Faculty Bibliography

A study was conducted to determine whether changes in thyroid and vitamin A dynamics were induced in ranch mink exposed to environmentally relevant concentrations of polyhalogenated aromatic hydrocarbons. Adult female mink were fed diets that contained 0% (control), 10%, 20%, or 30% wild carp (Cyprinus carpio) collected from the Saginaw River, Michigan, USA. Total polychlorinated biphenyls concentrations were 0.03, 0.83, 1.05, and 1.69 mg/kg feed, respectively; the 2,3,7,8-tetrachlorodibenzo-p-diozin toxic equivalents were 3.4, 27.9, 47.6, and 73.2 ng/kg, respectively. Diets were fed 3 weeks prior to breeding and throughout gestation and lactation. When the kits were weaned at 6 weeks of age, they were continued on their respective diets until 27 weeks of age. Plasma thyroid hormone concentrations, thyroid gland activity and structure, and vitamin A dynamics were assessed in young mink at 6 and 27 weeks of age. Plasma total T4 and free T4 in 6-week-old female and male kits fed the 10% carp diet were significantly higher than those of controls, while kits fed the 20% and 30% carp diet had nonsignificant decreases relative to the control mink. Plasma total T3 concentrations in 27-week-old juvenile males fed the 30% carp diet were significantly lower than those in individuals fed the 10% carp diet. No overt thyroid toxicity was apparent as thyroid weight, activity, and structure in kits and juveniles of both sexes were similar among diet groups. Plasma retinol and total ester concentrations in both kits and juveniles were reduced in mink fed the 30% carp diet relative to controls. The ratio of retinol to retinyl palmitate in livers of juveniles fed the 30% carp diet was two times higher than that in control mink. Significant reductions in kidney retinol and fatty acyl retinyl esters were observed in kits and juveniles fed the 30% carp diet relative to control values.

Concentrations of perfluorooctanesulfonate (PFOS) and several other perfluoroalkyl surfactants (PASs) were determined in nine major water bodies (n = 51) of New York State (NYS). These PASs were also measured in the livers of two species of sport fish (n = 66) from 20 inland lakes in NYS. Finally, perfluorinated compounds were measured in the livers of 10 species of waterfowl (n = 87) from the Niagara River region in NYS. PFOS, perfluorooctanoic acid (PFOA), and perfluorohexanesulfonate (PFHS) were ubiquitous in NYS waters. PFOA was typically found at higher concentrations than were PFOS and PFHS. Elevated concentrations of PFOS were found in surface waters of Lake Onondaga, and elevated concentrations of PFOA were found in the Hudson River. PFOS was the most abundant perfluorinated compound in all fish and bird samples. PFOS concentrations in the livers of fishes ranged from 9 to 315 ng/g wet weight. PFOS, PFOA, and PFOSA (perfluorooctanesulfonamide) concentrations in smallmouth and largemouth bass (taken together) caught in remote mountain lakes with no known point sources of PAS contamination were 14 to 207, < 1.5 to 6.1, and < 1.5 to 9.8 ng/g wet weight, respectively. PFOS concentrations in the livers of birds ranged from 11 to 882 ng/g wet weight. PFOS concentrations were 2.5-fold greater (p = 0.001) in piscivorous birds than in non-piscivorous birds. However, PFOA, PFOSA, and PFHS were not found in bird livers. Overall, average concentrations of PFOS in fish were 8850-fold greater than those in surface water. An average biomagnification factor of 8.9 was estimated for PFOS in common merganser relative to that in fish. This study highlights the significance of dietary fish in PFOS accumulation in the food chain. Furthermore, our results provide information on the distribution of PASs in natural waters, fish, and several bird species in NYS.

Wastewater treatment plants have recently been identified as a significant pathway for the introduction of perfluoroalkyl surfactants (PASs) to natural waters. In this study, we measured concentrations and fate of several PASs in six wastewater treatment plants (WWTPs) in New York State. We also monitored and measured matrix effects (ionization suppression and enhancement) by postcolumn infusion and standard additions. Concentrations of perfluorooctanoate (PFOA) in effluents of the six WWTPs ranged from 58 to 1050 ng/L. Perfluorooctanesulfonate (PFOS) was also ubiquitous in effluents of these WWTPs, albeit at much lower concentrations (3-68 ng/L). Two of these WWTPs employed identical treatment processes, with similar hydraulic retentions, but differed only in that Plant B treated domestic and commercial waste, whereas Plant A had an additional industrial influence. We found that this industrial influence resulted in significantly greater mass flows of all of the PASs analyzed. Primary treatment was found to have no effect on the mass flows of PASs. Secondary treatment by activated sludge in Plant A significantly increased (p < 0.05) the mass flows of PFOS, PFOA, perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA). However, in Plant B, only the mass flow of PFOA was significantly increased. The observed increase in mass flow of several PASs may have resulted from biodegradation of precursor compounds such as fluorotelomer alcohols, which is supported by significant correlations in the mass flow of PFOA/PFNA and PFDA/PFUnDA. Furthermore, the masses of PFDA and PFUnDA were significantly correlated only after the secondary treatment. In Plant A, concentrations of odd-number PFCAs were greater than those of even-number PFCAs, and concentration decreased with increasing chain length (from C8 to C12). A different pattern was observed in sludge samples, in which the dominance of PFOA decreased, and PFDA and PFUnDA increased, suggesting preferential partitioning of longer-chain PFCAs to sludge.

Occurrence of the polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronapthalene (AHTN), in wastewater influent and effluent, as well as in surface waters, has been reported. HHCB and AHTN were also reported to occur in human and wildlife tissues. The major sources for HHCB and AHTN to wastewater are thought to be consumer products such as shampoos, deodorants, laundry detergents, and household surface cleaners. However, the levels of HHCB and AHTN in consumer products are not known. For evaluation of the sources of human and environmental exposures, characterization of levels of HHCB and AHTN in consumer products is needed. In this study, we measured concentrations of HHCB (Galaxolide), AHTN (Tonalide), and HHCB-lactone (Galaxolidone) from a variety of consumer products, including perfumes, body lotions, and deodorants. Concentrations of HHCB, AHTN, and HHCB-lactone in consumer products ranged from <5 ng/g to over 4000 microg/g, <5 ng/g to 451 microg/g, and <5 ng/g to 217 microg/g, respectively. The highest concentrations were found in perfumes, body creams and lotions, and deodorants. The results suggest that a wide variety of source materials exist for HHCB and AHTN, and that these materials are used on a daily basis.

Fifty white leghorn chicken (Gallus domesticus) eggs per group were injected with 0.1, 1.0, 10.0, or 20.0 microg perfluorooctane sulfonate (PFOS)/g egg before incubation to investigate the effects of PFOS on the developing embryo. Hatchlings were weighed, examined for gross developmental abnormalities, and transferred to a battery brooder, where they were raised for 7 d. Chicks were then weighed, and 20 birds per treatment were randomly chosen for necropsy. The brain, heart, kidneys, and liver were removed and weighed. Livers were processed further for determination of PFOS concentrations and histological assessment. Hatchability was reduced significantly in all treatment groups in a dose-dependent manner. The calculated median lethal dose was 4.9 microg PFOS/g egg. Perfluorooctane sulfonate did not affect posthatch body or organ weights. Exposure to PFOS caused pathological changes in the liver characterized by bile duct hyperplasia, periportal inflammation, and hepatic cell necrosis at doses as low as 1.0 microg PFOS/g egg. Perfluorooctane sulfonate concentrations in the liver increased in a dose-dependent manner. Based on reduced hatchability, the lowest-observed-adverse-effect level was 0.1 microg PFOS/g egg.

Perfluorinated compounds (PFCs) have been measured in blood of humans and wildlife and are considered globally distributed contaminants. We examined 12 PFCs in the plasma of 73 loggerhead sea turtles (Caretta caretta) and 6 Kemp's ridley sea turtles (Lepidochelys kempii) captured from inshore waters of Core Sound, North Carolina (NC), and offshore waters of South Carolina, Georgia, and Florida (SC-FL). Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the dominant compounds, with respective mean concentrations of 11.0 ng/mL and 3.20 ng/mL for loggerhead turtles and 39.4 ng/mL and 3.57 ng/mL for Kemp's ridley turtles. Mean PFOS concentrations were 2- to 12-fold higher than typical mean sigmaPCB concentrations (approximately 5 ng/g wet mass) measured previously in sea turtle blood. More than 79% of the samples had detectable levels of perfluorocarboxylates (PFCAs) with 8-12 carbons, whereas only 17% or less of samples had detectable levels of PFCAs with 6 or 7 carbons. No samples had detectable levels of PFCAs with 4 or 5 carbons. In loggerhead turtles, sigmaPFC concentrations were not influenced by sex (p > 0.05), but were higher in turtles captured from inshore waters of NC than in turtles from offshore waters of SC-FL (p = 0.009). A backward stepwise multiple regression model showed that sigmaPFC concentrations were (1) significantly higher in Kemp's ridley turtles than loggerhead turtles (p < 0.0001), (2) higher in larger turtles (p = 0.018; carapace length used as a proxy for age), and (3) higher in turtles captured toward the north (p = 0.006). These findings suggest that bioaccumulation of PFCs in sea turtles is influenced by species, age, and habitat.

The existence of two subpopulations of polar bears in Alaska, the Beaufort Sea and the Chukchi Sea populations, has been documented. In this study, differences in concentrations and profiles of organochlorine pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and perfluorinated acids were examined in livers of polar bears from the two subpopulations in Alaska. Concentrations of most of the organohalogens analyzed were greater in the Beaufort Sea subpopulation than in the Chukchi Sea subpopulation, except for HCHs and perfluorononanoic acid (PFNA), which were high in samples from the Chukchi Sea subpopulation. Concentrations of chlordanes, PCBs, and perfluorooctanesulfonate (PFOS) were significantly different between the two subpopulations. Chlordane was the predominant contaminant in the Beaufort Sea population, and PFOS was the major contaminant in the Chukchi Sea population. Polar bears from the Beaufort Sea showed significantly higher proportions of more highly chlorinated PCBs than those from the Chukchi Sea. Concentrations of several perfluorinated acids were significantly correlated. Overall, the concentrations and profiles of organohalogens analyzed in the two subpopulations of polar bears suggest differences in the sources of exposures between the two regions of Alaska.

Fluorotelomer alcohols and fluorotelomer acids have been proposed as a source of the perfluorinated carboxylic acids found in remote marine locations. To examine the sources and fate of perfluorinated acids in the environment, a method to determine a wide range of poly- and perfluorinated acids in environmental and biological matrices is needed. In this study, a method has been developed to measure a suite of neutral and acidic fluorochemicals including, fluorotelomer alcohols, fluorotelomer acids, and short- and long-chain perfluorinated acids, in water and biological samples. The method involves solid-phase extraction with weak anion exchange (WAX) cartridges, followed by sequential elution with sodium acetate buffer, methanol, and 0.1% NH4OH in methanol. For biological samples, prior to solid-phase extraction, tissues are digested in 0.5N potassium hydroxide/methanol, diluted in water, and passed through the WAX cartridge. Neutral compounds and telomer alcohols are separated from other poly- and perfluorinated acids. The method is robust (i.e., capable of measuring neutral and acidic compounds), and can be applied for the analysis of a range of poly- and perfluorinated acids, including telomer alcohols, telomer acids, perfluoroalkylcarboxylates, and perfluoroalkylsulfonates in water and biota. With the use of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), a method detection limit in the range of several tens to hundreds of parts-per-quadrillion (pg/L) in water and at a few tens to hundreds of parts-per-trillion (pg/g) levels in biological matrices can be achieved.

Nine species of marine fish, including teleost fishes, sharks, and stingrays, and two species of marine mammals (dolphins) collected from Florida coastal waters were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) to evaluate biomagnification factors (BMF) of these contaminants in a coastal foodweb. In addition, bottlenose dolphins and bull sharks collected from the Florida coast during the 1990s and the 2000s were analyzed for evaluation of temporal trends in PBDE and PCB levels in coastal ecosystems. Mean concentrations of PBDEs in muscle tissues of teleost fishes ranged from 8.0 ng/g, lipid wt (in silver perch), to 88 ng/g, lipid wt (in hardhead catfish), with an overall mean concentration of 43 +/- 30 ng/g, lipid wt. Mean concentrations of PBDEs in muscle of sharks ranged from 37.8 ng/g, lipid wt, in spiny dogfish to 1630 ng/g, lipid wt, in bull sharks. Mean concentrations of PBDEs in the blubber of bottlenose dolphins and striped dolphins were 1190 +/- 1580 and 660 ng/g, lipid wt, respectively. Tetra-BDE 47 (2,2',4,4'-) was the major congener detected in teleost fishes and dolphin samples, followed by BDE-99, BDE-153, BDE-100, and BDE-154. In contrast, BDE-209 was the most abundant congener in sharks. Concentrations of PBDEs and PCBs in dolphins and sharks were 1-2 orders of magnitude greater than those in lower trophic-level fish species, indicating biomagnification of both of these contaminants in the marine foodweb. Based on the analysis of sharks and dolphins collected over a 10-year period, an exponential increase in the concentrations of PBDEs and PCBs has occurred in these marine predators. The doubling time of PBDE and PCB concentrations was estimated to be 2-3 years for bull sharks and 3-4 years for bottlenose dolphin.

Polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), are used as fragrance ingredients in numerous consumer products such as cleaning agents and personal care products. Studies have reported the widespread occurrence of these musks in surface waters and fish from western European countries. Nevertheless, little is known about their accumulation in humans and wildlife in the United States. In this study, we measured concentrations of HHCB and AHTN in human adipose fat collected from New York City. Furthermore, tissues from marine mammals, water birds, and fish collected from US waters were analyzed to determine the concentrations of HHCB and AHTN. Concentrations of HHCB and AHTN in human adipose fat samples ranged from 12 to 798 and from <5 to 134 ng/g, on a lipid weight basis, respectively. A significant correlation existed between the concentrations of HHCB and AHTN in human adipose fat. Concentrations of HHCB and AHTN were not positively correlated with age or gender of the donors. HHCB was found in tissues of several wildlife species, but not in the livers of polar bear from the Alaskan Arctic. Among wildlife species analyzed, spinner and bottlenose dolphins collected from Florida coastal waters contained measurable concentrations of HHCB.