Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: Kinetics and mechanism of reaction with OH

Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada
Environmental Science and Technology (Impact Factor: 5.33). 03/2006; 40(6):1862-8. DOI: 10.1021/es0520767
Source: PubMed


Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.

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    • "Several typical neutral PFASs, such as fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTAs), perfluorooctane sulfonamides (FOSAs) and perfluorooctane sulfonamidoethanols (FOSEs), are prone to release into the atmosphere and undergo long range atmospheric transport (LRAT) during their manufacture, use and disposal (Paul et al., 2009). These PFASs can degrade to, for example perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), under the condition of $OH radicals initiated oxidation in the atmosphere (Butt et al., 2009; D'Eon et al., 2006). "
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    Environmental Pollution 07/2015; 202. DOI:10.1016/j.envpol.2015.03.029 · 4.14 Impact Factor
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    • "Me-and EtFOSA, and Me-and EtFOSE). The high concentrations of the shorter chain compounds of PFBS and PFBA and their precursors found in this study possibly reflect the growing environmental occurrence of these compounds following increased production of MeFBSE, and other C 4 fluorocarbon products, following the industry phase out of perfluorooctanesulfonyl fluoride (POSF) (D'Eon et al., 2006 "
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    • "In contrast, PFOS is the predominant compound in wildlife (Kannan et al., 2001a,b), which can be explained by its higher bioaccumulation potential, whereas PFOA has a higher water solubility (Brooke et al., 2004) and lower sorption potential to sediment (Higgins and Luthy, 2006). On the other hand, the PFOA concentrations are usually higher in open-ocean waters compared to PFOS, which can be explained by different amount of discharge into the aqueous environment , different sources (Prevedouros et al., 2006; Paul et al., 2009), different degradation process of the precursors (Ellis et al., 2004; D'Eon et al., 2006) and different physico-chemical characteristics. "
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