Tropospheric Aqueous-Phase Oxidation of Isoprene-Derived Dihydroxycarbonyl Compounds.

The dihydroxycarbonyls 3,4-dihydroxy-2-butanone (DHBO) and 2,3-dihydroxy-2-methylpropanal (DHMP) formed from isoprene oxidation products in the atmospheric gas phase under low-NO conditions can be expected to form aqSOA in the tropospheric aqueous phase because of their solubility. In the present study, DHBO and DHMP were investigated concerning their radical-driven aqueous-phase oxidation reaction kinetics. For DHBO and DHMP the following rate constants at 298 K are reported: k(OH + DHBO) = (1.0 ± 0.1) × 109 L mol-1 s-1, k(NO3 + DHBO) = (2.6 ± 1.6) × 106 L mol-1 s-1, k(SO4-+ DHBO) = (2.3 ± 0.2) × 107 L mol-1 s-1, k(OH + DHMP) = (1.2 ± 0.1) × 109 L mol-1 s-1, k (NO3 + DHMP) = (7.9 ± 0.7) × 106 L mol-1 s-1, k(SO4- + DHMP) = (3.3 ± 0.2) × 107 L mol-1 s-1, together with their respective temperature dependences. The product studies of both DHBO and DHMP revealed hydroxydicarbonyls, short chain carbonyls, and carboxylic acids, such as hydroxyacetone, methylglyoxal, and lactic and pyruvic acid as oxidation products with single yields up to 25%. The achieved carbon balance was 75% for DHBO and 67% for DHMP. An aqueous-phase oxidation scheme for both DHBO and DHMP was developed on the basis of the experimental findings to show their potential to contribute to the aqSOA formation. It can be expected that the main contribution to aqSOA occurs via acid formation while other short-chain oxidation products are expected to back-partition into the gas phase to undergo further oxidation there.