Dialkylsulfate formation in sulfuric acid-seeded secondary organic aerosol produced using an outdoor chamber under natural sunlight

Abstract

Environmental context Laboratory and field studies have both provided evidence for organosulfate formation by esterification of H2SO4 with organic compounds in aerosols. Using an outdoor chamber, the production of dialkylsufate was measured for organic aerosols produced by photooxidation of various hydrocarbons in the presence of H2SO4 aerosol and NOx. The formation of organosulfates influences the decrease of both aerosol acidity and aerosol hygroscopicity. Abstract Secondary organic aerosols (SOA) were produced by the photooxidation of the volatile organic hydrocarbons (VOCs) isoprene, α-pinene and toluene, in the presence of excess amounts of sulfuric acid seed aerosol with varying NOx concentrations using a large, outdoor smog chamber. Aerosol acidity ([H+], μmol m–3) was measured using colorimetry integrated with a reflectance UV-visible spectrometer (C-RUV). The C-RUV technique measures aerosol acidity changes through the neutralisation of sulfuric acid with ammonia and the formation of dialkylsulfate, a diester of sulfuric acid. The concentration (μmol m–3) of dialkylsulfate in aerosol was estimated using the difference in [H+] obtained from C-RUV and particle-into-liquid-sampler ion chromatography (PILS-IC). The yield of dialkylsulfate (YdiOS) was defined as the dialkylsulfate concentration normalised by the concentrations of both the ammonium-free sulfate ([SO42–]free=[SO42–] – 0.5 [NH4+]) and organic carbon. The highest YdiOS appeared in isoprene SOA and the lowest YdiOS in α-pinene SOA. Under our experimental conditions, more than 50% of the total sulfates in sulfuric acid-seeded isoprene SOA were dialkylsulfates. For all SOA, higher YdiOS was observed under higher NOx conditions (VOC (ppb C)/NO (ppb)<15). Among the major functional groups (–COOH, –CO–H, –CHO and –ONO2) predicted to be present using a simple absorptive partitioning model of organic products in the multiphase system (gas, organic aerosol and inorganic aerosol), the concentrations of –CO–H, –CHO and –ONO2 groups were found to be correlated with YdiOS. In particular, a strong correlation was observed between YdiOS and the concentration of alcohol functional groups.