Faculty Bibliography

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are an emerging class of environmental contaminants, but the sources of these chemicals in the environment are not well-known. In this study, we developed a kinetic model describing the chlorination of PAHs to elucidate the mechanism of formation of ClPAHs during the combustion of organic waste containing chlorinated compounds and/or chlorine in an incinerator. Pyrene (Pyr) and polyvinyl chloride (PVC) were selected as a model PAH and a model organic substrate, respectively. All combustion experiments were carried out using a model furnace operated under similar experimental conditions. Combustion of PVC in the model furnace produced 1-ClPyr, 1,3-Cl₂Pyr, 1,6-Cl₂Pyr, 1,8-Cl₂Pyr, 1,3,6-Cl₃Pyr, and 1,3,6,8-Cl₄Pyr. The developed model supported the experimental data on the sequential chlorination of pyrene. The rate constants for the formation of mono- to trichlorinated pyrenes were over 30 times of those for the formation of tetra- and penta-chlorinated pyrenes. A qualitative analysis of the formation of highly chlorinated pyrenes based on the comparison of theoretical and empirical isotopic patterns of the mass spectrum revealed that penta- and hexa-chlorinated pyrenes, whose analytical standards were not available, were also produced by the combustion of PVC.

The use of novel brominated flame retardants (BFRs) and phosphate-based flame retardants (PFRs) has increased as substitutes for hexabromocyclododecane (HBCD) in many consumer products. To facilitate collection of data on chemicals used as flame retardants in textiles and fabrics, we developed an analytical method using liquid chromatography interfaced with tandem mass spectrometry (LC-MS/MS). We compared two extraction methods, one involving ultrasonic extraction (traditional method) using dichloromethane, toluene or acetone and the other encompassing complete dissolution of textile with 25% 1,1,1,3,3,3-hexafluoro-2-propanol/chloroform. The dissolution method extracted up to 204 times more BFRs and PFRs than the traditional ultrasonic extraction. Tris(2,3-dibromopropyl) isocyanurate (TDBP-TAZTO), triphenylphosphine oxide (TPhPO), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tricresyl phosphate (TCsP), and triphenyl phosphate (TPhP) were found in 40 flame-retarded curtain samples purchased from Japanese market in 2014. TDBP-TAZTO was detected in polyester curtains for the first time. Some of the flame-retarded curtain samples did not contain any of the known target analytes, which suggested the presence of other unknown flame retardants in those fabrics.

Phthalates are used as plasticizers to impart flexibility of plastics. Because of their toxicity, human exposure to phthalates is a concern. Little is known on the occurrence of and inhalation exposure to phthalates in indoor air. In this study, ten phthalates were measured in 97 indoor air samples collected from Northern Vietnam during September 2016 to January 2017. The mean concentrations of total phthalates (i.e., sum of ten phthalates) in particulate and gas phases ranged from 95.2 to 13,100μgg^-1 and from 57.0 to 14,900ngm^-3, respectively. In bulk indoor air samples (i.e., gas plus particulate phase), the mean concentration of total phthalates ranged from 106 to 16,000ngm^-3 (mean: 1040ngm^-3). Diethyl phthalate (DEP) was found at the highest concentration in indoor air at a concentration range of below the method quantitation limit (MQL) to 12,400ngm^-3 (mean: 376). Among various microenvironments, indoor air collected from hair salons contained the highest concentrations of phthalates (range: 596 to 16,000ngm^-3). Among the four northern Vietnamese cities studied, the highest concentrations of phthalates were found in indoor air samples from Hanoi. The calculated mean inhalation exposure doses to phthalates for infants, toddlers, children, teenagers, and adults were 780, 485, 416, 292, and 213ngkg-bw^-1d^-1, respectively.

BACKGROUND: Large amounts of various chemical contaminants, including perfluoroalkyl substances (PFASs), were released at the time of the World Trade Center (WTC) disaster. Thousands of children who lived and/or attended school near the disaster site were exposed to these substances but few studies have examined the possible consequences related to these exposures. OBJECTIVES: To examine the relationship of PFASs serum levels with cardiometabolic profile in children and adolescents enrolled in the World Trade Center Health Registry (WTCHR) and a matched comparison group. METHODS: We evaluated WTCHR enrollees who resided in New York City and were born between September 11, 1993 and September 10, 2001, and a matched comparison group consisting of individuals who were ineligible for WTCHR participation upon distance of their home, school or work from the WTC and lack of participation in rescue and recovery activities. Matching was based on date of birth, sex, race, ethnicity, and income. We assessed exposure to PFASs, as measured by serum levels and association with cardiometabolic profile as measured by arterial wall stiffness, body mass index, insulin resistance, fasting total cholesterol, HDL, LDL and triglycerides. RESULTS: A total of 402 participants completed the study and serum samples were analyzed from 308 participants, 123 in the WTCHR group and 185 in the comparison group. In multivariable regression analysis, after adjusting for relevant confounders, we observed a significant, positive association of perfluorooctanoic acid (PFOA) with triglycerides (beta coefficient=0.14, 95% CI: 0.02, 0.27, 15.1% change), total cholesterol (beta coefficient=0.09, 95% CI: 0.04, 0.14, 9.2% change), and LDL cholesterol (beta coefficient=0.11, 95% CI: 0.03, 0.19, 11.5% change). Perfluorohexanesulfonic acid levels were associated with decreased insulin resistance (beta coefficient=-0.09, 95% CI: -0.18, -0.003, -8.6% change); PFOA and perfluorononanoic acid were associated with increased brachial artery distensibility. CONCLUSIONS: This research adds to our knowledge of the physical health impacts in a large group of children exposed to the WTC disaster. Abnormal lipid levels in young adults might be an early marker of atherosclerosis and cardiovascular diseases and our findings highlight the importance of conducting longitudinal studies in this population.

This paper presents the first comprehensive survey of 19 novel brominated flame retardants (NBFRs) in soil samples collected among five Asian countries. High variability in concentrations of all NBFRs was found in soils with the geometric mean (GM) values ranging from 0.50 ng/g dry weight (dw) in Vietnam to 540 ng/g dw in the vicinity of a BFR manufacturer in China. In urban, rural, and background locations, the GM concentrations of ∑₁₉NBFRs decreased in the order of Japan > South Korea > China > India > Vietnam. Correlations among different NBFR compounds were positive and statistically significant (p < 0.05), suggesting that they originate from similar sources. Evidence for simultaneous application between polybrominated diphenyl ethers (PBDEs) and NBFRs were also noted. Principal component analysis of NBFR concentrations revealed specific pollution sources for different NBFRs coming from urban, BFR-related industrial, and e-waste sites. For the first time, this study demonstrates a "point source fractionation effect" for NBFRs and PBDEs. The concentrations of all NBFRs and PBDEs were negatively and significantly correlated with the distance from BFR-related industrial and e-waste regions. Positive and significant correlation between population density and NBFR concentrations in soils was identified. Our study revealed that the primary sources effects were stronger than the secondary sources effects in controlling the levels and distribution of NBFRs and PBDEs in soils in these five Asian countries.

Earlier studies have reported the occurrence of cyclic and linear siloxanes in personal care and household products. Nevertheless, there is a lack of information on the occurrence of siloxanes in indoor air. In this study, four cyclic and six linear siloxanes were measured in 97 indoor air samples collected from various micro-environments in four cities in northern, Vietnam, during September 2016 to January 2017. The total concentrations of siloxanes (TSi) in particulate and gas phases ranged from 141 to 7220 μg g^-1 (mean: 1880) and 23.8-1580 ng m^-3 (mean: 321), respectively. The total concentrations of cyclic siloxanes (TCSi), linear siloxanes (TLSi), and TSi in indoor air were 1.91-1500 ng m^-3, 21.8-817 ng m^-3, and 41.8-1950 ng m^-3, respectively. The highest mean concentration of siloxanes was found in indoor air from hair salons in Hanoi. The concentrations of siloxanes in air collected from homes in Hanoi were higher than those from other smaller cities such as Bacninh, Thaibinh, and Tuyenquang. The human exposures to siloxanes through inhalation were estimated for various age groups based on the measured concentrations. The mean inhalation exposure doses to total siloxanes for infants, toddlers, children, teenagers, and adults were 352, 219, 188, 132, and 95.9 ng kg-bw^-1 d^-1, respectively.

A liquid chromatography-triple quadrupole-tandem mass spectrometry (LC-qQq-MS/MS) method was developed for simultaneous determination of 89 legal neuropsychiatric pharmaceuticals and illicit drugs (both parent compounds and metabolites) and other micropollutants in unfiltered wastewater and freshwater. The target chemicals fall under the classes of amphetamine-type stimulants, cocaine compounds, opiates and opioids, benzodiazepines, lysergic compounds, antipsychotics, anesthetics, antiepileptics, antidepressants, sympathomimetics, cannabinoids, blood thinners, antihistamines, β-blockers, caffeine derivatives, nicotine derivatives, z-drugs, new designer drugs, and Alzheimer medications. The sample preparation procedure was designed for unfiltered wastewater and freshwater without the need to separate the particulate matter (if any) from the aqueous phase prior to extraction. Samples were pre-concentrated by rotary evaporation in the presence of a solvent. Method precision (absolute values; N = 6 replicate analyses at the fortification level of 50 ng, k = 6 days) for 87 out of 89 target analytes ranged from 2.8 to 34% (RSD %). The limits of detection ranged from 0.11 to 202 ng L^-1, and the matrix effects ranged from +16 to -84%. A total of 10 samples, 8 wastewater, 1 drinking water, and 1 lake water, were collected from New York State, USA, and were analyzed for the target compounds to demonstrate the applicability of the developed method. This is the first study to report the analysis of multiple classes of pharmaceuticals, illicit drugs, and other micropollutants in unfiltered wastewater. Graphical abstract Analysis of 89 micropollutants in unfiltered wastewater by LC-MS/MS.

Parabens (p-hydroxy benzoic acid esters) are antimicrobial agents, used widely as preservatives in personal care products (PCPs), pharmaceuticals, foods, and beverages. PCPs that contain parabens are a major source of these chemicals in sewage treatment plants (STPs). Very few studies have demonstrated the occurrence of parabens in wastewater. In this study, the occurrence and fate of six parabens, methyl-(MeP), ethyl-(EtP), propyl-(PrP), butyl-(BuP), hepty-(HpP) and benzyl-(BzP) parabens, and five of their metabolites (4-HB, 3,4-DHB, OH-MeP, OH-EtP and BA) were studied in five STPs in India. The concentrations of parent parabens (∑₆parent parabens) in five STPs ranged between 131 and 920ng/L in influent; 16 and 67ng/L in effluent; and 104 and 1090ng/g, dry weight, in sludge samples. The sum concentrations of five paraben metabolites (∑₅paraben metabolites) in five STPs ranged between 4110 and 34,600ng/L in influent; 2560 and 3800ng/L in effluent; and 1220 and 35,900ng/g, dry weight, in sludge samples. These values were higher than those reported for many industrialized countries. We calculated the mass loadings, removal efficiencies, and environmental emissions of parabens based on the measured concentrations in influents, effluents, and sludge. The mean removal efficiencies of parent parabens and their metabolites ranged from 80% to 100% and 28% to 76%, respectively.

Benzothiazoles (BTHs) and benzotriazoles (BTRs) are used in a wide range of applications, including rubber vulcanization and corrosion inhibition. Limited studies have reported the occurrence of BTHs and BTRs in textiles, including children's clothing. In this study, 79 textile samples (raw as well as tailored) collected in Albany, New York, USA, were analyzed to determine the occurrence of BTH, BTR and their seven common derivatives. BTH, 2-methylthio-benzothiazole (2-Me-S-BTH) and 2-hydroxy-benzothiazole (2-OH-BTH) were found in textiles at a detection rate (DR) of 86%, 54% and 19%, respectively. The DRs of tolyltriazole (TTR), BTR and 5-chloro-benzotriazole (5-Cl-BTR) in textiles were below 20%. Although BTH was the most frequently detected compound, BTR levels were elevated in certain textiles and the overall mean concentrations of BTR in textiles were higher than those of BTH. The concentrations of BTH in textiles ranged from 6.1 to 1120ng/g. The highest concentration of BTR (14,000ng/g) was found in a printed graphic of infant's bodysuit. On the basis of the measured concentrations, we calculated dermal exposure doses to BTHs and BTRs by infants. The dermal exposure doses were high from the use of socks (244 to 395pg/kg·bw/d), and the exposure doses of BTHs and BTRs from textiles were as high as 3740pg/kg·bw/d. Printed graphics on clothes, as well as socks, accounted for a major proportion of the exposure doses to BTHs and BTRs.

Little is known about the occurrence of emerging environmental contaminants, such as benzotriazoles (BTRs), benzothiazoles (BTHs), benzophenones (BzPs), and bisphenol analogues (BPs) in India. In this study, we determined the occurrence and removal of BTRs, BTHs, BzPs, and BPs in five Indian sewage treatment plants (STPs). The respective measured mean concentrations (N = 5) in influents and effluents were 370 and 57.4 ng L^-1 for BTRs, 50800 and 20200 ng L^-1 for BTHs, 351 and 163 ng L^-1 for BzPs, and 98.0 and 9.6 ng L^-1 for BPs. Among the target chemicals analyzed, BTHs were found at elevated levels, and the measured levels were some of the highest ever reported in the literature. The mean concentrations (N = 5) of BTRs, BTHs, BzPs, and BPs in sludge were 44.2, 51200, 124, and 200 ng g^-1 dry wt, respectively. The removal efficiencies for BTRs, BTHs, BzPs, and BPs ranged as follows: 54.2-85.6%, 23.4-85.0%, 51.8-71%, and 76.0-97.0%, respectively, and were comparable to those reported for other countries. Elevated concentrations of BTHs in Indian STPs can be related to consumption of these chemicals in a wide range of products including paper, textile and rubber materials.