153 Aldrin Factors Influencing Residues 9(1 ):34-38 Food and Feed 9(2):94-105 9(4):157-169 Sediment 9(1) 9(2) 9(2) Soil Water 9(1 ) 9(1) 9(2) 9(1) 9(2) 9(2) 9(3) 34-38 89-93 106-114 30-33 34-38 106-114 34-38 89-93 106-114 134-140 9(2);89-93 9(3);134-140 Aroclor ® (see also PCB's) Plants (other than those used for food and feed) 9(l);39-43 Water 9(1):2-10 9(l):39-43 Wildlife 9(11:2-10 9(l);39-43 Arsenic Factors Influencing Residues 9(2):94-105 Food and Feed 9(2);94-105 9(41:157-169 Atrazine Water 9(3):117-123 B BHC/Lindane Fac ors Influencing Residues 9(1) 34-38 9(2) 94-105 Foo d and Feed 9(2) 94-105 9(4) 157-169 Sed nient 9(1) 34-38 9(2) 106-114 Soil 9(1) 34-38 9(2) 106-114 Wa er 9(1) 34-38 9(2) 106-114 9(3) 134-140 Botran ® Factors Influencing Residues 9(2):94-105 Food and Feed 9(2):94-I05 Cadmium Factors Influencing Residues 9(2):94-105 9(4):155-I56 Food and Feed 9(2):94-105 9(4): 157-169 Water 9(4):155-156 Wildlife 9(4):155-156 Captan Factors Influencing Residues 9(2):94-105 Food and Feed 9(2):94-105 Carbaryl Factors Influencing Residues 9(2) :94-105 Food and Feed 9(2):94-105 9(4): 157-169 Cblordane Factors Influencing Residues 9(11:34-38 Food and Feed 9(2):94-105 9(4):157-169 Sediment 9(l):34-38 9(2):106-114 Soil 9(l):34-38 9(2) :106-1I4 Water 9(11:34-38 9(2):106-1I4 9(31:134-140 9(4):170-175 Wildlife 9(31:134-140 9(4):170-I75 CIPC Factors Influencing Residues 9(21:94-105 Food and Feed 9(21:94-105 9(4): 157-169 DDD (see also TDE) Factor s Influencing Residues 9(2) 79-88 9(2) 89-93 9(4) 155-156 9(4) 176-185 Sediment 9(2) 89-93 9(2) 106-114 Soil 9(1) 30-33 9(2) 106-114 Water 9(2) 89-93 9(2) 106-114 9(3) 134-140 9(4) 155-156 Wildlife 9(1) 11-14 9(2) 79-88 9(2) 89-93 9(3) 134-140 9(4) 155-156 9(4) 176-185 DDE Factors Influencing Residues 9(2):64-66 9(2):79-88 9(2):89-93 9(2):94-105 9(3): 134-140 9(41:155-156 9(4):170-175 9(41:176-185 Food and Feed 9(21:94-105 9(4): 157-169 Humans 9(2):64-66 Plants (other than those used for food and feed ) 9(l):39-43 Sediment 9(2):89-93 9(21:106-114 Soil 9(11:30-33 9(21:106-114 Water 9(1) 9(1) 9(1) 9(2) 9(2) 9(3) 9(3) 9(4) 9(4) 2-10 21-29 39-43 89-93 106-114 117-123 134-140 155-156 170-175 Wildlife 9(1):2-10 9(1):11-14 9(l):21-29 9(11:39-43 9(2):79-88 9(2):89-93 9(31:134-140 9(41:155-156 9(4): 170-175 9(4):176-185 Wildlife 9(31:134-140 D 2,4-D Food and Feed 9(2):94-l05 9(41:157-169 Dactlial,® see DCPA DCPA Food and Feed 9(41:157-169 DDT Factors Influencing Residues 9(11:34-38 9(2):64-66 9(2):79-88 9(2): 89-93 9(2):94-l05 9(41:155-156 9(4):170-I75 9(4):176-185 Food and Feed 9(2):94-105 9(4): 157-169 198 Pesticides Monitoring Journal Humans 9(1) 9(2) Plants (i)thc food and 9( 1 ) Sediment 9( 1 ) 9(2) 9(2) :30-33 :64-66 r than those used for feed 1 : 39-43 :34-38 : 89-93 : 106-1 14 Soil 9(1) 9(1) 9(2) 9(1) 9(1) 9(1) 9(1) 9(2) 9(2) 9(3) 9(4) 9(4) Wildlife 9(1) 9(1) 9(1) 9(1) 9(1) 9(1) 9(2) 9(2) 9(3) 9(4) 9(4) 9(4) 30-33 34-38 106-114 2-10 21-29 34-38 39-43 89-93 106-114 134-140 155-156 170-175 1 2-10 11-14 21-29 30-33 39-43 79-88 89-93 134-140 155-156 170-175 176-185 WildUfe 9(1) 2-10 9(1) 11-14 9(1) 39-43 9(2) 79-88 9(2) 89-93 9(3) 134-140 9(4) 155-156 9(4) 170-175 9(4) 176-185 9(4) 186-194 Diirsban ® Food and Feed 9(4) 157-169 E Eiidosulfan Factors Influencing Residues 9(2):94-l05 Food and Feed 9(2):94-105 9(4) :157-169 Endrin Diazinon Factors Influencing Residues 9(2):94-105 Food and Feed 9(2):94-105 9(4):157-169 Dicofol Factors Influencing Residues 9(2);94-105 Food and Feed 9(2):94-105 9(4); 157-169 Dieldrin Factors Influencing Residues 9(11:34-38 9(2):64-66 9(2):79-88 9(2):89-93 9(2):94-105 9(4):155-156 9(4):170-175 9(4):176-185 9(4):186-194 Food and Feed 9(21:94-105 9(4):157-169 9(4): 186-194 Humans 9(21:64-66 Plants (other than those used for food and feed) 9(l):39-43 Sediment 9(l):34-38 9(4):89-93 9(2);106-114 Factors Influencing Residues 9(I):34-38 Food and Feed 9(2):94-105 9(4):157-169 Sediment 9(l):34-38 9(2):89-93 9(2):I06-114 Soil Water 9(l):34-38 9(2):106-114 9(1 ):34-38 9(2):89-93 9(2):I06-114 9f4):170-175 Wildlife 9(2):89-93 9(4):170-175 Ethion Factors Influencing Residues 9(2) :94-105 Food and Feed 9(21:94-105 9(4):157-169 Soil Water 9(l):30-33 9(l):34-38 9(2): 106-114 9(1):2-10 9(l):34-38 9(l):39-43 9(2):89-93 9(2):106-114 9(3):117-123 9(31:134-140 9(41:155-156 9(4): 170-175 9(4): 186-194 Factors Influencing Residues Age cadmium 9(4):155-I56 DDD 9(2):79-88 DDE 9(2):79-88 DDT 9(2):79-88 lead 9f4):155-156 mercury 9(21:59-63 9(4):155-156 organochlorines 9(41:155-156 Environmental, Geographical, and Locational general 9(2):94-105 mercury 9(l):44-54 9(2):59-63 9(2): 67-78 organochlorines 9(21:89-93 9(3):134-140 9(4): 176-185 PCP 9(3):150-153 Seasonal and Temporal DDD 9(2):79-88 DDE 9(2):79-88 DDT 9(2):79-88 dieldrin 9(2):79-88 9(4): 186-194 mi rex 9(3):124-I33 9(31:141-149 organochlorines 9(11:34-38 9(2):89-93 PCP 9(31:150-153 Sex cadmium 9(41:155-156 DDD 9(21:79-88 DDE 9(2):79-88 DDT 9(2):79-88 lead 9(41:155-156 mercury 9(21:59-63 9(4): 155-156 organochlorines 9(4):155-156 Species DDD 9(21:79-88 DDE 9(2):79-88 DDT 9(2):79-88 mercury 9(l):44-54 9(41:170-175 organochlorines 9(2);89-93 9(4) :170-175 Weight and Size DDE 9(21:64-66 DDT 9(2):64-66 dieldrin 9(21:64-66 HCB 9(2):64-66 mercury 9(l):44-54 Food and Feed Animal Food Organisms dieldrin 9(4) : 186-194 Total Diet 9(2):94-105 9(4):157-169 H HCB Factors Influencing Residues 9(2):64-66 9(4):I55-156 Food and Feed 9(2):94-105 9(41:157-169 Humans 9(2): 64-66 Water 9(4):155-156 Wildlife 9(1):11-14 9(4):155-156 Vol . 9. No. 4, March 1976 199 Heptachlor Factors Influencing Residues 9(l):34-38 Sediment 9(l):34-38 9(2):89-93 9(2):106-n4 Soil 9(l):34-38 9(2):106-114 Water 9(1 );34-38 9(2l;89-93 9(2):106-114 9(3):134-140 Wildlife 9(2):89-93 9(31:134-140 Heptachlor Epoxide Factors Influencing Residues 9(11:34-38 9(2):94-105 9(3):134-140 Food and Feed 9(2):94-105 9(41:157-169 Sediment 9(l):34-38 9(2):89-93 9(2):106-114 Soil 9(11:34-38 9(2):106-114 Water 9(11:34-38 9(2):89.93 9(2):106-114 9(3):134-140 Willdlife 9(1):11-I4 9(2):89-93 9(3):134-140 Humans Blood organochlorines 9(11:30-33 PCP 9(3):150-153 Chromosomal Aberrations PCP 9(3):150-153 Milk DDE 9(2): DDT 9(2): dieldrin 64-66 64-66 64-66 64-66 9(2): HCB 9(2): Tissues mercury 9(2):59-63 Urine PCP 9(31:150-153 Kelthanc®, see Dicofol Lead Factors Influencing Residues 9(41:155-156 Food and Feed 9(4):157-169 Water 9(41:155-156 Wildlife 9(4):155-156 M Malathion Factors Influencing Residues 9(21:94-105 Food and Feed 9(21:94-105 9(4):I57-169 Mercury Factors Influencing Residues 9(1 ):44-54 9(21:59-63 9(21:67-78 9(21:94-105 9(41:155-156 9(4):I70-175 Food and Feed 9(21:94-105 9(41:157-169 Humans 9(21:59-63 Plants (other than those used for food and feed ) 9(11:39-43 Sediment 9(11:15-20 9(1 1:44-54 Water 9(11:15-20 9(1 1:39-43 9(1 1:44-54 9(4):155-I56 9(41:170-175 Wildlife 9(1): 15-20 9(11:39-43 9(11:44-54 9(21:67-78 9(4):155-156 9(4): 170-175 Methoxychlor Factors Influencing Residues 9(1 1:34-38 Food and Feed 9(21:94-105 9(41:157-169 Sediment 9(11:34-38 Soil 9(11:34-38 Water 9(11:34-38 Methyl Parathion Food and Feed 9(21:94-105 9(41:157-169 Mirex Water 9(11:34-38 Wildlife Factors Influencing Residues 9(3) 124-133 9(3) 141-149 Sediment 9(3) 141-149 Sail Wit 9(3) 141-149 Wat 9(4) 170-175 Wild life 9(1) 11-14 9(3) 124-133 9(3) 141-149 9(4) 170-175 N Nonachlor Factors Influencing Residues 9(1 1:34-38 Sediment 9(1 I : 34-38 Soil 9(11:34-38 9(1 1:11-14 o Orthophenylphenol Food and Feed 9(21:94-105 9(4): 157-169 Oxychlordane Wildlife 9(1):11-14 Parathion Food and Feed 9(21:94-105 9(4):157-169 PCA Food and Feed 9(2):94-I05 9(4):157-169 PCB's (see also Aroclor ®) Factors Influencing Residues 9(21:94-105 9(31:134-140 9(41:155-156 9(41:170-175 9(41:176-185 Food and Feed 9(21:94-105 9(41:157-169 Water 9(11:21-29 9(31:134-140 9(41:155-156 9(41:170-175 Wildlife 9(1 ):I1-14 9(l):21-29 9(3):134-140 9(41:155-156 9(41:170-175 9(4): 176-185 PCNB Food and Feed 9(21:94-105 9(41:157-169 PCP Air 9(31:150-153 Factors Influencing Residues 9(31:150-153 Food and Feed 9(41:157-169 Humans 9(31:150-153 Pentachlorophenol, see PCP. Perthane ® Factors Influencing Residues 9(21:94-105 Food and Feed 9(21:94-105 9(41:157-169 Phosalone Factors Influencing Residues 9(21:94-105 Food and Feed 9(21:94-105 9(41:157-169 200 Pesticides Monitoring Journal Plants (other than those for food and feed) Grasses mercury 9(l):39-43 organochlorines 9(l):39-43 Trees and Shrubs mercury 9(n:39-43 organochlorines 9(l):39-43 R Ronnel Food and Feed 9(2):94-105 9(4):157-169 used Water Sediment Canals and Ditches organochlorines 9(2):106-1I4 Lakes and Ponds organochlorines 9(2): 89-93 Ocean mercury 9(1): 15-20 Rivers and Streams mercury 9(l):44-54 mirex 9(3):141-149 organochlorines 9(l):34-38 Selenium Food and Feed 9(4): 157-169 Soil Croplands mirex 9(3):141-149 organochlorines 9(I):30-33 9(2):106-114 Riverbanks organochlorines 9(l):34-38 Strobane ® Food and Feed 9(4): 157-169 TCNB Food and Feed 9(4): 157-169 TDE (see also DDD) Factors Influencing Residues 9(2):94-in5 9(4): 170-175 Food and Feed 9(2):94-105 9(4): 157-169 Plants (other than those used for food and feed) 9(l):39-43 9(1):2-10 9(I):2l-29 9(l):39-43 9(4): 170-175 Wildlife 9(1):2-10 9(l):21-29 9(l):39-43 9(4) :I70-175 Toxaphene Food and Feed 9(2):94-105 Sediment 9(2):106-114 Soil 9(2):106-n4 Water 9(2): 106-1 14 9(4): 170-175 Wildlife 9(4): 170-175 w Water (see also Sediment) Canals and Ditches atrazine 9(3):I17-123 DDE 9(3):!17-123 dieldrin 9(3):117-123 organochlorines 9(l):34-38 9(2):106-114 Drinking atrazine 9(3):1I7-123 DDE 9(3):117-123 dieldrin 9(3):117-123 organochlorines 9(l):34-38 Estuaries and Marshes cadmium 9(4):155-156 lead 9(4):155-156 mercury 9(4):155-156 9(4):170-175 organochlorines 9(1):2-10 9(l):39-43 9(2): 106-1 14 9(3): 134-140 9(4):I55-156 9(4):170-175 Lakes and Ponds atrazine 9(3):117-123 DDE 9(3):117-I23 DDT 9(l):21-29 dieldrin 9(3):117-123 organochlorines 9(2):89-93 9(2):I06-I14 PCB's 9(l):21-29 Ocean mercury 9(1): 15-20 organochlorines 9(3) : 134-140 Rivers and Streams atrazine 9(3):117-I23 DDE 9(3):117-123 dieldrin 9(3):1I7-123 9(4): 186-194 mercury 9(l):44-54 organochlorines 9(l):34-38 9(2):106-114 9(3):134-140 Subsurface atrazine 9(3):117-123 DDE 9(3):117-123 dieldrin 9(3):117-123 organochlorines 9(l):34-38 Wildlife Amphibians mirex 9(3):124-133 Aquatic dieldrin 9(4): 186-194 mercury 9(1): 15-20 mirex 9(3):141-149 Birds DDD 9(2):79-88 DDE 9(2);79-88 DDT 9(l):l 9(2):79-88 dieldrin 9(2):79-88 mirex 9(3):141-149 organochlorines 9(1):11-I4 Ducks cadmium 9(41:155-156 lead 9(41:155-156 mercury 9(2):67-78 9(4):155-156 organochlorines 9(4):155-156 9(4): 176-185 Fish DDE 9(l):21-29 DDT 9(I):21-29 dieldrin 9(4):186-194 mercury 9(l):15-20 9(l):39-43 9(l):44-54 9(4):170-175 mirex 9(3):124-133 9(3):141-149 organochlorines 9(1):2-10 9(l):30-33 9(I):39j«3 9(2):89-93 9(3):134-140 9(4):170-175 PCBs 9(l):21-29 TDE 9(l):2l-29 Invertebrates dieldrin 9(4):186-194 mirex 9(3):124-133 9(3):141-149 organochlorines 9(2):89-93 Mammals mirex 9(3):124-133 9(3):14l-149 Vol. 9, No. 4, March 1976 201 Mongooses Reptiles organochlorines mercury mirex 9(1):2-I0 9(l):39-43 9(3):I24-133 9(l):39-43 mirex Shellfisli 9(3): 134-140 9(3): 141-149 dieldrin organochlorines 9(4): 186-194 9(l):39-43 mercury Plankton/ Algae 9(0:15-20 y mercury 9(l):39-43 9(l):15-20 9(1):44-S4 mirex mirex — , 9(3):141-149 9(3):141-149 *'""^ organochlorines Food and Feed 9(2):89-93 9(4): 157-169 202 Pesticides Monitoring Journai. AUTHOR INDEX Albright, L. J.. Northcote, T. G., Oloffs, P. C, and Szeto. S. Y. Chlorinated hydrocaibon residues in fish, crabs, and shellfish of the lower Fraser River, its estuary, and selected locations in Geor- gia Strait, British Columbia— 1972-73. 9(3):134-140 AvERV, M. J., see Richard, J. J. B Banks, W. A., see WnjciK, D. P. Barbehenn. K. R., see NrcKERsoN, P. R. Baskett, T. S. Mercury residues in breast muscle of wild ducks, 1970- 71. 9(2):67-78 Bei.isle, a. a., see Cro.martie. E. Benson, W., see Gabica, J. Benson, VV. W., see Wvelie, J. A. Bevenue, a., Ogata, J. N., Tengan, L. S., and Hvlin, J. W. Mirex residues in wildlife and soils, Hawaiian pineapple-growing areas — 1972-74. 9(3):14I-149 Brown, J. R., Chow, L. Y.. and Chai, F. C. Distribution of organo- chlorme i esticides in an agricultural environment, Holland Marsh. Ontario— 1970-72 9(l):30-33 BuLKLE't', R. v., see Kei.locg, R. L. Burns, B. G., Peach, M E., and Stiles. D. A. Organochlorine pesti- cide residues in a farming area. Nova Scotia — 1972-73. 9(I):34-38 Lamont, T. G., see Cromartie, E. Locke, L. N., see Cromartie, E. LoFGREN. C. S , see WojciK, D. P. LooMis, M., see Gabica, J. M Manske. D. D., and Johnson. R. D. Pesticide residues in total diet samples (VIH). 9(2):94-I05 MiNSKE, D. D.. see Johnson. R. D. Mattraw. H. C, Jr. Occurrence of chlorinated hydrocarbon insecti- cides, southern Florida— 1968-72. 9(2): 106-1 14 MuLHERN, B. M., see Cromartie, E. N Nehring. N. L., see Richard, J. J. NicKERSON. P. R.. and Barbehenn. K. R. DDT residues in starlings, 1974. 9(1): I Northcote, T. G., see Albright, L. J. o Caldwell, R. S.. see Clae'iS, R. R. Chai. F. C., see Brown, J. R. Chow. L. Y.. see Brown, J. R. Claeys. R. R., Caldwell, R. S., Cutshall. N. H., and Holton, R. Chlorinated pesticides and polychlorinated biphenyls in marine species, Oregon/ Washington coast, 1972. 9(1):2-10 Cromartie. E.. Reichel. W. L., Locke. L. N.. Belisle, A. A., Kaiser, T. E., Lamont. T. G., Mulhern, B, M.. Prouty, R. M., and SwiNEFORD, D. M. Residues of organochlorine pesticides and polychlorinated biphenyls and autopsy data for bald eagles. 1971- 72. 9(1):11-14 Cutshall. N. H.. see Claeys. R. R. Fritz. J S., see Richards. J. J. Gabica. J , Benson, W., and Loo.viis, M. Total mercury levels in selected human tissues. Idaho — 1973-74. S(2):59-63 Gabica. J., see Wyliie. J. A. Greig, R. A-. Wenzloff. D., and Shelpuk, C. Mercury concentrations in fish, North Atlantic offshore waters — 1971, 9(l):15-20 Ogata, J. N.. see Bevenue, A. Oloffs, P. C, see Albright, L. J. Peach, M. E., see Burns, B. G. Proutv, R. M., see Cromartie, E. Reichel. W. L.. see Cromartie, E. Reimold. R. J. Chlorinated hydrocarbon pesticides and mercury in coastal biota, Puerto Rico and the U.S. Virgin Islands — 1972-74. 9(l):39-43 Reimold. R. J., and Shealy, M. H., Jr. Chlorinated hydrocarbon pesticides and mercury in coastal young-of-the-year finfish. South Carolina and Georgia— 1972-74. 9(4): 170-175 Richard. J. J.. Junk. G. A., Avery, M J., Nehring, N. L., Frftz, J. S., and SvEC, H. J. Analysis of various Iowa waters for selected pesticides: atrazine. DDE, and dieldrin— 1974. 9(3):1I7-123 RicHiNS, R. T., and Risser, A. C, Jr. Total mercury in water, sedi- ment, and selected aquatic organisms, Carson River, Nevada — 1972. 9(1 ) :44-54 Risser. A. C, Jr., see Richins, R. T. H Heath. R. G., see Whiie. D. H. Holton, R., see Claeys. R. R. Hylin, J. W., see Bevenue, A. Shealy, M. H., Jr., see Reimold, R. J. Shelpuk, C, see Greig. R. A. Stacey. C. I., and Thomas. B. W. Organochlorine pesticide residues in human milk, western Australia — 1970-71. 9(2):64-66 Stiles. D. A., see Burns. B. G. SvEC, H. J., see Richard, J. J. Swineford. D. M., see Cromartie, E. SzETO, S. Y., see Albright, L. J. Johnson, R. D., and Manske, D. D. Pesticide residues in total diet samples (IX). 9i4):157-169 Johnson, R. D., see Manske, D. D. Johnston, D. W. Organochlorine pesticide residues in small migratory birds. 1964-73. 9(2):79-88 Jouvenaz, D. p., see Wojcik, D. P. Junk, G. A., see Ricfiard, J. J. Tengan. L. S., see Bevenlie. A. Thomas, B. W., see Stacey, C. ', K Kadoum, a. M., see Kl.aassen, H. E. Kaiser. T. E., see Cromartie, E. Kaiser, T. E., see White. D. H. Kellogg. R. L.. and Bulkley, R. V. Seasonal concentrations of diel- drin in water, channel catfish, and catfish-food organisms, Des Moines River, Iowa— 1971-73. 9(4): 186-194 Klaassen, H. E., and Kadoum. A. M. Insecticide residues in the Tuttle Creek Reservoir ecosystem. Kansas— 1970-71. 9(2):89-93 Van Middelem. C. H., see Wojcik, D. P. VeitH. G. D. Baseline concentrations of polychlorinaled biphenyls and DDT in Lake Michigan fish, 1971. 9(l):21-29 w Wenzloff, D., see Greig, R. A. Wheeler. W. B., sec Wojcik, D. P. Vol. 9, No. 4, March 1976 203 White, D. H., and Heath, R. G. Nationwide residues of organo- Wvllie, Joseph A., Gabica, J., Benson, W. W., and Yoder, J. Ex- chlorines in wings of adult mallards and black ducks, 1972-73. posure and contamination of the air and employees of a penta- 9(4);176-185 chlorophenol plant, Idaho— 1972. 9(3):150 153 White, D. H., and Kaiser, T. E. Residues of organochlorines and heavy metals in ruddy ducks from the Delaware River, 1973. 9(4):I55-156 WojciK, D. P., Banks, W. A., Wheeler, W. B., Jouvenaz, D. P., mr Van Middelem, C. H., and Lofgren, C. S. Mirex residues in * nontarget organisms after application of experimental haits for fire ant control, southwest Georgia — 1971-72. 9(3;: 124-133 YoDER, J., see Wyllie, J. A. 204 Pesticides Monitoring Journal Information for Contributors The Pesticides Monitoring Journal welcomes from all sources qualified data and interpretive information which contribute to the understanding and evaluation of pesticides and their residues in relation to man and his environment. The publication is distributed principally to scientists and technicians associated with pesticide monitoring, research, and other programs concerned with the fate of pesticides following their application. Additional circulation is maintained for persons with related in- terests, notably those in the agricultural, chemical manu- facturing, and food processing industries; medical and public health workers; and conservationists. Authors are responsible for the accuracy and validity of their data and interpretations, including tables, charts, and refer- ences. Accuracy, reliability, and limitations of the sam- pling and analytical methods employed must be clearly demonstrated through the use of appropriate procedures, such as recovery experiments at appropriate levels, confirmatory tests, internal standards, and inter-labora- tory checks. The procedure employed should be ref- erenced or outlined in brief form, and crucial points or modifications should be noted. Check or control samples should be employed where possible, and the sensitivity of the method should be given, particularly when very low levels of pesticides are being reported. Specific note should be made regarding correction of data for percent recoveries. Preparation of manuscripts should be in con- formance to the CBE Style Manual, 3d ed. Coun- cil of Biological Editors, Committee on Form and Style, American Institute of Biological Sciences, Washington, D. C, and/or the Style Manual of The United States Government Printing Office. An abstract (not to exceed 200 words) should accompany each manuscript submitted. All material should be submitted in duplicate (original and one carbon) and sent by first-class mail in flat form — not folded or rolled. Manuscripts should be typed on 8'/2 x 11 inch paper with generous margins on all sides, and each page should end with a completed paragraph. All copy, including tables and references, should be double spaced, and all pages should be num- bered. The first page of the manuscript must con- tain authors' full names listed under the title, with affiliations, and addresses footnoted below. Charts, illustrations, and tables, properly titled, should be appended at the end of the article with a notation in text to show where they should be inserted. -Charts should be drawn so the numbers and texts will be legible when considerably reduced for publication. All drawings should be done in black ink on plain white paper. -Photographs should be made on glossy paper. Details should be clear, but size is not important. -The "number system" should be used for litera- ture citations in the text. List references in the order in which they are cited in the text, giving name of author/ s/, year, full title of article, exact name of periodical, volume, and inclusive pages. The Journal also welcome^ "brief" papers reporting monitoring data of a preliminary nature or studies of limited scope. A section entitled Briefs will be included, as necessary, to provide space for papers of this type to present timely and informative data. These papers must be limited in length to two journal pages (850 words) and should conform to the format for regular papers accepted by the Journal. Pesticides ordinarily should be identified by common or generic names approved by national scientific so- cieties. The first reference to a particular pesticide should be followed by the chemical or scientific name in parentheses — assigned in accordance with Chemical Abstracts nomenclature. Structural chemical formulas should be used when appropriate. Published data and information require prior approval by the Editorial Advisory Board; however, endorsement of published in- formation by any specific Federal agency is not intended or to be implied. Authors of accepted manuscripts will receive edited typescripts for approval before type is set. After publication, senior authors will be provided with 100 reprints. Manuscripts are received and reviewed with the under- standing that they previously have not been accepted for technical publication elsewhere. If a paper has been given or is intended for presentation at a meeting, or if a significant portion of its contents has been published or submitted for publication elsewhere, notations of such should be provided. Correspondence on editorial matters or circulation mat- ters relating to official subscriptions should be addressed to: Paul Fuschini, Editorial Manager, PESTICIDES MONITORING JOURNAL, Technical Services Divi- sion. Office of Pesticides Programs, U. S. Environmental Protection Agency, Room B49 East, Waterside Mall, 401 M Street, S.W., Washington, D. C. 20460. Vol. 9, No. 4, March 1976 a U.S. GOVERNMENT PRINTING OFFICE: 1976 ■ 621-BS2/3 BOSTON PUBLIC LIBRARY 3 9999 05571 195 4