Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Unique daily measurements of water-soluble organics in fine (<2 μm) and coarse (>2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C2-C12), ω-oxocarboxylic acids (C2-C9) and α-dicarbonyls (C2, C3) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C2) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C3) and succinic (C4) acids. Concentrations of total diacids in the fine aerosol fraction (0.2-64 ng m−3) were 5-60 times higher than those in the coarse fraction (0.01-3 ng m−3). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3-5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C2-C4) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.