Urban and rural observations of carboxylic acids in rainwater in Southwest of China: the impact of urbanization

Abstract

Seven carboxylic acids in rainwater were simultaneously determined using ion chromatography for 13 months in two different sites, Guiyang and Shangzhong, southwest of China. Results showed formic, acetic and oxalic acids were the three predominant carboxylic acids. Their volume-weighted average concentrations were 14.24, 9.35, 2.79 μmol/L in Guiyang and 4.95, 1.35, 2.31 μmol/L in Shangzhong, respectively. A distinctive diurnal pattern in carboxylic acid concentrations (daytime>nighttime, t test, p < 0.05) was observed during the growing season in Guiyang. Shangzhong witnessed higher concentration of these acids during the growing season than that during the non-growing season. Direct emissions from growing vegetation or soils probably account for the main provenance of the acids in the rural area. However, the opposite trend were found in Guiyang and the anthropogenic sources during the non-growing season were the main reason. By comparison of our result with the previous data about 20 years ago, we calculated that at least 42% of acetic acids and 69% of formic acid originated from the anthropogenic sources in Guiyang. Furthermore, the ratio of formate/acetate in gas phase larger than 1 suggest the oxidation of unsaturated hydrocarbons from the human activity and/or natural sources were the main origin of carboxylic acids in Guiyang. While The F/A ratio in gas phase was less than 1 in Shangzhong which indicate the direct emissions from biogenic sources. Oxalic acid was in similar amounts in both sites, indicating the common source of the acid.