SO₂ photolysis as a source for sulfur mass-independent isotope signatures in stratospheric aerosols

Abstract

Abstract. Signatures of sulfur isotope mass-independent fractionation (S-MIF) have been observed in stratospheric sulfate aerosols deposited in polar ice. The S-MIF signatures are associated with stratospheric photochemistry following stratospheric volcanic eruptions, but the exact mechanism responsible for the production and preservation of these signatures is debated. In order to identify the origin and the mechanism of preservation for these signatures, a series of laboratory photochemical experiments were carried out to investigate the effect of temperature and added O2 on S-MIF produced by the two absorption band systems of SO2 photolysis in the 190 to 220 nm region and photoexcitation in the 250 to 350 nm region. The SO2 photolysis (SO2 + hν → SO + O) experiments showed S-MIF signals with large 34S / 32S fractionation, which increases with decreasing temperature. The overall S-MIF pattern observed for photolysis experiments, including high 34S / 32S fractionations, positive mass-independent anomalies in 33S, and negative anomalies in 36S, is consistent with a major contribution from optical isotopologue screening effects and measurements for stratospheric sulfate aerosols. SO2 photoexicitation produced products with positive MIF anomalies in both 33S and 36S that is different from stratospheric aerosols. SO2 photolysis in the presence of O2 produced SO3 with S-MIF signals, suggesting the transfer of the MIF signals of SO to SO3 by the SO + O2 + M → SO3 + M reaction. This is supported with energy calculations of stationary points on the SO3 potential energy surfaces, which indicate that this reaction occurs slowly on a single adiabatic surface, but that it can occur more rapidly through intersystem crossing. The results from our experiments constrain the termolecular reaction rate to between 1.0 × 10−37 cm6 molecule−2 s−1 and 1.0 × 10−36 cm6 molecule−2 s−1. This rate can explain the preservation of mass independent isotope signatures in stratospheric sulfate aerosols and provides a minor, but important, oxidation pathway for stratospheric SO2 above about 25 km altitude. The production and preservation of S-MIF signals in the stratosphere requires a high SO2 column density and an SO2 plume reaching an altitude of 25 km and higher.