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Atmospheric reaction of methanethiol with hydroxyl radicals and chlorine atoms: implications for the atmospheric sulfur cycle and HONO formation.

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Title: Atmospheric reaction of methanethiol with hydroxyl radicals and chlorine atoms: implications for the atmospheric sulfur cycle and HONO formation.
Authors: Gebru, Teklebirhan Arefaine1 (AUTHOR), Tsona Tchinda, Narcisse2 (AUTHOR) tsonatch@sdu.edu.cn, Du, Lin3 (AUTHOR) lindu@sdu.edu.cn
Source: Environmental Science: Processes & Impacts. Jun2026, Vol. 28 Issue 6, p1866-1876. 11p.
Subject Terms: *Sulfur cycle, *Chlorine, *Oxidation, *Atmospheric chemistry, Methanethiol, Hydroxyl group, Free radical reactions
Abstract: Despite the importance of the oxidation of reduced sulfur compounds in the biogeochemical sulfur cycle and climate, the mechanism of the transformation of methanethiol (CH3SH), the second highest gas-phase marine sulfur emission besides dimethyl sulfide, remains weakly explored. This work presents an investigation of the reaction of CH3SH with hydroxyl radicals (˙OH) and chlorine atoms (Cl˙) using the DLPNO-CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pV(T+d)Z method, both in the absence and presence of water. The results indicate that the hydrogen abstraction by ˙OH/Cl˙ from the –SH group is more favored than from the –CH3 group, leading to the formation of CH3S˙ and ˙CH2SH radicals, respectively, and HCl. While HCl is known to participate in tropospheric physicochemical processes, the fates of CH3S˙ and ˙CH2SH radicals were further examined. Their reactions with O2 lead to and H2CS formation while reactions with NO2 indicate fast formation of HONO and H2CS. Moreover, the CH3S˙ reaction with O2 also forms though at a relatively lower rate than The overall rate coefficients for CH3SH + ˙OH and CH3SH + Cl˙ reactions at 298 K were determined to be 1.69 × 10−11 and 7.49 × 10−10 cm3 per molecule per s, respectively, and were found to exhibit a negative temperature dependency in the temperature range 260–360 K. Besides its contribution to atmospheric sulfate, this study highlights the potential influence of CH3SH on the atmospheric oxidative capacity through HONO and formation, and the necessity to fully assess its chemistry and the contribution thereof to atmospheric chemistry. [ABSTRACT FROM AUTHOR]
Copyright of Environmental Science: Processes & Impacts is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Label: Title
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  Data: Atmospheric reaction of methanethiol with hydroxyl radicals and chlorine atoms: implications for the atmospheric sulfur cycle and HONO formation.
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  Data: <searchLink fieldCode="AR" term="%22Gebru%2C+Teklebirhan+Arefaine%22">Gebru, Teklebirhan Arefaine</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Tsona+Tchinda%2C+Narcisse%22">Tsona Tchinda, Narcisse</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> tsonatch@sdu.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Du%2C+Lin%22">Du, Lin</searchLink><relatesTo>3</relatesTo> (AUTHOR)<i> lindu@sdu.edu.cn</i>
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  Data: <searchLink fieldCode="JN" term="%22Environmental+Science%3A+Processes+%26+Impacts%22">Environmental Science: Processes & Impacts</searchLink>. Jun2026, Vol. 28 Issue 6, p1866-1876. 11p.
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  Data: *<searchLink fieldCode="DE" term="%22Sulfur+cycle%22">Sulfur cycle</searchLink><br />*<searchLink fieldCode="DE" term="%22Chlorine%22">Chlorine</searchLink><br />*<searchLink fieldCode="DE" term="%22Oxidation%22">Oxidation</searchLink><br />*<searchLink fieldCode="DE" term="%22Atmospheric+chemistry%22">Atmospheric chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Methanethiol%22">Methanethiol</searchLink><br /><searchLink fieldCode="DE" term="%22Hydroxyl+group%22">Hydroxyl group</searchLink><br /><searchLink fieldCode="DE" term="%22Free+radical+reactions%22">Free radical reactions</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Despite the importance of the oxidation of reduced sulfur compounds in the biogeochemical sulfur cycle and climate, the mechanism of the transformation of methanethiol (CH3SH), the second highest gas-phase marine sulfur emission besides dimethyl sulfide, remains weakly explored. This work presents an investigation of the reaction of CH3SH with hydroxyl radicals (˙OH) and chlorine atoms (Cl˙) using the DLPNO-CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pV(T+d)Z method, both in the absence and presence of water. The results indicate that the hydrogen abstraction by ˙OH/Cl˙ from the –SH group is more favored than from the –CH3 group, leading to the formation of CH3S˙ and ˙CH2SH radicals, respectively, and HCl. While HCl is known to participate in tropospheric physicochemical processes, the fates of CH3S˙ and ˙CH2SH radicals were further examined. Their reactions with O2 lead to and H2CS formation while reactions with NO2 indicate fast formation of HONO and H2CS. Moreover, the CH3S˙ reaction with O2 also forms though at a relatively lower rate than The overall rate coefficients for CH3SH + ˙OH and CH3SH + Cl˙ reactions at 298 K were determined to be 1.69 × 10−11 and 7.49 × 10−10 cm3 per molecule per s, respectively, and were found to exhibit a negative temperature dependency in the temperature range 260–360 K. Besides its contribution to atmospheric sulfate, this study highlights the potential influence of CH3SH on the atmospheric oxidative capacity through HONO and formation, and the necessity to fully assess its chemistry and the contribution thereof to atmospheric chemistry. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Environmental Science: Processes & Impacts is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1039/d6em00034g
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 11
        StartPage: 1866
    Subjects:
      – SubjectFull: Sulfur cycle
        Type: general
      – SubjectFull: Chlorine
        Type: general
      – SubjectFull: Oxidation
        Type: general
      – SubjectFull: Atmospheric chemistry
        Type: general
      – SubjectFull: Methanethiol
        Type: general
      – SubjectFull: Hydroxyl group
        Type: general
      – SubjectFull: Free radical reactions
        Type: general
    Titles:
      – TitleFull: Atmospheric reaction of methanethiol with hydroxyl radicals and chlorine atoms: implications for the atmospheric sulfur cycle and HONO formation.
        Type: main
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      – PersonEntity:
          Name:
            NameFull: Gebru, Teklebirhan Arefaine
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          Name:
            NameFull: Tsona Tchinda, Narcisse
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          Name:
            NameFull: Du, Lin
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          Dates:
            – D: 01
              M: 06
              Text: Jun2026
              Type: published
              Y: 2026
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              Value: 28
            – Type: issue
              Value: 6
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            – TitleFull: Environmental Science: Processes & Impacts
              Type: main
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