Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol

Phys Chem Chem Phys. 2015 Apr 21;17(15):10227-37. doi: 10.1039/c4cp06095d.

Abstract

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Aerosols / chemistry*
  • Benzene / chemistry*
  • Catechols / chemistry
  • Hydroquinones / chemistry
  • Hydroxyl Radical / chemistry*
  • Organic Chemicals / chemistry
  • Resorcinols / chemistry
  • Water / chemistry*

Substances

  • Aerosols
  • Catechols
  • Hydroquinones
  • Organic Chemicals
  • Resorcinols
  • Water
  • Hydroxyl Radical
  • Benzene
  • catechol
  • hydroquinone
  • resorcinol