A general scavenging rate constant for reaction of hydroxyl radical with organic carbon in atmospheric waters

Environ Sci Technol. 2013 Aug 6;47(15):8196-203. doi: 10.1021/es401927b. Epub 2013 Jul 18.

Abstract

Hydroxyl radical (OH) is an important oxidant in atmospheric aqueous phases such as cloud and fog drops and water-containing aerosol particles. We find that numerical models nearly always overestimate aqueous hydroxyl radical concentrations because they overpredict its rate of formation and, more significantly, underpredict its sinks. To address this latter point, we examined OH sinks in atmospheric drops and aqueous particles using both new samples and an analysis of published data. Although the molecular composition of organic carbon, the dominant sink of OH, is extremely complex and poorly constrained, this sink behaves very similarly in different atmospheric waters and even in surface waters. Thus, the sink for aqueous OH can be estimated as the concentration of dissolved organic carbon multiplied by a general scavenging rate constant [kC,OH = (3.8 ± 1.9) × 10(8) L (mol C)(-1) s(-1)], a simple process that should significantly improve estimates of OH concentrations in atmospheric drops and aqueous particles.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Atmosphere*
  • Carbon / chemistry*
  • Free Radical Scavengers / chemistry*
  • Hydroxyl Radical / chemistry*
  • Kinetics
  • Water / chemistry*

Substances

  • Free Radical Scavengers
  • Water
  • Hydroxyl Radical
  • Carbon