@article {86, title = {Current and historical concentrations of poly and perfluorinated compounds in sediments of the northern Great Lakes - Superior, Huron, and Michigan.}, journal = {Environ Pollut}, volume = {236}, year = {2018}, month = {2018 May}, pages = {373-381}, abstract = {

Current and historical concentrations of 22 poly- and perfluorinated compounds (PFASs) in sediment collected from Lake Superior and northern Lake Michigan in 2011 and Lake Huron in 2012 are reported. The sampling was performed in two ways, Ponar grabs of surface sediments for current spatial distribution across the lake and dated cores for multi-decadal temporal trends. Mean concentrations of the sum of PFASs (∑PFASs) were 1.5, 4.6 and 3.1 ng g dry mas (dm) in surface sediments for Lakes Superior, Michigan and Huron, respectively. Of the five Laurentian Lakes, the watersheds of Superior and Huron are the less densely populated by humans, and concentrations observed were typically less and from more diffuse sources, due to lesser urbanization and industrialization. However, some regions of greater concentrations were observed and might indicate more local, point sources. In core samples concentrations ranged from 7 that include perfluoro-n-octane sulfonate (PFOS) bind more strongly to sediment, which resulted in more accurate analyses of temporal trends. Shorter-chain PFASs, such as perfluoro-n-butanoic acid which is the primary replacement for C8 PFASs that have been phased out, are more soluble and were identified in some core layers at depths corresponding to pre-production periods. Thus, analyses of temporal trends of these more soluble compounds in cores of sediments were less accurate. Total elemental fluorine (TF) and extractable organic fluorine (EOF) indicated that identified PFASs were not a significant fraction of fluorine containing compounds in sediment (\<0.01\% in EOF).

}, keywords = {Environmental Monitoring, Fluorocarbons, Geologic Sediments, Great Lakes Region, Lakes, Water Pollutants, Chemical}, issn = {1873-6424}, doi = {10.1016/j.envpol.2018.01.065}, author = {Codling, Garry and Hosseini, Soheil and Corcoran, Margaret B and Bonina, Solidea and Lin, Tian and Li, An and Sturchio, Neil C and Rockne, Karl J and Ji, Kyunghee and Peng, Hui and Giesy, John P} } @article {88, title = {Simultaneous determination of (N-ethyl perfluorooctanesulfonamido ethanol)-based phosphate diester and triester and their biotransformation to perfluorooctanesulfonate in freshwater sediments.}, journal = {Environ Pollut}, volume = {234}, year = {2018}, month = {2018 Mar}, pages = {821-829}, abstract = {

While (N-ethyl perfluorooctanesulfonamido ethanol)-based phosphates (SAmPAPs) have been proposed as a group of perfluorooctanesulfonate (PFOS) precursors, investigation of their occurrence and fate has been limited to SAmPAP diester. In this study, SAmPAP diester and triester were simultaneously determined in freshwater sediment from Taihu Lake using a newly developed UPLC-MS/MS method, and their biotransformation to PFOS in lake sediment was investigated. SAmPAP diester and triester were detected in sediments with a detection frequency of 56\% and 88\%, and their mean concentrations were 0.24\ {\textpm}\ 0.11\ ng/g dry weight (dw) and 0.12\ {\textpm}\ 0.03\ ng/g dw, respectively. The SAmPAP diester/triester ratio in sediment was 1.1\ {\textpm}\ 4.2, much lower than that (6.7) observed in the technical product, and the positive correlation was found between the concentrations of SAmPAP diester and PFOS in sediments (r\ =\ 0.45, p\ =\ 0.01), suggesting that SAmPAP diester would be biotransformed to PFOS in the lake sediment. The microbial degradation test in the lake sediments further clarified that SAmPAP diester was biodegraded to PFOS, but SAmPAP triester was highly recalcitrant to microbial degradation. This study suggests that the occurrence of SAmPAP diester in freshwater lake sediments may be an important precursor of PFOS.

}, keywords = {Alkanesulfonic Acids, Bacteria, Biodegradation, Environmental, Biotransformation, China, Environmental Monitoring, Fluorocarbons, Geologic Sediments, Hydrocarbons, Fluorinated, Lakes, Organophosphates, Sulfonamides, Tandem Mass Spectrometry, Water Pollutants, Chemical}, issn = {1873-6424}, doi = {10.1016/j.envpol.2017.12.021}, author = {Zhang, Shiyi and Peng, Hui and Mu, Di and Zhao, Haoqi and Hu, Jianying} } @article {91, title = {Detection, Occurrence, and Fate of Fluorotelomer Alcohols in Municipal Wastewater Treatment Plants.}, journal = {Environ Sci Technol}, volume = {51}, year = {2017}, month = {2017 Aug 15}, pages = {8953-8961}, abstract = {

Fluorotelomer alcohols (FTOHs) are the most well-known precursors of perfluoroalkyl carboxylic acids (PFCAs), but limited information is available on their occurrence and fate in municipal wastewater treatment plants (WWTPs). The occurrence of FTOHs was investigated in influent, secondary effluent, and sludge of 12 municipal WWTPs in nine cities of China. FTOHs were detected in all WWTPs, and 8:2 FTOH was the predominant congener, with concentrations of 2.10-11.0 ng/L, 3.05-12.4 ng/L, and 0.36-1.91 ng/g dry weight in the influent, secondary effluent, and sludge, respectively. Relatively high proportions of long-chain FTOHs (C) were mainly detected in sludge samples. The mass balance of FTOHs and PFCAs in one of the WWTPs with an anaerobic-anoxic-oxic process was further explored. The decrease of mass loads was observed for 4:2 FTOH (mass change percentage: 21 {\textpm} 3.3\%), 8:2 FTOH (22 {\textpm} 1.5\%), and 10:2 FTOH (29 {\textpm} 7.3\%) through aerobic treatment, while the increase of mass loads was observed for 12 PFCAs from 18 {\textpm} 16\% (perfluorononanoic acid) to 165 {\textpm} 15\% (perfluorobutyric acid)), suggesting the potential biotransformation of FTOHs to PFCAs in the aerobic unit. This work provides the first report on the occurrence of FTOHs in sludge samples of municipal WWTPs and their mass balance and highlights a new emission route to environment via WWTPs.

}, keywords = {Alcohols, China, Cities, Fluorocarbons, Sewage, Waste Water}, issn = {1520-5851}, doi = {10.1021/acs.est.7b00315}, author = {Chen, Hongrui and Peng, Hui and Yang, Min and Hu, Jianying and Zhang, Yu} } @article {102, title = {Ubiquitous Occurrence of Fluorotelomer Alcohols in Eco-Friendly Paper-Made Food-Contact Materials and Their Implication for Human Exposure.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 Jan 19}, pages = {942-50}, abstract = {

The occurrence of fluorotelomer alcohols (FTOHs) was investigated in 94 food-contact materials (FCMs). We detected 6:2 FTOH (\<0.60-1110 ng/g), 8:2 FTOH (\<0.40-8490 ng/g), and 10:2 FTOH (\<0.02-9350 ng/g) in most FCM samples, and four longer-chain C14-20 FTOHs were, for the first time, identified in FCMs with relatively high concentrations (\<0.02-8450 ng/g for 12:2 FTOH, \<0.02-1640 ng/g for 14:2 FTOH, \<0.02-372 ng/g for 16:2 FTOH, and \<0.02-130 ng/g for 18:2 FTOH). There were three typical profiles of FTOHs that were dominated by 6:2 FTOH (95.6 {\textpm} 8.1\% in 9 FCMs), 8:2 FTOH (50.9 {\textpm} 20.8\% in 22 FCMs), and 10:2 FTOH (44.5 {\textpm} 20.9\% in 30 FCMs), indicating the congener-specific usage of FTOHs for different commercial purposes. All nine detectable FCMs produced in the United States were dominated by 6:2 FTOH, which was significantly different from those produced in China. The median concentration of total FTOHs in eco-friendly paper tableware was 2990 ng/g, which was lower than in popcorn bags (18 200 ng/g) but much higher than other FCMs (\<0.55-38.7 ng/g). FTOHs could migrate from paper bowls, with migration efficiencies of 0.004-0.24\% into water, 0.004-0.24\% into 10\% ethanol, 0.009-2.79\% into 30\% ethanol, 0.06-13.0\% into 50\% ethanol (v/v) simulants, and 0.04-2.28\% into oil. Migration efficiencies decreased with increasing carbon chain lengths of FTOHs.

}, keywords = {Alcohols, Biodegradation, Environmental, Fluorocarbons, Food Contamination, Food Packaging, Humans, Paper}, issn = {1520-5851}, doi = {10.1021/acs.est.5b03806}, author = {Yuan, Guanxiang and Peng, Hui and Huang, Chong and Hu, Jianying} } @article {108, title = {Isomer-specific trophic transfer of perfluorocarboxylic acids in the marine food web of Liaodong Bay, North China.}, journal = {Environ Sci Technol}, volume = {49}, year = {2015}, month = {2015 Feb 03}, pages = {1453-61}, abstract = {

Trophic transfers of perfluorocarboxylic acids (PFCAs) have been well studied in aquatic food webs; however, most studies examined PFCAs as single compounds without differentiating isomers. In this study, an in-port derivatization GC-MS method was used to determine PFCA (perfluorooctanoic acid, PFOA; perfluorononanoic acid, PFNA; perfluorodecanoate acid, PFDA; perfluoroundecanoate acid, PFUnDA; perfluorododecanoate acid, PFDoDA; perfluorotridecanoate acid, PFTriDA, and perfluorotetradecanoate acid, PFTeDA) structural isomers in 11 marine species including benthic invertebrates, fishes, and gulls collected in November 2006 from Liaodong Bay in China. The total concentrations of linear PFCAs were 0.35-1.10, 0.93-2.61, and 2.13-2.69 ng/g ww, and the corresponding percentages of branched PFCAs to linear PFCAs were 6.6-15.5\%, 4.2-9.9\%, and 4.5-6.0\% in invertebrates, fishes, and birds, respectively. Except for linear PFOA, significant positive relationships were found between the concentrations of all the target linear PFCAs and trophic levels, and the trophic magnification factors (TMFs) ranged from 1.90 to 4.88. Positive correlations between the concentrations of branched PFCAs isomers and trophic levels were also observed but were without statistical significance. The relatively high biomagnification of linear isomers of PFCAs would lead to low percentages of branched PFCAs to total PFCAs in organisms at high trophic levels. This study for the first time clarified isomer-specific trophic transfers of PFCAs in a marine food web.

}, keywords = {Animals, Bays, Birds, Carboxylic Acids, China, Environmental Monitoring, Fishes, Fluorocarbons, Food Chain, Invertebrates, Isomerism, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/es504445x}, author = {Zhang, Zhong and Peng, Hui and Wan, Yi and Hu, Jianying} } @article {112, title = {Isomer-specific accumulation of perfluorooctanesulfonate from (N-ethyl perfluorooctanesulfonamido)ethanol-based phosphate diester in Japanese Medaka (Oryzias latipes).}, journal = {Environ Sci Technol}, volume = {48}, year = {2014}, month = {2014 Jan 21}, pages = {1058-66}, abstract = {

While (N-ethyl perfluorooctanesulfonamido)ethanol (FOSE) -based phosphate diester (diSPAP) has been proposed as a candidate precursor of perfluorooctanesulfonate (PFOS), its potential biotransformation to PFOS has not been verified. Metabolism of diSPAP was investigated in Japanese medaka ( Oryzias latipes ) after exposure in water for 10 days, followed by 10 days of depuration. Branched isomers of diSPAP (B-diSPAP) were preferentially enriched in medaka exposed to diSPAP, with the proportion of branched isomers (BF) ranging from 0.56 to 0.80, which was significantly greater than that in the water to which the medaka were exposed (0.36) (p \< 0.001). This enrichment was due primarily to preferential uptake of B-diSPAP. PFOS together with perfluorooctanesulfonamide (PFOSA), N-ethyl perfluorooctanesulfonamide (NEtFOSA), 2-(perfluorooctanesulfonamido)acetic acid (FOSAA), NEtFOSAA, FOSE, and NEtFOSE were detected in medaka exposed to diSPAP, which indicated the potential for biotransformation of diSPAP to PFOS via multiple intermediates. Due to preferential metabolism of branched isomers, FOSAA and PFOSA exhibited greater BF values (\>0.5) than those of NEtFOSA, NEtFOSAA, and NEtFOSE (\<0.2). Such preferential metabolism of branched isomers along the primary pathway of metabolism and preferential accumulation of B-diSPAP led to enrichment of branched PFOS (B-PFOS) in medaka. Enrichment of B-PFOS was greater for 3-, 4-, and 5-perfluoromethyl PFOS (P3MPFOS, P4MPFOS, and P5MPFOS), for which values of BF were 0.58 {\textpm} 0.07, 0.62 {\textpm} 0.06, and 0.61 {\textpm} 0.05 (day 6), respectively; these values are 5.8-, 7.8-, and 6.4-fold greater than those of technical PFOS. This work provides evidence on the isomer-specific accumulation of PFOS from diSPAP and will be helpful to track indirect sources of PFOS in the future.

}, keywords = {Alkanesulfonic Acids, Animals, Biotransformation, Chromatography, High Pressure Liquid, Environmental Monitoring, Esters, Fluorocarbons, Gas Chromatography-Mass Spectrometry, Half-Life, Hydrocarbons, Fluorinated, Isomerism, Kinetics, Metabolic Networks and Pathways, Organophosphorus Compounds, Oryzias, Phosphates, Reference Standards, Sulfonamides}, issn = {1520-5851}, doi = {10.1021/es404867w}, author = {Peng, Hui and Zhang, Shiyi and Sun, Jianxian and Zhang, Zhong and Giesy, John P and Hu, Jianying} } @article {114, title = {Derivatization method for sensitive determination of fluorotelomer alcohols in sediment by liquid chromatography-electrospray tandem mass spectrometry.}, journal = {J Chromatogr A}, volume = {1288}, year = {2013}, month = {2013 May 03}, pages = {48-53}, abstract = {

Fluorotelomer alcohols (FTOHs) are the main precursors of environmentally ubiquitous perfluorinated acids, and determination of FTOHs at low concentrations presents significant challenges. In this study, a new liquid chromatography-electrospray mass spectrometry (LC-ESI-MS) method in conjunction with low-energy collision dissociation tandem mass spectrometry (CID-MS/MS) was developed by employing an optimized derivatization reaction with dansyl chloride (DNS) in acetonitrile under catalysis of 4-(dimethylamino)-pyridine (DMAP). The instrument detection limits (IDLs) of the newly developed method were 0.014, 0.015, 0.014, 0.0075 and 0.0093μg/L for 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, 10:1 FTOH and 10:2 FTOH respectively, which were 7.5-241 times lower than those without derivatizaiton and 57-357 times lower than previous GC/MS method. The method was successfully applied to analyze FTOHs in sediments combined with WAX and silica cartridges cleanup. The overall method recoveries were from 67{\textpm}6.0\% to 83{\textpm}9.4\% with matrix effects of \<15\%. The limits of quantification for all FTOHs were 0.017-0.060ng/gdry weight (dw). The method was applied to analyze six marine sediment samples from Liaodong Bay, China. All FTOHs except for 10:1 FTOH were detected, and the total concentrations of FTOHs were 0.19-0.52ng/gdw. The developed method provides a new method to sensitively determine FTOHs in environmental matrices.

}, keywords = {Alcohols, China, Chromatography, High Pressure Liquid, Environmental Pollutants, Fluorocarbons, Geologic Sediments, Reproducibility of Results, Sensitivity and Specificity, Spectrometry, Mass, Electrospray Ionization, Tandem Mass Spectrometry}, issn = {1873-3778}, doi = {10.1016/j.chroma.2013.02.085}, author = {Peng, Hui and Hu, Kejun and Zhao, Fanrong and Hu, Jianying} } @article {116, title = {Simultaneous determination of mono- and disubstituted polyfluoroalkyl phosphates in drinking water by liquid chromatography-electrospray tandem mass spectrometry.}, journal = {J Chromatogr A}, volume = {1227}, year = {2012}, month = {2012 Mar 02}, pages = {245-52}, abstract = {

A sensitive liquid chromatography-electrospray tandem mass spectrometry method was established for the simultaneous determination of five monosubstituted polyfluoroalkyl phosphates (monoPAPs) and eight disubstituted polyfluoroalkyl phosphates (diPAPs) in drinking water. Complete separation and good retention for 13 polyfluoroalkyls phosphates (PAPs) were achieved with a Waters ACUITY UPLC BEH C8 column using a mixture of methanol/water containing 0.1\% NH$_{4}$OH as the mobile phases. Extraction of drinking water samples was performed on weak anion exchange (WAX) cartridges, and the recoveries of target compounds were from 65 to 110\%. The limits of quantization (LOQs) for 13 analytes were in the range of 0.4-40 ng/L. This method was applied to analyze the PAPs in drinking water samples from three cities in China. Of the 13 PAPs, six PAPs including 6:2 monoPAP (13.0 ng/L), 8:2 monoPAP (3.6 ng/L), 10:1 monoPAP (4.3-70.3 ng/L), 10:2 monoPAP (1.4-5.6 ng/L), 8:2 diPAP (0.10 ng/L), and 10:1 diPAP (0.8-3.8 ng/L) were detected.

}, keywords = {China, Chromatography, Ion Exchange, Drinking Water, Fluorocarbons, Phosphates, Reproducibility of Results, Sensitivity and Specificity, Solid Phase Extraction, Tandem Mass Spectrometry, Water Pollutants, Chemical}, issn = {1873-3778}, doi = {10.1016/j.chroma.2012.01.004}, author = {Ding, Huanhuan and Peng, Hui and Yang, Min and Hu, Jianying} } @article {119, title = {Tissue distribution and maternal transfer of poly- and perfluorinated compounds in Chinese sturgeon (Acipenser sinensis): implications for reproductive risk.}, journal = {Environ Sci Technol}, volume = {44}, year = {2010}, month = {2010 Mar 01}, pages = {1868-74}, abstract = {

It is critical to investigate the tissue distribution and maternal transfer of poly- and perfluorinated compounds (PFCs) in wild fish for assessing potential effects on ecosystems. Concentrations of 23 PFCs in nine organs and egg were measured in 16 17- to 25-year-old female Chinese sturgeon (Acipenser sinensis, an anadromous fish), that died during propagation. Three polyfluorinated amides were detected in stomach, intestine, and gills and 7:3 FTCA was specifically accumulated in liver. The greatest total concentration of PFCs in egg was 35.1 +/- 10.4 ng/g ww and was predominated by perfluorooctane sulfonate (PFOS) and perfluorotridecanoate acid (PFTriDA). The longer-chain C(11)-C(14) and C(16) perfluorinated carboxylates were more accumulated in Chinese sturgeon than PFOS, partly due to the increasing trends of PFCAs with fish age. Maternal transfer ratios of PFCs expressed as ratios of concentrations in the egg to those in the liver ranged from 0.79 (perfluorooctanoate) to 5.5 (PFTriDA), depending on their carbon chain lengths or protein-water coefficients. The PFOS equivalent of PFC mixtures, calculated by multiplying the relative potency factor of each PFC to PFOS by the corresponding concentration, ranged from 90.6 to 262 ng/g. The hazard quotient was 0.20, implying potential reproductive effects of PFCs on Chinese sturgeon.

}, keywords = {Alkanesulfonic Acids, Animals, Female, Fertility, Fertilization in Vitro, Fishes, Fluorocarbons, Organ Specificity, Reproduction, Risk Factors, Tissue Distribution}, issn = {0013-936X}, doi = {10.1021/es903248d}, author = {Peng, Hui and Wei, Qiwei and Wan, Yi and Giesy, John P and Li, Luoxin and Hu, Jianying} }