Atmospheric concentrations and deposition of trichloroacetic acid in Scotland: results from a 2-year sampling campaign.

The first long-term concurrent measurements of trichloroacetic acid (TCA) in rainwater, in cloudwater, and in air (both gas and particle phase) are reported. Measurements were made weekly between June 1998 and April 2000 at a rural forested upland site in SE Scotland. Rainwater TCA concentration did not differ significantly between two elevations (602 and 275 m asl), with precipitation-weighted mean values of 0.77 and 0.70 microg L(-1), respectively (n > 75). The precipitation-weighted mean concentration of TCA in cloudwater at the highest elevation was 0.92 microg L(-1), yielding an average cloudwater enrichment factor of 1.2, considerably lower than for other inorganic ions measured. Rainwater and cloudwater TCA concentrations did not vary systematically with season. Since wet precipitation depth also did not vary systematically with season, the wet deposition fluxes of TCA were likewise invariant (annual fluxes at the highest elevation of 880 and 130 microg m(-2), respectively, for rain and cloud interception to spruce forest). Weekly integrated concentrations of TCA in air (gas and particle) were very low (median 25 pg m(-3), range < LOD-110 pg m(-3)). The estimated upper limit for annual dry deposition of TCA at this site was approximately 20 microg m(-2), assuming a deposition velocity of 2 cm s(-1). Concentrations of TCA in air correlated reasonably strongly with concentrations in rainwater, with a partition ratio approximately equal to the Henry's law coefficient. On average, only about 23% of TCA measured in Edinburgh air was associated with the particle phase. These measurements are consistent with the observed high scavenging ratio of TCA (ratio of concentration in air to concentration in rainwater). Overall, these data confirm that the atmosphere is an important source of TCA to the environment and that precipitation is the dominant transfer mechanism. In line with previous work, the atmospheric deposition flux is greater than expected from the current understanding of atmospheric production of TCA from anthropogenic precursors. It is suggested that aqueous-phase processes could lead to greater atmospheric conversion of chlorinated solvent precursors to TCA than is currently accepted.