Measurement of the gas phase concentration of H₂SO₄ and methane sulfonic acid and estimates of H₂SO₄ production and loss in the atmosphere

Abstract

Measurements of gas phase sulfuric and methane sulfonic acid (MSA) have been performed using a relatively new atmospheric pressure selected ion chemical ionization mass spectrometric technique at two field sites. Both gas phase acids are photooxidation products, and their concentrations are seen to qualitatively follow solar flux. While sulfuric acid concentrations typically decline in conjunction with declining solar radiation, they sometimes level off in the mid 10 5 –10 6 molecules cm −3 range after dark, even in relatively clean air. The reason for this quasi‐stable nighttime sulfuric acid concentration is not well understood but may be a result of a steady state exchange of sulfuric acid between particles and the gas phase. Measurements of OH, H 2 SO 4 , and SO 2 concentrations in conjunction with aerosol number and size distribution also made possible the independent calculation of gas phase sulfuric acid production and loss rates. Calculated production and loss rates are seen to agree well in relatively clean air during the daylight hours. At night, however, the sulfuric acid concentrations and its calculated loss rate often have a nonzero value. In more polluted air masses, calculated gas phase sulfuric acid losses significantly exceed calculated production if H 2 SO 4 /aerosol reaction probabilities of 1.0 or 0.5 are assumed.