Document QJJmdxGdNVKMBpJbV3dNpwGZE

E. P. W heeler - St. Louis October 21, 1968 Polychlorinated Biphenyls In the E n viro n m e n t ________ w. rt. rtichara WHICH R. E. Kelly, M. D . / w. H. Hunt Scott Tuckr - Oueenv Plant a. A* t e l l e r - UJLLil* F ton - CJJTT Attached Is a Xerox copy ol a technical paper w h i c h S cott T u c k e r and I picked up in Washington recently. This was provided us by Donald A. S p e n c e r of the N a t i o n a l A g r i c u l t u r a l C h e m i c a l s Association. Mr. S p e n c e r requested that the paper be held "confidential" until such time as It may be published. Spencer indicated that if this paper were distributed one of his principal "sources'' would refuse to give him p r e p u b l i c a tion information in the future. Risebrough'a presentation (the attached) was made at a meeting of 20 to 30 t o x i c o l o g i s t s h eld at the U n i v e r s i t y of R o c h e s t e r in June. The meeting was billed as "The First Annuel Conference on Toxicology" and was underwritten presumably by the AEC whicn has had contracts at Rochester for many years. Attendance was by invitation only. The meeting dealt "exclusively with pesticides with about one-third of the papers relating to meroury. As far as Spencer knows the papers, including the attached, will undoubtedly be printed as p r oceedings of ths conference although I suspect individual authors were given permission to publish elsewhere. In s few words, Rleebrough has found PCBs along with chlorinated pesticides in s number of species of fish and birds along the California coast at well as in waters off Baja California and Central America. He further reports PCB in fish from the Channel Islands and Puget Sound. No PCB was detected in the liver of tuns taken in the Oalapagos Archipelago. Scott Tucker is going to scrutinize the analytical aspects and particularly the validity of some of the assumptions made by the author. cs Attachment E l m e r P. W h e e l e r Hi* 726683 ) POLYCHLORINATED BIPHENYLS IN THE GLOBAL ECOSYSTEM PERSONAL COMMUNICATION NOT A PUBLICATION NEV 018633 726684 POLYCHLORINATED BIPHENYLS IN THE GLOBAL ECOSYSTEM ABSTRACT Compounds identified as polychlorinated biphenyls, pollutants of Industrial and agricultural origin, are now widely dispersed in the global ecosystem. Tissues of peregrine falcons have contained the highest concentrations so far measured. Significant amounts are also present In several species of pelagic sea birds. The geographical distribution patterns Indicate that the polychlorinated biphenyls, DDT, and the other chlorinated hydrocarbon biocides, are dispersed predominately by air transport. The polychlorinated biphenyls are powerful Inducers of hematic enzymes which degrade oestradlol. Their enzyme Inducing activity In plgeonB is approximately four tlme6 as great as that of technical DDT and six times that of p , p '-DDE. Both the polychlorinated biphenyls and p,p'-DDE could account for a significant portion of the environmental deterioration which has caused the aberrant calcium metabolism observed In raptors and other species of birds since the Second World War. NEV 01863^ 726685 Deterioration of the environment has proceeded at a rapid pace and it is universally accepted that it has caused the extinction of some species and haB profoundly influenced the relative abundance of others. Whether chemical changes in the global ecosystem have been sufficient to cause widespread harmful effects is still a matter of controversy, yet the Interpretation of Ratcliffe's findings that the calcium metabolism of British peregrine falcons (raleo pereerlnus) changed adversely just after the Second World War is unambiguous (1). A widespread change in the chemical environment has occurred which has affected not only the calcium metabollan of the peregrine falcon but also of other raptors end terminal avian carziivores in both Britain and North America. In every case thin eggshells have been associated with populations which were declining and which were also contaminated with the synthetic chlorinated hydrocarbons which have come into general use since the war. Moreover, geographic variations in' eggshell thicknesses have been correlated with the amounts of chlorinated hydrocarbon residues in populations of peregrine falcons, bald eagles Ealiaeetus leucocephalus. ospreys Fendion haliaetus. double-crested cormorants Phalacrocorax auritus. and herring gulls Larue argentatus (1,2). Ho other environ mental change, such as radioactive fallout, has shown comparable variation over a vide geographical area. Calcium physiology la Intimately related to reproductive physiology and is to a large extent Tegulated by steroids such as estrogen and vitamin D (3), All or moBt of the synthetic chlorinated hydrocarbon biocides so far tested Induce hepatic enzymes which degrade steroids nev 018635 726686 6 3 by hydroxylating them, thereby increasing the rate at which they are excreted (4, 5, 6, 7, 8, 9). The relatively small amounts required to produce this effect (6-IQ,11,12,13) end the discovery that small amounts of DDT appear to have estrogenic effectB (4) have made Irrelevant much of the parts per million approach to pollutant ecology based only upon toxicity data* In both Great Britain and North America it was the decline of the peregrine falcon which has initiated concern about the possible harmful effects of environmental contamination. In the distinguished tradition of British field ornithology, the population collapse in Great Britain was well documented (14,15,16:17) but in the United States the eastern population was extinct before competent observers were aware of a general, widespread decline (18). Breeding peregrines persist in apparently normal numbers in the Pacific northwest (19) and in the Arctic (20,21). A small remnant population remains in southwestern North America. In 1967 we collected an unhatched, abandoned egg in Baja California, Mexico. Analysis of this egg (Table X) showed that it contained almost 3 milligrams of pjp'-DDE, indicating a high level of contamination In both the adult female and the local peregrine population. Considerable effort was made to identify the unknown peaks present In the chromatogrems but these attempts were unsuccessful until the reports appeared from Sweden (22,23) and Great Britain (2A) identifying polychlorinated biphenyls in European wildlife. The published chromatograms of the coiTBierclal mixture of polychlorinated biphenyls (PCB) and of an extract of a European kestrel (Falco tlnnunculus) (24) were very similar to those NEV 018636 726687 tlmea-of-tbe-unkaown-peaks-In-these eg.tr&cjts. proved -to be-Identical with those of several FCB compounds on DC-200 and QF-1 columns (25) and on a nixed SE-30:QF-1 column. The chlorine content of several extracts and standards was determined with a Dohrman microcoulometric detector and a method of quantification of the PCB peaks was deviced based upon peak heights produced In the electron capture detector related to standard p ,p'-DDE (25). Toxaphene, a mixture of polychlorinated P-, camphors, has been reported to be resistant to nitration, whereas DDT Is destroyed (26). FCB is also^destroyed by this procedure. In Table I are presented the results of analyses of peregrine falcons, all of which were originally trapped for the purpose of falconry, which died shortly afterwards In captivity from a variety of causes end were then donated to us for analysis. Significant amounts of PCB were present in Arctic peregrines only a few months old (Dos. 5 and 6), but higher residues were present In a second year Arctic bird (Ho. 2) and exceptionally high residues were present In an adult trapped in California (no. A). In birds 2 and A the total lipid reserves were very low, and in both the brain levels of DDE and FCB were high, perhaps at toxic levels. Fat mobilization during reproduction or In times of starvation or stress could be expected to cause significant changes In the Internal distribution of chlorinated hydrocarbons. Steroid hydroxylase activity in the liver might increase at this time. Dleldrln concentrations were lower than In the peregrines analyzed in Britain, but DDE concentrations were approximately comparable (28). NEV 0 1 8637 726688 .f 5 In Table 11 are presented the results of analyses of peregrine prey Bpecles remains of which were collected at eyries in Baja California, Mexico* With the exception of the remeins of one mourning dove (Zenaldura macroura) and of three fiph bats (rizonyx vivesl) , prey material found at four eyries consisted of sea birds. Of these, the eared grebe (Podiceps casplcus) and the black petrel (Loonelania melanla) constituted 32Z and 25X, respectively, of the remains. Black petrels, like other petrels and ahoarwaters (29,30, Table 111) contained especially high concentrations of both DDT and PCB, e fact which appears to result from their feeding upon organisms at the sea surface, which would receive the components of aerial fallout* Reproductive success in this population of peregrines appears to be subnormal. In 1968, each of two pairs hatched only one young, both of which were fledged* Two other pairs apparently fledged only one young per eyrie and none was observed to hatch or to fledge more than a single young. In the past, two to four young, the number normally produced by healthy peregrines (20), were raised by each pair (31). The region is wilderness, with little or no human interference, and is remote from sources of pollutant application. In California, numbers of breeding peregrines have been reduced by at least 80Z In recent years. Despite minimal human Interference, peregrines have disappeared from the nearby Islae Coronados in Mexico, where It can be inferred that they preyed upon seabirds. The remaining few pairs In California, however, appear to be reproducing normally and rear, when undisturbed, 2 to 4 young each year. They are found, like moat of the surviving peregrines In Great Britain (17), in a relatively NEV 018638 726689 6 lov levels of chlorinated hydrocarbons. Twenty seven remains of 16 prey species collected at a coastal eyrie which produced three young birds In 1968 included B mourning doves, one rock dove (Colunba llvla) , 2 woodpeckers, 8 passerine species, one grebe and 6 shoreblrds (Scolopacldae) Ho analyses of the prey species from that region have yet been made, but mourning doves from San Diego (Table 111) contained very low residues. On the baslB of the residue data available on land and water birds In California (29,32), It Is a reasonable hypothesis that the food species of this pair and of other successful pairs at inland eyries are less contaminated then water birds preyed upon by peregrines elsewhere. A clutch of eggs collected In this region contained the normal, prewar, amount of calcium, whereas other peregrine eggs from California collected since the Second World War have contained significantly smaller emounts (2) Despite official protection, the surviving birds are still subjected to shooting by sportsmen and to harraSsroent of the eyries. If these could be effectively reduced, the population might yet survive. In Table III are presented the results of analyses of marine and terrestrial birds and of three species of fresh water fishes for ?CB and DDT content and concentration. From the ratio of total DDT to PCB, it is apparent that regional fallout patterns for the two compounds exist. In almost all of the fishes (25) and the birds from San Francisco Bay which have been analyzed, this ratio is betv?cen one and two. Among the birds this was true for the peregrine falcons (Tabic I) , the western gull eggs, the Caspian tern eggs and one of two black-crowned night heron eggs (Table II). The other hlnck-erownfed night heron egg had a typically "ocean" profile, suggesting that the adult female had spent the winter 726690 along the coast. In.cost of the birds from the Farallon Islands, which are 27 miles west of the Golden Gate Bridge, this retlo is between 2 and 5. In Panama, where PCB contamination might come from the Canal Zone and Industrial areas In Panama City, the ratio is between 1 and 2 (Table 111). In the Gulf of California, a region relatively remote from the sources of either DDT or PCB contamination, this ratio Is In most cases approximately 9 or 10. This was true In the egg of the peregrine falcon (Table 1) In all of the black petrelB and least pctrelc analyzed, In the Craverl's Hurrelets (Table II), In five of six osprey eggs, and In six of seven western gull eggs (Table III). Among the exceptions, the fish bat, with relatively more DDT, but with low concentrations of both DDT end PCB, was the most divergent, with e ratio of 43 (Table II). It is not clear whether this reflects differences between avian and mammalian physiology or a fundamental difference In feeding habits. The exceptions among the osprey and western gull eggs had relatively more PCB; the profiles of the chromatograms resembled those of the Caspian tern from San Diego. The adult females might, therefore, have come from the other side of the peninsula of Baja California. In tha eggs of both the elegant terns and the Heermann's gullB, this retlo Is lower, reflecting higher amounts of PCB relative to DDT. Both species migrate out of the region following the nesting season and most likely acquire their PCB residues elsewhere. In sea birds from, the Pacific, whether In the fulmars, red phalarope, ancient murrelet end rhinoceros auklet, species nesting In the Arctic and the Porth Pacific, or In the shearwaters which breed In Australia, Hew Zealand and Chile, this ratio was usually between 5 and 10. PCB was not V 018640 726691 8 found In eggs of the Ad&Lie Penguin, brought frcm Cape Crozler, Antarctica and kindly made available for analysis by Dr* R. E. Feeney, In these, however, the amount of DDT on a lipid velght basis was very low and the ratio of DDT to the lowest amount of PCB which could have beer, detected was only 18, A larger amount of fat material from Antarctic organisms, which would yield a sufficient amount of DDT would, therefore, have to be analyzed before concluding that PCB has not yet reached the Antarctic. The presence of PCB In the few land birds analyzed shows that it is also distributed among terrestrial ecosystems in North America. The PCB concentrations in the three species of fresh water fish from Clear Lake, Lake County, California, were very low, lower than those in marine fish from San Francisco Bay and Puget Sound, and in several cases, lower than those in fish from the Pacific Ocean (25). Individuals of species resident in industrial areas have, as expected, higher PCB levels than individuals of the same species from more remote regions. Analysis of 10 eggs from 10 clutches of the western gull from the Farellon Islands showed, ar. average DDT concent of 412 micrograms with a standard error at the 95% confidence level of 102 and a PCB content of 136 + 55* DDT and PCB content of 4 eggs from 3 d u t c h e s from an island in San Francisco Bay was significantly higher (Table III), Seven eggs from 7 clutches in the Gulf of California contained 385 + 230 microgrems of DDT and 45 + 30 mlerograras of PCB. The DDT content is, therefore, not significantly different from that of the Ferallon eggs, but the PCB content is much lover. * Birds from the Gulf of California also contain dieldrln and endrin (Tables II and III) but the number of analyses is as yet insufficient to 726692 9 compare their relative abundance to that of DDT and PCS. Despite the Inability pf the Shell Chemical Company to find any chlorinated hydro carbons at the mouth of the Colorado Elver which dralne Into the Gulf (34) It Is likely that some do enter from that source. A significant fraction, however, must come from the atmosphere (35), and air transport best explains the presence of PCB in remote areas. They are poorly soluble in water and have very low but finite vapour pressures (36). Incineration of FCB-contalnlng materials would greatly Increase the rate of entry into the atmosphere. Since PCB Is used in the manufacture of many industrial products, the high amounts found in San Francisco Bay, Puget Sound (25) and San Diego Bay presumably result from direct discharge of industrial wastes Into these waters. The PCB compound with retention time 1.25 on DC-200 columns and 1.33 on QF-1 columns, relative to p,p'-DDE, Is one of the more prominent peaks in Sen Francisco Bey extracts end In the commercial mixtures, yet It Is not present or is present in relatively lower amounts in extracts from Baja California and Panama. To test the possibility that PCB might be subject to degradation by ultraviolet light, standard PCB solutions in hexane were evaporated to dryness in petrl dishes, or over layers of water and 3Z HaCI solution, and Irradiated at a distance of 4 inches with a 15-watt germicidal lamp emitting at 2537 A. In each case, the major change In the chromatograms of the Irradiated PCB was a reduction In the relative height of this peak. The effect was more pronounced when PCB was Irradiated on the aqueous surfaces. Peregrines could, therefore, acquire PCB as well as the other chlorinated hydrocarbons, over all of their global range. Mo PCB o i fl6^ 726693 10 residue data are available for prey species from.the Atlantic, but compounds which appear to be PCB have boon Isolated from seals (33). A second year male peregrine spent the winter of 1967-68 on Isla Facheca, Panama, where the pelican, booby, and frigate bird eggs of Table 111 vero collected. The high concentrations In all of the petrels analyzed suggest that the fork-tailed petrels (Oceanodroma furcata). a major prey species of the Peale's race of the peregrine falcon In British Columbia (19, might be similarly contaminated. T!.c telle! fcltj in becoming cf:undent in ar'-rn of California where Insecticide use le intense, yet because It preys primarily upon the short-lived and herbivorous vole Mlcrotus. the species accumulates very low residues of either DDT or PC5. The American kestrels and the barn owl eggs analyzed also contained very low residues. Both species are very common In California. In contrast, the oingle Cooper's Hawk, a species which elsewhere has shown thinning of eggshells (2) and which preys upon birds%contained high amounts of both DDT and PCB (Table III). The percentage of p,p'-DDE in the total DDT residue has been given In the tables below. In almost all cases It Is above 80 percent. It is most likely, therefore, the most ecologically relevant of the DDT compounds although the differences in estrogenic activity among the various DDT compounds (4) suggest that biological effect does not necessarily reflect parts per million concentrations. Previous work (13) has shown that both DDT and dleldrln Induce hepatic enzymes in the pigeon which, In an in vitro preparation, Increase the metabolism of progesterone and testosterone. This work has now been extended to study the metabolism of oestradiol by enzymes Induced by NV 0186*3 726694 11 p'P'-DDE, technical PDT (Dupont) and PCB (Aroclor 1262). The experimental procedure previously described (13) was followed except that the chlorinated hydrocarbons were Injected Intramuscularly rather than given orally and in the separation of oestradlol and lte metabolites, the solvent system used was the upper layer of a mixture of benzene:heptane:methenol:watcr 7:3 -8i2. The strips were monitored with an autographic strip scanner. The profiles obtained for the various inducing agents are shown In figure 1. It will be noted that the profile of the metabolites obtained following enzyme induction using DDE and DDT arc identical, but that a different metabolite is produced by the enzyme induced by FCB. The amount of metabolites formed was calculated from the radioactivity of the peaks. The results obtained are given in Table IV. p tp'-DDE at body concentrations of AO ppm In the pigeon significantly increases the rate of oestradlol degradation by the Induced hepatic enzymes under the experimental conditions. It may be concluded, therefore, that DDE in nature increases the rate of metabolism of estrogen and other steroids as they pass through the liver. The metabolites produced are more polar and their biological activity is most likely altered. On a weight basis, the FCB preparation had an oestradlol degrading potential approximately 5.6 times that of p,p'-DDE end 4.1 tlmeB that of technical - l DDT. FCB and p,pf-DDE may, therefore, be the most ecologically significant pollutants now accumulated by organisms. Studies on the activity of Induced enzymes in the rat at various times after a single Injection of DDT or dieldrln have been made by Ghazal (37). He found that it took 70 days for the activity to fall to half its maximum value In the case of DDT and 15 days In the case of nV 01864* 726695 i 12 dleldrin. Experiments with dieldrln on pigeons show that only a quarter of maximum activity remains after a month. Thus, there is evidence that the effects of these Induced enzymes can persist over a long period of time although more studies are needed to determine the steroid degrading potentials of livers of those species contaminated with chlorinated hydrocarbons. The profile of the metabolites should be some indication of the history of exposure to chlorinated hydrocarbons. Decreases In eggshell thickness and eggshell weight have amounted to as much as 19X in both Britain and America (1,2). Chances of eggshell breakage are thereby greatly Increased (1,14), Humidity may significantly affect the hatching success of duck eggs (38,39) and decreased eggshell thickness in poultry has been shown to cause decreased hatching success through increased water Ions from eggs (40,41). The environment in which birds now exist Is no longor the sano as that in which they evolved; it is unlikely that any species has the genetic capacity to meet the selection pressures resulting from the abrupt environmental change which has produced the thin eggshells. Several mechanisms may account for the aberrant calcium metabolism observed in peregrines and other birds. Vitamin D, a steroid, is essential for the absorption of calcium from the alimentary tract and increases the' level*of calcium avalleble from bone resorption (42,43). Hens deficient *ln Vitamin t lay eggs with lower eggshell weights, less yolk calcium, and presumably, with lower Vitamin D contents. The developing embryos of such eggs utilise leas calcium from the eggshell (44). Reduced levels of estrogen and androgen could be expected to reduce the deposition of medullary bone, a major source of calcium during egg and eggshell formation 726696 13 (3,45,46,47), Lowered estrogen levels could also affect both the amount of calcium normally excreted (46) and the concentration of serum calcium which normally Increases under estrogen stimulation as a result of liver synthesis of yolk proteins which are bound to calcium (45). Induction of steroid metabolising enzymes by chlorinated hydrocarbons could affect any of these processes. Vitamin A mobilization la also Influenced by estrogen (49,50) Indicating that eggs of contaminated birds might be deficient in vitamin A. Bumblefoot is a foot ailment that has showed an increased Incidence In captive peregrine falcons In recent years. Both prophylaxis and treatment Involve the administration of vitamin A. Fortunately, all of these hypotheses are subject to experimental test; alienated molecular biologists are now In a position to perform an enormous end Invaluable service to the world's wildlife and to those concerned with Its preservation. The peregrine falcon Is a species long highly revered and respected. G.II.Thayer (51) has described It as "tho embodiment of noble rapacity and lonely freedom1*. A subtle irony therefore exists In the fact that the peregrine may be the first species to be extirpated by global contamination. R, W. Risebrough, Institute of Marine Resources, Department of Nutritional Sciences, University of Califomia,Berkeley,Calif. 94720 D. B. Peakall, Established Investigator, American Heart Association, Langmuir Lab., Division of Ecology and Systematica, Cornell University, Ithaca, How York 14650 S. G. Herman, Department of Zoology, University of California, Davis, California 95616 M. II. Klrvcn, San Diego Natural History Museum, P.0, Box 1390, San Diego, California 92112 F. Reichc. Institute of Marine Resources, Department of Nutritional Sciences, University of California, Berkeley,Calif. 94720 NEV 01B646 726697 Table 1: Chlorinate - hydrocarbons in North American .eregrine Falcons. Concentrations in parts per million wet weight dry weight. * or lipid walght. Sample Dieldrin Total DDT*a* 2DDU PCB DDD/PCB 1. Unhatched egg ^ Baja California (vet) (c) 2. Second year ' migrant from Arctic breast muscle (wet) breast muscle (dry) brain (wet) carcass (wet) carcass (lipid) 3* Immature, California ^ breast muscle (wet) liver (wet) brain (wet) brain (lipid) carcass (wet) carcass (lipid}, . 4. Adult, California ^ breast muscle (wet) liver (wet) brain (wet) brain (lipid) carcass (vet) carcass (lipid) 5. Immature ^ migrant from Arctic breast muscle (vet) breast muscle (dry) liver (wet) 0.11 NH KM 0.07 62.5 Nil NH 0.04 0.50 0.11 1.6 Nil NM 0.31 3.7 1.7 50 NM Wi 102 97 10.2 10 99 94 28 296 84 65 98 21 70 93 19.7 5000 ' 1420 14.4 7.7 2.8 90 92 89 9.4 4.5 1.5 36 19.3 20.2 92 10.8 300 160 127 77 49.5 595 85 2600 87 98 B0 57 86 34.6 415 87 65 1980 3.5 4.7 3.5 1.5 1.7 1.9 1.9 1.3 1.4 1.4 1.3 2.3 81 7.8 1.0 92 0.16 0.54 0.10 14 10 N6* OlB6*7 726698 Table 1, continued brain (vet) KM body fet (wet) HM carcass (wet) 0.07 carcass (lipid) 0.44 Immature Arctic migrant (e) breast muscle (vet) NM breast muscle (dry) 0.43 50.3 9.3 63.7 83 82 82 1.9 89 6.0 0.031 3.2 0.80 5.5 12 16 12 0.6 3.4 1.9 a DDT residues Include: p,p'-DDT, p.p'-DDE, p,p*-DDD (ppp'-TDE), p ^ '-DDMU, o,p'-DDT and o,p'-DDE. NM: not measured. ^ Chlorinated hydrocarbon contents of the egg were: 4,700 micrograms p,p'DDE; 40 mlcrograms o,p'-DDE; 29 hicrograras p,p'-DDT; 7.4 mlcrograms p,pf-DDD; 37 mlcrograms p,p'"DDMU; 5 mlcrograms dleldrln; 12 mlcrograms heptachlor epoxide. Concentrations were calculated by assuming a volume of 47.3 m l . , the average value obtained by measuring 11 clutches of peregrine eggs from California in the Museum of Vertebrate Zoology, University of California, Berkeley, and by assuming a density of 1.0. c Second year female, captured in October on the Texas coast during migration. Died in captivity shortly afterwards, no apparent cause of death. No body fat. Total body content of chlorinated hydrocarbons: 35 mg. DDT, 10 mg. FCB, 0.44 mg. dleldrln, 0.16 mg. heptachlor epoxide. Total body lipid, 7 gn. ^ Plumage characteristics of both 3 and 4 were intermediate between those of typically resident California birds and the arctic race .j>. tundrius, as described by White (27). No. 3 was immature female of the year trapped in the southern San Francisco Bay area In the winter of 1966* Observed feeding In the area for a week prior to capture. Died suddenly after eating a dead gull. Moderate body fat. Total body chlorinated hydrocarbon content*. 13 mg DDT, MV 018646 79CCnn 6.8 mg. PCB, 0.07 tag* dieldrin, 0.09 mg. heptachlor epoxide. Total body lipid, 43 ga. 6 Adult female. Trapped In the southern San Francisco Bay area In the winter of 1966. Observed feeding In the ores for a month prior to capture. Died shortly afterwards with no apparent cause of death and no body fat. Total body chlorinated hydrocarbon content: 52 mg. DDT, 40 mg. FCB, 1.0 mg. dieldrin, 1.0 mg. heptachlor epoxide. Total body lipid, 20 go. * First year female trapped on the Texas coast In October. Lost at Ft. Mugu, California, the following January and was shot by a sportsman 3 weeks later. Abundant body fat. Total body content: 7 mg. DDT, 0.6 mg. PCB, 0.05 mg. dieldrin, 0.17 mg. heptachlor epoxide. Total body lipid, 110 gm. o First year female trapped on the Texas coast in October. Died shortly afterwards of heat prostration. OLa 726700 .* Table II. PCB and DDT In prey species of Peregrine Falcons In the Gulf of Califomia. Content In microgranB of whole bodies and eggs; concentrations In parts per million wet weight (W) or lipid weight (L). Species ^ DDT F8 DDT ZDDE PCB ppm W8 PCB DDT/PCB ppm Eared Grebe (13) Whole body 3 0.28,0.26, 97 12,1 TM < b> e vv Black Petrel (10) Whole body Least Petrel (6) Whole body Eggs Fish Bat (3) Whole body 8 exo (685-1344) 3 99 2 30 (23-37) 7 25 (15-31) 9.2 (W) 81 V 1.0(H) (0.90-1.14) 9.2 3.2(W) 83 f1 * 84 0.71(W) 62 a 0.35(W) 9.3 3.1 (1.2-5.0) VVV 10 0.58 0.02(H) 43 (0.45-1.06) Craveri16 Murrelet (2) eggs (one clutch) 2 Whole body, adult Whole body, adult 1 1 230 (223-233) 37.1 295 39 (L) 80 0.31(W) 85 2.4 (W) 85 Iti vea 4.5(1) 8.7 0*039(17) 1. 9 0.26(H) 9.2 Elegant Tern (1) Eggs 8 15.5 5.0 (L) 90 (9.6-24.3) v ee 1.5(L) 3.9 (0.8-3.6) Heerman's Gull (1) Eggs 3 195 (94-278) 48 (L) 95 8.1(1) (3.5-11.3) 5.9 ^ All specimens were collected In the vicinity of four peregrine eyries In Baja California. Humbers in parentheses are the number of remains of each prey species which were found at the eyries. Also found were remains of one cormorant. (Phalacrocorax b p .), one Red Phalarope (Phalaropus fullcarlus). one northern Phalarope (Loblpos lobatus). and one Mourning Dove (Zenaidura macroura). but local specimens of these species were not analyzed. Eggs of least petrels, elegant terns and Beermann's'gulls were from different clutches. Eared grebe: Podiceps casoicus: black petrel Loomelanla nelanla: least petrel: Halocyptena microsoroa: fish bat: Pizonvx vivesl: Craverl'a Murrelet: Endonvchura craveri; elegant tern: Thalasseus elegans: Heermann's gull: Larus heermannl. ^ not measured. Interfering peaks on chromatograms. ^ both eggs also contained 0.08 ppm dleldrln (lipid weight) and 0.17 ppm endrin (lipid weight). 01650 726701 Table 111. PCB and DDT In the global ecosystem. Content In nlcrograms and . concentratlonB in parts per million wet weight (W) or lipid weight (L). Species IThlte crapple ^ (2) Black crapple Bluegill<3> ,, (4) Adelle penguin, 8p.s (5) Western grebe, breast muscle Fulmar A B C Fink-footed^ shearwater (8) Sooty shearwater' 7 A B C Slender-billed^9* shearwater Ashy Petrel Brown Pelican,: 7 eggs, Panama-" eggs, Baja Calif. X Total DDT XDDE Jig ppm 1-- 1-- 1.83 (W) 6 2.10 (W) 6 1-- 5 0.7B (0.59-1.04) 5.5 (W) 6 0 . 1 2 8 (L) 74 1 26.4 (V) 5 PCB P8 DDT/PCB ppm --- 0.004 475 (W) 0.003 660 -- 0.005 1200 <0.044 jig/egg *ie 0.098 270 (W) 1-- 1-- 1 10,475 1 2,000 0.41 (W) 76 3.4 (W) 89 17.5 (W) 96 -- ---- 3900 3.0 (W) 93 277 0.08 () 0.34 (W) 6.5 (W) 5 10 2.7 0.420?) 7.2 1-- 1 1 1,265 1-- 3 2,158 lC1644-2826) 6 59 (IB-183) 2 53 (47-59) 12.3 (W) 94 10.3 0 0 86 -- -- 1.2(W) 10 0.9(W) 12 2.3 (H) 85 1IM 32.0 (W) 92 ---- S9.3 (K) 95 389 (298-482) 11.5 (L) 61 23.1 (47-78) (18-30) 2.1(W) 15 9.8 (W) 5.5 1.55 (0,973.2) 10.0 (L) 81 10.4 -- (9.0-11.7) 6.5, 4.0 o ie 65l 726702 Table 111, continued Frigateblrd eggs, Panama 3 9.6,8.7,30.0 (13) Brown Booby eggs, Panama 4 20.8 (16,4-24.5) (14) Brandt's Cormorant 17 eggs 326 Pelagic Cormorant eggs 2 128 (125-130) Cinnamon Teal^2^ 1 4340 White-tailed Kite^*^ eggs, clutch A Unhatched egg B Unhatched egg C Clutch I) Clutch E Clutch F 4 11.4 (9.8-12.9) 1 5.1 1 5.3 2 8.3/egg 3 10.2/egg 4 31.9/egg Cooper's H a w k ^ ^ Golden Eaglev(19)9 egg Osprey, Baja Calif. 1 8,500 *1 150 6 127 (30-264) Kerlin^21* 1 435 (22) American Kestrel Whole body, adult 1 5.1 eggs, 2 dutches 6 2.4/egg Bleck-crovmed night heron (23) egg egg 1 541 1 869 a a 8D 8.4,5.7,84.0 ... 1,1,1,5, 0.4 8.2 (L) 89 12.2 4.B(L) (6.5-18.9) j7 -- 91 113 " 2.9 -- 90 10.9 (W) 70 62 (48-75) - 0.91 2.1 12 0.76 (V?) 77 0.34 <W) 82 0.35 (W) 73 aas 82 9.0 (L) 57 aa 80 25.2 C O 90 2.0 (W) 98 6.4 (5.5-7.8) 0.84 -- -- 1.8 6,0 3.6 -- 4 . 3/egg ... 1.5 2.0 4.0/egg ... *2,6 3.8/egg ... 8.5 6.3 4.0 17.5 0.23(W) 8.5 55 (L) 85 (7.3,3.0, 103) (24, 7.0,19) 2.9 <W) 94 55.4 -- 8.5,10.1 2 9.7,11.1 0.39 (W) 12.7 0.044 39 0.20 () 93 3.7 0.031 1.4 1.0/egg 0.09(W) 2.3 -- 89 330 -- i-6 -- 99 23 " 36 NEV 016652 726703 table 111 continued Western G u l l ^ ^ esse, San Francisco Boy, 3 clutches A- 803 (632-1123) -- 85 805 (580-1310) 1.0 eggs, Farallon Is. 10 clutches 10 412+102 -- 89 136+55 3.0 eggs, Baja Calif. 7 dutches 7 ' 385*230 ` 97 45+30 9.1,10.5, 5.0,12.3, 10.6,10.7, 10.5 Forster's Tern^2^ eggs Caspian Tern^2^ eggs, San Francisco Bay eggs, San Diego Bay 2 665 (598-732) -- 2 1269 MW (1216-1322) . 5 1A30 (991-2430) 89 114 (91-137) 89 C05 (660-950) 88 1010 (550-1600) -- " 5.8 1X7r 11 ./4 Ked Phalerope^27^ Common Murrc ^2^ eggs 1-- 6 1945 (932-3621) 0.7 (K) 79 MM 0.10 151 (L) 90 558 (364-1010) 45 <L) 8 3.5 Casein'o Auklet^2^ Ancient M u r r e l e c ^ ^ Rhinoceros Auklet (32) Mourning Dove Barn Ovl^32* i eggs, one d u t c h egga;. one d u t c h Meadowlark/^ 1-- 1-- 1-- 2 12.0,33.1 3 27.7/egg 2 143/egg 2 21.2,443 5.8 (W) 98 -- 0.75 90 -- 2.7 97 -- 0.19(H) 77, Not 93 detected 1.25(H) 95 6.6 (VI) 96 0.18, 77, 3.3 (H) 93 10.4/ egg 14.4/ egg 2.5,28.1 0.16 0.15 0.36 tee 36 5 8 * 0.47(V) 2.7 0.66(W) 10 8.4 15.S Unless othcrvlso specified, analyses were of whole bodies. Endrin and dleldrln were identified on the bosls of retention times on both QF-1 and DC-200 columns. 1. Pomoxis annularis, 284 gm. Clear Lake, Lake Co., Calif. May 1968 2. PoooxIb n lgromaculatua 212 g m . , Clear Lake, Lake Co., Calif., May 1968. 3. Lftpomis rtacrochirus, 229 gn., Clear Lake, Lake Co., Calif., May 1968. NEV 018653 726704 Table III, continued 4. Py r o b c c IIb adellae. Cape Crosier, Antarctica, October, 1967. 5. Aechmophorus occldentalls. Clear Lake, Lake Co., Calif., May, 1963. 6- Fultnarus elaclalls. A and B* Monterey Bay, Calif., Nov. 1, 1966. C: Point Reyes, Calif., December, 1967. Fulmars breed in Alaska. 7. PuffinuB creatopus. Breeds in Chile. Collected in Kay, 1968, In the Gulf of California. 8. Pufflnua grlscua. Breeds In Hew Zealand and Chile. A and B: Monterey Bay, November 1, 1966. C: Gulf of California, May, 1968. HM: not measured, Interfering peaks. 9. Pufflnus tenulrostris. Breeds In Australia. Monterey Bay, Dec., 1966. 10. Oceanodroma homochroa. Farelion Islands, Calif. May, 1968. 11. Peljecanus occldentalls. Panama eggs were collected on Isla Pacheca and Isla Pachequllla, Gulf of Panama, Feb. 1968. One egg contained 0.06 ppm dieldrin and 0.06 ppm endrln, another contained 0.16 ppm dieldrin and 0.07 ppm endrln (lipid weight). Baja California eggs were collected at Bahia de los Angeles, March, 1968. One egg contained 0.24 ppm dieldrin and 1.13 ppm endrln (lipid weight). 12. Frebate maeniflcens. Isla Pacheca, Panama, February, 1968. 13. Sula leucocaster . Isla Pacheca and Isla Pachequllla, Tanana, February,1968. Two eggs were analyzed for dieldrin and endrln. Dieldrin: 0.08, 0.18; endrln: 0.06 and 0.011 ppm (lipid weight). 14. Phalacrocorax penicillatus. Farallon Islands, May, 1967 15. Phalacrocorcx pelaglcus. San Mateo Co., Calif. 16. Ana& evanoptera. San Diego, April, 1968. Adult male. 17. Elanus leucurus. A: Contra Costa Co., Calif. April, 1968. B and C: Contra Costa Co., May, 1968, 2.and 3 young raised, respectively. D: abandoned. Contra Costa Co., May, 1967. E and F; destroyed nests, Contra Costa Co., March, 1968, 16. Acciplter cooper!!. Balboa Park, San Diego, Feb., 1968. First year female, died of trlchomonaisl8. 19. Agulla chrysaetos. San Luis Obispo Co., Calif. April, 1968. Unhatched egg in nest where one young was raised. Egg also contained 4.7 microgrants of dieldrin, 1.9 micrograms of heptachlor epoxide, but no endrln. Fandlon haliaetus. Gulf of California, March, 1968. One egg also contained 0.10 ppm dieldrin and 0.25 ppm endrln (L). 21* Falco columbarlus. Immature, Utah. December, 1967. 22. Falco Bparverlu a. Adult was road kill, Mendocino Co., Calif., December,1967. Eggs from Davis, California, 1968. 23. Nycticorax nycticorsx. Eggs from different dutches, San Francisco Bay, May, 19577 24. Larus occldentalls. Standard errors, 95X confidence limits. 25. Sterna forsteri. San Diego Bay, Way, 1967. 26. Hydroprogne caspia. 1967. 27. Phalaronus fullcarlus. Monterey Bay, November 1, 1966. 726705  * Stable 111, continual. 28. Urla alee. Farallon Islands, Vay. 1567. 29. Ptvchorcnphus aloutlea. Farallon Islands, April, 1966. 30. SynthliboramphuB antiquum. Monterey Bay, Nov. 1, 1966. 31. Cerorhlaca monocerate, Monterey Bay, Nov. 1, 1966. 32. Zenaidura macroura. San Diego, July, 1968. 33. Tv to alba. Clutch A from Contra Costa Co., Calif. March, 1968. B from Yolo Co., Calif., April, 1968. 34. Sturnella neglccta. Davie, Calif., December, 1967. Clutch NEV 018655 726706 I Table IV Increase of oestradlol metabolism by pigeon liver homogenates from birds treated with various chlorinated hydrocarbons Control DDE (40 mg/kg) DDT (40 mg/kg) PCB (20 mg/kg) Amount of polar netabolltles formed In mpnules 29.3 + 6.5 76.2 + 13.1 93.1 + 11.2 160.0 + 10.5 Each figure is the average with standard deviation of a group of four birds. In all cases 500 mpmoles of oestradiol-*6t7-T (500 mc/mM) was present In the Incubation mixture. Incubation, time 30 mine, weight of microsomal fraction used was 300 mg. All chlorinated hydrocarbons were injected l.m. into the pectoral muscle 7 days before sacrifice. 0V& 726707 I Figure 1. Chromatographic separation of oestradiol and its metabolites. The. large peak is unaltered oestradiol. y NEV 018657 726708 References 1. Ratcliffs, D. A., Nature 215, 208 (1967). 2. Hickey, J. J. and Anderson, D. W., In preparation. Anderson, D. W . , personal communication. 3. Slmklss, K . , Calcium in Reproductive Physiology (Relnhold, New York, 1967). A. Welch, R. M . , Levin V . , and Conney, A, H., Chemical Fallout. First Rochester Conference on Toxicity, In press (1968) 5. Hart, L. G., Schultlce, R. W . , Fouts, J. R . , Toxicol. Ap p I. Pharmacol. 5, 371 (1963). 6. Hart, L. G., Fouts, J. R. , Haunvn-SchmledeborgB Arch. Exp. Path. Pharmakol. 2A9. 486 (1965). 7. Conney, A. H., Welch, R. 11., Kuntzman, R., Burns, J. J., Clin. Pharmacol. Theran. _8, 2 (1966). 6. Conney, A. K . , Pharmacol. Rev. 19. 317 (1967). 9. Kupfer, D., Residua Rev. 19, 11 (1967). 10. Gerboth, G., Schwabe, U., Arch. Exp. Pathol. Pharmakol. 246, 469 (1964). 11. Gillctt, J. W., J. Aer. Food Chem. 16. 295 (1968). 12. Bchvabe, U., Argnelnlttcl-Forsch. 14. 1265 (1964). 13. Pcakall, D. B., Nature 216. 505 (1967). , 14. Ratcliffe, D. A., British Birds 51. 23 (1958). 15. Ratcliffe, 0. A., Bird Study 10. 56 (1963). 16. Ratcliffo, D. A., Bird Study 12. 66 (1965). 17. Ratcliffo, D. A., Bird Study 14. 238 (1967) 16. Hickey, J. J., ed. The Population Biology of the Peregrine Falcon (University of Wisconsin Press, In the press). 19. Beebe, F. L., Condor 62, 145 (1960). NEV 018656 726709 Cade, T. J., White, C. M., and Haugh, J. R . > Condor 70. 170 (1968). Enderaon, J. H.,' and Berger, D, D . , Condor 70. 149 (1968). Jensen, S., Mew Scientist 32. 612 (1966) Widnark, G., J, Abb. Off. Anal. Chem. 50. 1069 (1967). Holmes, D. C., and Simmons, J. H., and Tattoo, J. O'G., Nature 216. 227 (1967). Risebrough, R. 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Pathol. Pharmakol. 249, 1 (1964). 38. Jonea, R. E, and Leopold, A. S., J. Wildlife Management 37. 221 (1967). NEV 018659 726710 39. Hayhev, W. W . , J. Wildlife Management 19. 36 (1955). 40. Buckner, G. D., Martin, J. II. and Peter, A. !!., Aner. Journ. Physiol. 71. 543 (1925). 41. Buckner, G. D . v Martin, J. U. and Peter, A. M., Ky. Agr. Expt. Sta. Bull. 291 (1929) 42. Nlcolayaen, R. and Eeg-Haraen, H., Vitamins and Hormones. 11. 29 (1953). 43. Coatee, M. E. and Holdsworth, E. S., Brit. Mutrit. 1 5 . 131 (1961). 44. Hart, E. B., Steenbock, H., Lepkovaky, S., Kletzien, S. V. P., Helpin, J. G., and Johnaon, 0. M., Jour. Biol. Chcm. 65 . 579 (1925). 45. Siroklsa, K . , Biol. Rev. 36, 321 (1961). 46. Clavert, J. and Benoit, J., C. R. Soc. Biol., Paris. 136, 509 (1942). 47. Ryes, P. and Potter, S-. Anat. Rec.'60. 377 (1934). 48. Cotvnon, P.. H., J. Aerie. Scl. 23. 555 (1933). 49 Gardener, U. E, Phillips, W. E., Mow, V. A. and Common, R. U . v Mature 170. 80 (1952). 50. Plack, P. A., Miller, W. S. and Ward, C. M., Proc. Biochcm. S o c . 9 0 . 33 (1964). 51. Thayer, G. H., Bird Lore 6. 47 (1904). 52. The major support was provided by the national Science Foundation Grant GP 6362. Work In Baja California was supported in part by the National Science Foundation Grant GB 7600 to the <*&n Diego Society of Natural KJ.?t'~ry. The oestradirj. degradation studies were supported by the United S t ' t o Public Health Service Grant E.S. 00306. Pure p,p'-DDE was kindly sv7?li.nd by the Federal Drug Administration. Aroclor samples were kindly cv.pplled by the Honsanto Chemical Company. Wc thank F. L. Ames, H. 6. Conltar, H, L. Davis, Mama Diaz, R. E. Feeney, Dr. Lula Uowe11 R., J. Jehl, W. Kerr, F. MacIntyre, Ing* E. Mayo, Sr. R. Harmolejo L. and other MEV 018660 726711 a* authorities of the United States of Mexico, E. McMillan, D. Mendola, the Morro Bay Audubon Society, H. S. Olcott, II. J. Festers, A. C* Risaer, R. L. Rudd, Janos Ssabo, Lie. Dario Tovar, L. W. Walker and R. Winslow for their assistance. NEV 016661 ^26712