Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol
<p>Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (<span class="inline-formula">H<sub>2</sub>SO<sub>4</sub></span>) are well-known natural precursors of...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2024-03-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/24/3379/2024/acp-24-3379-2024.pdf |
| _version_ | 1797257387025891328 |
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| author | L. Tashmim W. C. Porter Q. Chen B. Alexander C. H. Fite C. D. Holmes J. R. Pierce B. Croft S. Ishino |
| author_facet | L. Tashmim W. C. Porter Q. Chen B. Alexander C. H. Fite C. D. Holmes J. R. Pierce B. Croft S. Ishino |
| author_sort | L. Tashmim |
| collection | DOAJ |
| description | <p>Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (<span class="inline-formula">H<sub>2</sub>SO<sub>4</sub></span>) are well-known natural precursors of atmospheric aerosols, contributing to particle mass and cloud formation over ocean and coastal regions. Despite a long-recognized and well-studied role in the marine troposphere, DMS oxidation chemistry remains a work in progress within many current air quality and climate models, with recent advances exploring heterogeneous chemistry and uncovering previously unknown intermediate species. With the identification of additional DMS oxidation pathways and intermediate species that influence the eventual fate of DMS, it is important to understand the impact of these pathways on the overall sulfate aerosol budget and aerosol size distribution. In this work, we update and evaluate the DMS oxidation mechanism of the chemical transport model GEOS-Chem by implementing expanded DMS oxidation pathways in the model. These updates include gas- and aqueous-phase reactions, the formation of the intermediates dimethyl sulfoxide (DMSO) and methanesulfinic acid (MSIA), and cloud loss and aerosol uptake of the recently quantified intermediate hydroperoxymethyl thioformate (HPMTF). We find that this updated mechanism collectively decreases the global mean surface-layer gas-phase sulfur dioxide (<span class="inline-formula">SO<sub>2</sub></span>) mixing ratio by 40 % and enhances the sulfate aerosol (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow class="chem"><msubsup><mi mathvariant="normal">SO</mi><mn mathvariant="normal">4</mn><mrow><mn mathvariant="normal">2</mn><mo>-</mo></mrow></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="29pt" height="17pt" class="svg-formula" dspmath="mathimg" md5hash="6060a0eb6022af681aa55d19b3180df9"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-24-3379-2024-ie00001.svg" width="29pt" height="17pt" src="acp-24-3379-2024-ie00001.png"/></svg:svg></span></span>) mixing ratio by 17 %. We further perform sensitivity analyses exploring the contribution of cloud loss and aerosol uptake of HPMTF to the overall sulfur budget. Comparing modeled concentrations to available observations, we find improved biases relative to previous studies. To quantify the impacts of these chemistry updates on global particle size distributions and the mass concentration, we use the TwO-Moment Aerosol Sectional (TOMAS) aerosol microphysics module coupled to GEOS-Chem and find that changes in particle formation and growth affect the size distribution of aerosol. With this new DMS-oxidation scheme, the global annual mean surface-layer number concentration of particles with diameters smaller than 80 <span class="inline-formula">nm</span> decreases by 16.8 %, with cloud loss processes related to HPMTF being mostly responsible for this reduction. However, the global annual mean number of particles larger than 80 <span class="inline-formula">nm</span> (corresponding to particles capable of acting as cloud condensation nuclei, CCN) increases by 3.8 %, suggesting that the new scheme promotes seasonal particle growth to these sizes.</p> |
| first_indexed | 2024-04-24T22:36:49Z |
| format | Article |
| id | doaj.art-633f51f6252b4a298dc3c35ce87e97d1 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-24T22:36:49Z |
| publishDate | 2024-03-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-633f51f6252b4a298dc3c35ce87e97d12024-03-19T09:32:23ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242024-03-01243379340310.5194/acp-24-3379-2024Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosolL. Tashmim0W. C. Porter1Q. Chen2B. Alexander3C. H. Fite4C. D. Holmes5J. R. Pierce6B. Croft7S. Ishino8Department of Environmental Sciences, University of California, Riverside, CA, USADepartment of Environmental Sciences, University of California, Riverside, CA, USADepartment of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hong Kong SAR, ChinaDepartment of Atmospheric Sciences, University of Washington, Seattle, WA, USADepartment of Earth, Ocean and Atmospheric Science, Florida State University, Tallahassee, FL, USADepartment of Earth, Ocean and Atmospheric Science, Florida State University, Tallahassee, FL, USADepartment of Atmospheric Science, Colorado State University, Fort Collins, CO, USADepartment of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, CanadaInstitute of Nature and Environmental Technology, Kanazawa University, Kanazawa, Japan<p>Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (<span class="inline-formula">H<sub>2</sub>SO<sub>4</sub></span>) are well-known natural precursors of atmospheric aerosols, contributing to particle mass and cloud formation over ocean and coastal regions. Despite a long-recognized and well-studied role in the marine troposphere, DMS oxidation chemistry remains a work in progress within many current air quality and climate models, with recent advances exploring heterogeneous chemistry and uncovering previously unknown intermediate species. With the identification of additional DMS oxidation pathways and intermediate species that influence the eventual fate of DMS, it is important to understand the impact of these pathways on the overall sulfate aerosol budget and aerosol size distribution. In this work, we update and evaluate the DMS oxidation mechanism of the chemical transport model GEOS-Chem by implementing expanded DMS oxidation pathways in the model. These updates include gas- and aqueous-phase reactions, the formation of the intermediates dimethyl sulfoxide (DMSO) and methanesulfinic acid (MSIA), and cloud loss and aerosol uptake of the recently quantified intermediate hydroperoxymethyl thioformate (HPMTF). We find that this updated mechanism collectively decreases the global mean surface-layer gas-phase sulfur dioxide (<span class="inline-formula">SO<sub>2</sub></span>) mixing ratio by 40 % and enhances the sulfate aerosol (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow class="chem"><msubsup><mi mathvariant="normal">SO</mi><mn mathvariant="normal">4</mn><mrow><mn mathvariant="normal">2</mn><mo>-</mo></mrow></msubsup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="29pt" height="17pt" class="svg-formula" dspmath="mathimg" md5hash="6060a0eb6022af681aa55d19b3180df9"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-24-3379-2024-ie00001.svg" width="29pt" height="17pt" src="acp-24-3379-2024-ie00001.png"/></svg:svg></span></span>) mixing ratio by 17 %. We further perform sensitivity analyses exploring the contribution of cloud loss and aerosol uptake of HPMTF to the overall sulfur budget. Comparing modeled concentrations to available observations, we find improved biases relative to previous studies. To quantify the impacts of these chemistry updates on global particle size distributions and the mass concentration, we use the TwO-Moment Aerosol Sectional (TOMAS) aerosol microphysics module coupled to GEOS-Chem and find that changes in particle formation and growth affect the size distribution of aerosol. With this new DMS-oxidation scheme, the global annual mean surface-layer number concentration of particles with diameters smaller than 80 <span class="inline-formula">nm</span> decreases by 16.8 %, with cloud loss processes related to HPMTF being mostly responsible for this reduction. However, the global annual mean number of particles larger than 80 <span class="inline-formula">nm</span> (corresponding to particles capable of acting as cloud condensation nuclei, CCN) increases by 3.8 %, suggesting that the new scheme promotes seasonal particle growth to these sizes.</p>https://acp.copernicus.org/articles/24/3379/2024/acp-24-3379-2024.pdf |
| spellingShingle | L. Tashmim W. C. Porter Q. Chen B. Alexander C. H. Fite C. D. Holmes J. R. Pierce B. Croft S. Ishino Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol Atmospheric Chemistry and Physics |
| title | Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol |
| title_full | Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol |
| title_fullStr | Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol |
| title_full_unstemmed | Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol |
| title_short | Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol |
| title_sort | contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size resolved sulfate aerosol |
| url | https://acp.copernicus.org/articles/24/3379/2024/acp-24-3379-2024.pdf |
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