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Recent research in atmospheric chemistry suggested that gaseous amines may rapidly react with the acidic components in the aerosol to be incorporated in the particle phase. However, laboratory experiments suggested that these heterogeneous processes may be sensitive to the reaction conditions, such as relative humidity (RH), the initial aerosol acidity and the initial concentration of gaseous ammonia which is ubiquitous in the atmosphere. We studied the heterogenous reactions between several amines and ammonium sulfate using a series of thermodynamic simulations under varying initial conditions, including RH, particle-phase acidity and gaseous amine and ammonia concentrations. Several distinctively different trends in the particle-phase ammonium, amines and water content were observed, depending significantly on the particle-phase acidity and the initial amine to ammonia mole ratio. One notable observation was that alkylamines may facilitate the water uptake of ammonium sulfate even in the presence of 1000 times more ammonia gas. Such change in aerosol water content may alter the surface tension, uptake coefficient and could formation properties of aerosol and influence the radiative forcing of the particles.
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Glyoxal's impact on dry ammonium salts: fast and reversible surface aerosol browning
Abstract. Alpha-dicarbonyl compounds are believed to form browncarbon in the atmosphere via reactions with ammonium sulfate (AS) in clouddroplets and aqueous aerosol particles. In this work, brown carbon formationin AS and other aerosol particles was quantified as a function of relativehumidity (RH) during exposure to gas-phase glyoxal (GX) in chamberexperiments. Under dry conditions (RH < 5 %), solid AS,AS–glycine, and methylammonium sulfate (MeAS) aerosol particles brown withinminutes upon exposure to GX, while sodium sulfate particles do not. When GXconcentrations decline, browning goes away, demonstrating that this drybrowning process is reversible. Declines in aerosol albedo are found to be afunction of [GX]2 and are consistent between AS and AS–glycineaerosol. Dry methylammonium sulfate aerosol browns 4 times more than dryAS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol.Optical measurements at 405, 450, and 530 nm provide an estimatedÅngstrom absorbance coefficient of -16±4. This coefficient andthe empirical relationship between GX and albedo are used to estimate anupper limit to global radiative forcing by brown carbon formed by 70 ppt GXreacting with AS (+7.6×10-5 W m−2). This quantity is< 1 % of the total radiative forcing by secondary brown carbonbut occurs almost entirely in the ultraviolet range.
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- Award ID(s):
- 1826593
- PAR ID:
- 10199997
- Date Published:
- Journal Name:
- Atmospheric Chemistry and Physics
- Volume:
- 20
- Issue:
- 16
- ISSN:
- 1680-7324
- Page Range / eLocation ID:
- 9581 to 9590
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/acp-20-9581-2020
