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

Abstract

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/z=277 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.

Heterogeneous Formation of Organonitrates (ON) and Nitroxy-Organosulfates (NOS) from Adsorbed α-Pinene-Derived Organosulfates (OS) on Mineral Surfaces

“…Table S2 provides detailed information on the mass fragmentation of identified compounds. Similar OS compounds were identified in various field and chamber studies, suggesting the formation of these OS compounds from α-pinene occurs in a broader environment. ,,,,− …”

“…Similar OS compounds were identified in various field and chamber studies, suggesting the formation of these OS compounds from α-pinene occurs in a broader environment. 19 , 26 , 27 , 41 , 65 − 67 …”

Significant Conversion of Organic Sulfur from Hydroxymethanesulfonate to Inorganic Sulfate and Peroxydisulfate Ions upon Heterogeneous OH Oxidation

“…The aerosols were directly mixed with O 3 -laden gas and humidified gas. Inside the reactor, gas-phase OH radicals were produced from the photolysis of O 3 in the presence of water vapor under the irradiation of 254 nm ultraviolet (UV) lamps. , The concentration of gas-phase OH radicals was regulated by varying the amount of O 3 and determined by measuring the decay of sulfur dioxide (SO 2 ) . The OH exposure, representing the product of gas-phase OH radical concentration (0 to 9.02 × 10 9 molecules cm –3 ) and aerosol residence time (156 s), used herein ranged from 0 to 1.41 × 10 12 molecules cm –3 s, which is equivalent to about 11 days of atmospheric exposure (assuming a 24 h averaged ambient OH concentration = 1.5 × 10 6 molecules cm –3 ) .…”

Physical properties of short chain aqueous organosulfate aerosol

“…1 Organosulfates have been identified in aerosol collected during field campaigns, 2–12 and are commonly observed as key contributors to secondary organic aerosol (SOA) in laboratory studies. 1,3,13–19 These organosulfates are formed through chemical reactions between volatile organic compounds, such as limonene, isoprene and α-pinene, with atmospheric oxidants and with sulfuric acid. 3,13–18 Organosulfates can also be formed through reactions of fatty acids with sulfuric acid.…”

“…1,3,13–19 These organosulfates are formed through chemical reactions between volatile organic compounds, such as limonene, isoprene and α-pinene, with atmospheric oxidants and with sulfuric acid. 3,13–18 Organosulfates can also be formed through reactions of fatty acids with sulfuric acid. 16 After formation, organosulfates can be further transformed and shorter chain length alkylsulfates may be formed through fragmentation processes.…”