Brown Carbon Formation by Aqueous-Phase Carbonyl Compound Reactions with Amines and Ammonium Sulfate
Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV–vis and fluorescence spectroscopy monitoring. Glycolaldehyde–glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Åabs) of 2 to 11, overlapping the Åabs range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl–AS–amine reactions of ≤10% of global light absorption by brown carbon.
© 2013 American Chemical Society
Published in final form at:
M. H. Powelson, B. M. Espelien, L. N. Hawkins, M. M. Galloway, D. O. De Haan, "Brown carbon formation by aqueous-phase aldehyde reactions with amines and ammonium sulfate," Envrion. Sci. Technol. 48 (2) 985-993 (2014)
Powelson, Michelle H.; Espelien, Brenna M.; Hawkins, Leila N.; Galloway, Melissa M.; and De Haan, David O., "Brown Carbon Formation by Aqueous-Phase Carbonyl Compound Reactions with Amines and Ammonium Sulfate" (2014). Chemistry and Biochemistry Faculty Publications. 28.