Faculty Bibliography

Siloxanes are used in a wide variety of personal-care and other consumer products. Although there is clearly a potential for contamination of indoor dust with siloxanes, reports of occurrence of siloxanes in indoor dust were not available, prior to the present study. Here, we have determined the concentrations and profiles of four cyclic siloxanes, octamethylcyclotetrasiloxane (D(4)), decamethylcyclopentasiloxane (D(5)), dodecamethylcyclohexasiloxane (D(6)), and tetradecamethylcycloheptasiloxane (D(7)), as well as 11 linear siloxanes, from L(4)-L(14), in 100 dust samples collected in China. Cyclic and linear siloxanes were found in all dust samples, with the linear siloxanes L(9)-L(14) being the predominant compounds. Concentrations of total siloxanes in dust ranged from 21.5 to 21,000 (mean: 1540 +/- 2850) ng g(-1). The highest concentration of the individual linear siloxanes, L(9)-L(14), ranged between 2680 and 6170 ng g(-1). Concentrations of total linear siloxanes (TLS) were 1-2 orders of magnitude higher than concentrations of total cyclic siloxanes (TCS), in all indoor dust samples. Siloxane concentrations in dust were associated with the number of electrical/electronic appliances, number of occupants, and smokers living in the house. Based on the measured siloxane concentrations and on estimated daily ingestion rates of dust by toddlers and adults, we calculated the daily intake of siloxanes. For adults, daily exposure to total siloxanes, based on an average dust intake rate and median exposure concentration, was calculated to be 15.9 ng day(-1); the corresponding value for toddlers was 32.8 ng d(-1).

An extraction, separation, and purification method was developed for the identification and quantification of total bromine (TBr), extractable organobromine (EOBr), and five classes of identified EOBrs. Instrumental neutron activation analysis (INAA) was utilized to quantify EOBr and TBr. The method was then applied to liver samples of tuna, albatross, and polar bear collected from remote marine locations. Polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), bromophenols (BRPs), hydroxylated (OH-) and methoxylated (MeO-) PBDEs were analyzed as identified EOBr. The majority of the bromine in these marine organisms was nonextractable or inorganic, with EOBr accounting for 10-28% of the TBr. Of the identified EOBr, in tuna and albatross, naturally occurring compounds, including MeO-PBDEs, OH-PBDEs, and BPRs, were prevalent. However, the identifiable EOBr in polar bears consisted primarily of synthetic compounds, including PBDEs and PBBs. Overall, 0.08-0.11% and 0.008-0.012% of EOBr and TBr, respectively, were identified. The proportion of EOBr that was identified in marine organisms was relatively small compared to the proportions for organofluorine and organochlorine compounds. This could be related to the great diversity of naturally occurring organobromine compounds in the environment. Naturally occurring brominated fatty acids were estimated to be the predominant compounds in the EOBr fraction.

A rapid and reliable analytical method, based on ion-pair extraction, clean-up on Envicarb cartridge and detection by liquid chromatography-tandem mass spectrometry (LC-MS/MS), was developed for determination of 17 per- and polyfluorinated chemicals (PFCs) in digested sewage sludge. Envicarb cartridge and six labeled internal standards were selected for the elimination/reduction and correction of matrix effects, respectively. As a result, the matrix effect for perfluorooctane sulfonamides (FOSAs) and perfluorocarboxylic acids (PFCAs) with carbon chain length from C6 to C14 was lowered to a range of -14% to +28%. However, the matrix effect for other analytes was still great mainly due to the absence of appropriate internal standard. Mean recoveries of the target analytes based on matrix spikes, at different spike levels (10-300ng/g), ranged from 70% to 169%. Relative standard deviations (RSDs) were in the range of 2-20% at different spike levels. The limit of quantification (LOQ) ranged between 0.6 and 30ng/g. The method was successfully applied to several sewage sludge samples from wastewater treatment plants nearby Zürich, Switzerland. In addition, by comparing the accuracy and precision of ion-pair extraction method and methanol extraction method, we further demonstrated that the ion-pair extraction method can be used for the analysis of PFCs in sludge samples. To our knowledge, this is the first study to extract the PFCs in sewage sludge with ion-pair method and to find unsaturated fluorotelomer carboxylic acids (FTUCAs) in sewage sludge.

Information on the occurrence and distribution of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in marine mammals from Korean coastal waters is not available to date. This is the first study to investigate concentrations and accumulation of PCBs, OCPs, and PBDEs in liver and blubber of minke whales and common dolphins from Korean coastal waters. The concentrations of organochlorines and PBDEs in blubber were several times higher than in liver. The concentrations of PCBs and OCPs were generally low, but the concentrations of PBDEs were similar to those reported for cetaceans elsewhere. The accumulation profiles of OCPs differed between liver and blubber, while the profiles of PCBs and PBDEs were relatively similar in both tissues. The concentrations of PCBs, DDTs, CHLs and PBDEs in common dolphins were significantly higher than those in minke whales, while there were no inter-species differences for HCHs and HCB. The predominant OCP, PCB and PBDE congeners in cetaceans were p,p'-DDE, PCB 153 and BDE 47, respectively. The concentrations of PCBs and DDTs in Korean cetaceans were close to the threshold for adverse health effects.

Perchlorate can competitively inhibit iodide uptake by the thyroid gland (TG) via the sodium/iodide symporter, consequently reducing the production of thyroid hormones (THs). Until recently, the effects of perchlorate on TH homeostasis are being examined through measurement of serum levels of TH, by immunoassay (IA)-based methods. IA methods are fast, but for TH analysis, they are compromised by the lack of adequate specificity. Therefore, selective and sensitive methods for the analysis of THs in TG are needed, for assessment of the effects of perchlorate on TH homeostasis. In this study, we developed a method for the analysis of six THs: L-thyroxine (T(4)), 3,3',5-triiodo-L-thyronine (T(3)), 3,3',5'-triiodo-L-thyronine (rT(3)), 3,5-diiodo-L-thyronine (3,5-T(2)), 3,3'-diiodo-L-thyronine (3,3'-T(2)), and 3-iodo-L-thyronine (3-T(1)) in TG, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). TGs used in this study were from rats that had been placed on either iodide-deficient diet or iodide-sufficient diet, and that had either been provided with perchlorate in drinking water (10 mg/kg/day) or control water. TGs were extracted by pronase digestion and then analyzed by LC-MS/MS. The instrumental calibration range for each TH ranged from 1 to 200 ng/ml and showed a high linearity (r>0.99). The method quantification limits (LOQs) were determined to be 0.25 ng/mg TG for 3-T(1); 0.33 ng/mg TG for 3,3'- and 3,5-T(2); and 0.52 ng/mg TG for rT(3), T(3), and T(4). Rats were placed on an iodide-deficient or -sufficient diet for 2.5 months, and for the last 2 weeks of that period were provided either perchlorate (10 mg/kg/day) in drinking water or control water. Iodide deficiency and perchlorate administration both reduced TG stores of rT(3), T(3), and T(4). In iodide-deficient rats, perchlorate exacerbated the reduction in levels of THs in TG. With the advances in analytical methodology, the use of LC-MS/MS for measurement of hormone levels in TG will allow more comprehensive evaluations of the hypothalamic-pituitary-thyroid axis.

Blood plasma samples (n = 43) collected retrospectively from New York State employees and National Guard personnel who had been assigned to work in the vicinity of the World Trade Center (WTC) during the week after the collapse of the buildings were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs). On the basis of algorithms developed to rank individual exposures to dust and debris and to smoke, we categorized the samples as: more smoke exposure (MSE), more dust exposure (MDE), less smoke exposure (LSE), and less dust exposure (LDE). Mean concentrations of PCDDs were 1070, 223, 3690, and 732 pg/g lipid wt, and mean concentrations of PCDFs were 910, 1520, 230, and 117 pg/g lipid wt, for the MSE, MDE, LSE, and LDE groups, respectively. The concentrations of PCDFs were higher in the two "more exposure" groups than in the two "less exposure" groups. Calculated TEQ concentrations of coplanar PCBs and PCDD/Fs in plasma samples were, on average, 1.12 and 41.2 pg WHO-TEQ/g lipid wt, respectively. TEQ concentrations of PCDFs were higher than those of PCDDs in both "more exposure" groups but lower than those of PCDDs in "less exposure" groups. This result is suggestive of exposure of the WTC responders to PCDFs after the WTC collapse. PCDFs contributed the majority of TEQs and are therefore the critical dioxin-like compounds in MSE/MDE groups, whereas PCDDs are the critical compounds in the LSE/LDE groups.

Dioxins and related compounds (DRCs) and perfluorinated compounds were measured in the livers of pigs (Sus scrofa) collected from an open waste dumping site in South India. Hepatic concentrations of DRCs and perfluorooctanesulfonate (PFOS; up to 200 ng/g wet wt) were significantly higher in male and female pigs, respectively, collected from the dumping site than in those from a reference site. Results suggest that dumping sites are a source of DRCs and PFOS. Hepatic concentrations of DRCs in piglets were higher than in mothers, especially for the congeners with molecular weights in the range of 360 to 400, implying congener-specific maternal transfer of DRCs in swine. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans and some non-ortho dioxin-like polychlorinated biphenyls (PCBs) in the liver of pigs were higher than those in the adipose fat and muscle of the same specimens. In addition, the liver-to-adipose concentration ratios for each congener had a significant positive correlation with the levels of hepatic cytochrome P450 (CYP)1A-like protein, suggesting congener-specific and CYP1A-dependent hepatic sequestration of DRCs in the swine. Total hepatic 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs; 8.9-350 pg/g fat wt) had a significant positive correlation with CYP1A-like protein expression (r=0.56, p=0.012), suggesting the induction of CYP1A by DRCs. However, the total TEQs had a significant negative correlation with CYP4A-like protein (r=-0.49, p=0.029), suggesting repression of peroxisome proliferator-activated receptor-alpha (PPARalpha)-mediated signaling pathway by DRCs. Decreases in plasma total thyroxine (T4), free T4, and immunoglobulin (Ig) G were also found in pigs from the dumping site compared with those from the reference site. This study provides insight into the toxicological impacts of DRCs and perfluorinated compounds in wild animals from open waste dumping sites.

White-nose syndrome (WNS) is a condition associated with white fungal growth on ears, wings, and nose of hibernating bats; this condition has recently resulted in high bat mortality in the northeastern United States. Nevertheless, the pathogenesis of morbidity and mortality are still unknown. Elevated exposure to toxic contaminants could be a contributing factor via the consequent immunosuppression and endocrine disruption. In this study, diseased little brown bats (Myotis lucifugus) were collected from several hibernacula in eastern New York State in 2008. Fat tissues of bats were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), and organochlorine pesticides (OCPs; DDT, chlordanes, HCB, and HCH), and liver was analyzed for perfluorinated compounds (PFCs). A reference population of little brown bats, not affected by WNS, was also collected from a cave in Kentucky for the analysis of trace organic contaminants. Concentration of PCBs in fat tissues of bats from New York ranged from 1900 ng g(-1) to 35000 ng g(-1), lipid wt, with the highest concentrations found in bats collected from caves in Albany County. High concentrations of PCBs were also found in bats from Kentucky (17100-18400 ng g(-1), lipid wt). Total PBDE concentrations in fat tissues ranged from 520 ng g(-1) to 10900 ng g(-1), lipid wt, in bats from New York and from 4300 ng g(-1) to 13000 ng g(-1), lipid wt, in bats from Kentucky. High concentrations of DDT (26900 ng g(-1), lipid wt), chlordanes (6350 ng g(-1), lipid wt), and HCB (260 ng g(-1), lipid wt) were found in bats from New York. Concentrations of hexabromobiphenyl congener 153 (PBB 153) in bats from New York ranged from 8.6ngg(-1) to 124000 ng g(-1), lipid wt. Concentrations of PFCs were on the order of a few tens to a few hundreds of nanograms per gram liver, on a wet weight basis. Overall, high concentrations of PCBs, PBDEs, DDT, and chlordanes were found in fat tissues of diseased bats from New York, although the concentrations in bats from non-diseased, reference population, from Kentucky were also high.

This is the first study to report the concentrations and accumulation profiles of PFCs in marine mammals from Korea. The concentrations and profiles of 10 PFCs in the liver of minke whales and common dolphins from Korean coastal waters were recorded in this study. The mean concentrations of PFOS and PFUnDA were 3-20 times higher than that found for other PFCs analyzed. The concentrations of PFOS in cetaceans from Korea were relatively lower than those reported in other countries. Inter-species differences in the concentrations of PFOS, PFOSA and PFNA were found between two cetacean species, while no difference was observed in the concentrations of PFDA, PFUnDA and PFDoDA between the species. The dominant PFC compounds found in cetaceans were PFUnDA and PFOS, accounting for 70-80% of the PFCs. The accumulation profiles and correlation analysis indicated that two cetacean species have different exposure routes and metabolic capacity for PFCs.

Developmental effects of polybrominated diphenyl ethers (PBDEs) have been suspected due to their structural similarities to polychlorinated biphenyls (PCBs). This study evaluated neurobehavioral, hormonal, and reproductive effects in rat offspring perinatally exposed to a widely used pentabrominated commercial mixture, DE-71. Pregnant Long-Evans rats were exposed to 0, 1.7, 10.2, or 30.6 mg/kg/day DE-71 in corn oil by oral gavage from gestational day 6 to weaning. DE-71 did not alter maternal or male offspring body weights. However, female offspring were smaller compared with controls from postnatal days (PNDs) 35-60. Although several neurobehavioral endpoints were assessed, the only statistically significant behavioral finding was a dose-by-age interaction in the number of rears in an open-field test. Developmental exposure to DE-71 caused severe hypothyroxinemia in the dams and early postnatal offspring. DE-71 also affected anogenital distance and preputial separation in male pups. Body weight gain over time, reproductive tissue weights, and serum testosterone concentrations at PND 60 were not altered. Mammary gland development of female offspring was significantly affected at PND 21. Congener-specific analysis of PBDEs indicated accumulation in all tissues examined. Highest PBDE concentrations were found in fat including milk, whereas blood had the lowest concentrations on a wet weight basis. PBDE concentrations were comparable among various brain regions. Thus, perinatal exposure to DE-71 leads to accumulation of PBDE congeners in various tissues crossing blood-placenta and blood-brain barriers, causing subtle changes in some parameters of neurobehavior and dramatic changes in circulating thyroid hormone levels, as well as changes in both male and female reproductive endpoints. Some of these effects are similar to those seen with PCBs, and the persistence of these changes requires further investigation.