Lisa L. Williams

Effects of chronic dietary exposure to environmentally relevant concentrations to 2,3,7,8-tetrachlorodibenzo-p-dioxin on survival, growth, reproduction and biochemical responses of female rainbow trout (Oncorhynchus mykiss).

Adult female rainbow trout were exposed to dietary 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at concentrations of 1.8, 18 and 90 ng TCDD/kg (ww) food for up to 300 day. At the end of the exposure fish were spawned and the reproductive outcomes were assessed. TCDD was accumulated into tissues and eggs in a dose-dependent manner with steady state being achieved after 50-100 day of exposure. Biochemical and hematological parameters were monitored at 50, 100, 150, and 200 day after the beginning of exposure. The survival of adult female trout was reduced in a dose-dependent manner by exposure to TCDD in the diet. Fish fed 1.8 ng TCDD/kg, moist weight of diet, showed significantly reduced survival compared with those fed the control diet. TCDD also affected survival of fry from females fed 1.8 ng TCDD/kg. Observed adverse effects in adult fish were as sensitive as early life-stage endpoints. Liver EROD activity was only moderately increased in all exposure groups after 250+ day of exposure. Low rates of edema and deformities were observed in fry from all treatment groups including controls. This study has demonstrated adverse effects of TCDD to both adults and fry at concentrations comparable to current environmental concentrations. This suggests that direct adult toxicity as well as reproductive endpoints need to be incorporated in the current risk assessment paradigm for these compounds.

Spatial and temporal comparisons of legacy and emerging flame retardants in herring gull eggs from colonies spanning the Laurentian Great Lakes of Canada and United States

In the Laurentian Great Lakes basin of North America, an increasing number of chemicals of emerging concern (CECs) are being investigated, including legacy and replacement flame retardants (FRs). In the present study, 14 polybrominated diphenyl ethers (PBDEs), 23 non-PBDEs halogenated FRs (NPHFRs) and 16 organophosphate ester FRs (OPE-FRs) were analyzed in 100 individual eggs collected in 2012 and 2013 and in 15 egg pools of herring gulls collected in 2012 from 20 colonies across the entire Laurentian Great Lakes basin. For CEC-FRs in eggs from all colonies, 14 PBDEs, 12 NPHFRs and 9 OPE-FRs were quantifiable in at least one of the 115 analyzed samples. The mean sum PBDE (Σ14PBDE) concentrations ranged from 244 to 657 ng/g wet weight (ww), and on average were 1-2 orders of magnitude greater than the Σ12NPHFR concentrations (13.8-35.6 ng/g ww), and 2-3 orders of magnitude greater than Σ9OPE-FR concentrations (0.31-2.14 ng/g ww). Mean Σ14PBDE and sum of syn- and anti-Dechlorane Plus isomer (Σ2DDC-CO) concentrations in eggs from colonies within Laurentian Great Lakes Areas of Concern (AOCs) were in most cases greater than in eggs from nearby colonies outside of AOCs. Comparing CEC-FR concentrations in eggs collected in 2012-2013 to those previously measured in eggs collected approximately 7 years earlier (2006 and 2008) showed that Σ7PBDE (BDE-28, -47, -100, -99, -154,-153 and -183) mean concentrations in eggs from 6 colonies were approximately 30% less than they were in eggs from the same colonies from the earlier time period, whereas 3 current-use FR (BDE-209, HBCDD and Σ2DDC-CO) concentrations were significantly greater (p<0.05) than previously measured. Between 2006 and 2013 there were significant changes in individual PBDE patterns for BDE-71, -138, -153, -203, -206 and -207. Among all of the examined CEC-FRs, concentrations of Σ4PBDE (BDE-47, -99, -100 and -153) and HBCDD in gull eggs from all colonies were greater than or comparable to their lowest observed effect concentrations (LOECs) based on in ovo egg injection studies. Overall, the current profiles of a broad suite of FRs in Laurentian Great Lakes herring gull eggs highlights the need to better understand e.g., exposure-effect implications and metabolism of FRs, i.e. OPE-FRs, and emphasizes the importance of continued monitoring of CEC-FRs whose concentrations appear to be increasing, including BDE-209, HBCDD and DDC-COs.

Relationships Among Concentrations of Individual Polychlorinated Biphenyl (PCB) Congeners, 2,3,7,8-Tetrachlorodibenzo-P-Dioxin Equivalents (TCDD-EQ), and Rearing Mortality of Chinook Salmon (Oncorhynchus Tshawytscha) Eggs from Lake Michigan

A study was conducted to investigate possible correlations between concentrations of individual polychlorinated biphenyl congeners (PCBs) or 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TCDD-EQ) and mortality in early life stages of Chinook salmon. Eggs were collected from adult Lake Michigan Chinook salmon in October, 1986, and were analyzed for concentrations of individual PCB congeners and total PCBs. Concentrations of mono- and non-ortho-substituted congeners were determined after fractionation of PCB-containing extracts with a carbon column. Three types of TCDD-EQ were calculated using an additive potency model by multiplying concentrations of individual PCB congeners by each of three different sets of toxic equivalency factors (TEFs) and summing the products. The mean total concentration of PCBs in the eggs was 7.02 μ/g, wet weight, and measured concentrations of the non-ortho-substituted PCB congeners ranged from 0.2 to 12 ng/g, wet weight. Mean concentrations of TCDD-EQ depended on the set of TEFS which were used in the calculations and ranged from 29 to 514 pg/g. Concentrations of TCDD-EQ were positively correlated with total concentrations of PCBs (r2 = 0.60), although the magnitude of correlations between concentrations of individual non-ortho-substituted congeners and total PCBs were less than those for TCDD-EQ and total PCB. Mortality of eggs and fry differed significantly among clutches of eggs from different females but was not correlated with concentrations of TCDD-EQ, individual PCB congeners, or total PCBs in the eggs.

A Comparison of Water Quality Criteria for the Great Lakes Based on Human and Wildlife Health

Water quality criteria (WQC) can be derived in several ways. The usual techniques involve hazard and risk assessment procedures. For non-persistent, non-biomagnified compounds and elements, WQC are experimentally derived from their acute and chronic toxicity to aquatic organisms. For those persistent chlorinated hydrocarbons (PCHs) that are bioaccumulated and biomagnified, these traditional techniques have not been effective, partly because effects higher in the food web were not considered. Polychlorinated biphenyls (PCBs) are the bioaccumulative synthetic chemicals of primary toxicological significance to the Great Lakes biota which have caused widespread injury to wildlife. In the Laurentian Great Lakes, the primary emphasis of hazard assessments has been on the potential for adverse effects in humans who eat fish. The primary regulatory endpoint of traditional hazard and risk assessments underlying current WQC are the probabilities of additional cancers occurring in the human population. The analysis presented here indicates that this is not adequate to restore sensitive wildlife species that are highly exposed to PCBs, especially those that have suffered serious population declines. Because WQC are legal instruments, the methods of deriving WQC have large implications for remediation, litigation, and damage assessments. Here WQC are derived for six species based on the responses of wildlife in the field or produced by feeding fish to surrogate species, rather than projecting a potential of increased cancer rates in humans. If the most sensitive wildlife species are restored and protected for very sensitive reproductive endpoints, then all components of the ecosystem, including human health, should be more adequately protected. The management of Great Lakes wildlife requires an understanding of the injury and causal relationships to persistent toxic substances.

Concentrations of Dissolved and Particulate Polychlorinated Biphenyls in Water from the Saginaw River, Michigan

The Saginaw River receives water from a major drainage basin in the east-central portion of the lower peninsula of Michigan. Historically the river has been contaminated with polychlorinated biphenyls (PCBs) from several sources. The present study was conducted to determine the concentrations of PCBs in both the dissolved and particulate phases of water in the lower Saginaw River, as well as the relative contribution of PCBs from the lower portion of the river relative to more upstream locations. Water samples were collected in 1990–1991, during a range of discharge conditions. Suspended particulates were collected from water onto glass-fiber filters by use of a “Penta-plate” filtration apparatus. Filtered water was subsequently passed through XAD-2 macroreticular resin to collect the “dissolved” PCBs. Concentrations of PCBs in both phases were determined by congener specific gas chromatography with electron capture detection. Total concentrations of PCBs ranged from 11 to 31 ng/L. The concentrations of PCBs in the dissolved phase ranged from 1.9 to 16 ng/L. The ratio of total PCBs bound to suspended particulates, relative to dissolved PCBs, was 2:1 and remained fairly constant for discharges less than approximately 400 M3/sec. The loading of total PCBs to Saginaw Bay was estimated to be 225 kg/yr, of which approximately 60% was found to be contributed by the lower 8 km of the Saginaw River.

Polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents in eggs of double-crested cormorants from a colony near Green Bay, Wisconsin, USA.

Great Lakes colonial waterbirds have experienced poor reproduction and a greater incidence of birth defects than those in remote areas. An egg was collected from each of 1,000 marked cormorant nests at Spider Island (Lake Michigan). Nine pools comprised of three eggs were randomly selected for instrumental quantification of polychlorinated biphenyls (PCB) congeners, calculation of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEq) and measurement of equivalents by bioassay (TCDD-EQ). PCB analysis of the nine samples was semi-automated with high performance liquid chromatography (HPLC) columns including a porous graphitic carbon column. TEqs were calculated from concentrations of PCB congeners and bioassay-derived toxic equivalency factors (TEfs), and TCDD-EQ were measured directly with an H4IIE bioassay. Total PCB concentrations ranged from 9.7 to 38 μg/g, wet weight (ww). Mean concentrations of PCB 77, 126, and 169 were 2, 7, and 1 ng/g, ww. The mean TEqs and TCDD-EQ were 150 and 350 pg/g, ww, respectively. Thus, PCB congeners contributed less than 50% of the total TCDD-EQs as measured by the bioassay.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in muscle and eggs of salmonid fishes from the Great Lakes

Abstract. Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were measured in dorsal muscle and eggs of coho salmon, lake trout, and chinook salmon collected from Lakes Superior, Michigan, and Huron (Michigan waters). Absolute and relative concentrations of PCDDs and PCDFs varied among sampling locations (inter- and intralake) and fish species. Fish collected from Bay City (Saginaw Bay) contained the greatest concentrations of PCDDs and PCDFs both in muscle and eggs. Among the three fish species, chinook salmon accumulated greater concentrations than did coho salmon or lake trout. Concentrations of PCDFs were greater than those of PCDDs in all fishes. OCDF and TCDF were the predominant congeners of PCDF, whereas OCDD and TCDD concentrations predominated in PCDDs. Homolog compositions of PCDDs and PCDFs suggested the existence of multiple local sources in various locations. Concentrations of PCDDs and PCDFs in eggs of fishes were significantly correlated with those in muscle.

Perfluorinated sulfonate and carboxylate compounds and precursors in herring gull eggs from across the Laurentian Great Lakes of North America: Temporal and recent spatial comparisons and exposure implications

Chemicals of emerging concern (CECs) in the basin of the Laurentian Great Lakes of North America include per- and poly-fluoroalkyl substances (PFASs) classified as perfluoroalkyl acids. We investigated several PFASs, and specifically 13 C4-C16 perfluorinated carboxylic acids (PFCAs), 4 (C4, C6, C8 and C10) perfluorinated sulfonates (PFSAs), perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) and selected precursors (e.g. perfluorobutane sulfonamide and perfluorooctane sulfonamide) in herring gull (Larus argentatus) eggs collected in 2012-2013 from 19 Canadian and U.S. colony sites across the Great Lakes. C6, C8 and C10 PFSAs, PFEtCHxS, and C7-14 and C16 PFCAs were quantifiable at >97% of the 114 egg samples. PFEtCHxS concentrations ranged from n.d. to 3.1ng/g ww (highest in Lake Michigan eggs). Mean Σ4PFSA (92 to 97% perfluorooctane sulfonate (PFOS)) and Σ9PFCA concentration ranges were 44 to 740 and 4.8 to 118ng/g ww, respectively. Σ4PFSA showed a clear increasing concentration trend from the northwest to the southeast colonies. Also, Σ4PFCA to Σ9PFSA concentration ratios in gull eggs were greater in eggs from Lake Superior relative to colonies in the other lakes. PFOS concentrations in some egg samples were greater than some of the known lowest observed effect concentrations (LOECs) measured and reported in captive bird model studies. This study showed the increasing complexity of PFAS-CECs, and emphasized the importance of continuing monitoring of bioaccumulative PFAS in Great Lakes herring gulls.

Polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents in eggs of red-breasted mergansers near Green Bay, Wisconsin, USA, in 1977–78 and 1990

The hypothesis that the concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEqs) contributed by non-ortho- and mono-ortho-substituted (coplanar) PCB congeners have changed relative to total concentrations of PCBs over time was tested by analyzing eggs of red-breasted mergansers collected from the same locality in 1977–78 and in 1990. Twelve eggs from each time period were analyzed for coplanar PCBs, using a porous graphitic carbon HPLC column and GCECD. TEqs were calculated from coplanar PCB concentrations and bioassay-derived toxic equivalency factors. Median total PCB concentrations decreased from 25 to 13 μg/g, fresh weight (fw), and TEqs decreased from 320 pg/g to 160 pg/g, fw. The relative potency of the PCB mixtures, expressed as the ratio of TEqs contributed by the coplanar PCB congeners to total PCBs, did not change, nor did the ratio of concentrations of coplanar congeners to total PCBs. Thus, the relative potency of the mixture of PCBs in the eggs has not changed even as the concentrations declined significantly. The greater relative potency of TEqs relative to that which would be expected from the Aroclor® mixtures released into the environment is due to selective bioaccumulation, biomagnification, and metabolism, rather than as a result of differential weathering as a function of time.

Characterization studies of a semi‐automated separation method for analysis of non‐ortho substituted polychlorinated biphenyl (PCB) congeners in environmental samples

Non‐ortho substituted polychlorinated biphenyl (PCB) congeners can account for the majority of the dioxin‐like toxicity in environmental samples, yet analysis for these congeners is difficult because other PCB congeners co‐elute with them in most Chromatographic methods. An automated method was developed which incorporates a porous graphitic carbon (PGC) column which is commercially available. Non‐ortho substituted congeners were successfully separated from interfering PCB congeners. Recoveries of non‐ortho substituted congeners were consistently reproducible (CV < 9%) when chicken eggs were fortified with individual congeners.