Faculty Bibliography

Concentrations of perfluorochemicals (PFCs) including perfluoroalkylsulfonates (PFSAs) and perfluoroalkylcarboxylates (PFCAs) were determined in liver and serum of Baikal seals (Pusa sibirica) collected from Lake Baikal, Russia in 2005. Among the 10 PFC compounds measured, perfluorononanoic acid (PFNA, 3.3-72 ng/g wet wt) concentrations were the highest in liver, followed by perfluorooctanesulfonate (PFOS, 2.6-38 ng/g). The accumulation profile of long-chain (C7-C12) PFCAs in particular, the predominance of PFNA, indicated that 8:2 fluorotelomer alcohol or commercially manufactured PFNA is a major local source of PFCs in Lake Baikal. No gender-related differences in the concentrations of individual PFCs or total PFCs were found. Tissues from pups and juveniles contained relatively higher concentrations of PFCs than tissues from subadults and adults, suggesting that maternal transfer of PFCs is of critical importance. Comparison of concentrations of PFCs in livers and sera collected from the same individuals of Baikal seals revealed that residue levels of PFOS, PFNA, perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) were significantly higher in liver than in serum. The concentration ratios of PFNA and PFDA between liver and serum were calculated to be 14 and 15, respectively, whereas the ratio of PFOS was 2.4. This suggests preferential retention of both PFNA and PFDA in liver. Concentrations of PFOS, PFNA, and PFDA in liver were significantly correlated with those in serum, whereas concentrations of PFUnDA were not correlated in between the two tissues, suggesting differences in pharmacokinetics among these PFCs. Temporal comparisons of hepatic PFC concentrations in seals collected between 1992 and 2005 showed that the concentrations of PFOS (p = 0.0006), PFNA (p = 0.061) and PFDA (p = 0.017) were higher in animals collected in recentyears, indicating ongoing sources of PFC contamination in Lake Baikal.

Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.

Recently, we reported on the analysis of polychlorinated biphenyls (PCBs) and chlorinated pesticides in farmed Atlantic salmon (Salmo salar) from Maine, eastern Canada, and Norway, and wild Alaskan Chinook salmon (Oncorhynchus tshawytscha). In this paper, we extend the analysis to polybrominated diphenyl ethers (PBDEs) in these samples. Total PBDE concentrations in the farmed salmon (0.4-1.4ng/g, wet weight, ww) were not significantly different from those in the wild Alaskan Chinook samples (0.4-1.2ng/g, ww), nor were significant differences found among regions. However, significant intra-regional variations in concentrations of total PBDEs and tetra-BDE 47 were observed in the salmon from the Canadian farms (p<0.01). Congener profiles were dominated by BDE-47, followed by the penta-BDEs 99 and 100. PBDE concentrations in the Canadian samples were lower than those reported two years earlier. Removal of skin resulted in no overall reduction in PBDE concentrations in our farmed salmon, and in some cases, PBDE concentrations were higher in skin-off samples. PBDEs were correlated with lipids only in the skinned samples, suggesting that there is greater accumulation and retention of PBDEs in muscle lipids than in skin-associated fat. In skin-on samples, modest correlations were observed between concentrations of PBDEs and PCBs (R(2)=0.47) and mono-ortho PCBs (R(2)=0.50), whereas PBDEs were not correlated with non-ortho PCBs.

Organotin compounds (OTs) including mono- to tri-butyltins, -phenyltins, and -octyltins were determined in the liver of adult sea otters (Enhydra lutris) found dead along the coasts of California, Washington, and Alaska in the USA and Kamchatka, Russia. Total concentrations of OTs in sea otters from California ranged from 34 to 4100ng/g on a wet weight basis. The order of concentrations of OTs in sea otters was total butyltins>total octyltins> or = total phenyltins. Elevated concentrations of butyltins (BTs) were found in some otters classified under 'infectious-disease' mortality category. Concentrations of BTs in few of these otters were close to or above the threshold levels for adverse health effects. Total butyltin concentrations decreased significantly in the livers of California sea otters since the 1990s. Based on the concentrations of organotins in sea otters collected from 1992 to 2002, the half-lives of tributyltin and total butyltins in sea otters were estimated to be approximately three years.

Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were measured in livers of 81 adult female sea otters collected along the California coast in 1992-2002. Concentrations of summation operatorPAHs in livers of sea otters were in the range of 588-17400ng/g lipid wt (mean: 3880ng/g, lipid wt). On a wet weight basis, the concentrations ranged from 17 to 1430ng/g (mean: 146ng/g). Overall, di- and tri-cyclic aromatic hydrocarbons, namely, naphthalene, fluorene, phenanthrene/anthracene, and acenaphthylene, were the predominant compounds found in the livers. Although petroleum-related sources appear to be the major contributors to PAH exposure in sea otters, exposure sources varied by geographical sub-regions. Dibenz[a,h]anthracene was found to comprise a significant proportion of the summation operatorPAH concentrations in sea otters from the northern sub-region of the study area. No significant difference existed in the concentrations of summation operatorPAHs among sea otters that died from infectious diseases, emaciation, and noninfectious causes. Concentrations of summation operatorPAHs in livers of sea otters decreased significantly from 1992 to 2002. Because of the rapid metabolism of PAHs in marine mammals such as sea otters, further studies examining the association of PAHs with health effects should determine hydroxylated metabolites in livers.

Concentrations of tetrabromobisphenol A (TBBPA) and alpha-, beta-, and gamma-isomers of hexabromocyclododecanes (HBCDs) were determined by liquid chromatography-tandem mass spectrometry (LC-ESI-MS/MS) in human adipose tissue obtained in New York City, and in three marine top-level predators--bottlenose dolphin, bull shark, and Atlantic sharpnose shark--collected from coastal waters of Florida, USA. The overall mean concentrations (mean+/-SD) of TBBPA and HBCDs were 0.048+/-0.102 and 0.333+/-0.571 ng/g lipid wt in human adipose tissue samples, 1.2+/-3 and 7.38+/-18 ng/g lipid wt in bottlenose dolphin blubber, 9.5+/-12 and 77.7+/-128 ng/g lipid wt in bull shark muscle, and 0.872+/-0.5 and 54.5+/-88 ng/g lipid wt in Atlantic sharpnose shark muscle. Overall mean concentrations of HBCDs were 5-10-fold higher than mean TBBPA concentrations, in all of the samples analyzed. The highest concentrations of TBBPA and HBCDs were detected in the bull shark muscle at concentrations of 35.6 and 413 ng/g, lipid wt, respectively. Concentrations of TBBPA and HBCDs, after log-transformation, were significantly correlated with each other in human adipose tissue and bottlenose dolphin blubber, but not in bull shark muscle samples. In the human adipose tissue samples, the concentrations of HBCDs were 3-4 orders of magnitude lower than the concentrations of polybrominated diphenyl ethers (PBDEs) previously reported for the same set of tissue samples. Concentrations of HBCDs in human samples from the United States were 1-5-fold lower than the concentrations reported from several European countries. HBCD concentrations in bottlenose dolphins from the United States were 1-2 orders of magnitude lower than the concentrations reported for other cetacean species from Europe. The present report is the first to determine levels of TBBPA and HBCDs in humans, bottlenose dolphins, and sharks from the United States.

Sediments and fish bile collected from the Atlantic coastal waters of Colombia were analyzed for 16 parent polycyclic aromatic hydrocarbons (PAHs), and 23 hydroxylated PAHs (OH-PAHs), respectively. Sediments contained overall mean SigmaPAH concentrations of 2090, 234 and 170 ng/g, dry wt, for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The mean concentration of the summed OH-PAHs in fish bile was 1250, 180 and 64.1 ng/g bile wt for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The results suggest that Cartagena Bay is heavily polluted by PAHs, and that exposure to high concentrations of PAHs together with other factors could contribute to the decreased health of fish living in this ecosystem. This is one of the first studies to describe the analysis of 23 individual OH-PAHs in fish bile, using authentic standards.

Sediment and floodplain soils in the Saginaw River Watershed, Michigan, USA, have been demonstrated to be contaminated with a variety of organic compounds, including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs). Existing data indicate that, at some locations, the contamination exceeds human health risk-based regulatory levels and ecological risk-based screening levels. In this study, concentrations of PCBs including non-ortho coplanar congeners, PCDDs, and PCDFs were measured in more than 120 sediment and floodplain soil samples collected from the Shiawassee River (a tributary of the Saginaw River), the Saginaw River, and Saginaw Bay, to determine the sources and magnitude of contamination, and to elucidate the contributions from individual contaminant groups to the overall 2,3,7,8-tetrachlorodibezo-p-dioxin equivalents (TEQs). Sediment and soil extracts were also analyzed for total dioxin-like activity by means of the H4IIE-luc cell bioassay. Elevated concentrations of PCBs (>1000 ng/g, dry weight) were found in surface sediment and floodplain soil samples collected from the Shiawassee River near Chase Lake, from Middleground Island in the Saginaw River, and from subsurface sediments in Saginaw Bay. Concentrations of PCDDs and PCDFs in sediment and floodplain soils from the Saginaw River and Saginaw Bay were 2 to 3 orders of magnitude higher than concentrations in the samples from the Shiawassee River. The highest PCDD/F concentration (55,200 pg/g, dry weight in a subsurface layer) was found in sediment collected at the mouth of the Saginaw River. Concentrations of PCDFs were greater than the concentrations of PCDDs in sediment from the Saginaw River. 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, and 2,3,4,7,8-PeCDF were the major PCDF congeners found in sediments from the Saginaw River. The elevated concentrations of PCDFs, and the predominance of the less highly chlorinated PCDF congeners, in sediments from the Saginaw River were similar to previously determined characteristics of the PCDF contamination of the Tittabawassee River, another tributary of the Saginaw River. These results suggest the existence of a major source of PCDFs within the watershed. A few localized areas of high PCDD/F and PCB concentrations, with unique congener compositions, in the Saginaw River indicated the presence of other minor sources, such as wastewater treatment plants. PCDFs were the major contributors to TEQs in sediment and soils from the Saginaw River and Saginaw Bay. Approximately 30% of the samples analyzed in this study had values exceeding the screening level of 50 pg TEQ/g, dry wt, suggested for soils by the Agency for Toxic Substances and Disease Registry.