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j t> 'W- oj- . tv- / 'Ul^t SlkJd fc "tii ili*ilti.. PB - 235 359 1 /)* PESTICIDES, POLYCHLORINATED BIPHEN/o/.S AND HEAVY METALS IN UPPER FOOD CHAIN LEVELS, EVERGLADES NATIONAL PARK AND VICINITY John C. Ogden, el al Everglades National Park IMMM Pvepared for: , Department of the Interior August 1974 DISTRIBUTED BY: Rational Teefoieal lafcrination Service 0. S. DEWiRTraT 6F CGiftME 5285 Pott Roys' Rosd, Springfield Va. 22151 DSW 037696 '* * *+>** MM STLCOPCB4021520 BIBtlOCP.APHIC DATA SI-.-.ET ' 1. H trots No. Dl-SFEP-74-16 2. DO O Q C l O C-OvJ 4. 1 iflc ,\r.j >uncjf/e PESTICIDES, POLYCr.LORIHATED EIPHEHOLS AHD HEAVY METALS lit 5. Kcpc*;t Dote March 1973 UPPER FOOD CHAIR LEVELS, EVERCLAHES HATIOHAL PARK ARD VICINITY. 6. - QRQ 7. AutKor(t) Jolm <J. ugden, hj.J.Jlina b. Robertson, Jary E. Davis and Thonas \!. Schmidt 9. Pctfwmin/i ion Name j-'J AuJrc** Everglades Rational Park P 0 box 279 Homestead, Florida 33030 ' . 8. Performing Organization Rep;. No. 10. Fioirct/1 Loir No. M. Cootr*ct/Gf*m No. >2. Sponsoring Or^arination Xante and AJdtcus U. S. Department of the Interior National Fari: Service, Southeastern Region 2A01 VJhipple Avenue Atlanta, Georgia 303A^ . ' 13. Type of Report U Peiiod Coveted Final 14. 1$. Supple me mat y Notts South Florida Environmental Project: Ecological Report Ho. Dl-SFEP-74-16 16. /bttiacii *, A general concern over possible environmental pollution by nan-made poisons prompt ed the extensive survey of chlorinated insecticides, polychlorinated biphenyls, and metals in upper trophic levels of material collected in and adjacent to Everglades National Parle. Collections vere made between 1971 and 1973, and analyses conducted by VARF, Inc., Kedason, Wisconsin. The resulting analyses provides a base line for future analyses, and clues for particular poisons or particular species in need of more in tensive study. These data revealed that DDT, DDE, IJDD, Dicldrin and PCEs appear to exist in concentrations veil belovr amounts luiovn to have cither acute or chronic effect Less is l;nov.rn of the' significance of the various natal concentrations reported here, . although'levels of mercury in freshwater vertebrates and arsenic in marine species are great enough to deserve more intensive stud/. ! 17. Key VoiJs nrij Document Ati.i!>'sis. Pesticides Poisons ' Metals Environmental surveys 17c. Dcicripioift 17b. ldt-niificf* 'Oi rti-Kurlc.I Terns Everglades Rational Park Everglades Food chain ' Food v:cb . m. < I V A l l ! i. '. '/C Release un.t Jolted. rCHM t/T*4 '/fc IMfcV. ftcprotfuceU by NATIONAL TECHNICAL INFORMATION SERVICE U S forpnrtnicnf of Comnifrce SprJrvCftW VA ??IM I p.r \ A. THIS FORM MAV fil-l r.l-.l'KOPKUiO DSW 037697 STLCOPCB4021521 SOUTH FLORIDA ECOLOGICAL STUDY Pesticides, Polychlorinated Biphenols and Heavy Metals in upper food chain levels, Everglades National Park and vicinity Final Report John C. Ogden, Research Biologist William B. Robertson, Jr,, Research Biologist Gary E. Davis, Marine Research Biologist Thomas W. Schmidt, Aquatic Research Biologist Division of Natural Science and Resource Management Studies Everglades National Park March, 1973 Revised August, 1974 iP OSW 037698 STLCOPCB4021522 I/ * 'V A potentially serious threat to southern Florida wildlife is poisoning by certain human-produced toxic insecticides, industrial compounds or metals which escape or are released into the environ ment. Serious population declines in species of wildlife due to such poisoning have previously been documented in many other regions of the world, particularly among carnivorous species of vertebrates at the top of aquatic food chains (for example: Ames 19f5, Blus et al 1974, Herman et al 1969, Wurster and Wingate 1968). The poisons are absorbed or ingested at various levels of food chains, and become concentrated upward at highter trophic levels as each contaminated individual is consumed by a larger animal. In strong concentrations these poisons cause direct death to adult animals. Of equal concern, lesser concentrations may result in embryonic mortality, thinning of bird eggshells, or chromosomal alterations in first generation young produced by contaminated adults. i / 1 DSW 037699 STLCOPCB4021523 s. INTRODUCTION Southern Florida supports a good many species of aquatic vertebrates potentially endangered by environmental poisons. Field studies and surveys of some of the species (eagles, ospreys, wading birds, pelicans, and alligators) by National Park Service biologists have revealed levels of reproductive success during the 1960s and early 1970s which appear adequate for maintaining stable populations. Scattered samples of south Florida sediments, plants, water, vertebrate tissue, and avian eggs, which have previously been analysed for various environmental pollutants have generally contained quite low concentrations of these poisons, as one would expect from the successful vertebrate reproduction observed. However, it was apparent that at least small concentrations of various environmental poisons were distributed throughout south Florida eco systems. The total number of samples from south Florida which had been previously analysed, however, was altogether inadequate for a thorough understanding of this entire problem. This present project was design ed to improve the knowledge of the distribution of the environmental pollutants which arc known to, or strongly suspected of, adversely affecting upper trophic level vertebrates and invertebrates, and/or are known to be present in south Florida environments. 2 DSW 03 ?70G STLCOPCB4021524 STUDY AREA AMD METHODS In all, 95 samples were collected and submitted for chemical analyses by WARF, Inc.,' Madison, Wisconsin. This collection of samples repre sented an extensive rather than intensive look at local environmental contaminants in an effort to determine which contaminants and which species may be In need of further study. These samples were collected primarily between June, 1971 and January, 1973, as follows: *1. 5 Osprey eggs from western Florida Bay, 3 collected January 1969, 2 collected February-Harch 1972. 2. 8 Brown Pelican eggs from western Florida Bay, collected March 1972. 3. 5 Common Egret eggs from central Shark Slough everglades, collected March 1972. 4. 5 Common Egret eggs from western Florida Bay, collected March 1972. *5. Breast and brain tissue (total 6 samples) from 3 White Ibis, collected Chokoloskee Bay, June 1971. 6. 4 White Ibis eggs from western Florida Bay, collected April 1972. , 7. 5 White Ibis eggs from Conservation Area 3B everglades, collected April 1972. 8. 5 Double-crested Cormorant eggs from western Florida Bay collected March 1972. 3 DSW 037701 STLCOPCB4021525 r /i ; ( ' j `v t l j ' . ' ' ,, *9. Breast and brain (total 6 samples) fro:j 3 Sooty Terns from the Dry Tortugas, collected August 1971. *10. 5 Cattle Egret eggs from Taylor Slough everglades, collected June 1972. ;. *11. Combined breast and brain tissue from 1 Red-shouldered Hawk, near Mahogany Hammock, collected November 1972. 12, Combined breast and brain from 1 White Ibis, 40-mile Bend, collected September 1972, *13. 4 American Alligator eggs from central Shark Slough ever- glades collected June 1972. 14. 5 American Crocodile eggs from eastern Florida Bay, collected May 1972. j 15. 2 samples of Finfiah (0 and 4 fish respectively) from Florida Bay, collected December 1971, and feptember 1972. 16. 1 sample of 7 Pinfisli from south Biscayns Bay, March 1972. 17. 2 samples of Stone Crabs (4 and 4) from Florida Bay. collected December 1971, and May 1972. 18. 1 sample of 3 Stone Crabs from south Biscayne Bay, collected October 1972. 19. 2 samples of Sea Catfish (3 and 3) from Florida Bay, collected January 1972, and September 1972, 20. 2 samples of Crevalle Jacks (4 and 3) from Florida Bay, collected December 1971, andJune 1972. DSW 037702 STLCOPCB4021526 21. 2 samples of Silver Mullet (4 and 4) from Florida Bay, collected January 1972, and June 1972. 22. 1 sample of 3 Silver Mullet from south Biscayne Bay, collected November 1972. 23. 2 samples of Spiny Lobsters (4 and 7) from Florida Bay, collected December 1971 and May 1972. 24. 1 sample of 2 Spiny Lobsters from south Biscayne Bay, collected October 1972. 25. 1 sample of 6 Spiny Lobsters from Dry Tortugas, collected March 1972. . 26. 2 samples of Gray Snapper (5 and 3) from Florida Bay, collected December 1971, and June 1972. 27. 1 sample of 2 Gray Snapper from south Biscayne Bay, collected January, 1972. 28. 1 sample of 18 Pink Shrimp from south Biscayne Bay, collected March 1972. 29. 1 sample of 2 Blue Crab from south Biscayne Bay, collected October 1972. 30. 1 sample of 4 Eluegill from the upper Shark Slough everglades, collected July 1972. 31. 1 sample of 4 Bluegill from Taylor Slough everglades, collected November 1972. 32. 1 sample of 2 Florida Gar from upper Shark Slough everglades, collected August 1972. 5 DSW 037703 STLCOPCB4021527 33. 1 sample of 3 Largeroouth Bass from Taylor Slough everglades, collected October 1972. *34. 1 sample of 3 Leopard Frogs from upper Shark Slough everglades, collected October 1972. *35. 1 sample of 87 Mosquito Fish from upper Shark Slough everglades, collected October 1972. *36. 1 sample of 50 Mosquito Fish from Taylor Slough ever glades, collected January 1973. : *37. 1 sample of 9 Everglades Crayfish (Procambarus) from upper Shark Slough everglades, collected Octoler 1972. All samples were analysed for residues of certain persistent chlorinated insecticides (DDT, DDE, DDD, and Dieldrin), and for the persistent chlorinated industrial compounds known as Polychlorinated Biphenols, Each sample was also tested for residues of arsenic, mercury, cadmium, lead, xinc and copjer, with the exception of some of the samples in the groups marked with an asterisk (*) which lacked sufficient volume for total analyses. The analyses were done on whole eggs (excluding shells) of birds and crocodilians, breast and brain tissue of White Ibis and a Red-shouldered Hawk, and from homogenates of whole animals in the fish, frog and invertebrate samples. The results of these analyses are presented in Table 1, and are expressed in parts per million, whole wet weight basis. . 6 OSW 037704 STLCOPCB4021528 W*W' \ 4* DISCUSSION The egg analyses provide l>oth a measure of residue levels present in the adult females of each species, and a means for comparing residues in the eggs with a measure of shell thickness. Several research studies have previously shown that sufficient amounts of DDE, and possibly Dieldrin, affect calcium metabolism in birds, resulting in production of thin-shelled eggs (Birman et al 1970, Lockie et al 1969, Wiameyer and Porter 1970). Increased breakage of these eggs during Incubation, in some cases to the point of elimi nating all successful reproduction in a population or colony of contaminated birds, has been document"'' (Keith et al 1970). Other studies of laboratory or field contaminated populations of birds generally showed adversely altered hatching success when egg shell thickness was reduced by approximately 10-20 percent from normal thickness (Wiemeyer and Porter 1970, Wleroeyer et al 1972). We measured 6hell thickness for the eggs collected during this project and present these data in Table 11, Although no great amount of shell-thickness data from normal, non-contaminated populations of birds are available in the literature, it appears that for at least two species, Osprey and Brown Pelicans, the shell measurements from Florida Bay eggs are similar to shell measurements from eggs collected prior to 1947 from non-contaminated populations of these same two species (Anderson and Hickey 1972, Blvs et al 1974). We believe it quite likely, therefore, that 1971-1972 eggs produced in the south 7 DSW 037705 STLCOPCB4021529 Florida everglades region did not contain sufficient contaminants to produce a degree of shell-thinning that would reduce productivity for any species. ' The factors which determine rates and patterns of distribution, as well as toxicity of the various environmental pollutants, are extremely complex and only partially understood. Various studies have shown that temperature, turbidity, and flow rate of water, age and size of animals, presence of other chemicals in local environments, and rates of input of toxic chemicals into ecosystems are only some of the factors which determine distribution and toxicity of chemical pollutants in local areas (for example: Durham 1969, Gish and Chura 1969, Kearney et al 1969). An additional difficulty in interpreting residue data is that many potentially toxic metals occur naturally in small amounts in most environ ments. The natural levels of these metals are not well known in various tissues of most animals, making it difficult to understand the significance of concentrations detected during spot sampling. The metal residues revealed by WARF analyses, while representing a considerable increase in our knowledge of the distribution of these potential pollutants in south Florida, are still insufficient to allow definitive interpretation of the origins, rates of concentration, distribution or toxicity with the local conditions where they are found. Somewhat better understanding of the significance of insecticides and FCB residues can be made from the WARF analyses, primarily because of the voluminous amounts of background Information that have accumulated as a result of world wide attention and study of these chlorinated hydrocarbon conpounds. 8 DSW 037706 STLCOPCB4021530 Where WARF analyses proved most useful was in: 1) providing additional data on distribution and concentration of several potential environmental poisons, including the first information from several local species not previously tested; 2) by providing base-line data for futuie measurements of these same contaminants in the same species obtained by similar collecting procedures; and 3) by providing clues for wnere there is need for intensive investi gation of particular contaminants that may be at or near dangerous concentrations. Following is a summary of the apparent significance of levels of DDT and its metabolites, Dieldrin, PCBs, Arsenic, Mercury, Cadmium, Zinc, Lead and Copper revealed by the NARF analyses. ANALYTICAL INTERPRETATION 1, DDT and Metabolites (DDE, DDD). An import comment on DDT and it's break-down products, DDE and DDD, is that various species of vertebrates have been shown to exihlbit widely different sensitivities to these poisons, so that a lethal amount for one species cannot be assumed to be lethal for other similar sized species. In general, concentrations between 25 and 50 ppm in brain tissue can be considered approaching probably lethal levels for large aquatic and raptorial birds (for example: Beliele et al 1972, Blus et al 1974). The residues of DDT, DDE and DDD revealed by WARF analyses, however, are at quite low con centrations in all species tested, and it probably is true that no significant mortality or impaired reproduction in the Everglades National Park region is occurring due to these poisons. DDE in bird eggs at concentrations greater than 10 ppm might result in enough eg'; 9 OSW 037707 shell thinning to depress reproductive success on some species (Cade et al 1971, Wiemeyer and Porter 1970), but the highest concentrations of DDE detected by WARF in bird eggs were slightly above 1 ppm in three Osprey eggs. Ho other fish eating bird eggs, including pelican, cormorant, and Common Egret eggs collected from the same portion of Florida Bay as were the Osprey eggs, contained concentrations as high as 1 ppm. Two of five Cattle Egret eggs contained DDE greater than 1 ppm, including one egg with about 55 ppm DDE. Cattle Egrets are not fisb eaters, but feed on large insects captured in fields (Fogerty and Hetrick 1973), and individual egrets may accumulate relatively high concentrations by repeatedly feeding in agricultural fields recently sprayed with DDT. Tissues from Dry Tortugas Sooty Terns were particular ly clean of these compounds. The highest concentrations of DDE were found in eggs of American Alligators, (mean value for four eggs, 2.42 ppm; range 1.79-3.00 ppm), and American Crocodiles (mean for five eggs, 1*85 ppm; range 0.78-3.23 ppm). So little is known of the affects of DDT, and its metabolites, on crocodllians that it is difficult to interpret these data. It is interesting that the freshwater fish or invertebrate sample with highest DDE residues was the Florida Gar, a species thought to be important as food for alligators. Where crocodiles obtained high DDE concentrations is more puzzling, for residues of DDE in silver mullet and crabs, two important crocodile foods, were particularly low. 10 DSw 037708 STLCOPCB4021532 None of the species analyzed by WARF contained concentrations that approach residue levels known to produce chronic damage to these species. We also recognize, however, that the low levels in decapod crustaceans could reflect the extreme sensitivity these animals have for these compounds (Butler 1969). Greater concentrations, in the range of 1 to 10 ppm, tend to be lethal in some species. All samples submitted to WARF were from live, presumably healthy, individuals, and would almost have, to be clean of these poisons. This sensitivity is not surprising since these compounds were designed for destruction of closely related arthropod pests. 2. Dieldrin. In general, fai.ly low levels of Dieldrin in the range of 10-20 ppm in brain tissues, may result in death or abnormal behavior in come birds, particularly in combination with relatively 1 igli levels of other insecticides (Stickel et al 1969). Concentrations as low as 1-5 ppm in bird eggs have been reported to cause egg shell thinning in some species (Lockie et al 1969 and Stoewsand et al 1971). These con centrations are considerably greater than any detected by the WARF analyses. All samples tested by WARF contain concentrations of Dieldrin less than 1 ppm. Bird eggs general]v contained less than 0.10 ppm, except for Cattle Egrets, where 5 eggs contained a meal level of 0.18 ppm (range: none detected to 0.66 ppm). The relatively high concentrations in Cattle Egret eggs is a reflection of this species' food habits in south Florida of large insects captured by farmland fields, including fields where local applications of Dieldrin may occur. 11 DSW 037709 ' i STLCOPCB4021533 * 4v>. . \ 3. Polychlorinated Biphenols. PCBs occurring in the environment are industrial compounds used as plasticizers in the production of paints, resins, and electrical insulators, and they may be applied with pesti cides to extend the kill-life of the poisons (Hammond 1972, Peakall and Lincer 1970). PCBs have been found to be approximately 1/A to 1/5 as toxic as DDT in some birds studied, and two or three orders of magnitude less toxic to fish than DDT. Like DDT, PCBs which escape into the environment remain as persistent poisons, A steady diet of PCBs to adult birds, in concentrations of approximately 10 ppm, may result in chromosomal alteration in young produced by these adults, and concentrations of about 50 ppm in the eggs laid by these adults (Peakall et al 1972). PCB concentrations revealed by the WARF analyses were highest in fish eating birds from Florida Bay (mean value 1.43 ppm in Osprey eggs; 1.21 ppm in Common Egret eggs; and 0.84 ppm in pelican eggs). Highest concentrations in freshwater samples were from Common Egret eggs (mean 0.33 ppm) and Alligator eggs (mean 0.30 ppm), from the Shark Slough. These concentrations are well below those known to cause serious adverse effects on wildlife. Samples from several other fresh-water and marine vertebrates (White Ibis, cormorant, and crocodile eggs; Sooty Tern tissue) contained no detectable PCB residues. Marine and freshwater fish and invertebrate samples generally contained less than 0.10 ppm PCBs, con siderably below concentrations thought to affect these species (Hammond 1972). 12 OSW 037710 STLCOPCB4021534 4. Mercury. The U. S. Food and Drug Administration has declared that fish and other food which contain more than 0.5 ppm mercury are unsafe for human consumption. Recent studies of wildlife in the United States and Canada have revealed that several species of fish and game birds contain concentrations of mercury at or above this 0.5 ppm level (for example: Adley and Brown 1972, Firareite 1974). In fact, it appears that such concentrations may not be rare in wildlife, indicating that there is widespread mercury pollution, particularly in freshwater eco systems. There is little information on whether these mercury con centrations have chronic effects on the species. : Highest concentrations revealed by the WARF analyses were, as in other regions, primarily invertebrates which live or feed in freshwater. Brain and breast tissue from White Ibis ranged between approximately 1 and 2.5 ppm mercury, combined breast and brain from a Red-shouldered Hawk contain ed 0.78 ppm, 4 alligator eggs had a mean 0.69 ppm, two bluegill samples averaged 0.58 ppm, and a sample of Florida gar contained 0.60 ppm. Common Egret eggs from the Shark Slough contained a mean 0.37 ppm mercury, com pared with a mean 0.16 ppm in Common Egret eggs from Florida Bay. The same relationship was not apparent between White Ibis eggs collected in the everglades and Florida Bay, where the values were only slightly higher in the freshwater region. Highest mercury concentrations in marine species were a mean of 0.59 ppm from the seven carnivorous Crevalle Jack samples, and 0.36 ppm in 13 DSW 037711 STLCOPCB4021535 cormorant eggs. The relatively high concentrations of 0.24 ppm in bottom feeding Sea Catfish seemed to reflect their higher trophic position than the similar bottom feeding Silver Mullet, with mercury concentrations of 0.05 ppm. Species with similar feeding methods may be expected to contain more nearly similar amounts of various residues, but the fact that they do not points out the possibility of different rates of assimilation of these poisons by different species. The mercury concentrations reported here apparently are too low to have acute effects on wildlife, but there is no certainty that chronic problems do not occur. The relatively high concentrations in seme freshwater vertebrates deserves further monitoring and study, with emphasis on sources of the mercury, and the possible effects on pro ductivity in these freshwater species. Of particular interest are the seemingly high concentrations of arsenic, zinc, lead and copper in more marine species. Many marine organisms are known to selectively accumulate heavy metal6, a pheno menon that has been reported for over 50 years (Harvey, 1957). It has been established that marine biological systems accumulate arsenic, zinc, lead, copper and cadmium concentrations several thousand times greater than ambient sea water (FWPCA 1968, Goldberg 1970). Zinc and copper concentrations are well within a range considered normal for estuarine fish. The WART samples contain concentrations of these metals, other than arsenic, less than could be expected by biological accumulation from average sea water concentrations. Arsenic concentrations 14 OSW 037712 STLCOPCB4021536 * \\ . 0> . in some marine fish (7.5 ppm) and invertebrates (18.8 ppm) are slightly higher than expected by accumulation, but probably not by a significant amount. The levels of arsenic found in this study approached the present tolerance of 7 ppm for combined lead arsenate on food crops, and may constitute a health hazard (Pakhala et al., 1972). The possibility of arsenic at concentrations great enough to have adverse affects is real, and this situation deserves further in vestigation. We also recommend that monitoring of the other metals be scheduled on some regular basis, particularly in conjunction with any studies undertaken of the population dynamics of marine species in Everglades National Park. ; SUMMARY AND RECOMMENDATIONS A general concern over possible environmental pollution in southern Florida by man-made poisons prompted this extensive survey of chlorin ated insecticides, polychlorinated biphenols, and metals in upper trophic level samples. The resulting analyses provide a base line for future analyses, and clues o. particular poisons or particular species in need of more intensive study. These data revealed that DDT, DDE, DDD, Dieldrin, and PCBs appear to exist in concentrations well below amounts known to have either acute or chronic effects on local species. Less is known of the significance of the various metal concentrations reported here, although levels of mercury in freshwater vertebrates, and arsenic in marine species are great enough to deserve more intensive study. We recommend the following: 15 DSW 037713 / STLCOPC 1. A regular program to monitor amounts of environmental poisons in upper trophic level species in the southern everglades and adjacent estuaries should be established. Not less than 50 samples representing select freshwater and marine species, primarily those tested In this . present study, should be tested for insecticides, PCBs, and metals, on a routine basis every 2 or 3 years. Some effort should be made to collect samples from areas where little sampling has been done thus far, for example in the west coast rivers and bays south of Everglades City, the lower cypress sloughs, and in Conservation Area 3. 2. Concentrations of mercury in freshwater vertebrates, and arsenic in marine animals were high enough to warrent further investigations soon. Some money and time should be programmed for further analyses for mercury and arsenic to determine percent of methyl mercury present in total mercury reported, obtain a better understanding of distribution and source of mercury and arsenic in these ecosystems, and for further literature review to provide interpretation of significance of mercury and arsenic concentrations being detected locally. 16 DSW 037714 STLCOPCB4021538 TABLE L Felleidc, Poiychlctlnewd Blphonulj, and heavy metal concentration* (ppm) in aoclh Florida animal* 2 972-72. Sai.i.V.c N-?,Vr I.oettien 2 Florida liay > Florida Bay } r:o.-li= T-iy 4 Florida Bay 3 Florida J'ay 6 Florida Bay 7 Florida Lay 3 Florida Lay ? Florida Lay 10 Florida Lay 21 Fl'-r Ida Bay 12 Florida Bay 13 Florida Lay SArrnle Material Osprey Er;44 0.pry Err4* Osprey Err Otprcy Egg Oaproy ;g Brown Pelican egg Brown Pvlican egg Brown Pelican eg? Brown Pelican egg Brown PelUan egg Brown Pelican egg Brown Pelican egg Brown PaUcan egg nnr 1.9*1 0. 96 1.24 9.86 1.09 0.12 0.0* 0.11 0.0*. 0.22 0.63 0.20 0.14 OOP ODT C. 30 ND-* 0.21 0. 080 0.29 NO 0.23 0.016 C.C78 C. 016 C.C56 0.047 0.047 0.047 0.053 0.078 0.016 C. 01 u 0.0 53 0. 053 0.11O 0. no 0. 073 0. 047 0.034 0.047 Lit.*Id riff O.C37 0.011 0. 016 o.oio 0.010 0. 030 0. 020 0.0:5 0,012 0. 030 0.230 0. 030 0.030 pen A.-* w.* c-j ' -?-a. -___ Efc. r* 2,27 0.64 1.33 1.50 <0. 10 0. 07 <05 4.6 <0.2 0.7# 1.37 <0.20 0.21 <05 6. 5 <0.2 C. 54 0. 3) <0. 10 0.2? <.05 7. e <0.2 1.06 0.25 <0. 10 0.36 <.05 4.7 <r: 0*72 0.37 <c. 10 0, 30 <.05 7.3 <2.: 0, 31 <0. 10 0.33 <. 05 5.4 <0, * 1.02 1. 14 0.69 <0.10 3.24 0.10 1.00 <0. 10 0.C2 <0.10 0,44 0.65 C. 12 0.28 <. 05 <.25 6. 6 7.9 <.cs 6.2 <05 9.3 <:.2 ]. Cfo <0.2 5. 2 <9,2 0,o4 <0.2 1.04 DSW 0 3 7 7 1 5 TABLE!. Continued Sample ?:vr.Scf 14 15 1> 17 13 29 20 21 22 23 24 226 p* 28 Location Shark Valley Shark Valley Shark Valley Shark Valley Shark Valley Florida Bay Florida Cay Florida Bay Florida Bay Florida Cay Taylor Slough Taylor Slough Taylor Slough Taylor S*ough ....Taylor Slough Sample Matertai Common Egfct egg Common Egret egg Common Egret egg Common Egret egg Common Egret egg Common Egret egg Common Egret egg Common Egret egg Common Egret ceg Common Egret egg Cattle Egret egg*** Cattle Egret egg*** Cattle Egret egg Cattle Egrvt egg Cattle Egret egg DDE DDD 2.TT Dleldr'n PCD Am He Cd 7.n PI C<z C.47 0.041 0,062 0.010. 0.25 <0.10 0.28 <0.05 S. 7 <0.2 0.85 0.29 0. 022 O. 041 SD 0.19 <0, 10 0.1? <0.05 6.3 <0, 2 0.78 0.42 0.022 0.047 0.075 0.31 <0. 10 0. 20 <0.05 8.5 <0.2 1.26 0.52 0. 022 0. 047 0.010 0,28 <0.10 0.91 <0.05 6.7 <0.3 2.02 0. 39 0.031 0.002 ND 0.56 <0.10 0.22 oA n 9.8 <0.4 0.81 0.14 0.022 0.010 XD ND <0.10 0.19 <0.05 S.4 <0.2 l.OS 0. !4 ND 0.020 ND ' ND <0. 10 0.17 <0.05 5.9 <0.2 1.16 0. 52 0. 0TG 0.047 0. 025 0.S7 <0.10 0.13 0*03 a. 3 <C. 2 1.00 0. 94 0.031 0.094 0.030 5.00 <0.10 0,17 <0.05 a. l <0.2 l.os 0. 0*9* ND 0.016 0.025 0.19 <0. 10. 0.13 <0.05 . a TC.2 C, 94 0. IS 5. 49 0.19 1.63 0.016 0.11 0.008 0.035 0.073 ND 0.21 o. uo. 0.040 o. no 0.035 0.120 ND <0. 20 0.05 0. 35 <0.2 0 0,05 ND <0.07 0.05 ND <0.20 0.C5 -- -- __ __ __ __ __ 0.12 0.047 0.051 0.034 ND 0.3 0.05 DSW 0 3 7 7 1 6 TABI52 I. Continued V-:-rSor 29 20 . 23 32 35 24 _ 35 20 27 23 3? 40 41 42 434 Sa'v-ilo Van r:iV Florida Bay White Ibis egg Florida Hay White Ibis egg , Florida Say White lb's esS Florida. Say White Ibia egg Ce-. Area 53 White Ibis egi Cons. Area 13 V.-hiie Ibis css Cons. Area 13 V.*h;*.e Ibis cug Cans. Area 13 Cons. Ana 33 W hi*.c Toi* egg White Ibis ogg Florida 3-y Cormorant egg Florida Boy Cormorant egg FloricIs Bay Cormorant egg Flnricia Bay Cormorant egg Florida Say -Cormorant egg Chokoloskco Bay White 2bi breast ddf: DDD C. 031 0. oil 0. 062 C.C3I 0.16 0.CI6 O.U 0.Ci6 0. 07? 0.015 0. so 0. 0i9 c. u 0. 016 0. 16 o.oi: C. 062 NO C. 031 0.031 Q.031 ND O.C-17 ND 0.047 ND 0.053 Nil 0.094 KB onr DieXrin pcr> As r!: o* v, so 0.C37 ND <0.10 0.05 <.05 7. Q -0.3 0.032 ND ND <0,10 o. c? COS c. u c:.: 0.016 0.C20 o. :<? <0.10 C. 07 <- 03 9.6 <). i C. 016 0. 005 ND C.2-J G. C5 <.05 S. J <':.Z 0.CI5 0. CIO ND <9.2 0 <S. 05 COS 7. C> 4 u. 5 0. C37 0. 010 ND cc.ro t\oo Cos 6. & <C.2 N D 0. CiZ C. 031 ND ND Co. :o o.o? d. C5 1 --- ND C-.25 O.Cu . 25 ;o. 3 0. 9 C.CI5 0.020 ND <0. :o <n. cs Cos 9. 6 <f.S ND ND ND ND ND <0.2 0 0. 44 .05 ?. 2 ND <C.1j 0.32 . 05 ?. 4 V* -> ND ND ND ND ND <0.10 0.44 0.25 <0. JO 0.34 *05. .05 6.2 3.4 v. 4 0. 3 ND ND ND <0.20 0.44 ,05 C-.2 ND 0.01C ND __ 0.9? _ - _ ._ rC. 4 :. co 1 . K ! l.z? 0. ^4 1.C0 1.15 1.25 0. c9 C. ; C.6 :.2s 0. 50 _. DSW 0 3 7 7 1 7 TABLE I. Continued Sample N'Trbc Samole Material 43b Chokoler-.v Bay White Xble brain 44a Chokoloikee Bay Whil IbU breaat 44b Chokolotkee Bay White Ibis brain 45a ChdHoloil;Ctf Bay White Ibl* breast 45b Ctokoloikee Bay White Ibla brain 4b Mahogany HammceK Rad-akoudcred Hawk**** 47 40-Mile Ek-nd White rbu 4$ Dry Tortugaa Sooty Tern brcaal 49b Dry Tortuga* Sooty Tern brain 49a Dry T'jr:u*n Sooty Tern breast 40b Dry Tortuga* Sooty '1'ern brain 50a Dry Tortuga* Sooty Tern breaat 53b Dry Tcrt ijja Sooty Torn brain i i Shark Valley Alligator egg Shark Valley Alligator ogf 53 SUrk V.lloy Alligator egg * DDE PDD DOT Dlcldrlo 0.o9 ND 0.081 ND ND ND ND ND 0.092 0.092 ND ND 0.16 ND ND ND 0. 32 ND ND NO 0.091 0.005 c.ocs C. 005 0.010 0.005 O.C05 0.025 0.039 ND ND ND ND ND ND 0.13 0.031 ND :;d 0.015 ND ND ND 0.080 0.062 ND ND 0.020 0.16 ND ND 0.10 2.51 0.053 0.10 0.064 1.79 0.047 0.047 ND 2.33 0.044 0.044 0.019 PCB As III! Cd ND 0. 37 1.76 0.05 9.0 NO ND 7n Ph 0.2 *9.0 0.78 0.15 0.78 0.050 0.07 1.40 0.05 10. ND .05 ND ND -ND .05 -- - ND 1,92 0. 06 -- * 0.40 0.03 0.41 0.25 0.2 -* - 0.22 0.2 0,51 -- -- 0.2 ----- Cu 3.4 7.2 - * -- TABLE X. ContUucd . 54 55 SO 57 58 59 63 U 62 . 63 *4 i5 66 a 53 Lor ition Shark Valley Florida Say riw!* Day Florida 3*y Florida Bay Florida Bay Shark Valley Shark Valley Tuylor S!ovgh Taylor SloagH # Shark Vallty Shirk Valley Shark Valley Taylor Slough Florida Bay Samp*,* M.-vu-rlat Alligator egg Crocodile egg Crocodile egg Crocodile egg Crocodile egg Crocodile egg Biutjin Florl<ia Car (I) Oluc^ill (4) Largemouth Baa* (3) Leopard Frog (3) Moaqultofiah (87) Crayfish (9) Moqutioi*h (30) Crevalle Jack [4) DDK nnn DOT Dti'ldrin pen A* Hr CJ 3.CO 0.042 0.040 ND 0. 36 0.05 C. 53 3. 23 0.16 0. 59 C.0I9 ND 0.08 0.14 O.OS 8.2 1.44 0.11 0, 33 0. 024 ND 0.03 o.os 0.05 3. 3 la 72 0.15 0.29 ND ND 0.03 0.C8 O.OS 7.2 1.87 0.052 0. 31 0.011 ND 0.0b 0.10 0.05 a. 0.78 0.955 -0.15 ND ND 0.06 C. 07 0.05 1L c.on 0.0U6 0.006 ND * ND 0.0? 0.94 0.05 23. 0.20 0.063 0.052 ND 0.047 0.5 0.60 0.05 2t>. 3.050 0.014 0.027 0.006 0.073 0.0* 0.22 0.0? i-;. 0.0 C2 0.032 0.037 0.003 0. 02? 0.010 C 010 0.010 0.055 0.05 0.082 0,07 0.31 ' o.os 0.07 -- 16. -- 0.013 0.010 0.010 0.010 0.19 0.07 0.15 .... -- 0.005 0.005 0.006 0.006 0.037 0.008 o.oos 0.000 0.005 ND 0. 005 ND 0.10 0.12 0.3S 0.07 0.05 0.17 -- -- -- ND 0.55 0.39 0.05 13. Pb C.i 0.1 0.9 0.5 :.c: 0. J a. 0-. 0.4 0. 82 0.2 15.0 0, 5 a.'jT 0. 6 C. ?7 0. 5 0.5 0.5 S. 5 -- --. -- ' --' " * ' 0.4 -0.81 a GO o u> o VI O STLCOPCB4021543 DSW 0 3 7 7 2 0 Sor*, ole X'lr^b.'T 69 ?0 . 11 72 73 4 75 ?*> 77 Td 79 *0 63 kZ 33 Location Florida Bay Florida Bay Florida Bay Florida Bay Florida Bay Florida Bay Florida Hoy FZoii da Bay Florida Bay Ciac-iync Bay ULscoyns Bay So. Bisc. Say S. Bite. Bay So. Biss. Bay So. ise. Bay Sample Mrtcrinl Cray Snapper (5) Silver Mullet {4} Sea Catfl.h (3)' Pinn*h (8> ' PinfUh (4) Sea Catfiah (3) Crevoile Jack {3) Sliver Mullet (4) Cray Snapper (3) Plr.ti.sli i.7) Cray Sanpper (2) Silver Mullet (3) Stone Crab* (3} Eluo Crab (2) Spiny Lobster (Z) TABLE L ConUr.'uod DDK DDD DDT Pi eld? In M3 N3 0.008 0.005 NO NO 0.006 XD 0.032 0.095 0.005 0. C05 0.003 0.005 0.000 0. CCS Q.OQO 0.00*7 o.ooa 0.0C5 0.036 ND C. 005 0.005 0.029 0.017 0.037 0.037 0.022 0. 005 0.006 0.005 0.014 0.006 XD 0.015 0.00$ 0.005 C. 000 XD o. n 0.059 0.037 0,017 0.036 XD 0.010 0.012 0. 00J 0.003 0.005 0.005 0.003 0.00? 0.005 0.035 0.005 0.003 0.005 0,005 pen A* tie Cd Za V>y NO 1.4 0.13 0.07 1?.: 1.5 ND 1.5 0,07 0.05 30. 0.6 0.1S 3.12 0.09? 2.05 0,15 0.06 0, 3 2 119. o.i: 1 7 0.3 0. 5 0.11 3.52 0. 12 0.05 19.2 0.2 0.06 7.47 0.29 0.15 126. 0.2 0.12 0,50 C.fcv C. 05 12.2 0.2 0.79 2, 5! 0.05 0,05 2.231 0.29 0, 05 C.0J 25. 5 17. I 0.2 5.2 XD 2.7 0,06 0.03 22. 0,2 0.097 1.6 0.U 0. It :i. O, 4 0,073 1.22 0,05 0. 00 23. c.s 0. 024 11.8 o.os 0.76 37. 0. 5 0.02$ 7.66 0.03 0.92 27. 0.5 0. 024 IS. 5 0.03 0.17 26. 0.5 Ct C. 70 1.16 0. S 0.9 0. 66 0.SS C.73 2.4 0. 96 0.73 0.39 C.o 26, 7 n.i 32.2 T A B L E 1. C o n tin u e d o M ** d oa* ul o V TV ONO dodo 0 4(O10 oo d vtr. c ncaa /, z e n v\ l rs o o d Q 4 Q 4 o an d7 aion mo &DooQ Q C 4 d d 4 4 *4 c O mO Q a n O E 4o A4 4 V.l; r rs Q X N O O n o d r> 7. D 0 4 a c u * io*. VI ccl 6c. r. r- con d n v> QM 4 M 7d. A# J 40 c<* 3 e cn a. A 0 TJ CVO 04 I ! oO. N. ?. Ws*4 ^er3 o c r. fi ,0 ^ 2 , "HKi; ,"*n .5 r .cu*5 -cji -?"j, V It. n. * fne` < . v> * - Uft gn cAo r0 oVt Yt ii'i 2> DS W 037721 STLCOPCB4021545 TABLE n Eggshell thickness measurements pesticides and heavy metal monitoring South Florida Environmental Study Species Osprey Brown Pelican Brown Pelican Common Egret Common Egret Double-crested Cormorant Location Florida Bay Frank Key Palm Key Frank Key Shark Slough Frank Key A f . Number 2 4 4 5 '5 5 Mean (mm) .590 . 576 . 566 .336 .346 .436 Range (mm) .575 - .605 . 545 - . 621 .536 - . 640 . 287 - . 351 .335 - .371 .410 - .490 Literature Cited Adley, F. E., and D. W. Brown. 1972. Mercury concentrations in game birds. State of Washington -,1970 and 1971. Pesticides Monit. Jour. 6:91-93. . Ames, P. L. 1965. DDT residues in the eggs of the Osprey in the north-eastern United States and their relation to nesting success. Suppl. to Jour, Appl. Ecol. June 1966, 87-97. Anderson, D.W., and J. J. Hickey. 1972, Eggshell changes in certain North American birds. Proc. XV Internat. Ornithol. Cong.., 514-540 Belisle, A. A., W, L. Reichel, L. N. Locke, T. 0. Lamont, B. M. Mulhern, R. II. Prouty, R. B. DeWolf, and E. Cromartie. 1972. Residues of organchlorine pesticides, polychlorinated biphenyls, and mercury ard autopsy data for Bald Eagles, 1969 and 1970. Pesticides Monit> Jour. 6:133-138. Bitman, J., H. C. Cecil, and G. F. Fries. 1970. DDT-induced inhibition of avian shell gland carbonic anhydrase: a mechanism for thin eggshells. Science. 168:594-596. BIub, L. J., A. A. Belisle, and R. M. Prouty. 1974. Relations of the Brown Pelican to certain environmental pollutants. Pesticides Monit, Jour. 7:181-194. Butler, P. A. 1969. The significance of DDT residues in estuarine fauna. In: Chemical fallout (Eds.: M. W. Miller and G. G, Berg). Springfield, 111.t Charles C. Thomas, pp. 205-220, Cade, T. J., J. L. Lincer, C. M. White, D. G. Roseneau, and L. G. Swart* 1971. DDE residues and eggshell changes in Alaskan falcons and hawks. Science 172:955-957. Durham, W. F. 1969. The influence of other factors on the toxicity of pesticides. In: Chemical fallout (Eds.: M. W. Miller and G. G. Berg). Springfield, 111. Charles C. Thomas, pp. 433-446. Federal Water Pollution Control Administration. 1968. Water Quality Criteria. U. S. Dept. Int. Wash. D.C. Fiiareite, N, 1974. Mercury contamination of aquatic birds in north western Ontario, Jour, Wildlife Manag. 36:120-131. &5T DSW 037723 / Literature Cited - 2 \ Fogarty, M. J., and W. M. Hetrick. 1973. Summer foods of Cattle Egrets in north central Florida. Auk 90:268-280. Cish, C. D., and N. J. Chura. 1969. Toxicity of DDT to Japanese Ouail as influenced by body weight, breeding conditions and sex. Toxicology and Appl. Pharmacology 17:740-751 Goldberg, E. D, 1957. Biogeochemistry of trace elements. In: Treatise on marine ecology and paleoecology, Vol. 1 Ecology Ed. J. W. Hedgpeth. Geol. Soc. Amer. Hem. 67. 1296 p. Hammond, A. L. 1972. Chemical pollution: polychlorinated biphenyls. Science 175:155-156. Harvey, H. W. 1957. The chemistry and fertility of sea water, 2nd ed. Cambridge Dniv. Press. Cambridge, England. Herman, S. G., R. L. Garrett, and R. L. Rudd. 1969. Pesticides and the Western Grebe. In: Chemical fallout (Eds.: M. W. Miller and G. G. Berg). Springfield, 111. Charles C. Thomas, pp. 24-53. Kearney, P, C., R. G. Nash, and A. R. Isensee. 1969. Persistence of pesticide residues in soils. In: Chemical fallout (Eds.: H. W. Miller and G. G. Berg). Springfield, 111. Charles C. Thomas, pp. 54-67. Keith, J. 0., L. A. Woods, Jr., and E. G. Hunt. 1970. Reproductive , failure in Brown Pelicans on the Pacific coast. Trans. 31st North Am. Wlldl, Natur. Resour. Conf. 190-200. Lockie, J. D., D. A, Ratcliffe, and R. Balharry. 1969. Breeding success and organo-chlorine residues in Golden Eagles in west Scotland. Jour, Appl. Ecol. 6:381-389. Peakall, D. B., and J. L. Lincer. 1970. Polychlorinated biphenyls l:] Another long-life widespread chemical in the environment. BioSc^ie...n. c-e 20:958-964. Peakall, D. B., J. L. Lincer, and S. E. Bloom. 1972. Embryonic mortality and chromosomal alterations caused by Aroclor 1254 in Ring Doves. Environmental Health Perspectives, April 1972:103-104. Pakhala, I., G. E. Burdick, E. J. Harris, D. J.Lisk, and M.N. White. 1972, Arsenic content offish from New YorkStatewaters. N. Y. Fish and Gama J. 19(1)12-31. Stlckel, W. II., L. F. Stickel, and J. W. Spann. 1969. Tissue residues of dieldrin in relation to mortality in birds and mammals. In: Chemical fallout (Eds.: M. W. Miller and G. G. Berg). Springfield, 111. Charles, pp. 174-204. : : ` . . ' ; ' j : ! \ ! : j ; i I ) > J - i j \ ' > " \ : ' DSW 037724 STLCOPCB4021548 I Literature Cited - 3 Stickel, W, H., L. F. Stickel, and J. W. Spann. 1969. Tissue residues of dieldrln in relation to mortality in birds and mammals. In: Chemical fallout (Eds.: N. W, Miller and G. G. Berg). Springfield, 111. Charles, pp. 174-204. Stoesand, G. S., J. L. Anderson, W. H. Gutena.nn, C. A. Bache, and J, D. Lisk, 1971. Eggshell thinning in Japanese quail fed mercuric chloride. Science 173130-131. Wiemeyor, S. N,, and R. D. Porter. 1970. DDE thins eggshells of captive American Kestrels. Mature 227:737-738. Wiemeyer, S. N., B. M. Mulhern, F. J. Ligas, R. J. Hensel, J. E. Hathisen, F. C. Robards, and S. Postupalsky. 1972. Residues of organochlorine pesticides, polychorinated biphenyls, and mercury in Bald Eagle eggs and changes in shell thickness - 1969 and 1970. Pesticides Honit. Jour. 6:50-55. Wureter, C. F., Jr. and D. B. Wingate. 1968. DDT residues and declinging reproduction in the Bermuda Petrel. Science 159:979-981. DSW 037725 STLCOPCB4021549