David A. Verbrugge

Dietary exposure of mink to carp from Saginaw Bay, Michigan. 1. Effects on reproduction and survival, and the potential risks to wild mink populations

Carp (Cyprinus carpio) collected from Saginaw Bay, Michigan, containing 8.4 mg total polychlorinated biphenyls (PCBs)/kg and 194 ng of 2,3,7,8-tetrachloro-dibenzo-p-dioxin equivalents (TEQs)/kg, were substituted for marine fish at levels of 0, 10, 20, or 40% in the diets of adult ranch mink (Mustela vison). The diets, containing 0.015, 0.72, 1.53, and 2.56 mg PCBs/kg diet, or 1.03, 19.41, 40.02, and 80.76 ng TEQs/kg diet, respectively, were fed to mink prior to and throughout the reproductive period to evaluate the effects of a naturally-contaminated prey species on their survival and reproductive performance. The total quantities of PCBs ingested by the mink fed 0, 10, 20, or 40% carp over the 85-day treatment period were 0.34, 13.2, 25.3, and 32.3 mg PCBs/mink, respectively. The corresponding quantities of TEQs ingested by the mink over the same treatment period were 23, 356, 661, and 1,019 ng TEQs/mink, respectively. Consumption of feed by mink was inversely proportional to the PCB and TEQ content of the diet. The diets containing Saginaw Bay carp caused impaired reproduction and/or reduced survival of the kits. Compared to controls, body weights of kits at birth were significantly reduced in the 20 and 40% carp groups, and kit body weights and survival in the 10 and 20% carp groups were significantly reduced at three and six weeks of age. The females fed 40% carp whelped the fewest number of kits, all of which were stillborn or died within 24 hours. Lowest observable adverse effect levels (LOAEL) of 0.134 mg PCBs/kg body weight/day or 3.6 ng TEQs/kg body weight/day for adult female mink were determined. The potential effects of exposure of wild mink to contaminated Great Lakes fish were assessed by calculating “maximum allowable daily intakes” and “hazard indices” based on total concentrations of PCB residues in several species of Great Lakes fish and mink toxicity data derived from the study.

H4IIE rat hepatoma cell bioassay-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents in colonial fish-eating waterbird eggs from the Great Lakes

Fish-eating waterbirds from the Great Lakes of North America have shown symptoms of poisoning similar to those observed in laboratory exposures of various avian species to planar halogenated hydrocarbons (PHHs). PHHs, include among others, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) and have been implicated in some of the reproductive problems of Great Lakes waterbirds. The objectives of this study were to assess the overall potencies of PCB-containing extracts from colonial water-bird eggs taken from the Great Lakes and to compare the potencies with the location and spatial distribution of the colonies. The potencies of the extracts were assessed by their ability to induce cytochrome P450IA1-associated ethoxyresorufin O-deethylase (EROD) activity in H4IIE rat hepatoma cells as compared to the standard, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The H4IIE bioassay-derived TCDD-equivalents (TCCD-EQs) in the waterbird eggs concur with residue analyses and biological data from other studies. The greatest concentrations of TCDD-EQs were found in waterbird eggs from historically polluted, industrialized or urbanized areas in which the reproductive impairment of colonial waterbirds was most severe. However, significant concentrations of TCDD-EQs were detected at all sites tested; with a range of 49 to 415 pg TCDD-EQ/g egg, uncorrected for extraction efficiencies. The H4IIE bioassay proved to be a useful biomonitoring tool to assess the overall potency of complex PHH mixtures in environmental samples.

Contaminants in fishes from Great Lakes-influenced sections and above dams of three Michigan rivers. II: Implications for health of mink

Populations of mink (Mustela vison) have declined in many areas of the world. Such declines have been linked to exposures to synthetic, halogenated hydrocarbons. In the Great Lakes region, mink are fewer in areas along the shore of the Great Lakes and their tributaries where mink have access to fish from the Great Lakes. Recently, there has been discussion of the relative merits of passage of fishes around hydroelectric dams on rivers in Michigan. A hazard assessment was conducted to determine the potential for adverse effects on mink, which could consume such fishes from above or below dams on the rivers. Concentrations of organochlorine insecticides, polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachloridibenzo-p-dioxin equivalents (TCDD-EQ), and total mercury were measured in composite samples of fishes from above or below hydroelectric dams on the Manistee and Muskegon Rivers, which flow into Lake Michigan, and the Au Sable River, which flows into Lake Huron. Concentrations of organochlorine insecticides, PCBs, and TCDD-EQ were all greater in fishes from below the dams than those from above. Concentrations of neither organochlorine insecticides nor mercury in fishes are currently a risk to mink above or below the dams. All of the species of fishes collected from downstream of the dams contained concentrations of PCBs and TCDD-EQ, which represent a hazard to mink. The hazard index for PCBs was less than one for the average of all species from the upstream reaches of the Manistee and Au Sable Rivers, but not the Muskegon. The hazard index (concentration in fish/NOAEC) was greater than 1 for all of the species collected from below the dams, in all three rivers. The greatest hazard index was observed for carp (Cyprinus carpio) downstream on the Muskegon River. Because the concentrations of PCBs used in the hazard assessment were corrected for relative toxic potencies, the hazard ratios based on PCBs should be similar to those based on TCDD-EQ. This was found to be true. Thus, either total PCBs or TCDD-EQ could be used as the critical toxicant in the hazard assessment. However, if uncorrected concentrations of PCBs, expressed as Aroclors®, were used in the hazard assessment, the toxicity of the weathered mixture would have been underestimated by approximately five-fold, and, in that instance, TCDD-EQ would be the critical contaminant for the hazard assessment. The average maximum allowable percentage of fish from above the dams, which would result in no observable adverse effects of TCDD-EQ, was 70%. Based on the average TCDD-EQ concentrations in the fishes, an average of 8.6% of the diet could be made up of fishes from below dams on the rivers. The most restrictive daily allowable intakes were for carp on the Muskegon and steelhead trout (Onchorhyncus mykiss) on the Manistee Rivers. Only 2.7% of the diet could be made up of these two species from influenced portion of the Au Sable River, they would be exposed to 390 μg PCBs and 8.55 ng of TCDD-EQ per day, respectively (Giesy et al. 1994b). Thus, it would take 15.1 or 77 days for mink to receive their total annual dose of PCBs or TCDD-EQ, respectively. At least for chinook salmon, the critical contaminant for the purposes of hazard assessment would be total concentrations of PCBs. Consuming chinook salmon for as little as 2 weeks would deliver the annual allowable dose of PCBs to mink.

Polychlorinated biphenyls and chlorinated insecticides in plasma of Caspian terns: Relationships with age, productivity, and colony site tenacity in the great lakes

Chlorinated hydrocarbons such as polychlorinated biphenyls (PCBs) and chlorinated insecticides have often been detected in Great Lakes fish-eating birds at concentrations that are correlated with greater than expected embryo mortality and reduced reproductive success. Blood from 111 known-age, adult Caspian terns (Sterna caspia) nesting in several regions of the upper Great Lakes was collected in 1990 to examine bioavailability of PCBs, to compare concentrations of PCBs among nesting locations, and to determine relationships between concentrations of PCBs and age, productivity, and colony site tenacity. PCBs, DDE, dieldrin, and trans-nonachlor were detected in all the samples. Concentrations of PCBs were, on average, 10, 100, and 250 times greater than those of DDE, dieldrin, and trans-nonachlor, respectively. Concentrations of PCBs were not correlated with age, and were greater in Caspian terns from Saginaw and Green Bays than in Caspian terns from the North Channel and Georgian Bay. Concentrations of PCBs and DDE were significantly correlated with one-another and their accumulation patterns were the most similar among all the chemicals studied. Patterns of organochlorines as determined by cluster analysis were most similar for the nearest nesting locations. The bioaccumulation of PCBs in Great Lakes Caspian terns appeared to be seasonal and did not vary with adult age. A significant negative correlation was observed between mean concentrations of PCBs by region and percent terns returning to natal region. Those populations which were likely to be affected by PCBs were those nesting in Green Bay and Saginaw Bay.

2,3,7,8-Tetrachlorodibenzo-p-dioxin equivalents in tissues of birds at Green Bay, Wisconsin, USA

The environment has become contaminated with complex mixtures of planar, chlorinated hydrocarbons (PCHs) such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and structurally similar compounds. Because the potencies of individual congeners to cause the same adverse effects vary greatly and the relative as well as absolute concentrations of individual PCH vary among samples from different locations, it is difficult to assess the toxic effects of these mixtures on wildlife. These compounds can cause a number of adverse effects, however, because the toxic effects which occur at ecologically-relevant concentrations such as embryo-lethality and birth defects appear to be mediated through the same mechanism, the potency of individual congeners can be reported relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) which is the most toxic congener in the PCH class. The concentations of 2,3,7,8-TCDD Equivalents (TCDD-EQ) were determined in the tissues of aquatic and terrestrial birds of Green Bay, Wisconsin by the H4IIE bioassay system and compared toxic equivalency factors (TEFs) with the concentration predicted by the use of toxic equivalency factors applied to concentrations of PCH, which were determined by instrumental analyses. Concentrations of TCDD-EQ ranged from 0.52 to 440 ng/kg, wet weight. The greatest concentrations occurred in the fish-eating birds. Concentrations of TCDD-EQ, which were determined by the two methods were significantly correlated, but the additive model which used the TEFs with concentrations of measured PCB, PCDD and PCDF congeners underestimated the concentrations of TCDD-EQ measured by the H4IIE bioassay by an average of 57%. This is thought to be due to contributions from un-quantified PCH, which are known to occur in the environment. Of the quantified PCH congeners, PCDD and PCDF contributed a small portion of the TCDD-EQ in the aquatic birds, while most of the TCDD-EQ were due to non-ortho-substituted PCBs. In the terrestrial birds, the proportion of the TCDD-EQ contributed by the PCDD and PCDF was greater.

Bioaccumulation of polychlorinated biphenyls from sediments to aquatic insects and tree swallow eggs and nestlings in Saginaw Bay, Michigan, USA

Sediments in the Saginaw Bay region of the Great Lakes contain concentrations of polychlorinated biphenyls (PCBs) that may adversely affect biotic species in various trophic levels. In this study we collected and analyzed sediments, benthic invertebrates, tree swallow eggs, and nestlings to evaluate linkages between PCBs in sediments and at various trophic levels in the Saginaw River, Michigan, USA. Our results indicate that patterns of relative concentrations of PCB congeners change with trophic level, specifically from sediment to invertebrates and from tree swallow eggs to nestlings. However, if biota–sediment accumulation factor (BSAF) values are based on only the nonand mono-ortho-substituted PCB congeners or 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEq), calculated BSAF values are close to those predicted by fugacity theory. The use of site-specific BSAF values and reference doses for toxic effects in wildlife can be used to derive sediment quality criteria (SQC) that are protective of wildlife at the top of the sediment-based food chain. The threshold concentration of TEq in sediments that would protect sensitive avian species at the same trophic level as tree swallows was calculated to be 1.5 3 1021 TEq/g total organic carbon. Based on this value and the BSAF determined for tree swallow nestlings, the hazard quotient for sediments in this area was determined to be 0.7. This indicates that current concentrations of TEq due to PCB congeners in the sediments should be below the threshold for adverse effects on tree swallows. The uncertainty in the concentrations of PCB congeners in the sediments was approximately a factor of 2, which determined the degree of resolution that could be obtained from the observations made in this study. Keywords—Biota–sediment accumulation factor Bioaccumulation Benthic invertebrates Birds Fugacity

Contaminants in fishes from great lakes-influenced sections and above dams of three Michigan Rivers. I: Concentrations of organo chlorine insecticides, polychlorinated biphenyls, dioxin equivalents, and mercury

Fishes of the Great Lakes contain hazardous chemicals such as synthetic halogenated hydrocarbons and metals. These fish can move from the lakes into the Great Lakes tributaries of Michigan. In doing so, they transport concentrationsof contaminants which may represent a risk to wildlife. Concentrations of mercury (Hg), total polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TCDD-EQ), total DDT complex, aldrin, endrin, dieldrin, heptachlor, heptachlor epoxide, lindane, hexachlorobenzene, cis-chlordane, oxychlordane, endosulfan-I, methoxychlor, trans-chlordane, and trans-nonachlor were determined in composite samples of fishes from above and below Michigan hydroelectric dams, which separate the fishes which have access to the Great Lakes from fishes that do not. Mean concentrations of total PCBs, TCDD-EQ, DDT, and most of the other pesticides were greater in composite samples of six species of fishes from below than above the dams on the Au Sable, Manistee, and Muskegon Rivers. Concentrations of mercury, were the same or greater above the dams than below. However, this difference was statistically significant only on the Au Sable. Mercury concentrations ranged from less than 0.05 mg/kg to 0.73 mg Hg/kg, ww. Total concentrations of PCBs ranged from 0.02 to 1.7 mg/kg, ww. Concentrations of 2,3,7,8-tetrachlordibenzo-p-dioxin equivalents varied among fishes and locations. The concentrations of TCDD-EQ ranged from 2.4 to 71 μg/kg, ww, with concentrations in carp being the greatest. Concentrations of TCDD-EQ were greater than the concentrations which would be expected to occur, due solely to the presence of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and technical mixtures of PCBs.

Dietary Exposure of Mink to Carp from Saginaw Bay, Michigan: 2. Hematology and Liver Pathology

The effects of consumption of environmental contaminants contained in carp (Cyprinus carpio) from Saginaw Bay, Michigan on various hematological parameters and liver integrity of adult female mink (Mustela vison) were determined. Mink were fed diets that contained 0 (control), 10, 20, or 40% carp prior to and throughout the reproductive period (182 days). The diets contained 0.015, 0.72, 1.53, and 2.56 mg polychlorinated biphenyls (PCBs)/kg diet and 1.0, 19, 40, and 81 pg 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs)/g diet, respectively. Mink fed the diets containing carp showed a general dose-dependent occurrence of clinical signs commonly associated with chlorinated hydrocarbon toxicity, including listlessness, nervousness when approached, anorexia, and melena. Erythrocyte counts were less in mink exposed to Saginaw Bay carp than in controls, while the number of white blood cells was greater than in controls. Significant differences (p<0.05) in the concentrations of neutrophils, lymphocytes, monocytes, and eosinophils were also found between the control and carp-fed groups, but are considered to be of limited clinical or biological importance. Hematocrit values for the mink fed the 20 and 40% carp diets were significantly less than those of mink in the control and 10% carp groups. There were no significant differences in hemoglobin concentrations among the groups. Necropsies revealed enlarged yellowish livers in many of the carp-fed mink, especially those fed the 40% carp diet. Liver, spleen, and lung weights of carp-fed mink were significantly greater than those of control mink. Histopathologic examination of the livers revealed various degrees of congestion, hepatocellular fatty changes, and scattered portal lymphocytic infiltration which were most prevalent in mink fed the carp diets. These clinical signs, hematological effects, and histologic alterations are similar to those previously described for chlorinated hydrocarbon toxicoses in mink.

Biomagnification of bioassay derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents

Abstract In recent years contamination of the Great Lakes ecosystem with planar chlorinated hydrocarbons (PCHs) has attracted considerable concern due to their known reproductive and teratogenic effects. The H4IIE bioassay has been standardized as a means of measuring the biological potency of a PCH mixture as 2,3,7,8-tetrachloro-p-dibenzodioxin equivalents (TCDD-EQ). Using this bioassay we have investigated the biomagnification of TCDD-EQ in a semi-closed ecosystem. The biomagnification of TCDD-EQ is demonstrated and results indicate that the food chain is the major pathway for TCDD-EQ through this ecosystem. The H4IIE assay system is demonstrated to be a viable integrative measure of the total concentration of TCDD-EQ in different trophic levels.

Assessment of Sediment Quality in Dredged and Undredged Areas of the Trenton Channel of the Detroit River, Michigan USA, using the Sediment Quality Triad

The “sediment quality triad” approach was used to assess the effects of dredging on the sediment quality of a new marina in the Trenton Channel of the Detroit River, and to evaluate spatial and temporal variation in sediment quality in the Trenton Channel. Samples were collected in November of 1993 (10 months after dredging) and characterized by chemical analysis, sediment bioassays, and assessment of benthic invertebrate communities. The three study components indicated little difference in sediment quality at dredged sites in the marina relative to nearby areas in the Trenton Channel, and little change in sediment quality of Trenton Channel sites relative to conditions reported in the mid-1980s. These results suggest that improvement in sediment quality in the Trenton Channel, due to dredging or natural processes, will depend on elimination of sediment “hot spots” and other upstream contaminant sources. Concentrations of chemical contaminants, especially metals and polycyclic aromatic hydrocarbons, exceeded concentrations associated with effects on biota and were significantly correlated with results of sediment bioassays and characteristics of benthic communities. Laboratory sediment bioassays with Hyalella azteca and Chironomus tentans produced better discrimination among sites with differing degrees of contamination than did characterization of benthic communities, which were dominated by oligochaetes at all sites in the marina and the Trenton Channel.