Ammonium addition (and aerosol pH) has a dramatic impact on the volatility and yield of glyoxal secondary organic aerosol

Environ Sci Technol. 2014;48(1):255-62. doi: 10.1021/es4035667. Epub 2013 Dec 20.

Abstract

Glyoxal is an important precursor to secondary organic aerosol (SOA) formed through aqueous chemistry in clouds, fogs, and wet aerosols, yet the gas-particle partitioning of the resulting mixture is not well understood. This work characterizes the volatility behavior of the glyoxal precursor/product mix formed after aqueous hydroxyl radical oxidation and droplet evaporation under cloud-relevant conditions for 10 min, thus aiding the prediction of SOA via this pathway (SOACld). This work uses kinetic modeling for droplet composition, droplet evaporation experiments and temperature-programmed desorption aerosol-chemical ionization mass spectrometer analysis of gas-particle partitioning. An effective vapor pressure (p'L,eff) of ∼10(-7) atm and an enthalpy of vaporization (ΔHvap,eff) of ∼70 kJ/mol were estimated for this mixture. These estimates are similar to those of oxalic acid, which is a major product. Addition of ammonium until the pH reached 7 (with ammonium hydroxide) reduced the p'L,eff to <10(-9) atm and increased the ΔHvap,eff to >80 kJ/mol, at least in part via the formation of ammonium oxalate. pH 7 samples behaved like ammonium oxalate, which has a vapor pressure of ∼10(-11) atm. We conclude that ammonium addition has a large effect on the gas-particle partitioning of the mixture, substantially enhancing the yield of SOACld from glyoxal.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aerosols / analysis
  • Aerosols / chemistry*
  • Ammonium Compounds / chemistry*
  • Glyoxal / chemistry*
  • Hydroxyl Radical / chemistry
  • Kinetics
  • Oxidation-Reduction
  • Volatilization
  • Water / chemistry

Substances

  • Aerosols
  • Ammonium Compounds
  • Water
  • Hydroxyl Radical
  • Glyoxal