Monitoring the Elimination of Persistent Toxic Substances from the Great Lakes; Chemical and Physiological Evidence from Adult Herring Gulls

To assess progress towards virtual elimination of PCBs, DDE, dieldrin and Mirex and their associated physiological effects, we compared their concentrations in pooled livers of adult herring gulls (Larus argentatus) repeatedly sampled at 8 Great Lakes colonies and a reference colony on the Atlantic coast between 1974 and 1993. We measured the relative thyroid mass and concentrations of highly carboxylated porphyrins and retinyl palmitate in the liver of each individual. PCBs, dieldrin and mirex declined in 7 of 8 colonies while DDE decreased in six. The greatest decreases occurred pre-1985. PCBs and DDE did not decrease in gulls from Middle Island in western L. Erie. Middle Island and Saginaw Bay had the highest concentrations of PCBs of 11 Great Lakes colonies in the 1990s. Thyroids of gulls from Great Lakes colonies were slightly enlarged but the degree of enlargement has decreased over time. In 1991, gulls from Great Lakes colonies had slight to moderately elevated concentrations of highly carboxylated porphyrins. In the early 1990s, hepatic stores of retinyl palmitate were very seriously depleted in gulls from the Detroit River, western basin of Lake Erie, and Lake Ontario, reflecting decreased availability and altered storage. We conclude that PCBs and/or other persistent toxic substances in the food of herring gulls have not been virtually eliminated.     

Contaminant levels in colonial waterbirds from Green Bay and Lake Michigan, 1975–80

Residues of organochlorine pesticides, polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), polychlorinated styrenes (PCSs), and mercury were measured in the eggs of 10 species of colonial waterbirds nesting in areas around Green Bay or Lake Michigan from 1975 to 1980. Residues also were measured in the carcasses and brains of black-crowned night-herons (Nycticorax nycticorax). The highest residues were of PCBs, DDE, mercury, and dieldrin; for some species, levels of these chemicals possibly were high enough to have caused reproductive effects. Other organochlorine pesticides were found at low levels. Only trace amounts of PCSs and PBBs were found. Eggs of herring gulls (Larus argentatus) collected in 1977 from an island in Lake Michigan contained an average of 100 ppm PCBs and 33 ppm DDE; this was the most-contaminated species. Cattle egrets (Bubulcus ibis), the only bird that is not a fish eater, contained only small quantities of DDE and mercury.     

Residues of organochlorine pesticides and polychloribiphenyls in starlings (Sturnus vulgaris), from the continental United States, 1982

Starlings were collected from 129 sites throughout the contiguous United States in the fall of 1982 and analyzed for organochlorine compounds as part of a nationwide monitoring program. Residues of 14 organochlorine compounds were found. Only DDE, polychlorobiphenyls (PCB), dieldrin, and heptachlor epoxide occurred in more than 50% of the 10-starling pools. Geographical variation in the occurrence of seven organochlorine compounds was noted. Mean DDE levels were higher in the southwestern United States. Mean PCB levels were higher in the eastern United States. The occurrence frequency of most organochlorines in 1982 was similar to that which was reported in the previous nationwide study in 1979. A slight increase in occurrence was noted for trans-nonachlor. Mean DDE level in 1982 was similar to that of 1979. Mean PCB level in 1982 was lower than the 1979 mean, but this change may not reflect a decrease in environmental PCB levels.     

High PCB residues in birds from the Sheboygan River,Wisconsin

Organochlorine residues were measured in the carcasses and, in some cases, brains and stomach contents of four species of birds collected along the Sheboygan River, Wisconsin during the years 1976 to 1980. Polychlorinated biphenyls (PCBs) were high in all samples and were the contaminants of greatest concern. Carcass residues ranged from 23 to 218 ppm PCBs on a wet weight basis; these are levels associated with reproductive impairment in laboratory studies with some birds. Food items in the stomachs of collected birds contained from 12 to 58 ppm PCBs, indicating a heavy contamination of food sources. The brain of one bird contained 220 ppm PCBs, a level that is not in the lethal range but is very high. Birds feeding in the contaminated portions of the Sheboygan River may have been harmed by high PCB levels.     

Organochlorine pesticide residues in moths from the Baltimore,MD-Washington,D.C. area

Moths were collected with a light trap from 15 sites in the Baltimore, Maryland-Washington, D.C. area and analyzed for organochlorine pesticide residues. On the average, the species sampled contained 0.33 ppm heptachlor-chlordane compounds, 0.25 ppm DDE, and 0.11 ppm dieldrin. There were large differences in the concentrations detected in different species. Concentrations were especially high in moths whose larvae were cutworms, and were virtually absent from moths whose larvae fed on tree leaves. It was concluded that at least some species sampled could be an important source of insecticides to insectivorous wildlife. In some instances moths may be useful indicators of environmental contamination, especially when insectivorous wildlife species cannot be collected. However, the differences in residues observed among species means that only similar species should be compared, and this limits their potential for monitoring.     

Pesticide,PCB, and lead residues and necropsy data for bald eagles from 32 states-1978–81

In 1978–81, 293 bald eagles (Haliaeetus leucocephalus) from 32 states were necropsied and analyzed for organochlorine pesticides, polychlorinated biphenyls (PCB), and lead residues. DDE was found in all carcasses; PCB, DDD, trans-nonachlor, dieldrin and oxychlordane were next in order of percent frequency of detection. The median levels of DDE and PCB have declined when compared with previous collections. Five specimens contained high levels of dieldrin in their brains which may have contributed to their deaths. Seventeen eagles contained liver lead residues greater than 10 ppm and probably died of lead poisoning. Trauma and shooting are the most common causes of death.     

Changes in levels of organochlorines in woodcock wings from 1971 to 1975

Wings from woodcock (Philohela minor) were first monitored for organochlorine pesticides and polychlorinated biphenyls (PCBs) in the eastern U.S. in 1971. Regional differences in these compounds were clearly demonstrated and baseline residue levels were obtained for later comparisons. An expanded sampling of wings in 1972 revealed that residues in wings of adult woodcock may differ significantly from those in immatures, and that residues of several important agricultural insecticides and PCBs had declined significantly. More extensive sampling was undertaken in 1975 to determine if changes in residue levels had taken place in the intervening years. PCBs, mirex, and heptachlor epoxide increased significantly between 1972 and 1975 in adult woodcock wings. In immature woodcock wings mirex, dieldrin, and PCBs increased significantly between 1972 and 1975, but DDT residues decreased significantly.     

Contaminant exposure of willets feeding in agricultural drainages of the Lower Rio Grande Valley of South Texas

Willets (Catoptrophorus semipalmatus) were collected in June and August 1986 at the outlets of two agricultural drainages into the Lower Laguna Madre of South Texas and at two other Texas coastal sites. Mean liver concentration of arsenic was higher in August than June. Over 20% of the livers had arsenic concentrations elevated above a suggested background level of 5.0 ppm dry weight (DW), but concentrations (maximum 15 ppm) were below those associated with acute toxicity. Selenium concentration in livers varied from 2.3 to 8.3 ppm DW for all locations and represented background levels. Mercury concentrations in livers for all locations (means = 2.0 to 3.4, maximum 17 ppm DW) were below those associated with avian mortality and similar to levels found in other estuarine/marine birds. DDE in carcasses was higher in adults (mean = 1.0 ppm wet weight) than juveniles (0.2 ppm), and higher in August (1.0 ppm) than June (0.5 ppm); however, DDE concentrations were generally at background levels. Based on brain cholinesterase activity, willets were not recently exposed to organophosphate pesticides.     

Contaminant concentrations in whole-body fish and shellfish from US estuaries

Persistent bioaccumulative and toxic (PBT) pollutants are chemical contaminants that pose risks to ecosystems and human health. For these reasons, available tissue contaminant data from the US EPA Environmental Monitoring and Assessment Program’s National Coastal Assessment were examined to estimate to what areal extent PBTs are found in US estuarine resources. The data document composite, whole-body tissue chemical concentrations for 736 sampling sites across Northeast, Southeast, Gulf of Mexico, and West Coast estuaries. Tissue chemical concentrations were compared to US EPA non-cancer risk guidelines for recreational fishers, because of a lack of ecological guidelines for these chemical concentrations. Samples were analyzed for 23 PAH compounds, 21 PCB congeners, 6 DDT derivatives and metabolites, 14 chlorinated pesticides (other than DDT) and 13 metals, including mercury. Total PCBs were found to exceed recreational fisher guidelines most frequently (31% of samples evaluated), followed by mercury (29%), total PAHs (21%), and DDT and its metabolites, DDD and DDE (11%). Toxaphene, cadmium and dieldrin were found but in fewer than 1% of the samples.     

Geographical distribution of organochlorine contaminants and reproductive parameters in Herring Gulls on Lake Superior in 1983

As part of the Great Lakes International Surveillance Plan, 1978–83, egg contaminant levels and reproductive output were determined for Herring Gull colonies on Lake Superior in 1983. Since 1974, the Herring Gull has been widely used in the Great Lakes as a spatial and temporal monitor of organochlorine (OC) contaminant levels and associated biological effects. Most eggs contained a wide range of OCs, the main compounds being DDE, polychlorinated biphenyls (PCBs), dieldrin, heptachlor epoxide, oxychlordane, hexachlorobenzene and mirex. Levels of an additional ten OCs and five polychlorinated dibenzo-p-dioxin (PCDD) congeners were also determined for some sites. Overall, levels varied significantly among colonies, but there was no obvious relationship to spatial distribution of contaminants in sediments or fish species. OC levels in eggs had declined by up to 84% since 1974. Eggshells were only 8% thinner than before the introduction of DDT, and shell thinning was not a cause of breeding failure. Average reproductive output varied from 0.15 to 1.57 young per apparently occupied nest in 1983: at 56% of colonies the value was below that thought necessary to maintain stable populations. The main causes of failure were egg disappearence and cannibalism of chicks. Despite this, the population appeared to have been increasing at about 4% per annum. Reduced availability of forage fish during the early 1980s was the most likely reason for the poor reproductive output in 1983.     

Environmental contaminants in freshwater fish and their risk to piscivorous wildlife based on a national monitoring program

Organochlorine chemical residues and elemental concentrations were measured in piscivorous and benthivorous fish at 111 sites from large U.S. river basins. Potential contaminant sources such as urban and agricultural runoff, industrial discharges, mine drainage, and irrigation varied among the sampling sites. Our objectives were to provide summary statistics for chemical contaminants and to determine if contaminant concentrations in the fish were a risk to wildlife that forage at these sites. Concentrations of dieldrin, total DDT, total PCBs, toxaphene, TCDD-EQ, cadmium, chromium, mercury, lead, selenium, and zinc exceeded toxicity thresholds to protect fish and piscivorous wildlife in samples from at least one site; most exceedences were for total PCBs, mercury, and zinc. Chemical concentrations in fish from the Mississippi River Basin exceeded the greatest number of toxicity thresholds. Screening level wildlife risk analysis models were developed for bald eagle and mink using no adverse effect levels (NOAELs), which were derived from adult dietary exposure or tissue concentration studies and based primarily on reproductive endpoints. No effect hazard concentrations (NEHC) were calculated by comparing the NOAEL to the food ingestion rate (dietary-based NOAEL) or biomagnification factor (tissue-based NOAEL) of each receptor. Piscivorous wildlife may be at risk from a contaminant if the measured concentration in fish exceeds the NEHC. Concentrations of most organochlorine residues and elemental contaminants represented no to low risk to bald eagle and mink at most sites. The risk associated with pentachloroanisole, aldrin, Dacthal, methoxychlor, mirex, and toxaphene was unknown because NOAELs for these contaminants were not available for bald eagle or mink. Risk differed among modeled species and sites. Our screening level analysis indicates that the greatest risk to piscivorous wildlife was from total DDT, total PCBs, TCDD-EQ, mercury, and selenium. Bald eagles were at greater risk to total DDT and total PCBs than mink, whereas risks of TCDD-EQ, mercury, and selenium were greater to mink than bald eagle.     

Within-and among-clutch variation of organochlorine residues in eggs of black-crowned night-herons

Within-clutch variability of DDE and PCB residues in eggs from 62 clutches of black-crowned night-herons (Nycticorax nycticorax) was small (12% and 17%) compared to among-clutch variability (88% and 83%). Significant correlations between concentrations of DDE (median r=0.8885) and of PCBs (median r=0.8244) occurred when 501 correlations were run on two randomly selected eggs from within the same clutch; no significant correlation occurred for either concentrations of DDE (median r=0.0353) or PCBs (median r=–0.0843) when eggs were not restricted to the same clutch but were restricted to the same colony. The probability of finding infrequently detected organochlorine contaminants (e.g., DDT, cis-chlordane) in eggs from the same clutch varied from 43–96% and increased as the chemical became more prevalent and the number of eggs per clutch became smaller. These results further support one of the basic assumptions of the sample egg technique, that the chemical residues in one egg in a clutch accurately reflect residues in the remaining eggs of the clutch.     

Further declines in organochlorines in eggs of red-breasted mergansers from Lake Michigan, 1977–1978 versus 1990 versus 2002

From 1977-1978 to 1990, concentrations of polychlorinated biphenyls (PCBs) and most organochlorine pesticides declined in eggs of red-breasted mergansers (Mergus serrator) nesting on islands in northwestern Lake Michigan. Further declines took place between 1990 and 2002. Between 1977-1978 and 1990 total PCBs decreased 60% (from 21 to 8.5 microg/g, wet weight). An additional decline of 46% took place between 1990 and 2002 (8.5 to 4.6 microg/g). Between 1977-1978 and 1990 p,p (')-DDE decreased 66% (from 6.5 to 2.2 microg/g), and from 1990 to 2002 an additional decline of 36% took place (from 2.2 to 1.4 microg/g). Between 1977-1978 and 1990 dieldrin decreased only 16% (from 0.82 to 0.69 microg/g), but from 1990 to 2002 a 96% decrease occurred (from 0.69 to 0.03 microg/g).     

Organochlorine residues in adult mallard and black duck wings, 1981–1982

Ten organochlorine compounds were identified in pools of black duck (Anas rubripes) and mallard (A. platyrhynchos) wings from the 1981–82 hunting season. Most organochlorine compounds occurred very infrequently. Among those compounds positively identified by mass spectrometry, DDE and, secondarily, PCB had the highest frequencies of occurrence. Other compounds, positively identified and occurring less frequently, included DDT, DDD, DDMU, dieldrin, heptachlor epoxide, trans-nonachlor, cis-chlordane and mirex. Compounds looked for but not positively identified include oxychlordane, cis-nonachlor, endrin, hexachlorobenzene and toxaphene. PCB levels in black duck wings declined between the 1979–80 and 1981–82 collections. PCB levels in black duck wings from the northern region of the Atlantic Flyway were higher than those in wings from the southern region. Mean DDE residues in mallard wings declined between collections and differed among flyways and regions. PCB levels in mallard wings differed only among flyways and regions.     

Trace elements and organochlorines in surf scoters from San Francisco Bay, 1985

Surf scoters (Melanitta perspicillata) were collected from 6 locations in San Francisco Bay during January and March 1985. Overall, mean concentrations of cadmium and zinc were higher in livers of scoters from the southern region of the Bay, whereas mean iron and lead were higher in those from the northern Bay region. Mean concentrations of arsenic, copper, lead, zinc, aluminum (January only) and iron (January) also differed among individual locations. Mean concentrations of copper and zinc increased, arsenic decreased, and cadmium remained the same between January and March. Selenium and mercury concentrations in scoter livers were not significantly correlated (P>0.05), but cadmium concentrations in livers and kidneys were positively correlated (P<0.0001), and body weight was negatively related to mercury concentration in the liver (P<0.05). Body weight differed among locations but not between January and March. Body weight was correlated with lipid content (P<0.0001). DDE and PCBs were each detected in 34 of 36 scoter carcasses. DDE increased significantly between January and March at Richmond Harbor, but BCBs did not differ between January and March at the 3 locations that could be tested.     

Organochlorine contamination in shorebirds from Washington state and the significance for their falcon predators

Arctic-breeding shorebirds collected in western Washington state during winter and spring, and a comparative sample collected in coastal California during the winter were analyzed for organochlorine contaminants to determine the potential impact of these residues on populations of peregrine falcons (Falco peregrinus) and merlins (F. columbarius) which prey upon shorebirds in western Washington. Dunlins (Calidris alpina), an important winter prey for falcons in western Washington, were collected between 1975 and 1981. During winter 1980–81, dunlins carried low organochlorine residues; DDE levels ranged from 0.01 to 1.2 ppm, and PCB levels ranged from 0.02 to 0.82 ppm (wet weight). Levels of other organochlorine contaminants (HCB, Chlordane compounds, Dieldrin, and Heptachlor Epoxide), analyzed in a subsample of dunlins, were consistently lower than DDE and PCB levels, and ranged from 0.001 to 0.22 ppm (wet weight). Dunlins in western Washington did not significantly increase their DDE or PCB burdens over the 1980–81 winter. A decline in DDE residues between 1978 and 1981 was noted, and declines in PCB residues from both 1975 and 1978 to 1980–81 were noted. Residues in other wintering shorebirds from western Washington were similar. Wintering sanderlings (Calidris alba) from California, revealed much higher DDE contamination than in Washington (up to 32 ppm, wet weight). Spring migrant shorebirds in western Washington contained both low and very high DDE residues (up to 417 ppm, wet weight). There is evidence suggesting these high DDE concentrations are accumulated along the Pacific coast of North America.     

Declines in organochlorines in eggs of red-breasted mergansers from Lake Michigan, 1977–1978 versus 1990

From 1977–1978 to 1990, concentrations of polychlorinated biphenyls (PCBs) and most organochlorine pesticides declined in eggs of red-breasted mergansers (Mergus serrator) nesting on islands in northwestern Lake Michigan. Total PCBs decreased 60% (from 21 ppm in 1977–1978 to 8.5 ppm in 1990) and p,p-DDE decreased 66% (from 6.5 to 2.2 ppm). Dieldrin decreased only 16% (from 0.82 to 0.69 ppm). In 1990, 79.1% of incubated eggs hatched, which was not significantly different from the 83.5% that hatched in 1977–1978.The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Concentrations of DDTs and dieldrin in Long Island Sound sediment

The concentrations of three frequently detected organochlorine pesticides (OCPs) and one degradation product, p,p'-DDT, p,p'-DDD, dieldrin, and p,p'-DDE were determined in recently collected (2005-2006) and archived (1986-1989) surficial sediments and sediment cores from Long Island Sound (LIS). The concentration of dieldrin ranged from 0.05 to 5.27 ng g(-1) dry weight in the surficial sediments, and from 0.05 to 11.7 ng g(-1) dry weight in the sediment cores. Total DDXs (the sum of p,p'-DDE, p,p'-DDD and p,p'-DDT) concentrations ranged from 1.31 to 33.2 ng g(-1) in surficial sediments and 1.11 to 66.4 ng g(-1) in sediment cores. The results indicate that the three OCPs and DDE were still widely present in LIS surficial sediments two decades after the use of these pesticides in the United States was banned. In addition, the surficial concentrations did not decrease significantly when compared to the concentrations in archived samples collected two decades ago. Sediments in the western part of LIS were more contaminated (with concentrations in some western sites being still above probable effect levels) than those in the eastern part, probably as a result of the net westward sediment transport in LIS. The three OCPs and DDE were detected at all depths (down to ~50 cm) in the sediment cores, and concentration profiles indicated a depositional sedimentary environment with significant sediment mixing. Such mixing may redistribute OCPs deposited earlier (deeper in sediment bed) to the sediment surface and lead to enhanced persistence of OCP concentrations in surficial sediments.     

Temporal and Spatial Trends in Chlorinated Hydrocarbon Concentrations of Mink in Canadian Lakes Erie and St. Clair

Mink (Mustela vison) carcasses were collected from local commercial trappers from fall 1998 to spring 2003 from tributaries and marshes within 4.8km from the shores of Lakes Erie and St. Clair, including the Wheatley Harbour and St. Clair River Areas of Concern (AOCs), as well as from inland sites (8 to 40km from shore). Liver concentrations, on a lipid weight basis, of chlorinated hydrocarbons were measured and compared among sites and to tissue concentrations of mink from two previous collections from similar sites over the past 25 years. Mink from the western Lake Erie sites, which included the Wheatley Harbour AOC, had significantly higher concentrations of sum PCBs and PCB Aroclors than those from the St. Clair corridor or inland sites, with concentrations from the rest of Lake Erie being intermediate. Dieldrin concentrations were also significantly higher in western Lake Erie than many other sites, and those of oxychlordane and mirex also tended to be higher (0.05 < p < 0.1). There were no differences in contaminant concentrations between the St. Clair River AOC and the downstream non-AOC Lake St. Clair site, with the exception of slightly higher levels of octachlorostyrene (OCS). Concentrations of PCBs and other chlorinated hydrocarbons in mink showed a general decrease over the past two decades. In contrast, PCBs and some organochlorine pesticides tended to increase, significantly so with oxychlordane, in western Lake Erie mink over the same time period. DDE declined at all sites. Currently, mink liver PCB concentrations are within the range associated with reproductive impairment, as determined from captive mink studies, in 11.7% of all animals collected from the Lakes Erie and St. Clair basin overall, but in almost 40% of individuals from western Lake Erie.     

Survey and evaluation of contaminants in earthworms and in soils derived from dredged material at confined disposal facilities in the Great Lakes Region

Soils derived from dredged material were collected, together with earthworms from nine confined disposal facilities located in the Great Lakes Region. These samples were analyzed for 18 elements, 11 organochlorine pesticides, PCBs, and 24 polycyclic aromatic hydrocarbons. The concentrations detected in earthworms were evaluated in terms of their potential hazard to wildlife, which for the sake of the evaluation were assumed to prey entirely either on earthworms or on other soil invertebrates having similar concentrations. The soil concentrations (dry wt.) of the contaminants of greatest concern were <1.9 to 32 ppm Cd, <0.053 to 0.94 ppm Hg, 4.6 to 550 ppm Pb, and <0.1 to 1.0 ppm PCBs. The concentrations in earthworms (dry wt., ingested soil included) were as high as 91 ppm Cd, 1.6 ppm Hg, 200 ppm Pb, and 1.8 ppm PCBs. Based on laboratory toxicity studies of relatively sensitive species, and on concentration factors calculated from the earthworm and soil data, we estimated that lethal or serious sublethal effects on wildlife might be expected at concentrations of 10 ppm Cd, 3 ppm Hg, 670 ppm Pb, and 1.7 ppm PCBs in alkaline surface soils derived from dredged material. Concentrations of polycyclic aromatic hydrocarbons in earthworms were well below those in soil.