Molecular distributions of dicarboxylic acids, ketocarboxylic acids and alpha-dicarbonyls in biomass burning aerosols: implications for photochemical production and degradation in smoke layers

Aerosols in the size class < 2.5 mu m (6 daytime and 9 nighttime samples) were collected at a pasture site in Rondonia, Brazil, during the intensive biomass burning period of 16-26 September 2002 as part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia - Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC). Homologous series of dicarboxylic acids (C-2-C-11) and related compounds (ketocarboxylic acids and alpha-dicarbonyls) were identified using gas chromatography (GC) and GC/mass spectrometry (GC/MS). Among the species detected, oxalic acid was found to be the most abundant, followed by succinic, malonic and glyoxylic acids. Average concentrations of total dicarboxylic acids, ketocarboxylic acids and alpha-dicarbonyls in the aerosol samples were 2180, 167 and 56 ng m(-3), respectively. These are 2-8, 3-11 and 2-16 times higher, respectively, than those reported in urban aerosols, such as in 14 Chinese megacities. Higher ratios of dicarboxylic acids and related compounds to biomass burning tracers (levoglucosan and K+) were found in the daytime than in the nighttime, suggesting the importance of photochemical production. On the other hand, higher ratios of oxalic acid to other dicarboxylic acids and related compounds normalized to biomass burning tracers (levoglucosan and K+) in the daytime provide evidence for the possible degradation of dicarboxylic acids (>= C-3) in this smoke-polluted environment. Assuming that these and related compounds are photo-chemically oxidized to oxalic acid in the daytime, and given their linear relationship, they could account for, on average, 77% of the formation of oxalic acid. The remaining portion of oxalic acid may have been directly emitted from biomass burning as suggested by a good correlation with the biomass burning tracers (K+, CO and ECa) and organic carbon (OC). However, photochemical production from other precursors could not be excluded.