LAUSR

Abstract. Photochemistry plays an important role in the evolution of atmospheric water-soluble organic carbon (WSOC), which dissolves into clouds, fogs, and aerosol liquid water. In this study, we tentatively examined the molecular composition and evolution of a WSOC mixture extracted from field-collected wheat straw burning aerosol (WSBA) samples upon photolysis, using direct infusion electrospray ionisation (ESI) coupled to high-resolution mass spectrometry (HRMS) and liquid chromatography (LC) coupled with HRMS. For comparison, two typical phenolic compounds (i.e. phenol and guaiacol) emitted from lignin pyrolysis in combination with hydrogen peroxide ( H2O2 ) as a typical OH radical precursor were simultaneously exposed to simulated sunlight irradiation. Their photochemical products such as phenolic dimers (e.g. m∕z  185.0608 for phenol dimer and m∕z  245.0823 for guaiacol dimer) or their isomers, were also observed in field-collected WSBA samples, suggesting that the aqueous-phase reactions might contribute to the formation of emitted biomass burning aerosols. The aqueous photochemistry of both the phenols (photooxidation) and WSBA extracts (direct photolysis) could produce a series of highly oxygenated compounds, which in turn increases the oxidation degree of organic composition and acidity of the bulk solution. In particular, the LC/ESI-HRMS technique revealed significant photochemical evolution of the WSOC composition in WSBA samples, e.g. the photodegradation of low oxygenated species and the formation of highly oxygenated products. We also tentatively compared the mass spectra of photolytic time-profile WSBA extracts with each other for a more comprehensive description of the photolytic evolution. The calculated average oxygen-to-carbon ratio ( O∕C ) of oxygenated compounds in bulk extract increases from 0.38±0.02 to 0.44±0.02 (mean  ±  standard deviation), while the intensity ( S∕N )-weighted average O∕C ( O∕Cw ) increases from 0.45±0.03 to 0.53±0.06 as the time of irradiation extends from 0 to 12 h. These findings indicate that the water-soluble organic fraction of combustion-derived aerosols has the potential to form more oxidised organic matter, contributing to the highly oxygenated nature of atmospheric organic aerosols.