Faculty Bibliography

Perfluorinated chemicals (PFCs) have emerged as global environmental contaminants. Studies have reported the widespread occurrence of PFCs in biota from marine coastal waters and in remote polar regions. However, few studies have reported the distribution of PFCs in biota from offshore waters and open oceans. In this study, concentrations of nine PFCs were determined in the livers of 60 skipjack tuna (Katsuwonus pelamis) collected from offshore waters and the open ocean along the Pacific Rim, including the Sea of Japan, the East China Sea, the Indian Ocean, and the Western North Pacific Ocean, during 1997-1999. At least one of the nine PFCs was found in every tuna sample analyzed. Overall, perfluorooctanesulfonate (PFOS) and perfluoroundecanoic acid (PFUnDA) were the predominant compounds found in livers of tuna at concentrations of <1-58.9 and <1-31.6 ng/g, wet wt, respectively. Long-chain perfluorocarboxylates such as perfluorodecanoic acid (PFDA) and perfluorododecanoic acid (PFDoDA) were common in the tuna livers. In livers of tuna from several offshore and open-ocean locations, concentrations of PFUnDA were greater than the concentrations of PFOS. The profiles and concentrations of PFCs in tuna livers suggest that the sources in East Asia are dominated by long-chain perfluorocarboxylates, especially PFUnDA. High concentrations of PFUnDA in tuna may indicate a shift in sources of PFCs in East Asia. The spatial distribution of PFOS in skipjack tuna reflected the concentrations previously reported in seawater samples from the Pacific and Indian Oceans, suggesting that tuna are good bioindicators of pollution by PFOS. Despite its predominance in ocean waters, PFOA was rarely found in tuna livers, indicative of the low bioaccumulation potential of this compound. Our study establishes baseline concentrations of PFCs in skipjack tuna from the oceans of the Asia-Pacific region, enabling future temporal trend studies of PFCs in oceans.

Air samples from automobile cabins were collected and analyzed for polybrominated diphenyl ethers (PBDEs), polybrominated dibenzofurans (PBDFs), and polybrominated dibenzo-p-dioxins (PBDDs). The concentration of total PBDEs (sigmaPBDE; sum of 19 congeners) varied from 0.4 to 2644 pg m(-3), with a median of 201 pg m(-3), while BDE 47, 99, and 209 collectively accounted for 70 +/- 30% of sigmaPBDE concentrations. Multiple linear regression analysis revealed that sigmaPBDE concentration was significantly influenced by vehicle's age and interior temperature. More specifically, sigmaPBDE decreased over time and increased with the rise of temperature. The daily inhalation intake of PBDEs during commuting was estimated to range from 0.5 to 2909 pg day(-1) (median 221 pg day(-1)) and contributed 29% of the overall daily exposure to PBDEs via inhalation. When excluding BDE 209, a lower contribution was calculated for this source (18%), but this was still comparable with residential exposure (22%). The levels of PBDD/Fs were generally below the limits of detection and only in one case were hepta-BDFs positively detected at a concentration of 61 pg m(-3). This study demonstrates that car interiors, especially when new, contain high levels of airborne PBDEs and represent a potential route of human exposure via inhalation.

Concentrations of perfluoroalkyl acids (PFAs) were measured in egg yolks of three species of birds, the little egret (Egretta garzetta), little ringed plover (Charadrius dubius), and parrot bill (Paradoxornis webbiana), collected in and around Lake Shihwa, Korea, which receives wastewaters from an adjacent industrial complex. Mean concentrations of perfluorooctanesulfonate (PFOS) ranged from 185 to 314 ng/g ww and were similar to those reported for bird eggs from other urban areas. Long-chain perfluorocarboxylic acids (PFCAs) were also found in egg yolks often at great concentrations. Mean concentrations of perfluoroundecanoic acid (PFUnA) ranged from 95 to 201 ng/g ww. Perfluorooctanoic acid was detected in 32 of 44 egg samples, but concentrations were 100-fold less than those of PFOS. Relative concentrations of PFAs in all three species were similar with the predominance of PFOS (45-50%). There was a statistically significant correlation between PFUnA and perfluorodecanoic acid in egg yolks (p < 0.05), suggesting a common source of PFCAs. Using measured egg concentrations and diet concentrations, the ecological risk of the PFOS and PFA mixture to birds in Lake Shihwa was evaluated using two different approaches. Estimated hazard quotients were similar between the two approaches. The concentration of PFOS associated with 90th centile in bird eggs was 100-fold less than the lowest observable adverse effect level determined for birds, and those concentrations were 4-fold less than the suggested toxicity reference values. On the basis of limited toxicological data, current concentrations of PFOS are less than what would be expected to have an adverse effect on birds in the Lake Shihwa region.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota, and humans. PFOS and PFOA have been detected in water in Japan. Nevertheless, occurrence of PFOS and PFOA in potable water from municipal water treatment plants is not clearly known. We analyzed PFOS and PFOA in raw and tap water samples collected from 14 drinking water treatment plants in winter and summer seasons in Osaka to determine the concentrations of PFOS and PFOA in raw and potable tap water samples. PFOS and PFOA were detected in all raw water samples. Concentration ranges of PFOS and PFOA in raw water were 0.26-22 ng/l and 5.2-92 ng/l, respectively. Whereas the concentrations PFOS in raw water from Osaka were similar to those in other areas in Japan, the concentrations of PFOA were higher than in other areas. Concentration ranges of PFOS and PFOA in potable tap water were 0.16-22 ng/l and 2.3-84 ng/l, respectively. There were positive correlations between PFC concentrations in raw water and tap water samples. Therefore, the removal efficiency of PFCs by the present water treatment may be low. Based on the current action value reported by U.S. Environmental Protection Agency, PFOA concentrations found in tap water in Osaka is not expected to pose health risks.

Temporal biomonitoring studies can assess changes in population exposures to contaminants, but collection of biological specimens with adequate representation and sufficient temporal resolution can be resource-intensive. Newborn Screening Programs (NSPs) collect blood as dried spots on filter paper from nearly all infants born in the United States (U.S.). In this study, we investigated the use of NSP blood spots for temporal biomonitoring by analyzing perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (PFOSA), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in 110 New York State (NYS) NSP blood spot composite specimens collected between 1997 and 2007, representing a total of 2640 infants. All analytes were detected in > or =90% of the specimens. Concentrations of PFOS, PFOSA, PFHxS, and PFOA exhibited significant exponential declines after the year 2000, coinciding with the phase-out in PFOS production in the U.S. Calculated disappearance half-lives for PFOS, PFHxS, and PFOA (4.4, 8.2, and 4.1 years, respectively) were similar to biological half-lives reported for retired fluorochemical workers. Our results suggest sharp decreases in perinatal exposure of NYS infants to PFOS, PFOSA, PFHxS, and PFOA and demonstrate, for the first time, the utility of NSP blood spots for assessment of temporal trends in exposure.

A method has been developed to measure 29 perfluorinated acids (PFAs) including short-chain perfluorocarboxylates (PFCAs) such as trifluoroacetic acid (TFA; C2) and long-chain PFCAs, perfluoroalkylsulfonates, fluorotelomer acids, and two perfluorooctylsulfonamides in water matrices. The method involves solid phase extraction (SPE) using a weak anion-exchange (WAX) cartridge, an ion-exchange high-performance liquid chromatography (HPLC) column separation, and tandem mass spectrometry (MS/MS) detection. To our knowledge, this is the first HPLC-MS/MS method to determine TFA in water at sub-ng L(-1) concentrations. The method is selective, simple, and robust, capable of measuring 29 PFAs in a single analysis, with overall recoveries of the target analytes ranging from 75% to 132%. The method was applied to the analysis of rainwater samples collected from two cities in Japan. TFA and several short-chain PFAs were the major compounds found in rainwater.

Despite known historical release of polybrominated biphenyls (PBBs; brominated flame retardants) into the Pine River (St. Louis, MI, USA), a tributary of the Tittabawassee River which subsequently forms the Saginaw River and flows into Saginaw Bay-Lake Huron, little is known about spatial patterns of sediment contamination by PBBs in this watershed. In this study, concentrations of two groups of brominated flame retardants, polybrominated diphenyl ethers (summation PBDE; BDE-28, -47, -66, -100, -99, -85, -154, -153, -138, and -209) and PBBs were measured in more than 120 floodplain soil samples, surface sediment samples, and sediment cores collected in 2004 from the Shiawassee River, the Saginaw River, and Saginaw Bay, Michigan. In addition, sediment samples collected in 2002 from the Pine River and the Tittabawassee River were analyzed, to elucidate riverine transport and attenuation of PBBs and PBDEs in this watershed. The mean concentration of summation PBDE decreased from upstream to downstream, from the Shiawassee River and the Tittabawassee River to Saginaw Bay. BDE-209 was the predominant congener, accounting for 79% of the total PBDE concentration in the Shiawassee River and 90% in the Saginaw River. BDE-209 was followed, in order of decreasing abundance, by BDE-47, -99, and -100. The proportions of BDE congeners varied by water body, and by sample type, whether floodplain soil or sediment. High summation PBDE concentrations were found in floodplain soil collected from the Shiawassee River near Chase Lake (55 ng/g, dry weight) and in sediment from the Saginaw River near Middleground Island (49 ng/g, dry weight). There was a significant positive correlation between summation (9)PBDE (tri- to hexa-BDE) and BDE-209 in samples collected from the Shiawassee River and Saginaw Bay, but not in samples from the Saginaw River. Among PBBs, bromobiphenyl congener 153 (BB-153) was found in sediments from the Saginaw River but not in sediments from the Shiawassee River. An elevated concentration of BB-153 (13.5 ng/g, dry weight) was found in floodplain soil collected from the Pine River. The BB-153 concentration in sediment decreased by two to three orders of magnitude, from the Pine River downstream to Saginaw Bay. An elevated concentration of BB-153 (4.7 ng/g) was found in sediment collected from the mouth of the Saginaw River. Surface sediments collected near the mouth of the Saginaw River contained higher concentrations of both PBDEs and PBBs than did the subsurface sediments at these locations.

The collapse of the World Trade Center (WTC) on September 11, 2001 resulted in the release of several airborne pollutants in and around the site. Perfluorochemicals including perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), which are used in soil- and stain-resistant coatings on upholstery, carpets, leather, floor waxes, polishes, and in fire-fighting foams were potentially released during the collapse of the WTC. In this pilot study, we analyzed 458 plasma samples of New York State (NYS) employees and National Guard personnel assigned to work in the vicinity of the WTC between September 11 and December 23, 2001, to assess exposure to perfluorochemicals released in dust and smoke. The plasma samples collected from NYS WTC responders were grouped based on estimated levels of exposure to dust and smoke, as follows: more dust exposure (MDE), less dust exposure (LDE), more smoke exposure (MSE), and less smoke exposure (LSE). Furthermore, samples were grouped, based on self-reported symptoms at the time of sampling, as symptomatic and asymptomatic. Eight perfluorochemicals were measured in 458 plasma samples. PFOS, PFOA, perfluorohexanesulfonate (PFHxS), and perfluorononanoic acid (PFNA), were consistently detected in almost all samples. PFOA and PFHxS concentrations were approximately 2-fold higher in WTC responders than the concentrations reported for the U.S. general population. No significant difference was observed in the concentrations of perfluorochemicals between symptomatic and asymptomatic groups. Concentrations of PFHxS were significantly (p < or = 0.05) higher in the MDE group than in the LDE group. Concentrations of PFNA were significantly higher in the MSE group than in the LSE group. Significantly higher concentrations of PFOA and PFHxS were found in individuals exposed to smoke than in individuals exposed to dust. A significant negative correlation existed between plasma lipid content and concentrations of certain perfluorochemicals. Our initial findings suggest that WTC responders were exposed to perfluorochemicals, especially PFOA, PFNA, and PFHxS, through inhalation of dust and smoke released during and after the collapse of the WTC. The potential health implications of these results are unknown at this time. Expansion of testing to include all archived samples will be critical to help confirm these findings. In doing so, it may be possible to identify biological markers of WTC exposure and to improve our understanding of the health impacts of these compounds.

Perfluorinated compounds (PFCs), notably perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), have been reported in human blood. Furthermore, the occurrence of PFCs in the blood of newborn babies, coupled with the need to study the potential association of PFC exposure with birth outcomes in neonates, suggests the need for determining the sources and magnitude of exposure in infants. In this study, nine PFCs were measured in 45 human breast milk samples collected in 2004 from Massachusetts, U.S.A. PFOS and PFOA were the predominant PFCs found at mean concentrations of 131 and 43.8 pg/mL, respectively. Comparison of the ratio of PFOS to PFOA in human milk with the ratios published for human serum from the U.S. female population suggested preferential partitioning of PFOA to milk. Concentrations of PFOA were significantly higher in the milk of mothers nursing for the first time (n = 34) than in the milk of mothers who have previously nursed (n = 8). Based on the estimated body weight and milk intake, the average and highest daily intakes of total PFCs by infants were 23.5 and 87.1 ng/kg bw, respectively. We found that the daily ingestion rates of PFOS and PFOA did not exceed the tolerable daily intake recommended by the U.K. Food Standards Agency. This is the first study to measure the occurrence of PFCs in human milk from the U.S.A.

To investigate the biological effects of perfluorochemicals (PFCs) and to identify biomarkers of exposure to PFCs, this study focused on the effects mediated by peroxisome proliferator-activated receptor alpha (PPARalpha) in Baikal seals (Pusa sibirica). We cloned a full-length cDNA, encoding PPARalpha from the liver of Baikal seal, which has a deduced open reading frame of 468-amino acid residues with a predicted molecular mass of 52.2 kDa. Comparison of the amino-acid sequence of Baikal seal PPARalpha with that of other mammalian PPARalpha showed considerable similarities with PPARalpha of dog (97%), human (95%), rat (92%), and mouse (91%). The quantitative real-time RT-PCR analyses of tissues from Baikal seals revealed that PPARalpha mRNAs were primarily expressed in the liver, kidney, heart, and muscle. The hepatic expression levels of PPARalpha mRNA showed a positive correlation with the expression levels of immunochemically detected cytochrome P450 (CYP) 4A-like protein, indicating that the PPARalpha-CYP4A signaling pathway in Baikal seal is likely conserved. This study also developed an in vitro PPARalpha reporter gene assay using African green monkey kidney CV-1 cells transiently transfected with Baikal seal PPARalpha cDNA expression vector and a reporter vector containing a peroxisome proliferator-responsive element The in vitro reporter gene assay displayed significant response to clofibrate, which is a known PPARalpha agonist in humans and rodents. Treatmentwith perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), or perfluorooctane sulfonate (PFOS) induced PPARalpha-mediated transcriptional activity in a dose-dependent manner, showing the lowest-observed-effect concentrations of 62.5, 125, 125, 62.5, and 125 microM, respectively. In the livers of wild Baikal seals, expression levels of PPARalpha mRNA showed a significant positive correlation with PFNA levels. Moreover, expression of hepatic CYP4A-like protein was significantly correlated with the hepatic concentrations of PFNA and PFDA. These results suggest modulation of the PPARalpha-CYP4A signaling pathway by PFCs in the wild Baikal seals. Our study demonstrates that the PPARalpha-mediated response may be a useful biomarkerto evaluate potential biological effects of PFCs in wildlife.