@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 {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 {110, title = {Occurrences of three classes of antibiotics in a natural river basin: association with antibiotic-resistant Escherichia coli.}, journal = {Environ Sci Technol}, volume = {48}, year = {2014}, month = {2014 Dec 16}, pages = {14317-25}, abstract = {

To investigate the occurrence of antibiotics in urban rivers and their association with antibiotic-resistant Escherichia coli, 20 (fluoro)quinolone antibiotics (FQs), 16 tetracycline antibiotics (TCs) and their degradation products, and 25 sulfonamides (SAs) and some degradation products were determined in 45 river samples and 13 discharged wastewater samples collected from Wenyu River and its tributaries and 4 composite effluent samples from sewage treatment plants in Beijing, China. Fifteen FQs, eight TCs, including four degradation chemicals, and sixteen SAs, including four acetylated products, were detected in the river water. The SAs were the dominant antibiotic (total concentrations up to 3164.0 ng/L) in river water, followed by FQs (1430.3 ng/L) and TCs (296.6 ng/L). The sum concentrations for each class of detected antibiotic in the 13 discharge site samples were higher than those in river samples, up to 12326.7 ng/L for SAs, 6589.2 ng/L for FQs, and 730.1 ng/L for TCs, largely contributing to the high concentrations in the river basin. Log-linear regression analysis confirmed that the concentrations of FQs, TCs, and SAs in the Wenyu River basin were strongly correlated with the number of E. coli resistant to FQs (p \< 0.05), TCs (p \< 0.05), and SAs (p \< 0.05), providing evidence for the environmental impacts of antibiotic usage.

}, keywords = {Anti-Bacterial Agents, China, Drug Resistance, Bacterial, Environmental Monitoring, Escherichia coli, Fluoroquinolones, Rivers, Sulfonamides, Tetracyclines, Waste Water, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/es503700j}, author = {Zhang, Qinqin and Jia, Ai and Wan, Yi and Liu, Hong and Wang, Kunping and Peng, Hui and Dong, Zhaomin and Hu, Jianying} } @article {117, title = {Occurrence and source apportionment of sulfonamides and their metabolites in Liaodong Bay and the adjacent Liao River basin, North China.}, journal = {Environ Toxicol Chem}, volume = {30}, year = {2011}, month = {2011 Jun}, pages = {1252-60}, abstract = {

The presence of antibiotics in the environment is of great concern because of their potential for resistance selection among pathogens. In the present study we investigated the occurrence of 19 sulfonamides, five N-acetylated sulfonamide metabolites, and trimethoprim in the Liao River basin and adjacent Liaodong Bay, China, as well as 10 human/agricultural source samples. Within the 35 river samples, 12 sulfonamides, four acetylated sulfonamides, and trimethoprim were detected, with the dominant being sulfamethoxazole (66.6 ng/L), N-acetylsulfamethoxazole (63.1 ng/L), trimethoprim (29.0 ng/L), sulfadiazine (14.0 ng/L), and sulfamonomethoxine (8.4 ng/L); within the 36 marine samples, 10 chemicals were detected, with the main contributions from sulfamethoxazole (25.2 ng/L) and N-acetylsulfamethoxazole (28.6 ng/L). Sulfamethoxazole (25.9\%), N-acetylsulfamethoxazole (46.6\%), trimethoprim (22.9\%), and sulfapyridine (1.4\%) were the main chemicals from human sources, while sulfamonomethoxine, sulfamethazine, sulfaquinoxaline, sulfaguanidine, sulfadiazine, sulfanilamide, and sulfamethoxypyridazine were dominant in the animal husbandry sources, specifically, swine and poultry farms, and sulfamethoxazole (91\%) was dominant in the mariculture source. A principal component analysis with multiple linear regression was performed to evaluate the source apportionment of total sulfonamides in Liaodong Bay. It was found that animal husbandry contributed 15.2\% of total sulfonamides, while human sources contributed 28.5\%, and combined human and mariculture sources contributed 56.3\%. In addition, the mariculture contribution was 24.1\% of total sulfonamides into the sea based on mass flux estimation. The present study is the first report that the environmental levels of sulfonamide metabolites were comparable to the corresponding parents; therefore, we should pay attention to their environmental occurrence. Source apportionment showed human discharge (60.7\%) significantly contributed to these antibiotics in Liaodong Bay, which provides important information for environmental management.

}, keywords = {Agriculture, Anti-Bacterial Agents, Aquaculture, China, Environmental Monitoring, Humans, Linear Models, Principal Component Analysis, Rivers, Seawater, Spectrometry, Mass, Electrospray Ionization, Sulfamethazine, Sulfamethoxazole, Sulfamethoxypyridazine, Sulfamonomethoxine, Sulfapyridine, Sulfaquinoxaline, Sulfonamides, Tandem Mass Spectrometry, Trimethoprim, Water Pollutants, Chemical, Water Pollution, Chemical}, issn = {1552-8618}, doi = {10.1002/etc.508}, author = {Jia, Ai and Hu, Jianying and Wu, Xiaoqin and Peng, Hui and Wu, Shimin and Dong, Zhaomin} }