@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 {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} } @article {118, title = {Determination and occurrence of retinoic acids and their 4-oxo metabolites in Liaodong Bay, China, and its adjacent rivers.}, journal = {Environ Toxicol Chem}, volume = {29}, year = {2010}, month = {2010 Nov}, pages = {2491-7}, abstract = {

Retinoic acids (RAs) and their metabolites play an important role in abnormal morphological development and are speculated to be a possible cause for the increased rates of deformities in wild frog populations. In the current study, a method using ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry was developed for simultaneously analyzing all-trans-RA (at-RA), 13-cis-RA (13c-RA), 9-cis-RA (9c-RA), and their 4-oxo metabolites, all-trans-4-oxo-RA (at-4-oxo-RA), 13-cis-4-oxo-RA (13c-4-oxo-RA), and 9-cis-4-oxo-RA (9c-4-oxo-RA) in wastewaters and surface waters. Method detection limits were matrix dependent, ranging from 0.02 to 0.37 ng/L. The method was used to investigate the occurrence of RAs and 4-oxo-RAs in Liaodong Bay and its adjacent rivers. Of these six retinoids, at-RA, 13c-RA, at-4-oxo-RA, and 13c-4-oxo-RA were detected in river waters at detection frequencies of 100\%, 92\%, 48.6\%, and 21.6\%, and concentrations of 0.05 to 1.23 ng/L, less than 0.03 to 0.41 ng/L, less than 0.02 to 1.00 ng/L, and less than 0.06 to 0.81 ng/L, respectively. Retinoic acids were detected for the first time in the aquatic environment and were found to be more persistent than 4-oxo-RAs. The hazard quotient for mortality of frog embryos caused by induction by retinoids detected in the current study was then estimated, and the value was calculated to be 0.09. No retinoid was detected in seawaters.

}, keywords = {China, Chromatography, High Pressure Liquid, Rivers, Spectrometry, Mass, Electrospray Ionization, Stereoisomerism, Tretinoin, Water Pollutants, Chemical}, issn = {1552-8618}, doi = {10.1002/etc.322}, author = {Wu, Xiaoqin and Hu, Jianying and Jia, Ai and Peng, Hui and Wu, Shimin and Dong, Zhaomin} }