Trifluoroacetic acid from degradation of HCFCs and HFCs: A three‐dimensional modeling study

Trifluoroacetic acid (TFA; CF 3 COOH) is produced by the degradation of the halocarbon replacements HFC‐134a, HCFC‐124, and HCFC‐123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF 3 COX (X = F or Cl), followed by in‐cloud hydrolysis of CF 3 COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long‐term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC‐134a, HCFC‐124, and HCFC‐123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 μg/L if washout were the only removal mechanism for TFA. We present 3‐D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse‐resolution (8° latitude by 10° longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 μg/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15–0.20 μg/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3–0.45 μg/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF 3 CHFO is produced in the degradation of HFC‐134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.