Photochemistry of Products of the Aqueous Reaction of Methylglyoxal with Ammonium Sulfate

Abstract

Aqueous reactions of methylglyoxal (MG) and glyoxal with ammonium sulfate (AS) produce light-absorbing compounds (chromophores) and may serve as a source of atmospheric secondary “brown carbon” (BrC). The molecular composition of these chromophores is ambiguous, and their transformation due to exposure to solar UV radiation is not well understood. We examined the molecular composition, mass absorption coefficients, and fluorescence spectra of BrC samples produced by the evaporation of aqueous MG/AS solutions. Chromatograms of BrC produced by evaporation were different from those of BrC produced by slow MG/AS reaction in water, highlighting the substantial sensitivity of BrC to its formation conditions. The BrC samples were characterized before and after their exposure to broadband (270–390 nm) UV radiation. Irradiation led to rapid photobleaching, a decrease in the characteristic 280 nm absorption band, a complete loss of fluorescence, and a dramatic change in molecular composition. By comparing the compo...