Multiple lines of evidence risk assessment of American robins exposed to polychlorinated dibenzofurans (PCDFS) and polychlorinated dibenzo-P-dioxins (PCDDS) in the Tittabawassee River floodplain, Midland, Michigan, USA.

Concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) in Tittabawassee River floodplain soils and biota downstream of Midland, Michigan, USA, are greater than regional background concentrations. From 2005 to 2008, a multiple lines of evidence approach was utilized to evaluate the potential for effects of PCDD/DFs on American robins (Turdus migratorius) breeding in the floodplains. A dietary-based assessment indicated there was potential for adverse effects for American robins predicted to have the greatest exposures. Conversely, a tissue-based risk assessment based on site-specific PCDD/DF concentrations in American robin eggs indicated minimal potential for adverse effects. An assessment based on reproductive endpoints indicated that measures of hatch success in study areas were significantly less than those of reference areas. However, there was no dose-response relationship between that endpoint and concentrations of PCDD/DF. Although dietary-based exposure and reproductive endpoint assessments predicted potential for adverse effects to resident American robins, the tissue-based assessment indicates minimal to no potential for adverse effects, which is reinforced by the fact the response was not dose related. It is likely that the dietary assessment is overly conservative given the inherent uncertainties of estimating dietary exposure relative to direct tissue-based assessment measures. Based on the available data, it can be concluded that exposure to PCDD/DFs in the Tittabawassee River floodplain would not likely result in adverse population-level effects to American robins.

Reproductive success of three passerine species exposed to dioxin-like compounds near Midland, Michigan, USA.

Nests of three passerine birds, house wren (HOWR), tree swallow (TRES), and eastern bluebird (EABL) were monitored daily (2005-2007) at study areas (SAs) downstream of Midland, Michigan where soil and sediment concentrations of polychlorinated dibenzofurans (PCDFs) were significantly greater than the regional background concentrations and upstream reference areas (RAs). Similarly, TRES research conducted at sites contaminated with dioxin-like compounds indicated that concentrations of polychlorinated dibenzo-p-dioxins and PCDFs, expressed as ΣPCDD/DFs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents observed in the diet and eggs of these three species would be predicted to cause significant effects on reproduction. However, site-specific reproductive parameters including hatching success and fledging success at downstream SAs were similar to or greater than those at upstream RAs. Specifically, hatching success was not significantly different among years, species, locations, or between early and late nesting attempts. Of all initiated clutches, 66% (n = 427), 73% (n = 245), and 64% (n = 122) successfully fledged at least one nestling for HOWR, TRES, and EABL, respectively. Overall reproductive performance was similar between SAs and RAs. The reason for these unexpected results is consistent with the fact that there are species-specific and congener-specific differences in sensitivities to the effects of aryl hydrocarbon receptor agonists.

Dietary- and tissue-based exposure of belted kingfisher to PCDFs and PCDDs in the Tittabawassee River floodplain, Midland, MI, USA.

Concentrations of polychlorinated dibenzofurans (PCDFs) and other dioxin-like compounds in soils and sediments of the Tittabawassee River and associated floodplains downstream of Midland, Michigan, USA, are greater than upstream sites. As a result of these concentrations, which are some of the greatest ever reported, a site-specific exposure assessment of belted kingfisher breeding in the assessment area was conducted. To reduce the uncertainty associated with predicting exposure from abiotic matrices, concentrations of residues were quantified in site-specific prey items and in eggs and nestlings of belted kingfisher. Dietary exposure, expressed as the potential average daily dose, based on site-specific concentrations of PCDFs, polychlorinated dibenzo-p-dioxins (PCDDs), and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)) in prey items was consistently greater along the Tittabawassee River than in associated reference areas and further downstream sites in the Saginaw River. Concentrations of PCDD/DFs in eggs and nestlings of belted kingfisher varied among sampling areas, being greater in both eggs and nestlings nesting along the Tittabawassee River compared to those of belted kingfisher from upstream reference areas. Geometric mean concentrations of PCDD/DFs were 130 and 200 ng/kg wet weight in eggs and nestlings of belted kingfisher, respectively. These concentrations are the equivalent of 84 and 95 ng TEQ(WHO-Avian)/kg. Site-specific biomagnification factors for select PCDD/DF congeners ranged from <1.0 to 1.8 in belted kingfisher.

Multiple Lines of Evidence Risk Assessment of Terrestrial Passerines Exposed to PCDFs and PCDDs in the Tittabawassee River Floodplain, Midland, Michigan, USA.

A site-specific multiple lines of evidence risk assessment was conducted for house wrens (Troglodytes aedon) and eastern bluebirds (Sialia sialis) along the Tittabawassee River downstream of Midland, Michigan, where concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) in flood-plain soils and sediments are greater compared to upstream areas and some of the greatest anywhere in the world. Lines of evidence supporting the population-level assessment endpoints included site-specific dietary- and tissue-based exposure assessments and population productivity measurements during breeding seasons 2005-2007. While a hazard assessment based on site-specific diets suggested that populations residing in the downstream floodplain had the potential to be affected, concentrations in eggs compared to appropriate toxicity reference values (TRVs) did not predict a potential for population-level effects. There were no significant effects on reproductive success of either species. The most probable cause of the apparent difference between the dietary- and tissue-based exposure assessments was that the dietary-based TRVs were overly conservative based on intraperitoneal injections in the ring-necked pheasant. Agreement between the risk assessment based on concentrations of PCDFs and PCDDs in eggs and reproductive performance in both species supports the conclusion of a small potential for population-level effects at this site.

Effects on tree swallows exposed to dioxin-like compounds associated with the Tittabawassee River and floodplain near Midland, Michigan, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs), in soils and sediments downstream of Midland, Michigan (USA) were greater than upstream sites and prompted a site-specific hazard assessment of tree swallows breeding in the associated floodplains. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated at study areas (SAs) along the Tittabawassee and Saginaw rivers downstream of Midland. The site-specific multiple lines of evidence approach to hazard assessment included endpoints for dietary- and tissue-based exposures, and population productivity measurements for tree swallows ([TS]; Tachycineta bicolor) measured during the 2005, 2006, and 2007 breeding seasons. Exposure to dioxin-like compounds in TS eggs were some of the greatest recorded and were similar among all upstream and downstream study sites. Conversely, concentrations in nestlings from SAs were significantly greater compared to reference areas (RAs). The pattern of relative concentrations of PCDD/DFs in eggs and nestlings at RAs was dominated by dioxin congeners, whereas at SAs it was dominated by furan congeners. No statistically significant differences were noted in exposure to PCDD/DFs or in population-level responses when compared among locations, and total clutch failures were rare. Hatching success and fledging success were weakly negatively correlated with concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in individual eggs and nestlings, respectively. On-site concentrations of TEQs in floodplain soils were some of the greatest ever reported in the environment, and several lines of evidence indicate potential population-level effects on TS overall reproductive productivity.

Dietary exposure of great blue heron (Ardea herodias) to PCDD/DFs in the Tittabawassee River floodplain, MI, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs), in soils and sediments of the Tittabawassee River (TR) and associated floodplains downstream of Midland, Michigan (USA) were greater than upstream sites and prompted a site-specific risk assessment of great blue herons (GBH). Dietary exposure of GBH to PCDFs and polychlorinated dibenzo-p-dioxins (PCDDs) was evaluated based on site-specific concentrations of residues in prey items. Concentrations of ∑PCDD/DFs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)) in prey items collected from the TR were consistently greater than those collected from associated reference areas (RAs) and further downstream in the Saginaw River (SR). The average daily dose (ADD(pot)) of ∑PCDD/DFs to GBH was 45- to 54-fold greater along the TR and 12-fold greater along the SR when compared to the RA. ∑PCDD/DFs were normalized to TEQ(WHO-Avian), and fold differences in the ADD(pot) increased, being 150- to 190-fold greater along the TR and 36-fold greater along the SR than they were in the RA. Greater fold changes in the ADD(pot) based on TEQ(WHO-Avian) between the RA and the TR and SR was due to prey items from the latter reaches having a greater relative toxic potency of ∑PCDD/DFs, primarily from greater amounts of 2,3,7,8-tetrachlorodibenzofuran but also 2,3,4,7,8-pentachlorodibenzofuran. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated via comparison to selected toxicity reference values. The prediction of minimal to no risk of adverse population-level effects resultant from the assessment of site-specific dietary exposure of GBH to ∑PCDD/DFs along the TR and SR is consistent with site-specific assessments of tissue-based exposures as well as population condition.

Tissue-based risk assessment of great blue heron (Ardea herodias) exposed to PCDD/DF in the Tittabawassee River floodplain, Michigan, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs), in soils and sediments of the Tittabawassee River (TR) and associated floodplains downstream of Midland, Michigan, USA, were greater than upstream sites and prompted a site-specific risk assessment of great blue herons (GBH). Tissue exposure of PCDF and polychlorinated dibenzo-p-dioxins (PCDDs) was assessed in multiple GBH tissue types, including blood plasma of adults and eggs, as well as blood plasma, adipose, liver, and muscle of nestlings. Adult GBH exposure was associated with foraging area and age class, with concentrations of PCDD/DF being greater in blood plasma of adult GBH foraging in the TR compared with those foraging in upstream reference areas and in older birds as compared with their younger cohorts. Concentrations of PCDD/DFs and dioxin-like polychlorinated biphenyls (PCBs) in eggs and nestling tissues of GBH collected from rookeries within the TR floodplain were generally similar among rookeries. Mean concentrations of PCDD/DFs in eggs of GBH ranged from 45 to 67 ng/kg, wet weight for the rookeries studied, with a maximum concentration of 210 ng/kg, wet weight observed. Adipose consistently had the greatest concentration of PCDD/DFs of all tissues collected from nestlings of GBH, ranging from 98 to 430 ng/kg, wet weight. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated by comparison with selected toxicity reference values (TRVs). Minimal risk of adverse population-level effects were predicted when exposures measured in tissues of GBH collected from rookeries within the TR were compared with appropriate TRVs. This prediction is consistent with site-specific measures of population condition, which included clutch size and number of nestlings per successful nest.

Effects of in ovo exposure of white leghorn chicken, common pheasant, and Japanese quail to 2,3,7,8-tetrachlorodibenzo-p-dioxin and two chlorinated dibenzofurans on CYP1A induction.

In birds, activation of the aryl hydrocarbon receptor (AhR) by some polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) results in induction of cytochrome P4501A (CYP1A) expression. This response has been useful for predicting relative sensitivity of birds to dioxin-like compounds. To further investigate species-sensitivity to dioxins and dioxin-like compounds induction of cytochrome P450 1A4 and 1A5 (CYP1A4 and CYP1A5) mRNA and ethoxyresorufin O-deethylase (EROD) activity were quantified in liver of posthatch white leghorn chicken, common pheasant, and Japanese quail exposed to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,4,7,8-pentachlorodibenzofuran (PeCDF), or 2,3,7,8-tetrachlorodibenzofuran (TCDF) via air cell injection. The rank-order of sensitivity of TCDD- and TCDF-exposed birds, based on CYP1A, was chicken>pheasant>quail. Based on CYP1A5 mRNA expression and EROD induction, the order of sensitivity of PeCDF-exposed birds was identical to that for TCDD and TCDF. However, based on CYP1A4 mRNA expression the rank-order was pheasant>chicken>quail. When comparing the potency of the three compounds in each species, based on CYP1A4 mRNA expression, TCDD was the most potent compound in chicken. However, PeCDF was equally potent to TCDD in quail and was more potent than TCDD in pheasant. These results suggest that quantitative real-time polymerase chain reaction (Q-PCR) analysis of CYP1A expression, particularly CYP1A4 mRNA expression, may be a more sensitive biomarker of exposure than analysis of EROD induction, especially in less responsive avian species. Based on these findings future risk assessments should consider the sensitivity of the species inhabiting a site and the congeners of concern that are present.

Ecological risk assessment of great horned owls (Bubo virginianus) exposed to PCDD/DF in the Tittabawassee River floodplain in Midland, Michigan, USA.

Soils and sediments downstream of Midland, Michigan, USA have elevated polychlorinated dibenzofuran (PCDF) and polychlorinated dibenzo-p-dioxin (PCDD) concentrations. To determine if the PCDD/DF concentrations have the potential to adversely affect terrestrial avian predators, a site-specific, multiple lines of evidence risk assessment was conducted for the great horned owl (Bubo virginianus; GHO). As long-lived resident top predators, the GHO has the potential to be exposed to relatively great concentrations of bioaccumulative compounds such as PCDD/DF. From 2005 to 2008, concentrations of PCDD/DF were measured in blood plasma of adult and nestling GHOs and addled eggs. Indicators of the condition of the population, including abundance and reproductive success, were collected along 115 km of river corridor. Fifty-five active 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) equivalents (TEQ(WHO-Avian)) nests were monitored in 21 breeding territories from 2005 to 2008. The geometric mean concentration in blood plasma of GHOs was greater in the study area (SA) than in the reference area (RA) for both adults (RA: 3.1; SA: 9.4 ng TEQ(WHO-Avian)/kg) and nestlings (RA: 0.82 ng TEQ(WHO-Avian)/kg, SA: 2.1 ng TEQ(WHO-Avian)/kg) GHOs, but less than concentrations expected to cause adverse effects based on laboratory studies. Concentrations of TEQ(WHO-Avian) in addled GHO eggs were also greater in the SA than the RA (50 and 7.3 ng/kg, wet weight, respectively), but were less than concentrations expected to cause adverse effects. The GHO population condition and productivity were both greater in the study area than in the reference area and were similar to other GHO populations. This result suggests the GHO population in the Tittabawassee River floodplain is consistent with what would be expected for this area.

Great horned owl (Bubo virginianus) dietary exposure to PCDD/DF in the Tittabawassee River floodplain in Midland, Michigan, USA.

Soils and sediments in the floodplain of the Tittabawassee River downstream of Midland, Michigan, USA contain elevated concentrations of polychlorinated dibenzofurans (PCDF) and polychlorinated dibenzo-p-dioxins (PCDD). As a long-lived, resident top predator, the great horned owl (Bubo virginianus; GHO) has the potential to be exposed to bioaccumulative compounds such as PCDD/DF. Site-specific components of the GHO diet were collected along 115 km of the Tittabawassee, Pine, Chippewa, and Saginaw Rivers during 2005 and 2006. The site-specific GHO biomass-based diet was dominated by cottontail rabbits (Sylvilagus floridanus) and muskrats (Ondatra zibethicus). Incidental soil ingestion and cottontail rabbits were the primary contributors of PCDD/DF to the GHO diet. The great horned owl daily dietary exposure estimates were greater in the study area (SA) (3.3 to 5.0 ng 2,3,7,8-TCDD equivalents (TEQ(WHO-avian))/kg body wt/d) than the reference area (RA) (0.07 ng TEQ(WHO-Avian)/kg body wt/d). Hazard quotients (HQs) based on central tendency estimates of the average daily dose and no-observable-adverse effect level (NOAEL) for the screech owl and uncertainty factors were <1.0 for both the RA and the SA. Hazard quotients based on upper end estimates of the average daily dose and NOAEL were <1.0 in the RA and up to 3.4 in the SA.

Bioaccumulation of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in fishes from the Tittabawassee and Saginaw Rivers, Michigan, USA.

Characterizing biological factors associated with species-specific accumulation of contaminants is one of the major focuses in ecotoxicology and environmental chemistry studies. In this study, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non- and mono-ortho-substituted polychlorinated biphenyl (PCB) congeners were analyzed in various fish species from the Tittabawassee and Saginaw Rivers (12 fish species; n=314 individuals), Michigan, USA. Due to their migratory habits, greater delta(13)C stable isotope values were found in walleye and white sucker among 12 fish species. Meanwhile, the delta(15)N values indicated that the trophic status was least in carp and greatest in largemouth bass. The greatest total concentrations of dioxins were found in fishes with the lowest trophic status (carp (n=50) followed by channel catfish (n=49)), and concentrations of SigmaPCDD/Fs (20-440pg/g ww (wet weight)), SigmaPCBs (16-690ng/g ww), and TEQs (6.8-350pg/g ww) in carp were also greater than the least mean concentrations in other fishes. Contributions of various biological factors to the species accumulation were assessed. Body weight and lipid content were found to be the most significant factors influencing accumulation of SigmaPCDD/Fs. Lipid content and trophic level seemed to be dominant factors determining accumulation of SigmaPCB and TEQs, but negative correlations between trophic status and concentrations of SigmaPCBs and TEQs were observed possibly due to the great concentrations in benthivorous fishes such as carp occupying lower trophic levels. These factors can be used to predict the contaminant levels of dioxins and health risks of the fishes in the river ecosystem.

Passerine exposure to primarily PCDFs and PCDDs in the river floodplains near Midland, Michigan, USA.

House wren (Troglodytes aedon), tree swallow (Tachycineta bicolor), and eastern bluebird (Sialia sialis) tissues collected in study areas (SAs) downstream of Midland, Michigan (USA) contained concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) greater than in upstream reference areas (RAs) in the region. The sum of concentrations of PCDD/DFs (SigmaPCDD/DFs) in eggs of house wrens and eastern bluebirds from SAs were 4- to 22-fold greater compared to those from RAs, whereas concentrations in tree swallow eggs were similar among areas. Mean concentrations of SigmaPCDD/DFs and sum 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (SigmaTEQs(WHO-Avian)), based on 1998 WHO avian toxic equivalency factors, in house wren and eastern bluebird eggs ranged from 860 (430) to 1500 (910) ng/kg wet weight (ww) and 470 (150) to 1100 (510) ng/kg ww, respectively, at the most contaminated study areas along the Tittabawassee River, whereas mean concentrations in tree swallow eggs ranged from 280 (100) to 760 (280) ng/kg ww among all locations. Concentrations of SigmaPCDD/DFs in nestlings of all studied species at SAs were 3- to 50-fold greater compared to RAs. Mean house wren, tree swallow, and eastern bluebird nestling concentrations of SigmaPCDD/DFs and SigmaTEQs(WHO-Avian) ranged from 350 (140) to 610 (300) ng/kg ww, 360 (240) to 1100 (860) ng/kg ww, and 330 (100) to 1200 (690) ng/kg ww, respectively, at SAs along the Tittabawassee River. Concentrations of SigmaTEQs(WHO-Avian) were positively correlated with SigmaPCDD/DF concentrations in both eggs and nestlings of all species studied. Profiles of relative concentrations of individual congeners were dominated by furan congeners (69-84%), primarily 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran, for all species at SAs on the Tittabawassee and Saginaw rivers but were dominated by dioxin congeners at upstream RAs.

Hepatic P450 enzyme activity, tissue morphology and histology of mink (Mustela vison) exposed to polychlorinated dibenzofurans.

Dose- and time-dependent effects of environmentally relevant concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzofuran (TCDF), 2,3,4,7,8-pentachlorodibenzofuran (PeCDF), or a mixture of these two congeners on hepatic P450 enzyme activity and tissue morphology, including jaw histology, of adult ranch mink were determined under controlled conditions. Adult female ranch mink were fed either TCDF (0.98, 3.8, or 20 ng TEQ(TCDF)/kg bw/day) or PeCDF (0.62, 2.2, or 9.5 ng TEQ(PeCDF)/kg bw/day), or a mixture of TCDF and PeCDF (4.1 ng TEQ(TCDF)/kg bw/day and 2.8 ng TEQ(PeCDF)/kg bw/day, respectively) for 180 days. Doses used in this study were approximately eight times greater than those reported in a parallel field study. Activities of the cytochrome P450 1A enzymes, ethoxyresorufin O-deethylase (EROD) and methoxyresorufin O-deethylase (MROD) were significantly greater in livers of mink exposed to TCDF, PeCDF, and a mixture of the two congeners; however, there were no significant histological or morphological effects observed. It was determined that EROD and MROD activity can be used as sensitive biomarkers of exposure to PeCDF and TCDF in adult female mink; however, under the conditions of this study, the response of EROD/MROD induction occurred at doses that were less than those required to cause histological or morphological changes.

Chronic effects of polychlorinated dibenzofurans on mink in laboratory and field environments.

Mink are often used as a sentinel species in ecological risk assessments of chemicals such as polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) that cause toxicity mediated through the aromatic hydrocarbon receptor. Considerable toxicological information is available on the effects of PCBs and PCDDs on mink, but limited toxicological information is available for PCDFs. Thus, exposure concentrations at which adverse effects occur could not be determined reliably for complex mixtures in which PCDFs dominate the total calculated concentration of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalent (TEQ). Two studies were conducted to evaluate the potential toxicity of PCDFs to mink. The first was a chronic exposure, conducted under controlled laboratory conditions, in which mink were exposed to 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) concentrations as great as 2.4 x 10(3) ng 2,3,7,8-TCDF/kg wet-weight (ww) diet or 2.4 x 10(2) ng TEQ(2006-WHO-mammal)/kg ww diet. In that study, transient decreases in body masses of kits relative to the controls was the only statistically significant effect observed. The second study was a 3-y field study during which indicators of individual health, including hematological and morphological parameters, were determined for mink exposed chronically to a mixture of PCDDs and PCDFs under field conditions. In the field study, there were no statistically significant differences in any of the measured parameters between mink exposed to a median estimated dietary dose of 31 ng TEQ(2006-WHO-mammal)/kg ww and mink from an upstream reference area where they had a median dietary exposure of 0.68 ng TEQ(2006-WHO-mammal)/kg ww. In both studies, concentrations of TEQ(2006-WHO-mammal) to which the mink were exposed exceeded those at which adverse effects, based on studies with PCDD and PCB congeners, would have been expected. Yet in both instances where PCDF congeners were the sole or predominant source of the TEQ(2006-WHO-mammal), predicted adverse effects were not observed. Taken together, the results of these studies suggest that the values of the mammalian-specific toxicity equivalency factors suggested by the World Health Organization overestimate the toxic potency of PCDFs to mink. Therefore, hazard cannot be accurately predicted by making comparisons to toxicity reference values derived from exposure studies conducted with PCBs or PCDDs in situations where mink are exposed to TEQ mixtures dominated by PCDFs.

Toxicokinetics of 2,3,7,8-TCDF and 2,3,4,7,8-PeCDF in mink (Mustela vison) at ecologically relevant exposures.

Wild mink (Mustela vison) living along the Tittabawassee River in central Michigan exhibit elevated hepatic and dietary polychlorinated dibenzofuran (PCDF) concentrations exceeding mink-specific, literature-reported toxicity reference values (TRVs) on a toxicity equivalents basis. However, no apparent effects on individuals or population are evident, suggesting that available TRVs may overpredict risk for the site-specific mix of congeners. To investigate this discrepancy, a 180-day spiked feed study was conducted to assess: (1) the dosages of key congeners necessary to achieve liver concentrations bracketing those observed in wild mink, (2) time to achieve steady-state concentrations, and (3) effect of coadministration of 2,3,7,8-tetrachlorodibenzofuran (TCDF) and 2,3,4,7,8-pentachlorodibenzofuran (4-PeCDF) on the toxicokinetics and distribution of each congener. Adipose and hepatic PCDF concentrations were measured at 0, 90, and 180 days. PCDF concentrations in mink scat were determined at several time points and indicated nearly complete absorption of both TCDF and 4-PeCDF from the diet. Elimination half-times of TCDF were < 15 h and were inversely proportional to dose, while those for 4-PeCDF were approximately 7-9 days with no clear dose dependency in the tested dose range. Coadministration of 4-PeCDF and TCDF accelerated clearance of TCDF compared to administration of TCDF alone. Clearance of 4-PeCDF was not affected by TCDF coadministration. Distribution of 4-PeCDF, but not TCDF, demonstrated increased hepatic sequestration with increasing dose. 4-PeCDF toxicokinetics were described using a previously published two-compartment model. Overall, the toxicokinetic information gathered here illustrates the impact of CYP1A1 induction on bioaccumulation and toxicity potential of TCDF and 4-PeCDF. This information may provide insight into why the current TRVs do not appear to correctly characterize the risk for these two congeners when they are the primary components of an environmental mixture.

Exposure and effects assessment of resident mink (Mustela vison) exposed to polychlorinated dibenzofurans and other dioxin-like compounds in the Tittabawassee River basin, Midland, Michigan, USA.

Historically, sediments and floodplain soils of the Tittabawassee River (TR; MI, USA) have been contaminated with polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated biphenyls (PCBs). Median concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) based on 2006 World Health Organization tetrachlorodibenzo-p-dioxin toxic equivalency factors (TEFs) in the diet of mink (Mustela vison) ranged from 6.8 x 10(-1) ng TEQ/kg wet weight upstream of the primary source of PCDF to 3.1 x 10(1) ng TEQ/kg wet weight downstream. Estimates of toxicity reference values (TRVs) derived from laboratory studies with individual PCDDs/PCDFs and PCB congeners or mixtures of those congeners, as well as application of TEFs, were compared to site-specific measures of mink exposure. Hazard quotients based on exposures expressed as concentrations of TEQs in the 95th percentile of the mink diet or liver and the no-observable-adverse-effect TRVs were determined to be 1.7 and 8.6, respectively. The resident mink survey, however, including number of mink present, morphological measures, sex ratios, population age structure, and gross and histological tissue examination, indicated no observable adverse effects. This resulted for multiple reasons: First, the exposure estimate was conservative, and second, the predominantly PCDF congener mixture present in the TR appeared to be less potent than predicted from TEQs based on dose-response comparisons. Given this, there appears to be great uncertainty in comparing the measured concentrations of TEQs at this site to TRVs derived from different congeners or congener mixtures. Based on the lack of negative outcomes for any measurement endpoints examined, including jaw lesions, a sentinel indicator of possible adverse effects, and direct measures of effects on individual mink and their population, it was concluded that current concentrations of PCDDs/PCDFs were not causing adverse effects on resident mink of the TR.

Risk assessment methodologies for exposure of great horned owls (Bubo virginianus) to PCBs on the Kalamazoo River, Michigan.

Dietary exposures of great horned owls (GHO; Bubo virginianus) to polychlorinated biphenyls (PCBs) in the terrestrial food web at the Kalamazoo River, Michigan, USA, were examined. Average potential daily doses (APDD) in GHO diets were 7- to 10-fold and 3-fold greater at the more contaminated location versus a reference location for site-specific exposures quantified as total PCBs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)), respectively. Wetland/aquatic prey contributed significantly to PCB exposure and APDD. Estimates of risk based on comparison of modeled dietary intake (e.g., APDD) to toxicity reference values (TRVs), using a hazard quotient (HQ) methodology, varied between diet composition methods (mass basis vs numeric basis). Mass-basis compositions yielded greater HQs at all sites. Potential risks associated with dietary exposures ("bottom-up" risk assessment methodology) were less than (HQ < 1) benchmarks for effects. This result is consistent with risk estimates based on concentrations in tissues ("top-down" risk assessment methodology), and indicated PCBs posed no significant risk to terrestrial raptor species. Colocated and concurrent studies that evaluated GHO reproductive performance (nestling productivity) and relative abundance were consistent with results of the risk assessment. Measures of risk based on HQs were consistent with direct measures of ecologically relevant endpoints (reproductive fitness). Uncertainty in risk estimates is contributed during the selection of TRVs for effects in GHO based on TEQ(WHO-Avian) because of the absence of species-specific, dose-response thresholds. This evaluation indicated that a multiple-lines-of-evidence approach provided the best estimate of risk.

Nondestructive scat sampling in assessment of mink (Mustela vison) exposed to polychlorinated dibenzofurans (PCDFs).

The mink (Mustela vison) is often utilized as a sentinel species for ecological assessments at sites where contaminants of concern include dioxins and dioxin-like compounds. Utilizing mink scat as a nondestructive tool to determine internal exposure to dioxin-like compounds may allow for rapid, accurate estimates of exposure without the need to capture mink or their prey. To determine the relationships between concentrations of polychlorinated dibenzofurans (PCDFs) in tissues (liver and adipose) and those in scat, mink were fed PCDFs in scat during a controlled laboratory study for 180 days. Mink were fed a control diet, diets with three doses of 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF) or 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF), and a diet with an environmentally relevant mixture of the two congeners. Concentrations of PCDFs in liver and adipose were measured after 0, 90, and 180 days of exposure. Concentrations of the two PCDF congeners in mink scat were determined after 2, 23, 45, 90, and 180 days of exposure. Concentrations of both PCDF congeners in scat were significantly correlated with those in liver and adipose tissue (r(2) = 0.94-0.97, p < 0.01). This indicates that measurements of concentrations of both PCDFs in scat can be used to predict concentrations of PCDFs in liver and adipose. Assimilation and elimination characteristics of 2,3,4,7,8-PeCDF or 2,3,7,8,-TCDF and a mixture of the two congeners by mink could be predicted from concentrations of these congeners in scat. Overall, concentrations of PCDFs in mink scat can be used as a rapid and inexpensive nondestructive method to predict concentrations of PCDFs in mink when certain assumptions are met.

Passaic river sediment interstitial water phase I toxicity identification evaluation.

A suite of tests was conducted to evaluate and identify the cause or causes of toxicity in Passaic River sediments. Sediment toxicity was measured with three types of bioassays: a whole sediment bioassay with the marine amphipod, Ampelisca abdita, and interstitial water bioassays with A. abdita and the bioluminescent bacterium Vibrio fisheri (Microtox((R))). In addition, a Phase I Toxicity Identification Evaluation (TIE) was conducted to elucidate the cause of observed toxicity. Analytical concentrations of selected residues in whole sediment and interstitial water from the five sampling stations were considered in conjunction with the conclusions drawn from the toxicity tests and Phase I TIE results. Finally, a toxic units approach was used to evaluate the predicted toxicity of measured interstitial water residue concentrations. There was a lack of toxic response in the short-term interstitial water bioassays, indicating that oxidants, soluble forms of metals, and dissolved phase neutral organics were not likely toxicants. However, there was significant toxicity indicated by the whole sediment A. abidita bioassays. After 10 days, there was complete or near complete mortality in amphipods exposed to all of the sediment samples tested. Removal of interstitial water toxicity by filtration was common to all four stations that exhibited measurable initial toxicity. The observed toxicity characteristics are consistent with particle associated neutral organics. This conclusion is supported by toxicity removal via filtration, lack of toxicity in the Microtox((R)) assays, and the fact that whole sediments were more toxic than was interstitial water.

Risk assessment of great horned owls (Bubo virginianus) exposed to polychlorinated biphenyls and DDT along the Kalamazoo River, Michigan, USA.

The great horned owl (GHO; Bubo virginianus) was used in a multiple lines of evidence study of polychlorinated biphenyls (PCBs) and p,p'-dichlorodiphenyltrichloroethane (DDT) exposures at the Kalamazoo River Superfund Site (KRSS), Kalamazoo, Michigan, USA. The study examined risks from total PCBs, including 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQWorld Health Organization [WHO]-Avian Toxicity Equivalency Factor [TEF]), and total DDTs (sum of DDT, dichlorodiphenyldichloroethylene [DDE], and dichlorodiphenyldichloroethane [DDD]; sigmaDDT) by measuring concentrations in eggs and nestling blood plasma in two regions of the KRSS (upper, lower) and an upstream reference area (RA). An ecological risk assessment compared concentrations of the contaminants of concern (COCs) in eggs or plasma to toxicity reference values. Productivity and relative abundance measures for KRSS GHOs were compared with other GHO populations. Egg shell thickness was measured to assess effects of p,p'-DDE. The concentrations of PCBs in eggs were as great as 4.7 x 10(2) and 4.0 x 10(4) ng PCB/g, wet weight at the RA and combined KRSS sites, respectively. Egg TEQ(WHO-Avian) calculated from aryl hydrocarbon receptor-active PCB congeners and WHO TEFs ranged to 8.0 and 1.9 x 10(2) pg TEQ(WHO-Avian)/g, (wet wt) at the RA and combined KRSS, respectively. Egg sigmaDDT concentrations were as great as 4.2 x 10(2) and 5.0 x 10(3) ng sigmaDDT/g (wet wt) at the RA and combined KRSS, respectively. Hazard quotients (HQs) for the upper 95% confidence interval (UCI) (geometric mean) and least observable adverse effect concentration (LOAEC) for COCs in eggs were < or = 1.0 for all sites. Hazard quotient values based on the no observable adverse effect concentration (NOAEC) 95% UCI in eggs were < or = 1.0, except at the LKRSS (PCB HQ = 3.1; TEQ(WHO-Avian) HQ = 1.3). Productivity and relative abundance measures indicated no population level effects in the UKRSS.