Particulate and dissolved organic carbon in cloud water in southern Scotland

Total particulate carbon (TPC), which includes both elemental carbon and particulate organic carbon, total suspended particulate matter (TSP) and dissolved organic carbon (DOC) were measured in 53 cloud water samples collected using a passive 'Harp-wire' cloud collector at weekly intervals at a hill-top site in southern Scotland (Dunslair Heights, 602 m above sea level) between December 1990 and April 1992. The concentrations of TPC, TSP and DOC were in the range 0.03-6.9 mg 1(-1) (median 1.05 mg l(-1)), 2.6-51.6 mg l(-1) (median 13.6 mg l(-1)) and 0.-14 mg l(-1) (median 3.6 mg l(-1)), respectively. The concentrations of TPC, TSP and DOC were greatest in winter (December-February), up to 6.9, 42 and 4.6 mg l(-1) respectively in 1990-1991 and up to 6.0, 51 and 14 mg l(-1), respectively, in 1991-1992. Particulate carbon in cloud water samples comprised 1-47% of the TSP. Concentrations of major anions (Cl(-), NO(-)(3), SO(2-)(4)) and pH were measured on the same water samples. Estimates of cloud liquid water content from January to April 1992 were derived from measured wind speeds and volumes of water collected. These estimates suggested that the air contained up to 1.2 microg TPC m(-3), 16 microg TSP m(-3) and 2.3 microg DOC m(-3), which are typical of concentrations to be expected in rural air. There was no correlation between concentrations of DOC in cloud water and either TPC or TSP, indicating that the sources and partitioning of DOC and TPC in the atmosphere are different. The largest concentrations of TPC coincided with the largest concentrations of non-marine sulphate, and although there was a significant linear correlation between the two sets of data, the log-transformed data were not correlated. Concentrations of TPC were significantly correlated with concentrations of other particulate matter (TSP-TPC), suggesting that similar sources and/or partitioning processes were involved in determining concentrations in cloud. Concentrations of DOC in cloud were significantly correlated (p < 0.02) with concentrations of nitrate, suggesting that sources of DOC were related to the emission and chemistry of nitrogen oxides. The very large concentrations of particulate carbon, especially in winter, indicate that carbon-catalysed oxidation of sulphur dioxide by molecular oxygen in cloud water may be a significant pathway when concentrations of hydrogen peroxide are small.