Faculty Bibliography

Organic corrosion inhibitors (OCIs), including ultraviolet light filters, are widely used in plastics, rubbers, colorants, and coatings to increase the performance of products. Derivatives of benzotriazole (BTR), benzothiazole (BTH), and benzophenone (BP) are high-production volume OCIs that have been detected in the environment and human tissues. However, knowledge of their occurrence in indoor environments, as well as human exposure to them, is still lacking. In this study, BTR, BTH, BP and their 12 derivatives were determined in indoor dust for the first time. All three groups of OCIs were found in all 158 indoor dust samples from the U.S. and three East Asian countries (China, Japan, and Korea). The geometric mean (GM) concentration of the sum of six BTRs (GM CΣBTRs) ranged from 20 to 90 ng/g among the four countries studied, with a maximum CΣBTRs of ∼2000 ng/g found in a dust sample from China. Tolyltriazole was the major derivative of BTR measured in dust. GM CΣBTHs in indoor dust from the four countries ranged from 600 to 2000 ng/g. 2-OH-BTH was the predominant BTH in dust from the U.S., Japan, and Korea. GM CΣBPs in dust ranged from 80 to 600 ng/g, with 2-OH-4-MeO-BP and 2,4-2OH-BP, contributing to the majority of ∑BP concentrations. Based on the concentrations of three types of OCIs in indoor dust, human exposure through dust ingestion was calculated. Daily intake of OCIs through dust ingestion was higher for people in the U.S., Japan, and Korea than in China; the residents in urban China are exposed to higher levels of OCIs via dust ingestion than are those in rural China.

Limited information exists on exposure to bisphenol A (BPA) by children, adults, and pregnant women in China. In the present study, we determined BPA concentrations in whole blood collected from 10 children (1-5 years), 40 women (30 pregnant and 10 nonpregnant), and 30 fetuses (i.e., cord blood). Further, to evaluate the relationship between urinary and blood BPA concentrations, paired specimens of blood and urine (n = 50 pairs) were collected from an adult population. BPA was found in 46% of all blood samples analyzed, with a geometric mean (GM) concentration of 0.19 ng/mL. BPA was found in 84% of urine samples from adults, with a GM concentration of 1.01 ng/mL [0.48 μg/g creatinine (Cr)]. Gender and age were not good predictors of blood BPA concentrations. However, we did find that the creatinine-adjusted urinary BPA concentrations in females were significantly higher (p < 0.05) than the concentrations found in males and that the blood BPA concentrations in children were significantly higher (p < 0.05) than the concentrations found in adults. Among all adults, unadjusted urinary BPA concentrations (i.e., volume-based) were inversely (r = -0.312, p < 0.05) correlated with age when an outlier value (8.70 ng/mL) was excluded from analysis. Concentrations of BPA in urine (creatinine-adjusted) and blood were significantly correlated (r = 0.571, p < 0.01), with concentrations measured in urine approximately an order of magnitude higher than the concentrations found in blood. The mean and GM values for ratios of concentration of BPA between blood and urine were 0.109 and 0.057, respectively. The ratio of mean concentrations of BPA between cord blood and maternal blood was 0.108. On the basis of urinary BPA levels, we estimated the total daily intake (EDI) of BPA by Chinese adults. The mean (range) EDIs of BPA by adult males and females in China were 0.041 (<0.005-0.224) and 0.048 (<0.005-0.151) ug/kg bw/day, respectively. The pregnant women who underwent intravenous drug administration immediately before delivery had significantly higher concentrations of BPA in their blood than did those who did not receive intravenous drug administration. This is the first study to document the occurrence of and human exposure to BPA by pregnant women and fetuses from China.

Despite the widespread use of benzotriazoles and benzothiazoles and the occurrence of these compounds in wastewater treatment plants (WWTPs), no earlier study has comprehensively examined their fate in WWTPs. In this study, an integrated liquid chromatography-tandem mass spectrometry (LC-ESI(+)MS/MS) method was developed and validated for simultaneous determination of four benzotriazoles and four benzothiazoles in dissolved and particulate phases of wastewater (raw and treated), and in dewatered sewage sludge. The target benzotriazoles (BTRs) were 1H-benzotriazole, 1-hydroxy-benzotriazole, tolyltriazole, and xylyltriazole (or 5,6-dimethyl-1H-benzotriazole), and the target benzothiazoles (BTHs) were benzothiazole, 2-hydroxy-benzothiazole, 2-methylthio-benzothiazole, and 2-amino-benzothiazole. The limits of detection ranged from 0.08 (2-methylthio-benzothiazole) to 17 ng/L (benzothiazole) for dissolved phase samples, and from 0.04 (2-methylthio-benzothiazole) to 13 ng/g dry weight (dw) (benzothiazole) for particular matter and sludge samples. The method was applied in the analysis of wastewater and sludge samples from the WWTP in Athens, Greece. All target chemicals were detected in wastewater samples, and in some cases the concentrations were significant, on the order of a few μg/L. In sludge samples, benzothiazole and tolyltriazole were present at the highest concentrations (174 and 116 ng/g dw, respectively). For benzotriazole and tolyltriazole, the removal efficiency was below 68%, and for benzothiazoles, the removal efficiency was greater than 64% in the activated sludge treatment process. Both BTRs and BTHs showed low solid-liquid distribution coefficients.

Perfluorinated alkyl substances (PFASs) have been found widely in the environment including remote marine locations. The mode of transport of PFASs to remote marine locations is a subject of considerable scientific interest. Assessment of distribution of PFASs in wet precipitation samples (i.e., rainfall and snow) collected over an area covering continental, coastal, and open ocean will enable an understanding of not only the global transport but also the regional transport of PFASs. Nevertheless, it is imperative to examine the representativeness and suitability of wet precipitation matrixes to allow for drawing conclusions on the transport PFASs. In this study, we collected wet precipitation samples including rainfall, surface snow, and snow core from several locations in Japan to elucidate the suitability of these matrixes for describing local and regional transport of PFASs. Rain water collected at various time intervals within a single rainfall event showed high fluxes of PFASs in the first 1-mm deposition. The scavenging rate of PFASs by wet deposition varied depending on the fluorocarbon chain length of PFAS. The depositional fluxes of PFASs measured for continental (Tsukuba, Japan) and open ocean (Pacific Ocean, 1000km off Japanese coast) locations were similar, on the order of a few nanograms per square meter. The PFAS profiles in "freshly" deposited and "aged" (deposited on the ground for a few days) snow samples taken from the same location varied considerably. The freshly deposited snow represents current atmospheric profiles of PFASs, whereas the aged snow sample reflects sequestration of local sources of PFASs from the atmosphere. Post-depositional modifications in PFAS profiles were evident, suggesting reactions of PFASs on snow/ice surface. Transformation of precursor chemicals such as fluorotelomer alcohols into perfluoroalkylcarboxylates is evident on snow surface. Snow cores have been used to evaluate time trends of PFAS contamination in remote environments. Snow collected at various depths from a core of up to 7.7m deep, at Mt. Tateyama (2450m), Japan, showed the highest concentrations of PFASs in the surface layer and the concentrations decreased with increasing depth for most PFASs, except for perfluorobutanesulfonate (PFBS). Downward movement of highly water soluble PFASs such as PFBS, following melting and freezing cycles of snow, was evident from the analysis of snow core.

Dried blood spots (DBS), collected as part of the newborn screening program (NSP) in the USA, is a valuable resource for studies on environmental chemical exposures and associated health outcomes in newborns. Nevertheless, determination of concentrations of environmental chemicals in DBS requires assays with great sensitivity, as the typical volume of blood available on a DBS with 16-mm diameter disc is approximately 50 μL. In this study, we developed a liquid-liquid extraction and high-performance liquid chromatography/tandem mass spectrometry method for the detection of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and bisphenol A (BPA) in DBS. The method was validated for accuracy, precision, and sensitivity, by spiking of target chemicals at different levels on Whatman 903 filter cards, which is used in the collection of DBS by the NSP. Contamination arising from collection, storage, and handling of DBS is an important issue to be considered in the analysis of trace levels of environmental chemicals in DBS. For the evaluation of the magnitude of background contamination, field blanks were prepared from unspotted portions of DBS filter cards collected by the NSP. The method was applied for the measurement of PFOS, PFOA, and BPA in 192 DBS specimens provided by NSP of New York State. PFOS and PFOA were detected in 100 % of the specimens analyzed. The concentrations of PFOS and PFOA measured in DBS were similar to those reported earlier in the whole blood samples of newborns. BPA was also found in 86 % of the specimens at concentrations ranging from 0.2 to 36 ng/mL (excluding two outliers). Further studies are needed to evaluate the sources of BPA exposures and health outcomes in newborns.

Parabens are esters of p-hydroxybenzoic acid and are widely used as preservatives in cosmetics, pharmaceuticals, foodstuffs, including beverages. Information on the occurrence of parabens in foodstuffs and dietary exposure of humans to these chemicals is not available. In this study, food samples (n = 267) collected from Albany, New York, United States, were grouped into eight categories, namely, beverages, dairy products, fats and oils, fish and shellfish, grains, meat, fruits, and vegetables, and analyzed for five parabens by high-performance liquid chromatography-tandem mass spectrometry. The majority (>90%) of food samples contained measurable concentrations of parabens, and the total concentrations (Σparabens; sum of five parabens) ranged from below the limit of quantitation to 409 ng/g fresh weight (mean: 9.67 ng/g; median: 0.92 ng/g). Methyl-, ethyl-, and propyl-parabens were the predominant compounds, accounting for ∼90% of the total concentrations. Butyl- and benzyl-parabens were less frequently detected. There were no significant differences in paraben concentrations among the eight food categories, including the canned foods. On the basis of the concentrations measured and per capita daily ingestion rates of foods, we estimated the daily intake (EDI; ng/kg of body weight (bw)/day)) of parabens through food ingestion. The EDI values of total parabens (calculated from the mean concentrations measured and the mean daily ingestion rates of food items) were 940, 879, 470, 273, and 307 ng/kg bw/day for infants, toddlers, children, teenagers, and adults, respectively. To our knowledge, this is the first study to report the occurrence of parabens in foodstuffs.

The ISO 25101 (International Organization for Standardization, Geneva) describes a new international standard method for the determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) in unfiltered samples of drinking and surface waters. The method is based on the extraction of target analytes by solid phase extraction, solvent elution, and determination by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). For the determination of the performance of this method, more than 20 laboratories from 9 different countries participated in an inter-laboratory trial in 2006. In addition, inter-laboratory trials were conducted in 2008 and 2009 for the analysis of perfluoroalkylsubstances (PFASs), including PFOS and PFOA, in water samples by following the protocols of Japanese Industrial Standard (JIS). Overall, the repeatability coefficients of variation (i.e., within-laboratory precision) for PFOS and PFOA in all water samples were between 3 and 11%, showing a adequate precision of the ISO and JIS methods. The reproducibility coefficients of variation (i.e., between-laboratory precision) were found to vary within a range of 7-31% for surface water and 20-40% for wastewater. The recoveries of PFOS and PFOA, as a measure of accuracy, varied from 84 to 100% for surface water and from 84 to 100% for wastewater among the samples with acceptable criteria for internal standards recovery. The determined concentrations of PFASs in samples compared well with the "true" values. The results of the inter-laboratory trial confirmed that the analytical methods are robust and reliable and can be used as a standard method for the analysis of target compounds in water samples.

BACKGROUND:Phthalates have been found in many personal care and industrial products, but have not previously been reported in food purchased in the United States. Phthalates are ubiquitous synthetic compounds and therefore difficult to measure in foods containing trace levels. Phthalates have been associated with endocrine disruption and developmental alteration. OBJECTIVES/OBJECTIVE:Our goals were to report concentrations of phthalates in U.S. food for the first time, specifically, nine phthalates in 72 individual food samples purchased in Albany, New York, and to compare these findings with other countries and estimate dietary phthalate intake. METHODS:A convenience sample of commonly consumed foods was purchased from New York supermarkets. Methods were developed to analyze these foods using gas chromatography-mass spectroscopy. Dietary intakes of phthalates were estimated as the product of the food consumption rate and concentration of phthalates in that food. RESULTS:The range of detection frequency of individual phthalates varied from 6% for dicyclohexyl phthalate (DCHP) to 74% for di-2-ethylhexyl phthalate (DEHP). DEHP concentrations were the highest of the phthalates measured in all foods except beef [where di-n-octyl phthalate (DnOP) was the highest phthalate found], with pork having the highest estimated mean concentration of any food group (mean 300 ng/g; maximum, 1,158 ng/g). Estimated mean adult intakes ranged from 0.004 μg/kg/day for dimethyl phthalate (DMP) to 0.673 μg/kg/day for DEHP. CONCLUSIONS:Phthalates are widely present in U.S. foods. While estimated intakes for individual phthalates in this study were more than an order of magnitude lower than U.S. Environmental Protection Agency reference doses, cumulative exposure to phthalates is of concern and a more representative survey of U.S. foods is indicated.

A great blue heron (Ardea herodias) colony on Pig's Eye Island on the Mississippi River near St. Paul, Minnesota, USA, is located near several potential perfluorinated compound (PFC) sources. The PFC concentrations in great blue heron eggs reported from a 1993 collection from the Pig's Eye colony were among the highest measured in bird eggs worldwide. The objective of this investigation was to determine whether PFC concentrations in great blue heron eggs at the Pig's Eye colony have changed since 1993. Total PFC concentrations in great blue heron eggs collected at the Pig's Eye colony in 2010 and 2011 (geometric mean=340 and 492 ng/g wet wt) were 60% lower than the 1993 collection (1,015 ng/g wet wt). Among PFCs, perfluoroalkyl sulfonate concentrations were lower and perfluoroalkyl carboxylate concentrations were higher in the 2010 and 2011 collections. Two of 20 (10%) of the eggs analyzed from Pig's Eye in 2010 and 2011 were >1,000 ng PFCs/g wet weight and the maximum PFC value (2,506 ng PFCs/g wet wt) measured in 2010 and 2011 was among the highest PFC concentration reported in bird eggs. These high concentrations are at levels associated with physiological and neurological effects in birds.

BACKGROUND:Thyroid hormone (TH) is best known for its role in development in animals, and for its control of metabolic heat production (thermogenesis) during cold acclimation in mammals. It is unknown whether the regulatory role of TH in thermogenesis is derived in mammals, or whether TH also mediates thermal responses in earlier vertebrates. Ectothermic vertebrates show complex responses to temperature variation, but the mechanisms mediating these are poorly understood. The molecular mechanisms underpinning TH action are very similar across vertebrates, suggesting that TH may also regulate thermal responses in ectotherms. We therefore aimed to determine whether TH regulates thermal acclimation in the zebrafish (Danio rerio). We induced hypothyroidism, followed by supplementation with 3,5-diiodothyronine (T2) or 3,5,3'-triiodothyronine (T3) in zebrafish exposed to different chronic temperatures. We measured whole-animal responses (swimming performance and metabolic rates), tissue-specific regulatory enzyme activities, gene expression, and free levels of T2 and T3. RESULTS:We found that both T3 and the lesser-known T2, regulate thermal acclimation in an ectotherm. To our knowledge, this is the first such study to show this. Hypothyroid treatment impaired performance measures in cold-acclimated but not warm-acclimated individuals, whereas supplementation with both TH metabolites restored performance. TH could either induce or repress responses, depending on the actual temperature and thermal history of the animal. CONCLUSIONS:The low sensitivity to TH at warm temperatures could mean that increasing temperatures (that is, global warming) will reduce the capacity of animals to regulate their physiologies to match demands. We suggest that the properties that underlie the role of TH in thermal acclimation (temperature sensitivity and metabolic control) may have predisposed this hormone for a regulatory role in the evolution of endothermy.