Molecular Characteristics of Organosulfur Compounds in Guangzhou, South China: Heterogeneous Secondary Reactions Drivers the Molecular Distribution

Abstract

Abstract. Organosulfur compounds (OrgSs), especially organosulfates, have been widely reported at large quantities in particulate organic matter found in various atmospheric environments. Despite various kinds of organosulfates and their formation mechanisms being previously identified, a large fraction of OrgSs remain unexplained at the molecular level, impeding further knowledge on additional formation pathways and critical environmental parameters that help to explain their concentrations. In this work, the abundance and molecular composition of OrgSs in fine particulate samples collected in Guangzhou was reported. Our results revealed that organic sulfur can averagely contribute to 30 % of total particulate sulfur, and showed positively correlations with the SO2 (r = 0.37, p < 0.05) and oxidants (NOx+O3, r = 0.40, p < 0.01). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results presented that more than 80 % by number of the detected OrgSs in our samples have the elemental composition of O/(4S+3N) ≥ 1, indicating that they were largely in the form of oxidized organosulfates and/or nitrooxy organosulfates. Many OrgSs, which are tentatively attributed to previously identified biogenic and anthropogenic origins, were also present in aerosols derived from freshly-emitted combustion sources. Results show that the formation of OrgSs through an epoxide intermediate pathway could be as much as 46 %, and the oxidants levels could explain 20 % variation of organic sulfur mass. The analysis from our large FT-ICR MS dataset suggests that relative humidity, oxidation of biogenic volatile organic compounds via ozonolysis, and NOx-related nitrooxy organosulfate formations were the major reasons for the molecular variation of OrgSs, possibly highlighting the importance of heterogeneous reactions involving either the uptake of SO2 or the heterogeneous oxidations of particulate organosulfates into additional unrecognized OrgSs.

Chemical transformation of a long-chain alkyl organosulfate via heterogeneous OH oxidation: a case study of sodium dodecyl sulfate

“…[6][7][8][9][10][11][12][13][14][15] For instance, organosulfur compounds found in cleaner cities like Mainz, Germany are mainly derived from biogenic organic compounds, whereas those in polluted atmospheres in China are attributed also to anthropogenic organic precursors. [16][17][18][19][20] These studies convey that organosulfur compounds contribute to an important fraction in aerosols worldwide, particularly in where photochemical activities are strong. 5,17,21,22 Among all organosulfur species (including organosulfates (OS), sulfoxides, sulfonates, and sulfones), OS with sulfate ester functional group (R-O-SO 3 -) are quantified as the most abundant classes.…”