Chemical transformation of α-pinene-derived organosulfate via heterogeneous OH oxidation : implications for sources and environmental fates of atmospheric organosulfates

Abstract

Organosulfur compounds are found to be ubiquitous in atmospheric aerosols - a majority of which are expected to be organosulfates (OSs). Given the atmospheric abundance of OSs, and their potential to form a variety of reaction products upon aging, it is imperative to study the transformation kinetics and chemistry of OSs to better elucidate their atmospheric fates and impacts. In this work, we investigated the chemical transformation of an α-pinene-derived organosulfate (C10H17O5SNa, αpOS-249) through heterogeneous OH oxidation at a relative humidity of 50 % in an oxidation flow reactor (OFR). The aerosol-phase reaction products were characterized using high-performance liquid chromatography-electrospray ionization-high-resolution mass spectrometry and ion chromatography. By monitoring the decay rates of αpOS-249, the effective heterogeneous OH reaction rate was measured to be (6.72±0.55)×10-13 cm3 molecule-1 s-1. This infers an atmospheric lifetime of about 2 weeks at an average OH concentration of 1.5×106 molecules cm-3. Product analysis shows that OH oxidation of αpOS-249 can yield more oxygenated OSs with a nominal mass-to-charge ratio (m/z) at 247 (C10H15O5S-), 263 (C10H15O6S-), 265 (C10H17O6S-), 277 (C10H13O7S-), 279 (C10H15O7S-), and 281 (C10H17O7S-). The formation of fragmentation products, including both small OSs (C <10) and inorganic sulfates, is found to be insignificant. These observations suggest that functionalization reactions are likely the dominant processes and that multigenerational oxidation possibly leads to formation of products with one or two hydroxyl and carbonyl functional groups adding to αpOS-249. Furthermore, all product ions except m/zCombining double low line277 have been detected in laboratory-generated α-pinene-derived secondary organic aerosols as well as in atmospheric aerosols. Our results reveal that OSs freshly formed from the photochemical oxidation of α-pinene could react further to form OSs commonly detected in atmospheric aerosols through heterogeneous OH oxidation. Overall, this study provides more insights into the sources, transformation, and fate of atmospheric OSs.