posted on 2021-04-22, 18:48authored byShira Joudan, John J. Orlando, Geoffrey S. Tyndall, Teles C. Furlani, Cora J. Young, Scott A. Mabury
Many
per- and polyfluoroalkyl substances (PFAS) have been regulated
or phased-out of usage due to concerns about persistence, bioaccumulation
potential, and toxicity. We investigated the atmospheric fate of a
new polyfluorinated alcohol 2-(1,1,2-trifluoro-2-heptafluoropropyloxy-ethylsulfanyl)-ethanol
(C3F7OCHFCF2SCH2CH2OH, abbreviated FESOH) by assessing the kinetics and products
of the gas-phase reaction of FESOH with chlorine atoms and hydroxyl
radicals. Experiments performed in a stainless-steel chamber interfaced
to an FTIR were used to determine reaction kinetics and gas-phase
products. We report reaction rate constants of k(Cl
+ FESOH) = (1.5 ± 0.6) × 10–11 cm3 molecule–1 s–1 and k(OH + FESOH) = (4.2 ± 2.0) × 10–12 cm3 molecule–1 s–1. This leads to a calculated FESOH gas-phase lifetime of 2.8 ±
1.3 days with respect to reaction with OH, assuming [OH] = 106 molecule1 cm–3. Gas-phase products
of FESOH oxidation included at least two aldehydes, likely C3F7OCHFCF2SCH2C(O)H and C3F7OCHFCF2SC(O)H, and secondary products including
COF2, SO2 and C3F7OC(O)F.
Additional gas-phase experiments performed in a Teflon chamber were
used to assess aqueous products by collecting gaseous samples offline
into an aqueous sink prior to analysis with ultrahigh performance
liquid chromatography-tandem mass spectrometry, resulting in four
acidic products: C3F7OCHFCF2SCH2C(O)OH, C3F7OCHFCF2S(O)(O)OH,
C3F7OCHFC(O)OH, and perfluoropropanoic acid
(C2F5C(O)OH).