Faculty Bibliography

Perfluorinated compounds (PFCs) are known to biomagnify in temperate and Arctic food webs, but little is known about their behavior in subtropical systems. The environmental distribution and biomagnification of PFCs, extractable organic fluorine (EOF), and total fluorine were investigated in a subtropical food web. Surface water, sediment, phytoplankton, zooplankton, gastropods, worms, shrimps, fishes, and waterbirds collected in the Mai Po Marshes Nature Reserve in Hong Kong were analyzed. Trophic magnification was observed for perfluorooctanesulfonate (PFOS), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnDA), and perfluorododecanoate (PFDoDA) in this food web. Risk assessment results for PFOS, PFDA, and perfluorooctanoate (PFOA) suggest that current PFC concentrations in waterbird livers are unlikely to pose adverse biological effects to waterbirds. All hazard ratio (HR) values reported for PFOS and PFOA are less than one, which suggests that the detected levels will not cause any immediate health effects to the Hong Kong population through the consumption of shrimps and fishes. However, only 10-12% of the EOF in the shrimp samples was comprised of known PFCs, indicating the need for further investigation to identify unknown fluorinated compounds in wildlife.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as global environmental pollutants. Although PFOS and PFOA have been detected in tap water from Japan and several other countries, very few studies have examined the fate, especially removal, of perfluorinated compounds (PFCs) in drinking water treatment processes. In this study, we analyzed PFOS and PFOA at every stages of drinking water treatment processes in several water purification plants that employ advanced water treatment technologies. PFOS and PFOA concentrations did not vary considerably in raw water, sand filtered water, settled water, and ozonated water. Sand filtration and ozonation did not have an effect on the removal of PFOS and PFOA in drinking water. PFOS and PFOA were removed effectively by activated carbon that had been used for less than one year. However, activated carbon that had been used for a longer period of time (>1 year) was not effective in removing PFOS and PFOA from water. Variations in the removal ratios of PFOS and PFOA by activated carbon were found between summer and winter months.

Perchlorate can perturb thyroid hormone (TH) homeostasis by competitive inhibition of iodide uptake by the thyroid gland. Until recently, the effects of perchlorate on TH homeostasis were examined by measuring serum concentrations of THs by immunoassay (IA) methods. IA methods are sensitive, but for TH analysis they are compromised by lack of adequate specificity. In this study, we determined the concentrations of six THs: L-thyroxine (T₄), 3,3',5-triiodo-L-thyronine (T₃), 3,3',5'-triiodo-L-thyronine (rT₃), 3,5-diiodo-L-thyronine, 3,3'-diiodo-L-thyronine, and 3-iodo-L-thyronine in the serum of rats administered perchlorate by isotope (¹³C₆-T₄)-dilution liquid chromatography-tandem mass spectrometry. The method recoveries for THs spiked into a serum matrix were between 97.0% and 115%, with a coefficient of variation of 2.1% to 9.4%. Rats were placed on an iodide-deficient or iodide-sufficient diet for 2.5 months, and for the last 2 weeks of that period they were provided drinking water either without or with perchlorate (10 mg/kg body weight/day). No significant differences in serum concentrations of T₃ and T₄ were observed between rats given iodide-deficient and iodide-sufficient diets for 2 or 2.5 months. After 24 h of perchlorate exposure, significantly lower concentrations of T₃ and T₄ were found in the serum of rats administered the iodide-deficient diet but not in rats administered the iodide-sufficient diet. However, after 2 weeks of perchlorate exposure, TH levels in rats fed the iodide-sufficient diet were also significantly lower than those in control rats. Our results suggest that perchlorate affects TH homeostasis and that such effects are more pronounced under iodide-deficient nutrition.

Phthalates are esters of phthalic acid and are mainly used as plasticizers (added to plastics to increase their flexibility, transparency, durability, and longevity). Humans are exposed to phthalates through several routes. Urinary phthalate metabolites can be used as biomarkers of human exposures to phthalates. In this study, 14 phthalate metabolites were analyzed in 183 urine samples collected in 2010 from Shanghai, Guangzhou, and Qiqihaer, China. Phthalate metabolites were found in all urine samples and their total concentrations ranged from 18.6 to 3160 ng/mL (median: 331 ng/mL). Mono-n-butyl phthalate (mBP) and mono-2-isobutyl phthalate (miBP) were the major metabolites found in urine, and their respective median concentrations were 61.2 and 51.7 ng/mL; concentrations of miBP were higher than the concentrations reported for other countries, to date. Based on the urinary concentrations of phthalate metabolites, we estimated the daily intake rates in the Chinese population. The estimated daily intakes of dibutyl phthalate (DBP), diethyl phthalate (DEP), and di-(2-ethylhexyl) phthalate (DEHP) in China were 12.2, 3.8, and ~5 μg/kg bw/day, respectively. Thirty nine percent of the samples exceeded the tolerable daily intake of 10 μg/kg bw/day, proposed for DBP, by the European Food Safety Authority, but none of the estimated daily intake values exceeded the reference dose recommended by the U.S. Environmental Protection Agency.

INTRODUCTION/BACKGROUND:Chlorobenzenes are used as solvents or as feedstocks in the production of pesticide formulations, dyes, room deodorizers, moth-proofing agents, and de-inking solvents. Chlorobenzenes were produced by the Dow Chemical Company in Midland, Michigan, for several decades. In this study, concentrations of 12 chlorobenzene (CBz) congeners, from mono- to hexachlorobenzenes, were measured in more than 150 floodplain soil (FPS), surface sediment, and sediment core (SC) samples collected during 2002-2004 from the Pine River, Tittabawassee River, Shiawassee River, Saginaw River, and Saginaw Bay, Michigan. METHODS:Five grams of wet sediment were homogenized with anhydrous sodium sulfate and extracted with 20% dichloromethane/hexane. The extracts were purified by silica gel column chromatography and analyzed by a gas chromatograph interfaced with a mass spectrometer (GC/MS). RESULTS:Mean concentrations of ΣCBz in FPS and surface sediment were seven to 30 times higher in the Tittabawassee River (80 and 60 ng/g dry weight (dw), respectively) than in the Saginaw River (2.4 and 8.1 ng/g dw, respectively) and Saginaw Bay (5.5 and 8.0 ng/g dw, respectively). Concentrations of ΣCBz were low in surface sediment and FPS from locations upstream of Midland, Michigan, on the Tittabawassee River. Concentrations of ΣCBz were higher in FPS than in surface sediment of the Tittabawassee River; on the contrary, surface sediment contained higher concentrations of CBz than FPS from the other rivers studied. High concentrations of hexachlorobenzene were found in FPS of the Tittabawassee River. All CBz congeners, except for dichlorobenzenes (DCBz), showed a trend of spatial decrease with downstream of the Dow Chemical Company in Midland. The CBz congener composition of the samples showed multiple patterns that reflected differences in historical emissions and environmental partitioning, arising from variations in physico-chemical properties of CBz. 1,4-Dichlorobenzene (1,4-DCBz) was found in all of the samples and accounted for a high proportion of total CBz. The relationship between concentrations of CBz and previously reported concentrations of PCDD/Fs for the same set of samples (Kannan et al. 2008) was significant, indicating similarities in sources and depositions of these two classes of compounds in the watershed.

Bisphenol A (BPA) is used in the production of polycarbonate plastics and epoxy resins, which are used in many consumer products. Sources of human exposures to BPA include packaged and canned food products, indoor air, and dust ingestion. Information on the relative contributions of the pathways to BPA exposures is limited. In this study, we measured concentrations BPA in indoor dust collected from two locations in the Eastern United States and evaluated the contribution of dust to total BPA exposures. BPA was found in 95% of the dust samples analyzed (n = 56) at concentrations ranging from <0.5 to 10,200 ng/g (mean 843; median 422). The median values for BPA intake by way of the ingestion of dust by adults and toddlers were calculated to be 0.35 and 5.63 ng/kg body weight/day. These estimated exposure doses of BPA through dust ingestion are of the same order of magnitude as the recently reported low concentrations that induced health effects in laboratory animal studies. The contribution of dust to total human BPA intake was estimated to be <1%, however, suggesting that dietary intake is the predominant source of exposures in humans.

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.

DABSE, a database for avian blood spot examination for exposure to toxicants, is a new biomonitoring project in wild birds that has the goal of providing reference values of harmful agents, as measured in whole blood stored as dried blood spots. Once these "normal" values have been established, the diagnosis of environmental contaminant-mediated ill-health (such as manifestations of sickness, increased mortality, a reduction in population, poor breeding success, abnormal behavior) in an individual bird or in a population could be facilitated by comparing exposure values in the investigation to reference values of the same species in the database. One might then identify the cause and pave the way for a mitigating response. The toxicant component of DABSE is being examined at the low ng ml(-1) level in 200 µl of whole blood. As these analyses are invariably very costly, an effort has been made to lower these costs and so enable more testing by quantitating representative compounds as markers for the whole group. These markers are invariably found in birds' blood at the highest concentration of all the constituents in that group. The toxicant groups comprise:- (a) elements-arsenic, cadmium, lead, mercury and selenium; (b) organochlorine pesticides, markers being p,p'-DDT, p,p'-DDE, β-HCH, HCB and oxychlordane; (c) polychlorinated biphenyls (PCBs), the marker being congener 153; (d) polybrominated diphenyl esters (PBDEs), the marker being congener 47; (e) perfluorinated compounds (PFCs), the markers being perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). DABSE will be expanded to determine exposure to infectious diseases and perhaps acute toxicoses.

Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzotriazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in sediment and sewage sludge samples, using liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2-yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.06-0.33 ng g⁻¹ dry weight (dw) and 0.1-1.65 ng g⁻¹ dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.32-13.8%) and from 82% to 106% (RSD: 2.89-8.09%) for the compounds analyzed by LC-MS/MS and GC-MS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.29-9.93, 5.81-22.5, and 190-389 ng g⁻¹ dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 104-6370 ng g⁻¹ dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g⁻¹ dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2'OH-4MeO-BP, 2,2',4,4'OH-BP, and 4OH-BP in sediment and sludge samples.

Because of volatilization and leaching from their application in consumer and personal care products, phthalate esters are ubiquitous contaminants in the indoor environment. In this study, we measured concentrations and profiles of 9 phthalate esters in indoor dust samples collected from six cities in China (n = 75). For comparison, we also analyzed samples collected from Albany, New York, USA (n = 33). The results indicated that concentrations, except for dicyclohexyl phthalate (DCHP) and bis(2-ethylhexyl) phthalate (DEHP), and profiles of phthalate esters varied significantly between the two countries. Concentrations of diethyl phthalate (DEP), di-n-hexyl phthalate (DNHP), and benzyl butyl phthalate (BzBP) were 5 to 10 times higher in dust samples collected from Albany than those from the Chinese cities. In contrast, concentrations of di-iso-butyl phthalate (DIBP) in dust samples from Albany were 5 times lower than those from the Chinese cities. We estimated the daily intake (DI) of phthalate esters through the routes of dust ingestion and dermal dust absorption. The extent of contribution of indoor dust to human exposures varied, depending on the type of phthalate esters. The contribution of dust to DEHP exposure was 2-5% and 10-58% of the estimated total DIs in China and the USA, respectively. On the basis of the estimates of total DIs of phthalates, extrapolated from urinary metabolite concentrations, the contributions of inhalation, dermal absorption, and dietary intake to total DIs were estimated. The results indicated that dietary intake is the main source of exposure to DEHP (especially in China), whereas dermal exposure was a major source for DEP. This is the first study to elucidate sources of human exposure to phthalates among the general population in China.