Atmospheric perfluorinated acid precursors: chemistry, occurrence, and impacts

Perfluorocarboxylic acids (PFCAs) can be found from the hydrolysis of perfluoroacyl fluorides and chlorides, which can be produced in three separate ways in the atmosphere. Alternatively, PFCAs can be formed directly in the gas phase through reaction of perfluoroacyl peroxy radicals or perfluorinated aldehyde hydrates. All five mechanisms have been elucidated using smog chamber techniques. Yields of the PFCAs from this process vary from less than 10% to greater than 100%, depending on the mechanism. The formation of perfluorosulfonic acids in the atmosphere can also occur, though the mechanism has not been entirely elucidated. A large number of compounds have been confirmed as perfluorinated acid precursors, including CFC-replacement compounds, anesthetics, fluorotelomer compounds, and perfluorosulfonamides. Levels of some of these compounds have been measured in the atmosphere, but concentration for the majority have yet to be detected. It is clear that atmospheric oxidation of volatile precursors contributes to the overall burden of PFAs, though the extent to which this occurs is compound and environment dependent and is difficult to assess accurately.