Faculty Bibliography

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.

Elevated concentrations of dioxins in ancient ball clay from the Mississippi Embayment suggest natural formation of dioxins in the environment. Evidence for such natural formation in ball clay derives from unique congener profiles in undisturbed ancient clay deposits and from the lack of other anthropogenic contaminants. Here we present novel evidence of natural formation of dioxins based on congener-specific carbon isotopic analysis of octachlorodibenzo-p-dioxin (OCDD) in ball clays from the USA and Japan. The analyses were performed using a combination of double-column high performance liquid chromatography clean-up and two-dimensional gas chromatography-isotope ratio mass spectrometry. Elevated concentrations of OCDD found in ball clays from the USA and Japan were isotopically distinguished from the anthropogenic source materials (fly ash and pentachlorophenol) and environmental samples (sediment and soil). The isotopic signatures and the occurrence of OCDD in ancient ball clays deposited in the Tertiary Era provide evidence for the in situ formation of dioxins.

Concentrations of perfluorinated acids (PFAs) were measured in various environmental matrices (air, rain, snow, surface runoff water, and lake water) in an urban area, to enable identification of sources and pathways of PFAs to urban water bodies. Total PFA concentrations ranged from 8.28 to 16.0 pg/ m3 (mean 11.3) in bulk air (sum of vapor and particulate phases), 0.91 to 13.2 ng/L (6.19) in rainwater, 0.91 to 23.9 ng/L (7.98) in snow, 1.11-81.8 ng/L (15.1 ng/L) in surface runoff water (SRW), and 9.49 to 35.9 ng/L (21.8) in lake water. Perfluorooctanoic acid (PFOA) was the predominant compound, accounting for > 35% of the total PFA concentrations, in all environmental matrices analyzed. Concentrations and relative compositions of PFAs in SRW were similar to those found for urban lakes. SRW contributes to contamination by PFOA in urban lakes. The measured concentration ratios of FTOH to PFOA in air were 1-2 orders of magnitude lower than the ratios calculated based on an assumption of exclusive atmospheric oxidation of FTOHs. Nevertheless, the mass balance analysis suggested the presence of an unknown input pathway that could contribute to a significant amount of total PFOA loadings to the lake. Flux estimates of PFOA at the air-water interface in the urban lake suggest net volatilization from water.

Discharge of effluents from municipal wastewater treatment plants (WWTPs) is a route for the introduction of certain organic contaminants into aquatic environments. Earlier studies have reported the occurrence of perfluorochemicals in effluents from WWTPs. In this study, contamination profiles of perfluorinated compounds (PFCs), including perfluoroalkyl sulfonates (PFASs; PFOS, PFOSA, PFHxS) and perfluoroalkyl carboxylates (PFACs; PFOA, PFNA, PFDA, PFDoDA, PFUnDA), were determined in samples collected at various stages of wastewater treatment during different seasons. The two WWTPs selected for this study represent rural (Plant A, Kentucky) and urban (Plant B, Georgia) areas. PFOS was a major contaminant in samples from Plant A (8.2-990 ng/g dry wt in solid samples and 7.0-149 ng/L in aqueous samples), followed by PFOA (8.3-219 ng/g dry wt in solid samples and 22-334 ng/L in aqueous samples). PFOA was the predominant contaminant in samples from Plant B (7.0-130 ng/g dry wt in solid samples and 1-227 ng/L in aqueous samples), followed by PFOS (<2.5-77 ng/g dry wt in solid samples and 1.8-22 ng/L in aqueous samples). PFHxS, PFNA, PFDA, and PFOSA were detected in most of the samples, whereas PFUnDA and PFDoDA were detected in very few samples. Concentrations of some PFCs, particularly PFOA, were slightly higher in effluent than in influent, suggesting that biodegradation of some precursors contributes to the increase in PFOA concentrations in wastewater treatment processes. No large-magnitude seasonal variations in concentrations were found, although mass flow of PFCs was higher in winter than in summer. In general, samples from the rural plant in Kentucky contained greater concentrations of PFCs than did those from the urban plant in Georgia. Incineration of sludge reduced the PFC levels significantly. The mass flows of PFCs in these two plants were several hundreds of mg/day, comparable to flow values reported earlier.

Concentrations of polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs; DDTs, HCHs, CHLs, and HCB) were measured in human breast milk samples collected across Massachusetts, USA, in 2004. Seventeen PBDE congeners were found in the samples, ranging in concentration from 0.06 to 1910 ng g(-1) lipid wt. BDE-47 (2,2',4,4'-tetraBDE), BDE-99 (2,2',4,4',5-pentaBDE), and BDE-100 (2,2',4,4',6-pentaBDE) were the major congeners detected in breast milk samples. Overall mean (+/-SD) concentrations of DDTs, HCHs, CHLs, and HCB were 64.5 +/- 75, 18.9 +/- 19, 32.4 +/- 36, and 2.3 +/- 2.2 ng g(-1) lipid wt, respectively. Concentrations of PBDEs were strongly correlated with concentrations of OCPs in the samples. Based on the concentrations of organohalogens and the intake rates of breast milk by infants in the United States, daily ingestion rates of contaminants were calculated. The median ingestion rates for PBDEs, HCHs, DDTs, CHLs, and HCB were 4.0, 212, 141, 44, and 5.79 ng kg(-1) body wt day(-1), respectively. The estimated daily intake of organohalogens by infants was compared with threshold reference values suggested by the United States Environmental Protection Agency (USEPA) and the Agency for Toxic Substances and Disease Registry (ATSDR), for calculation of hazard quotients (HQs). HQs for individual organohalogens and the sum of HQ for all organohalogens were calculated as HQ indices (HQI). The results suggest that one or more of the contaminants analyzed in this study exceeded the threshold reference values in at least 26% of the breast milk samples.

Perfluorinated organic compounds (PFCs) such as PFOS, PFOA, PFBS, PFHxS, PFOSA and PFDoA were determined in river water, river sediment, liver of market fish and liver of wildlife samples from Japan. Concentrations of PFOA and PFOS in water samples were 7.9-110 and <5.2-10 ng/L. Only PFOA were detected in sediment from Kyoto river at 1.3-3.9 ng/g dry wt. Among fish, only jack mackerel showed PFOA and PFOS at 10 and 1.6 ng/g wet wt. Wildlife liver contained PFOSA, PFOS, PFDoA, PFOA and PFHxS in the range of 0.31-362, 0.15-238, <0.03-28, >0.07-7.3 and <0.03-1.5, respectively, on ng/g wet wt. Cormorants showed maximum accumulation followed by eagle, raccoon dog and large-billed crow.

Concentrations of 20 trace elements (V, Cr, Mn, Co, Cu, Zn, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb, and Bi) were measured in livers of polar bears (Ursus maritimus) collected from Northern and Western Alaska from 1993 to 2002 to examine differences in the profiles of trace metals between the Beaufort Sea (Northern Alaska) and the Chukchi Sea (Western Alaska) subpopulations in Alaska. Among the trace elements analyzed, concentrations of Cu (50-290 microg/g, dry wt) in polar bear livers were in the higher range of values that have been reported for marine mammals. Concentrations of Hg in polar bears varied widely, from 3.5 to 99 microg/g dry wt, and the mean concentrations in polar bears were comparable to concentrations reported previously for several other species of marine mammals. Mean concentrations of Pb and Cd were 0.67 and 1.0 microg/g dry wt, respectively; these concentrations were lower than levels reported elsewhere for polar bears from Greenland and Canada. Age- and gender-related variations in the concentrations of trace elements in our polar bears were minimal. Concentrations of Hg decreased slowly in samples collected during 1993-2002, whereas Cd and Pb concentrations were found to be stable or slowly increasing, in the livers of Alaskan polar bears. Concentrations of Ag, Bi, Ba, Cu, and Sn were significantly higher in the Chukchi Sea subpopulation than in the Beaufort Sea subpopulation. Concentrations of Hg were significantly higher in the Beaufort Sea subpopulation than in the Chukchi Sea subpopulation. Differences in the profiles and concentrations of Hg, Ag, Bi, Ba, Cu, and Sn suggest that the sources of exposure to these trace elements between Western and Northern Alaskan polar bears are different, in agreement with findings reported earlier for several organic contaminants.

Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in coastal sediments from heavily industrialized areas and major harbors in Korea. SummationPBDE(20) concentrations in sediments ranged from 2.03 to 2253ng/g dry weight. PBDE concentrations were higher at estuarine and inner bay locations close to industrial complexes and large harbors, indicating that the PBDE contamination in the sediments is due to local discharges from industrial complexes. Deca-BDE was the predominant congener and the concentrations were comparable to or higher than those reported from other countries. Non-parametric multidimensional scaling (MDS) ordination showed that deca-BDE technical mixture is the main source of PBDE contamination in Korean coastal waters, with minor contamination by octa-BDE product. This result is consistent with the consumption pattern of brominated flame-retardants (BFRs) in Korea. Significant correlations existed among BDEs 28, 47, 99, 100, 153, and 154; however, BDEs 183 and 209 showed little correlation with less highly brominated congeners.

Southern sea otters (Enhydra lutris nereis) from the California coast continue to exhibit a slower population regrowth rate than the population in Alaska. Infectious diseases have been identified as a frequent cause of death. Infectious diseases caused by varied pathogens including bacteria, fungi, and parasites were suggestive of compromised immunological health of mature animals in this population. To test the hypothesis that elevated exposure to immunotoxic contaminants such as polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) contribute to disease susceptibility via immunosuppression, we determined concentrations of PBDEs and PCBs in livers of 80 adult female sea otters that died of infectious diseases, noninfectious causes, or emaciation. Concentrations of PBDEs and PCBs in sea otter livers varied widely (10-26,800 ng/g and 81-210,000 ng/g, lipid weight, respectively). Concentrations of PBDEs in sea otters were some of the highest values reported for marine mammals so far. Although PCB concentrations in sea otters have declined during 1992-2002, the mean concentration was at the threshold at which adverse health effects are elicited. Concentrations of PBDEs and PCBs were significantly correlated, suggesting co-exposure of these contaminants in sea otters. No significant association was found between the concentrations of PBDEs and the health status of sea otters. Concentrations of PCBs were significantly higher in otters in the infectious disease category than in the noninfectious category, suggesting an association between elevated PCB concentrations and infectious diseases in Southern sea otters.

Wastewater treatment plants (WWTPs) are a potential of source of polycyclic musks in the aquatic environment. In this study, contamination profiles and mass flow of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), and HHCB-lactone (oxidation product of HHCB), in two WWTPs, one located in Kentucky (Plant A, rural area) and the other in Georgia (Plant B, urban), USA, were determined. HHCB, AHTN and HHCB-lactone were detected in the influent, effluent, and sludge samples analyzed. The concentrations in wastewater samples varied widely, from 10 to 7,030 ng/l, 13 to 5,400 ng/l, and 66 to 790 ng/l, for HHCB, AHTN, and HHCB-lactone, respectively. Sludge samples contained HHCB at <0.02-36 microg/g dry weight, AHTN at <0.02-7.2 microg/g dry weight, and HHCB-lactone at <0.05-17 microg/g dry weight. Based on the daily flow rates and mean concentrations of polycyclic musks, the estimated discharge of total polycyclic musks to the rivers was 21 g/day from Plant A and 31 g/day from Plant B. Mass balance analysis suggested that only 30% of HHCB and AHTN entering the plants was accounted for in the effluent and the sludge. Removal efficiencies of HHCB and AHTN in the two WWTPs ranged from 72% to 98%. In contrast, HHCB-lactone concentrations increased following the treatment. Concentrations of polycyclic musks in sludge were on the order of several parts per million. Incineration of sludge at one plant reduced the concentration of polycyclic musks.