Volatility of methylglyoxal cloud SOA formed through OH radical oxidation and droplet evaporation

Abstract

The volatility of secondary organic aerosol (SOA) formed through cloud processing (aqueous hydroxyl radical (OH) oxidation and droplet evaporation) of methylglyoxal (MGly) was studied. Effective vapor pressure and effective enthalpy of vaporization (ΔHvap,eff) were determined using 1) droplets containing MGly and its oxidation products, 2) a Vibrating Orifice Aerosol Generator (VOAG) system, and 3) Temperature Programmed Desorption Aerosol-Chemical Ionization Mass Spectrometry (TPD Aerosol-CIMS). Simulated in-cloud MGly oxidation (for 10–30 min) produces an organic mixture of higher and lower volatility components with an overall effective vapor pressure of (4 ± 7) × 10−7 atm at pH 3. The effective vapor pressure decreases by a factor of 2 with addition of ammonium hydroxide (pH 7). The fraction of organic material remaining in the particle-phase after drying was smaller than for similar experiments with glycolaldehyde and glyoxal SOA. The ΔHvap,eff of pyruvic acid and oxalic acid + methylglyoxal in the mixture (from TPD Aerosol-CIMS) were smaller than the theoretical enthalpies of the pure compounds and smaller than that estimated for the entire precursor/product mix after droplet evaporation. After 10–30 min of aqueous oxidation (one cloud cycle) the majority of the MGly + OH precursor/product mix (even neutralized) will volatilize during droplet evaporation; neutralization and at least 80 min of oxidation at 10−12 M OH (or >12 h at 10−14 M) is needed before low volatility ammonium oxalate exceeds pyruvate.