Trifluoroacetic acid (TFA; CF₃ 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 CF₃COX (X = F or Cl), followed by in-cloud hydrolysis of CF₃COX 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 CF₃CHFO 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.

We simulate accumulation of Al₂O₃ particles in the atmosphere produced by solid-fueled rocket motors by using the Goddard Institute for Space Studies/University of California at Irvine three-dimensional (3-D) chemistry-transport model (CTM). Our study differs from Jackman et al. (1998) by applying a 3-D CTM, considering 13 size bins for the emitted particles from 0.025 to 10 μm and taking into account their washout, gravitational sedimentation, and coagulation with background sulfate aerosol. We assume an initial trimodal size distribution of Al₂O₃ particles (Beiting, 1997) with 2.8% by mass of the alumina emitted as particles with radius of less than 1 μm. Our test case adopts a stratospheric source of 1120 tons/yr equivalent to nine space Shuttle and four Titan IV launches annually. The calculated steady state surface area density (SAD) and mass density for the scenarios with sedimentation of alumina particles have maximum values in the lower stratosphere in the Northern Hemisphere of up to 7×10⁻⁴ μm²/cm³ and 0.09 ng/m³, respectively, or about 1000 times smaller than those of the background sulfate aerosol. Our results are sensitive to the emitted mass fractionation of alumina (EMFA) showing the values for the SAD or mass density higher or lower by an order of magnitude owing to a poorly known EMFA. Chemical implications of alumina particle accumulation for the ozone balance are estimated by using the Atmospheric and Environmental Research 2-D model assuming chlorine activation on Al₂O₃ surfaces via the C1ONO₂ + HCl → Cl₂ + HNO₃ reaction with a probability of 0.02 (Molina et al., 1997). Owing to the very small Al₂O₃ SAD, any additional ozone depletion due to Al₂O₃ emissions is also small (0.0028% on a global annually averaged basis for the scenario with sedimentation, or about 4 times smaller than the ozone response to chlorine emissions only). The ozone depletion potential of the alumina emissions is about 0.03–0.08 for the scenarios using the EMFA of Beiting (1997) and larger by an order of magnitude for the EMFA of Brady and Martin (1995).