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

Environ Sci Technol. 2006 Mar 15;40(6):1862-8. doi: 10.1021/es0520767.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Air Pollutants*
  • Atmosphere / chemistry*
  • Fluorocarbons / analysis
  • Fluorocarbons / chemistry*
  • Gas Chromatography-Mass Spectrometry
  • Hydroxyl Radical / chemistry*
  • Kinetics
  • Spectroscopy, Fourier Transform Infrared
  • Sulfonamides / analysis
  • Sulfonamides / chemistry*
  • Sulfonic Acids / analysis
  • Sulfonic Acids / chemistry
  • Trifluoroacetic Acid / analysis
  • Trifluoroacetic Acid / chemistry

Substances

  • Air Pollutants
  • Fluorocarbons
  • N-methyl perfluorobutane sulfonamidoethanol
  • Sulfonamides
  • Sulfonic Acids
  • Hydroxyl Radical
  • perfluorobutyric acid
  • Trifluoroacetic Acid
  • perfluorobutane