Second-Order Kinetic Rate Coefficients for the Aqueous-Phase Sulfate Radical (SO4•-) Oxidation of Some Atmospherically Relevant Organic Compounds

J Phys Chem A. 2022 Sep 22;126(37):6517-6525. doi: 10.1021/acs.jpca.2c04964. Epub 2022 Sep 7.

Abstract

The sulfate anion radical (SO4•-) is a reactive oxidant formed in the autoxidation chain of sulfur dioxide, among other sources. Recently, new formation pathways toward SO4•- and other reactive sulfur species have been reported. This work investigated the second-order rate coefficients for the aqueous SO4•- oxidation of the following important organic aerosol compounds (kSO4): 2-methyltetrol, 2-methyl-1,2,3-trihydroxy-4-sulfate, 2-methyl-1,2-dihydroxy-3-sulfate, 1,2-dihydroxyisoprene, 2-methyl-2,3-dihydroxy-1,4-dinitrate, 2-methyl-1,2,4-trihydroxy-3-nitrate, 2-methylglyceric acid, 2-methylglycerate, lactic acid, lactate, pyruvic acid, pyruvate. The rate coefficients of the unknowns were determined against that of a reference in pure water in a temperature range of 298-322 K. The decays of each reagent were measured with nuclear magnetic resonance (NMR) and high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS). Incorporating additional SO4•- reactions into models may aid in the understanding of organosulfate formation, radical propagation, and aerosol mass sinks.

MeSH terms

  • Aerosols / chemistry
  • Lactic Acid
  • Nitrates*
  • Organic Chemicals / chemistry
  • Oxidants
  • Oxidation-Reduction
  • Pyruvic Acid
  • Sulfates / chemistry
  • Sulfur
  • Sulfur Dioxide* / chemistry
  • Water

Substances

  • Aerosols
  • Nitrates
  • Organic Chemicals
  • Oxidants
  • Sulfates
  • sulfate radical
  • Water
  • Sulfur Dioxide
  • Lactic Acid
  • Sulfur
  • Pyruvic Acid