Faculty Bibliography

Nonylphenol (NP) is a degradation product of nonylphenol polyethoxylate surfactants and has been reported to occur in water and sediments from urban areas. Technical NP is composed of several structural isomers, and conventional gas chromatography-mass spectrometry techniques have tentatively identified up to 22 components. Isolation and characterization of individual isomers in a technical NP mixture is important, because of the differences in estrogenic and bioaccumulation potential among the isomers. In this study, comprehensive two-dimensional gas chromatography (GC x GC) combined with mass spectrometry (MS) enabled tentative identification of 102 components of NP from a technical mixture. GC x GC-MS was also used to quantify two NP isomers in river water samples. This is the first study to use GC x GC-MS to characterize NP isomers in technical mixtures and for quantitative analysis of NP in river waters.

Human adipose tissue samples (n=52) collected in New York City during 2003-2004 were analyzed for the presence of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Concentrations of PBDEs in adipose tissues ranged from 17 to 9630 ng/g, lipid wt (median: 77; mean: 399 ng/g, lipid wt; sum all di- through hexaBDE congeners). Average PBDE concentrations in human adipose tissues from New York City were 10- to 100-times greater than those reported for European countries. A concentration of 9630 ng/g, lipid wt, found in a sample of adipose tissue, is one of the highest concentrations reported to date. PBDE 47 (2,2',4,4'-tetraBDE) was the major congener detected in human tissues, followed by PBDE congeners #99 (2,2',4,4',5-penta BDE), 100 (2,2',4,4',6-pentaBDE), and 153 (2,2',4,4',5,5'-hexaBDE). A few individuals contained PBDE 153 as the predominant congener in total PBDE concentrations, suggesting alternative exposure sources, possibly occupational. Principal component analysis of PBDE congener composition in human adipose tissues revealed the presence of five clusters, each characterized by varying composition. No significant difference was found in the concentrations of PBDEs between gender. Concentrations of PBDEs were, on average, similar to those for PCBs in human adipose tissues, and substantially higher when PBDE outliers were retained. PBDE and PCB concentrations were not correlated. PBDE concentrations did not increase with increasing age of the subjects, whereas concentrations of PCBs increased with increasing age in males but not in females in this study. These results suggest differences between PBDEs and PCBs in their sources or time course of exposure and disposition. The presence of comparable or greater concentrations of PBDEs, relative to PCBs, highlights the importance of recentvoluntary and regulatory effortsto cease production of commercial penta- and octa-BDE in North America, although these efforts do not address continuing emissions from existing sources, such as polyurethane foams.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in sediment cores collected from 11 inland lakes in Michigan for examination of spatial and temporal trends in accumulation and sources. Concentrations of PAHs varied widely among these lakes; the highest concentrations were found in sediment collected from Cass Lake, located in an urbanized watershed. Concentrations of PAHs were correlated with watershed population density on a spatial scale. PAH concentrations have decreased over time since the 1980s in nine of the 11 lakes studied, most of which are located in suburban and rural areas. The rate of decline in PAH concentration was faster in Gratiot Lake, a remote lake with no known local sources of pollution in recent years. Concentrations of PAHs in surface sediments from Cass and Cadillac Lakes were greater than the threshold for adverse effects. Despite the wide variations in total PAH concentrations, fluoranthene, pyrene, chrysene, benzo[b]fluoranthene, and benzo[k]fluoranthene were the major PAHs in all of the lakes studied. The proportions of individual PAHs within the total PAH concentrations have changed both temporally and spatially, suggesting a shift in the sources of PAHs in the environment. A general increase in the proportion of high-molecular-weight PAHs suggests an increase in combustion-related sources recently.

Sediments from inland areas and open bays along the Korean coast were analyzed to examine the distribution of dioxin-like and estrogenic compounds. Concentrations of target chemicals varied considerably among locations (Lake Shihwa, Masan Bay, and Kwangyang Bay) and between inland and coastal areas. Principal component analysis (PCA) of contaminants measured in sediments showed that all of the inland locations from Lake Shihwa were highly contaminated, and the variations among locations were explained predominantly by the distribution of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). PCA of PAH congener profiles among locations indicated that automobiles were a major source of PAH contamination. Dioxin-like and estrogenic activities associated with sediment from inland sites were approximately three- and six-fold, respectively, greater than those associated with open bay locations. The target dioxin-like and estrogenic compounds measured in raw extracts of sediments accounted for approximately 20% and 40% of the activities measured in the sediment extracts. The results suggest that a combination of instrumental and bioanalytical measurements of dioxin-like and estrogenic compounds is a valuable approach to screen, identify, and prioritize the risks posed by contaminants in complex environmental matrices.

Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.

Trophic transfer of perfluorooctanesulfonate (PFOS) and other related perfluorinated compounds was examined in a Great Lakes benthic foodweb including water-algae-zebra mussel-round goby-smallmouth bass. In addition, perfluorinated compounds were measured in livers and eggs of Chinook salmon and lake whitefish, in muscle tissue of carp, and in eggs of brown trout collected from Michigan. Similarly, green frog livers, snapping turtle plasma, mink livers, and bald eagle tissues were analyzed to determine concentrations in higher trophic-level organisms in the food chain. PFOS was the most widely detected compound in benthic organisms at various trophic levels. Concentrations of PFOS in benthic invertebrates such as amphipods and zebra mussels were approximately 1000-fold greater than those in surrounding water, which suggested a bioconcentration factor (BCF; concentration in biota/concentration in water) of 1000 in benthic invertebrates. Concentrations of PFOS in round gobies were two- to fourfold greater than those in their prey organisms such as zebra mussels and amphipods. Concentrations of PFOS in predatory fishes (Chinook salmon and lake whitefish) were 10 to 20-fold greater than those in their prey species. Concentrations of PFOS in mink and bald eagles were, on average, 5- to 10-fold greater than those in Chinook salmon, carp, or snapping turtles. Because of the accumulation of PFOS in liver and blood, the biomagnification factor (BMF) of perfluorinated compounds in higher trophic-level organisms such as salmonid fishes, mink, and eagles were based on the concentrations in livers or plasma. Overall, these results suggest a BCF of PFOS of approximately 1000 (whole-body based) in benthic invertebrates, and a BMF of 10 to 20 in mink or bald eagles, relative to their prey items. Eggs of fish contained notable concentrations of PFOS, suggesting oviparous transfer of this compound. PFOA was found in water, but its biomagnification potential was lower than that of PFOS.

Concentrations and accumulation of 13 fluorinated organic compounds (FOCs) in human sera and seminal plasma were measured in an Asian developing country, Sri Lanka. Six of the FOCs, PFOS (perfluorooctanesulfonate), PFHS (perfluorohexanesulfonate), PFUnA (perfluoroundecanoic acid), PFDA (perfluorodecanoic acid), PFNA (perfluorononanoic acid) and PFOA (perfluorooctanoic acid), were detected in all of the sera samples. Measurable quantities of two main perfluorosulfonates, PFOS and PFHS, were found in all seminal plasma samples. The detection frequency of the predominant perfluoroalkylcarboxylate, PFOA, in seminal plasma was >70%. Accumulation of PFOS in sera was significantly positively correlated with PFOA, PFHS and PFNA. Positive linear regressions were also found between PFNA and PFUnA and PFNA and PFDA suggesting that these compounds may have a similar origin of exposure and accumulation. Significantly positive associations were observed for partitioning of both PFOS and PFNA between sera and seminal plasma. The accumulation of FOCs was not significantly different in sera from Colombo (urban population) and Talawakele (rural conventional tea workers). However, the Haldummulla population (rural organic tea workers) had relatively lower exposure to FOCs compared to the other two groups, urban and rural conventional tea workers. Concentrations of FOCs in Sri Lanka were similar to those reported for industrialized countries suggesting that human exposure to such chemicals is widespread even in developing countries. The novel finding of FOCs in human seminal plasma implies that further studies are needed to determine whether long-term exposure in humans can result in reproductive impairments.

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.

Perfluorinated acids and their salts have emerged as an important class of global environmental contaminants. Biological monitoring surveys conducted using tissues of marine organisms reported the occurrence of perfluorooctanesulfonate (PFOS) and related perfluorinated compounds in biota from various seas and oceans, including the Arctic and the Antarctic Oceans. Occurrence of perfluorinated compounds in remote marine locations is of concern and indicates the need for studies to trace sources and pathways of these compounds to the oceans. Determination of sub-parts-per-trillion (ng/L) or parts-per-quadrillion (pg/L) concentrations of aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. Our research group has developed a reliable and highly sensitive analytical method by which to monitor perfluorinated compounds in oceanic waters. The method developed is capable of detecting PFOS, perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at a few pg/L in oceanic waters. The method was applied to seawater samples collected during several international research cruises undertaken during 2002-2004 in the central to eastern Pacific Ocean (19 locations), South China Sea and Sulu Seas (five), north and mid Atlantic Ocean (12), and the Labrador Sea (20). An additional 50 samples of coastal seawater from several Asian countries (Japan, China, Korea) were analyzed. PFOA was found at levels ranging from several thousands of pg/L in water samples collected from coastal areas in Japan to a few tens of pg/L in the central Pacific Ocean. PFOA was the major contaminant detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.

To quantitatively characterize the substances contributing to estrogenic activity in river water, in vitro bioassay using MVLN cells and instrumental analysis using liquid chromatograph-mass spectrometer (LC/MS) or liquid chromatograph-tandem mass spectrometer (LC/MS/MS) were applied to river water extracts taken from various locations in the Tama River, Japan. Tama River water samples were extracted using solid phase extraction and the crude extracts were fractionated by high-performance liquid chromatography (HPLC) into 10 fractions. The sixth fraction contained nonylphenol (NP) and octylphenol (OP) at concentrations in the range of 51.6-147 and 6.9-81.9 ng/L, respectively (concentrations corresponding to the original sample volumes). No estrogenic activity, expressed as 17beta-estradiol equivalents (E2-EQ(B)), however, was observed in this fraction (<0.6 ng-E2eq/L). Instrumentally determined estrogenic activity (E2-EQ(C)), which is the concentrations of NP and OP multiplied by their corresponding relative potency, was below the detection limit of the MVLN cell bioassay. Estrogenic activities were detected only in HPLC fraction nos. 7, 8 and 9. Estrone (E1), estradiol (E2) and bisphenol A (BPA) were detected in these fractions. Estriol (E3) and ethynylestradiol (EE2) were not detected (<0.2 ng/L) in these fractions. The calculated E2-EQ(C) for BPA was below the detection limit of bioassay. The E2-EQ(C) for E1 and E2 were on the same order as the estrogenic activity determined by the bioassay (E2-EQ(B)). The ratios of E2-EQ(C) and E2-EQ(B) for E1 and E2 in the three factions collectively (nos. 7-9) were 0.49-0.97 and 0.29-1.12, respectively. Above results indicated that the major causal substances to the estrogenic activity in the Tama River were E1 and E2.