MEASUREMENTS OF H2O2, ALDEHYDES AND ORGANIC-ACIDS IN LOS-ANGELES RAINWATER - THEIR SOURCES AND DEPOSITION RATES

Rainwater samples were collected in Los Angeles, during 1985-1991 to d etermine concentration. levels, sources and deposition rates of atmosp heric H2O2, aldehydes and organic acids, in addition to major cations, anions and pH. Volume-weighted mean concentrations of H2O2, aldehydes (formaldehyde + acetaldehyde + glyoxal + methylglyoxal) and organic a cids (formic acid + acetic acid) in rain collected at Westwood were 4. 4, 3.9 and 16.5 muM respectively, during the 6-year study period. Mono carboxylic organic acids were estimated to account for 27% (2-80%) of total free acidity (as on overall average) in rain collected at Westwo od, whereas sulfuric acid and nitric acid accounted for 39% and 34% of the total acidity, respectively. Concentrations of aldehydes were str ongly dependent on precipitation volume and with increasing precipitat ion volume, whereas H2O2 and organic acids were only weakly dependent on precipitation volume. These results indicate that concentrations of aldehydes in rain are mainly controlled by dilution, whereas H2O2 and organic acid concentrations are controlled by other factors, such as decomposition of H2O2 by reacting with S(IV) and continuous aqueous fo rmation/decomposition of organic acids by reactions involving aldehyde s, dissolved OH radicals and H2O2. Principal component analyses indica te that aldehydes in rainwater mainly originate from gases and aerosol s derived from anthropogenic sources, whereas the sources of H2O2 and organic acids in rain do not correlate with anthropogenic sources or m arine and continental sources. There is good agreement between reporte d gas-phase concentrations of H2O2, aldehydes and organic acids in Los Angeles and calculated equilibrium concentrations of these chemical s pecies from their rainwater concentrations and Henry's law constants. Temporal variations of concentrations of chemical species indicate tha t H2O2, aldehydes and organic acids were highest in the early afternoo n. Summer rains contained the highest concentration of these chemical species, suggesting the photochemical activities during rain storms si gnificantly affect their concentration levels. Estimation of annual ra te of wet and dry depositions of H2O2, aldehydes and organic acids for the period studied, indicates that 84% of H2O2, 97% of aldehydes and 94% of organic acids, respectively, are annually scavenged from the at mosphere, by dry deposition, which is the dominant process for removal of these atmospheric pollutants in Los Angeles.