Determination of fluorotelomer alcohols and their degradation products in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry

Abstract

a b s t r a c tDegradation of fluorotelomer alcohols (FTOHs) was recognized as an additional source of perfluorocarboxylic acids (PFCAs). Quantification of FTOHs and their degradation products can help shed light on the sources and fates of PFCAs in the environment. In this study, an analytical method was developed for the determination of 6:2 and 8:2 FTOHs, and their degradation products of poly-and perfluorinated acids, including fluorotelomer saturated and unsaturated carboxylic acids (FTCAs and FTUCAs), secondary polyfluorinated alcohols and PFCAs in biosolids-amended soils and plants using ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The extract efficiencies of different methods including ethyl acetate and methanol (MeOH) for FTOHs and acetonitrile, MeOH, methyl tertbutyl ether (MTBE), NaOH-MeOH and NaOH-MTBE for poly-and perfluorinated acids were tested. The results showed that 6:2 and 8:2 FTOHs and their degradation products could be simultaneously and satisfactorily extracted by MeOH, cleaned up by Envi-Carb graphitized carbon and solid phase extraction, respectively, and determined by UPLC-MS/MS separately. NaOH in the extractant caused the conversion of 6:2 FTCA and 8:2 FTCA into the corresponding FTUCAs. The selected methods have matrix recoveries ranged from 52% to 102%, and detection limits of 0.01-0.46 ng/g dry weight for FTOHs and their degradation products in soil and plant. The optimized method was applied successfully to quantify FTOHs and their degradation products in two biosolids-amended soils and plants. The total concentrations of FTOHs in the soils were 44.1 ± 5.8 and 82.6 ± 7.1 ng/g, and in plants tissues 3.58 ± 0.25 and 8.33 ± 0.66 ng/g. The total concentrations of poly-and perfluorinated acids in the soils were 168.0 ± 13.2 and 349.6 ± 11.2 ng/g, and in plants tissues 78.0 ± 6.4 and 75.5 ± 5.3 ng/g.

Occurrence and Phase Distribution of Neutral and Ionizable Per- and Polyfluoroalkyl Substances (PFASs) in the Atmosphere and Plant Leaves around Landfills: A Case Study in Tianjin, China

“…Fluorotelomer alcohols (FTOHs), 13,14 perfluorooctane sulfonamides (FOSAs), 15 and perfluorooctane sulfonamidoethanols (FOSEs) 16 are precursors of most concern, and their degradation in various media has been well investigated in laboratory studies, where PFAAs and other saturated and unsaturated polyfluorinated acids were proposed as stable metabolites. 17 Hence, the long-range atmospheric transport (LRAT) of precursors and their subsequent degradation are proposed as a dominant source of PFAAs detected in the remote environment. 13 For the past ten years, polyfluoroalkyl phosphoric acid diesters (diPAPs) that are ionizable and biodegradable to perfluoroalkyl carboxylic acids (PFCAs) have been detected in human specimens, 18,19 indoor dust 20,21 as well as seawater.…”

Uptake, Translocation, and Metabolism of 8:2 Fluorotelomer Alcohol in Soybean (Glycine max L. Merrill)

“…Electrospray ionization was operated in negative mode, and multiple reaction monitoring (MRM) was used for all analysis. Details of the UPLC gradient, mass spectrometer operational parameters and quantification ion transitions for each of the analytes have been reported in our previous paper 27 and are summarized in Tables S3 and S4 of the SI. Glutathione (GSH)-conjugated metabolites were detected in soybean tissue extracts using an ACQUITY UPLC BEH Shield RP18 column (1.7 μm particles, 150 mm × 2.1 mm, Waters) with 2 mM ammonium acetate and methanol as mobile phases.…”

“…The solution samples were extracted immediately after sampling. The analyte extraction and cleanup procedures were based on our previous paper 27 with some modifications. The distribution of 8:2 FTOH in unplanted controls sampled at 144 h was determined.…”

“…In our previous study, FTOHs and their degradation products were found in soils and crops collected from a biosolidsamended agricultural field, suggesting the transfer and degradation potential of FTOHs in soil-plant systems. 27 The degradation products of FTOHs in plants are the integrated effects of plant degradation and plant uptake from soils. Rankin et al 28 reported the biodegradation products of fluorotelomerbased acrylate polymer (FTACP) in a soil-plant microcosm system; however, neither the FTACP nor 8:2 FTOH level was determined in plants.…”

Simultaneous determination of triclosan, triclocarban, triclocarban metabolites and byproducts in urine and serum by ultra‐high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry

“…Enzymatic hydrolysis of the conjugated compounds and the target analyte extraction are essential procedures for sample preparation 20 . Liquid–liquid extraction (LLE) and solid‐phase extraction (SPE) are widely applied for the analysis of organic compounds in biological matrices 21–23 . Asimakopoulos et al developed a LLE protocol, followed by LC/ESI‐MS/MS methodology, for the determination of multiple analytes, including TCS and TCC, in human urine 24 .…”