Atmospheric chemistry of 4:2 fluorotelomer acrylate [C4F9CH2CH2OC(O)CH=CH2]: kinetics, mechanisms, and products of chlorine-atom- and OH-radical-initiated oxidation.

Relative rate techniques were used to measure the rate constants k[Cl + C(4)F(9)CH(2)CH(2)OC(O)CH=CH(2)] = (2.21 +/- 0.16) x 10(-10) and k[OH + C(4)F(9)CH(2)CH(2)OC(O)CH=CH(2)] = (1.13 +/- 0.12) x 10(-11) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air diluent at 296 K. The atmospheric lifetime of C(4)F(9)CH(2)CH(2)OC(O)CHCH(2) (4:2 FTAc) is determined by its reaction with OH radicals and is approximately 1 day. The chlorine-atom-initiated oxidation of 4:2 FTAc in 700 Torr of air at 296 K gives C(4)F(9)CH(2)C(O)H in molar yields of 18% and 10% in the absence and presence of NO, respectively. The OH-radical-initiated oxidation of 4:2 FTAc in 700 Torr of air in the presence of NO gives HCHO in a molar yield of (102 +/- 7)%, with C(4)F(9)CH(2)CH(2)OC(O)C(O)H (4:2 fluorotelomer glyoxylate) as the expected coproduct. The atmospheric fate of the 4:2 fluorotelomer glyoxylate will be photolysis and reaction with OH radicals, which will lead to the formation of C(4)F(9)CH(2)C(O)H and ultimately perfluorinated carboxylic acids. The atmospheric oxidation of fluorotelomer acrylates is a potential source of perfluorinated carboxylic acids in remote locations.