Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer
<p>Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO<span cl...
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Copernicus Publications
2025-02-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/25/1931/2025/acp-25-1931-2025.pdf |
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| author | D. B. Kilgour C. M. Jernigan C. M. Jernigan O. Garmash O. Garmash S. Aggarwal S. Aggarwal S. Zhou C. Mohr C. Mohr C. Mohr M. E. Salter M. E. Salter J. A. Thornton J. Wang P. Zieger P. Zieger T. H. Bertram |
| author_facet | D. B. Kilgour C. M. Jernigan C. M. Jernigan O. Garmash O. Garmash S. Aggarwal S. Aggarwal S. Zhou C. Mohr C. Mohr C. Mohr M. E. Salter M. E. Salter J. A. Thornton J. Wang P. Zieger P. Zieger T. H. Bertram |
| author_sort | D. B. Kilgour |
| collection | DOAJ |
| description | <p>Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO<span class="inline-formula"><sub>2</sub></span>). Recent work has shown that HPMTF is efficiently lost to marine boundary layer (MBL) clouds, thus arresting OCS and SO<span class="inline-formula"><sub>2</sub></span> production and their contributions to new-particle formation and growth events. To date, no long-term field studies exist to assess the extent to which frequent cloud processing impacts the fate of HPMTF. Here, we present 6 weeks of measurements of the cloud fraction and the marine sulfur species methanethiol, DMS, and HPMTF made at the Atmospheric Radiation Measurement (ARM) research facility on Graciosa Island, Azores, Portugal. Using an observationally constrained chemical box model, we determine that cloud loss is the dominant sink of HPMTF in this region of the MBL during the study, accounting for 79 %–91 % of HPMTF loss on average. When accounting for HPMTF uptake to clouds, we calculate campaign average reductions in DMS-derived MBL SO<span class="inline-formula"><sub>2</sub></span> and OCS of 52 %–60 % and 80 %–92 % for the study period. Using yearly measurements of the site- and satellite-measured 3D cloud fraction and DMS climatology, we infer that HPMTF cloud loss is the dominant sink of HPMTF in the eastern North Atlantic during all seasons and occurs on timescales faster than what is prescribed in global chemical transport models. Accurately resolving this rapid loss of HPMTF to clouds has important implications for constraining drivers of MBL new-particle formation.</p> |
| format | Article |
| id | doaj-art-0e7d980f46d04430a67611711c8d02a5 |
| institution | OA Journals |
| issn | 1680-7316 1680-7324 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Copernicus Publications |
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| series | Atmospheric Chemistry and Physics |
| spelling | doaj-art-0e7d980f46d04430a67611711c8d02a52025-08-20T02:13:32ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242025-02-01251931194710.5194/acp-25-1931-2025Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layerD. B. Kilgour0C. M. Jernigan1C. M. Jernigan2O. Garmash3O. Garmash4S. Aggarwal5S. Aggarwal6S. Zhou7C. Mohr8C. Mohr9C. Mohr10M. E. Salter11M. E. Salter12J. A. Thornton13J. Wang14P. Zieger15P. Zieger16T. H. Bertram17Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USADepartment of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USAnow at: Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, USADepartment of Atmospheric Sciences, University of Washington, Seattle, WA 98195, USAnow at: Department of Chemistry, University of Copenhagen, 2100 Copenhagen, DenmarkDepartment of Environmental Science, Stockholm University, Stockholm 10691, SwedenBolin Centre for Climate Research, Stockholm University, Stockholm 10691, SwedenCenter for Aerosol Science and Engineering, Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO 63130, USADepartment of Environmental Science, Stockholm University, Stockholm 10691, Swedennow at: Department of Environmental Systems Science, ETH Zurich, 8092 Zürich, Switzerlandnow at: Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, SwitzerlandDepartment of Environmental Science, Stockholm University, Stockholm 10691, SwedenBolin Centre for Climate Research, Stockholm University, Stockholm 10691, SwedenDepartment of Atmospheric Sciences, University of Washington, Seattle, WA 98195, USACenter for Aerosol Science and Engineering, Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO 63130, USADepartment of Environmental Science, Stockholm University, Stockholm 10691, SwedenBolin Centre for Climate Research, Stockholm University, Stockholm 10691, SwedenDepartment of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA<p>Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO<span class="inline-formula"><sub>2</sub></span>). Recent work has shown that HPMTF is efficiently lost to marine boundary layer (MBL) clouds, thus arresting OCS and SO<span class="inline-formula"><sub>2</sub></span> production and their contributions to new-particle formation and growth events. To date, no long-term field studies exist to assess the extent to which frequent cloud processing impacts the fate of HPMTF. Here, we present 6 weeks of measurements of the cloud fraction and the marine sulfur species methanethiol, DMS, and HPMTF made at the Atmospheric Radiation Measurement (ARM) research facility on Graciosa Island, Azores, Portugal. Using an observationally constrained chemical box model, we determine that cloud loss is the dominant sink of HPMTF in this region of the MBL during the study, accounting for 79 %–91 % of HPMTF loss on average. When accounting for HPMTF uptake to clouds, we calculate campaign average reductions in DMS-derived MBL SO<span class="inline-formula"><sub>2</sub></span> and OCS of 52 %–60 % and 80 %–92 % for the study period. Using yearly measurements of the site- and satellite-measured 3D cloud fraction and DMS climatology, we infer that HPMTF cloud loss is the dominant sink of HPMTF in the eastern North Atlantic during all seasons and occurs on timescales faster than what is prescribed in global chemical transport models. Accurately resolving this rapid loss of HPMTF to clouds has important implications for constraining drivers of MBL new-particle formation.</p>https://acp.copernicus.org/articles/25/1931/2025/acp-25-1931-2025.pdf |
| spellingShingle | D. B. Kilgour C. M. Jernigan C. M. Jernigan O. Garmash O. Garmash S. Aggarwal S. Aggarwal S. Zhou C. Mohr C. Mohr C. Mohr M. E. Salter M. E. Salter J. A. Thornton J. Wang P. Zieger P. Zieger T. H. Bertram Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer Atmospheric Chemistry and Physics |
| title | Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer |
| title_full | Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer |
| title_fullStr | Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer |
| title_full_unstemmed | Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer |
| title_short | Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO<sub>2</sub>) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer |
| title_sort | cloud processing of dimethyl sulfide dms oxidation products limits sulfur dioxide so sub 2 sub and carbonyl sulfide ocs production in the eastern north atlantic marine boundary layer |
| url | https://acp.copernicus.org/articles/25/1931/2025/acp-25-1931-2025.pdf |
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