A prominent
source of hydroxyl radicals (•OH),
nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart
from direct emission, HONO (or its conjugate base nitrite, NO2
–) can be formed secondarily in the atmosphere.
Yet, how secondary HONO forms requires elucidation, especially for
heterogeneous processes involving numerous organic compounds in atmospheric
aerosols. We investigated nitrite production from aqueous photolysis
of nitrate for a range of conditions (pH, organic compound, nitrate
concentration, and cation). Upon adding small oxygenates such as ethanol, n-butanol, or formate as •OH scavengers,
the average intrinsic quantum yield of nitrite [Φ(NO2
–)] was 0.75 ± 0.15%. With near-UV-light-absorbing
vanillic acid (VA), however, the effective Φ(NO2
–) was strongly pH-dependent, reaching 8.0 ± 2.1%
at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant
pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance
the nitrite production from the aqueous nitrate photolysis through
photosensitizing reactions, where the triplet excited state of BrC
may generate solvated electrons, which reduce nitrate to NO2 for further conversion to nitrite. This photosensitization process
by BrC chromophores during nitrate photolysis under mildly acidic
conditions may partly explain the missing HONO in urban environments.
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