Brown
carbon (BrC) formed from glyoxal+ammonium sulfate (AS) and
methylglyoxal+AS reactions photobleaches quickly, leading to the assumption
that BrC formed overnight by Maillard reactions will be rapidly destroyed
at sunrise. Here, we tested this assumption by reacting glyoxal, methylglyoxal,
glycolaldehyde, or hydroxyacetone in aqueous mixtures with reduced
nitrogen species at pH 4–5 in the dark and in sunlight (>350
nm) for at least 10 h. The absorption of fresh carbonyl+AS mixtures
decreased when exposed to sunlight, and no BrC formed, as expected
from previous work. However, the addition of amines (either methylamine
or glycine) allowed BrC to form in sunlight at comparable rates as
in the dark. Hydroxyacetone+amine+AS aqueous mixtures generally browned
faster in sunlight than in the dark, especially in the presence of
HOOH, indicating a radical-initiated BrC formation mechanism is involved.
In experiments with airborne aqueous aerosol containing AS, methylamine,
and glyoxal or methylglyoxal, browning was further enhanced, especially
in sunlight (>300 nm), forming aerosol with optical properties
similar
to “very weak” atmospheric BrC. Liquid chromatography-electrospray
ionization-mass spectrometry (LC-ESI-MS) analysis of aerosol filter
extracts indicates that exposure of methylglyoxal+AS aqueous aerosol
to methylamine gas, sunlight, and cloud processing increases incorporation
of ammonia, methylamine, and photolytic species (e.g., acetyl radicals)
into conjugated oligomer products. These results suggest that when
amines are present, photolysis of first-generation, “dark reaction”
BrC (imines and imidazoles) initiates faster, radical-initiated browning
processes that may successfully compete with photobleaching, are enhanced
in aqueous aerosol particles relative to bulk liquid solutions, and
can produce BrC consistent with atmospheric observations.