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Residues of Organochlorine Pesticides and Polychlorinated Biphenyls and Autopsy Data for Bald Eagles} 1971-721 Eugene Cromartie, William L. Reichei, Louis V Locke, Andre A. Belisie, T. Earl Kaiser, Thair G- Lamont, Bernard M. Mulhern, Richard M. Prouty, and Douglas M. Swineford ABSTRACT TIurty-ieven batd eagles found sick or dead in IS Slates during 1971-72 were analyzed for organochlorine pesticides and pohihloonuied biphenyls (PCB's). DDE and PCB s were detected in all bald eagle carcasses; JO 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 hoi the most common cause of mortality. Since 1964 when data were first collected, 8 of the 17 eagles obtained fton 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 (Haliaeetm leucocephalus) collected in 1971 and 1972. Data for specimens collected in 1964 through 1970 have been previously reported (.1-3). Sampling Bald eagles found dead or moribund in the field are collected by Federal, Slate, and private cooperators, pecked 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 Patuaen' Wile:.:* Research Cenier. Kish anil Wildlife Seisice. L' S Deparimeni ft Inferior, Laurel, Md. 20*11. Voi.. 9, No. I. Junk 1975 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 I. Distribution of eaglet collected by State and year of death, 1971-72 California Florida lllinoit Indiana low* Mama Michiian Minnesota Mil-oi.rl New Mexico New York Ohio South Carolina Texai Utah Virginia Wisconsin Wyoming TOTAL lO. FjkCltt COLUTTV* 1971 |___ 1972 Autopsy and Analytical Procedures Procedures for autopsy followed those reported previ ously by Belislc et al. (.?). After removal of the skin, feet. wings, liver, and gastrointestinal tract, the carcass v.as ground and homogenized in a Hobart food cutter. A 10-g aliquot of the carcass and the entire bruin were MGNS 0d2i75 11 mixed separately with anhydrous sodium sulfate in a hiendor and extracted for 7 hours with hexane in a Soxhlet apparatus. Extracts were evaporated. lipid weights were determined, and the extracts were redissolvctl in 20 ml hexane. A 10-ml aliquot of extract containing not more than 0.5 g lipid was cleaned on a florisil column. The florisil had been washed and rcculcined at 675* C according to Hall's method (41 and partly deactivated with 1.0*1.5 percent water to permit the elution of dieldrin with the other pesticides. Approximately 21 g of the treated florisil wns placed in each 2-by-20-cm column with a 250*m! reservoir and topped with I cm anhy drous sodium sulfate. Columns were prewashed with 50 ml hexane and the extract was cluled 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) wax used with the following modifications: (he silicic acid, Mallinckrodt Silicar CC-4, was healed 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 scaled 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, hevachlorobenzene (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 rale. 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 NiM 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 (J) except that a I 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 front spiked mallard carcass tissue were: DDE. 96 percent: DDD, 103 percent; DDT, 110 percent; riicldrin. 101 percent; hcptachlor epoxide, 104 percent; jnirex. 106 percent; oxychlordane, 98 percent; cfj-chlordane. 100 percent; cis nonachlor, 98 percent; HCB, 69 percent; and Aroclor 1254, 101 percent. Resi due levels for eagle samples were not corrected fui recovery. The lower limit of sensitivity was 0.05 ppm; residue levels less than 0.05 ppm were not repurted "trace" as in the previous reports. Samples were not analyzed for oxychlordane, cft-chlordane, rrs-nonachlor, or HCB in 1971. GLC/MS analy ses using temperature programming revealed both cischlordane and. fr<w.r-onachlor. In one sample, only rrorrr-nnnachlor 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 c/f-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 RESIDUES 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 at. (7) concluded from an experimental study on Japanese quail (Coturnix coturnix) and from residues in brains of several kinds of animals found dead in the Held following heavy dieldrin treatments that a concen tration of 4-5 ppm indicated that the animal was in the danger zone. Linder et al. (5) 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 Pi sricinns Monitorino Journal MANS 032176 TADLfi 2. Pesticide and PCB residues in $7 bulti eagles, 1971-72 TABLE .V Data on four suspected cases of dieldrin poisoning of adult eagles, 1971-72 Sim vi Sax low* South Carolina Vlrital* Virgin!* 1971 197! 1*71 1972 r M M P 1 Ot'fO = no dUgtvl could be mde on (he bull of ulopiy finding*. DltLOUN Rimui IN BMIM, M>M 7.1 . .s 4.0 i.6 AlTTOW FlHVINQI ' Qp*0, M f rfcpwMft EfluchulM Open, no Cm dtpo*U Opaa, oo fai dcpo*M* of dieldrin poisoning. Two eagles suspected of dieldrin poisoning were collected from each State. It is of special concern that at) 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. Bight 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 end 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 Vo.. 9, No. I. June 1975 TABLE 4. Probable causes of bald eagle mortality, 1971-72 Oi; oe DbaTM No. ExCltl Shoot Inn Thallium potwnlng Dieldrin poboning NephrotM Drowning Drowning; corcidioii* CoccldtocJ* Strychnine poljontng Impact Elecirocuilutt Open* TOTAL I) .* l 1 1 t 1* t 4 37 Specimen from Mew Mexico; analysed for myctiaiM by Denver Wildlife RcacsTch Center. Denver, Colo. No CiifiiMl* could be made on die batit of autopvy (lading* or chemical analytic. listed as emaciated showed marked atrophy of the pec toral and leg muscles, and had no fat deposits. Coccidiosis caused by Isosfiora sp. was apparently re sponsible for ihe 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. MOMS 062177 13 A H- i imam Drowning wns also the immediate cause of the death mitted specimens and provided the field data. V. Polen. of an adult female eagle from Michigan that had high Vclsicol Chemical Corporation, provided the various levels of DDE (55 ppm) and PCU's (190 ppm) in the chlordane standards, Larry Young prepared tissue sec brain. The eagle, which had been observed perched on tions for histoiogical examination, and Marian Krcamer a snag over the water, suddenly fell into the water and assisted in assembling the data. drowned. No injuries were found, and both aerobic and anaerobic cultures of liver, heart blood, and in* tcatinal tract failed to reveal any pathogenic bacteria. LITERATURE CITED (/) Ri ichel, W. E. Croniartir, T. G. Lamont, It. M. The thallium-poisoned eagles usually had normal Mttlhern, and R. M. Prouty, 1969. Pesticide residues 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 in eagles. Pestic. Monit. J. 3(3): 142-144. (2) Mttlhern, ii. AL, W. L. Reichel. L S. Locke, 1. G. Lamont, A. A. llelhle, . Crotnuriie, C. fc. Bugley, and R. At. Prouty. 1970. Organochloi ine residues and au 3 intranuclear inclusion bodies which sometimes indicate lead poisoning, and examination of the kidney sections topsy data from bald eagles 1966-68. Pesliv. Monit. J 4(3):141-144. stained by the Pritschow technique proved to be equivocal. (.?) Betide. A. A.. W /.. Reichel, L N. Locke. T. G. Limoni, B. Al. AUdhern, R. M. Prouty, R. B. DrWolf, and . Ctomnrtie. 1972. Residues of organochlorine An adult female eagle from Missouri had a shattered lower left leg, the result of an earlier gunshot wound. pesticides, polychlorinated biphenyls, and mercury and autopsy data for baid eagles, 1969 and 1970. Pestic. Monit. J. 6(3)133-138. She had valvular endocarditis, probably the result of (4) Hull, L. T. 1971. Variations of florisil activity: method a secondary bacterial infection from the leg wound. to increase retentive properties and improve recovery 4 Escherichia coli appeared in the heart blood but not in and elution patterns of insecticides. J. Ass. Olflc. Anal. Chem. 54(6): 1349-1351. the lungs and liver; thus the cause of death is listed as (5) Armour, l. A., and l. A. ffurlir. /970. Method for shooting (Table 4). separating polychlorinated biphenyls from DDT and 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 PCD's in eagles continue to be high, reflect ing widespread contamination by these compounds. its analogs. J. Ass. Oflte. Anal. Chem. 53(4);761-76. (6) Curry, A. S., J. F. Rend, and A. R. Knott. 1969. De termination of thallium in biological material by dame spectrophotometry and atomic absorption. Analyst 94 (1122):744-753. (7) Siickel, W. H., L. F. Stickel, and 1. W. Spann. 1969. Tissue residues of dieldrin in relation to mortality in birds and mammals. Pp. 174-204 in M. W. Miller und G. C. Berg, editors. Chemical Fallout: Current Re A cknowledgments search on Persistent Pesticides. Obas. C. Thomas, Springfield, III. 1 Authors acknowledge organizations and individuals, (d) Linder, R. L., R. B. Dahlgren, and Y. A. Greichus. 1970. Residues in the brain of adult pheasants given particularly U.S. Game Management Agents, who sub dietdrin. J. Wild!. Manage. 34(4):934-936. u. l $ I 14 MUNS 08<U78 Ptisrinots MoNiTontNO Journal