title: Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.
abstract: 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 (Å(abs)) of 2 to 11, overlapping the Å(abs) 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of San Diego , 5998 Alcala Park, San Diego California 92110.
authors.forename: Michelle H
authors.initials: MH
authors.lastname: Powelson
authors.forename: Brenna M
authors.initials: BM
authors.lastname: Espelien
authors.forename: Lelia N
authors.initials: LN
authors.lastname: Hawkins
authors.forename: Melissa M
authors.initials: MM
authors.lastname: Galloway
authors.forename: David O
authors.initials: DO
authors.lastname: De Haan
mesh_terms: D000588:Amines / Q000737:chemistry*; D000645:Ammonium Sulfate / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D045424:Complex Mixtures / Q000737:chemistry; D005453:Fluorescence; D005998:Glycine / Q000737:chemistry; D006037:Glyoxal / Q000737:chemistry; D008744:Methylamines / Q000737:chemistry; D009930:Organic Chemicals / Q000737:chemistry*; D011765:Pyruvaldehyde / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*
chemical_list: D000588:Amines; D045424:Complex Mixtures; D008744:Methylamines; D009930:Organic Chemicals; D014867:Water; D006037:Glyoxal; D011765:Pyruvaldehyde; D002244:Carbon; C027451:methylamine; D000645:Ammonium Sulfate; D005998:Glycine