Missing SO₂ oxidant in the coastal atmosphere? – Evidence from high resolution measurements of OH and atmospheric sulfur compounds

Abstract

Abstract. Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in N.E. Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected ion/chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 10 4 cm−3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analysed in conjunction with the condensational sink for both compounds derived from 3 nm–10 μm (diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed leading to estimated atmospheric lifetimes of the order of 7 min and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s) their ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated concentrations were consistently lower than the measured concentrations by a factor 4.8 ± 3.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photo-oxidation of biogenic iodine compounds. As to the identity of the oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on ab initio calculations. Stabilized Criegee intermediates (sCI) produced from ozonolysis of alkenes potentially contribute to the oxidation efficiency of the coastal and marine atmosphere. However, analysis of the CIMS background signal in context with recently published kinetic data currently suggests that larger Criegee intermediates produced from ozonolysis play no significant role for SO2 oxidation in the marine atmosphere. The possibility of H2SO4 formation without SO2 as precursor or from SO2 oxidation by small sCI produced photolytically should be explored.