Molecular characteristics, sources, and formation pathways of organosulfur compounds in ambient aerosol in Guangzhou, South China
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Published:2022-05-30
Issue:10
Volume:22
Page:6919-6935
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ISSN:1680-7324
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Container-title:Atmospheric Chemistry and Physics
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language:en
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Short-container-title:Atmos. Chem. Phys.
Author:
Jiang HongxingORCID, Li JunORCID, Tang Jiao, Cui Min, Zhao Shizhen, Mo YangzhiORCID, Tian Chongguo, Zhang Xiangyun, Jiang Bin, Liao Yuhong, Chen YingjunORCID, Zhang Gan
Abstract
Abstract. Organosulfur compounds (OrgSs), especially
organosulfates, have been widely reported to be present in large quantities
in particulate organic matter found in various atmospheric environments.
Despite hundreds of organosulfates and their formation mechanisms being
previously identified, a large fraction of OrgSs remain unexplained at the
molecular level, and a better understanding of their formation pathways and
critical environmental parameters is required to explain the variations in
their concentrations. In this study, the abundance and molecular composition
of OrgSs in fine particulate samples collected in Guangzhou were reported.
The results revealed that the ratio of the annual average mass of organic
sulfur to total particulate sulfur was 33 ± 12 %, and organic sulfur
had positive correlations with SO2 (r=0.37, p<0.05) and
oxidant (NOx + O3, r=0.40, p<0.01). A Fourier transform
ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis revealed that
more than 80 % of the sulfur-containing formulas detected in the samples had
the elemental composition of o/(4s+3n)≥1, indicating that they were
largely in the form of oxidized organosulfates or nitrooxy organosulfates.
Many OrgSs that were previously tentatively identified as having biogenic or
anthropogenic origins were also present in freshly emitted aerosols derived
from combustion sources. The results indicated that the formation of OrgSs
through an epoxide intermediate pathway could account for up to 46 %
of OrgSs from an upper bound estimation, and the oxidant levels could
explain 20 % of the variation in the mass of organic sulfur. The analysis
of our large dataset of FT-ICR MS results suggested that relative humidity,
oxidation of biogenic volatile organic compounds via ozonolysis, and
NOx-related nitrooxy organosulfate formation were the major reasons for
the molecular variation of OrgSs, possibly highlighting the importance of
the acid-catalyzed ring-opening of epoxides, oxidation processes, and
heterogeneous reactions involving either the uptake of SO2 or the
heterogeneous oxidation of particulate organosulfates into additional
unrecognized OrgSs.
Funder
Guangdong Provincial Applied Science and Technology Research and Development Program National Key Research and Development Program of China National Natural Science Foundation of China
Publisher
Copernicus GmbH
Subject
Atmospheric Science
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