Estimated congener specific gas-phase atmospheric behavior and fractionation of perfluoroalkyl compounds: rates of reaction with atmospheric oxidants, air-water partitioning, and wet/dry deposition lifetimes.
A quantitative structure-activity model has been validated for estimating congener specific gas-phase hydroxyl radical reaction rates for perfluoroalkyl sulfonic acids (PFSAs), carboxylic acids (PFCAs), aldehydes (PFAls) and dihydrates, fluorotelomer olefins (FTOls), alcohols (FTOHs), aldehydes (FTAls), and acids (FTAcs), and sulfonamides (SAs), sulfonamidoethanols (SEs), and sulfonamido carboxylic acids (SAAs), and their alkylated derivatives based on calculated semi-empirical PM6 method ionization potentials. Corresponding gas-phase reaction rates with nitrate radicals and ozone have also been estimated using the computationally derived ionization potentials. Henry's law constants for these classes of perfluorinated compounds also appear to be reasonably approximated by the SPARC software program, thereby allowing estimation of wet and dry atmospheric deposition rates. Both congener specific gas-phase atmospheric and air-water interface fractionation of these compounds is expected, complicating current source apportionment perspectives and necessitating integration of such differential partitioning influences into future multimedia models. The findings will allow development and refinement of more accurate and detailed local through global scale atmospheric models for the atmospheric fate of perfluoroalkyl compounds.
Rayne
Sierra
S
Department of Chemistry, University of Winnipeg, Winnipeg, Manitoba, Canada. rayne.sierra@gmail.com
Forest
Kaya
K
Friesen
Ken J
KJ
D000388:Air; D000393:Air Pollutants / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007536:Isomerism; D008956:Models, Chemical; D010083:Oxidants, Photochemical / Q000737:chemistry*; D010126:Ozone / Q000737:chemistry*; D021281:Quantitative Structure-Activity Relationship; D014867:Water / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000737:chemistry*
D000393:Air Pollutants; D005740:Gases; D006845:Hydrocarbons, Fluorinated; D010083:Oxidants, Photochemical; D014874:Water Pollutants, Chemical; D014867:Water; D010126:Ozone