Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework
<p>Understanding dimethyl sulfide (DMS) oxidation can help us constrain its contribution to Earth's radiative balance. Following the discovery of hydroperoxymethyl thioformate (HPMTF) as a DMS oxidation product, a range of new experimental chamber studies have since improved our knowledge...
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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/24/3329/2024/acp-24-3329-2024.pdf |
| _version_ | 1797258554451689472 |
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| author | L. S. D. Jacob C. Giorio A. T. Archibald A. T. Archibald |
| author_facet | L. S. D. Jacob C. Giorio A. T. Archibald A. T. Archibald |
| author_sort | L. S. D. Jacob |
| collection | DOAJ |
| description | <p>Understanding dimethyl sulfide (DMS) oxidation can help us constrain its contribution to Earth's radiative balance. Following the discovery of hydroperoxymethyl thioformate (HPMTF) as a DMS oxidation product, a range of new experimental chamber studies have since improved our knowledge of the oxidation mechanism of DMS and delivered detailed chemical mechanisms. However, these mechanisms have not undergone formal intercomparisons to evaluate their performance.</p>
<p>This study aimed to synthesise the recent experimental studies and develop a new, near-explicit, DMS mechanism, through a thorough literature review. A simple box model was then used with the mechanism to simulate a series of chamber experiments and evaluated through comparison with four published mechanisms. Our modelling shows that the mechanism developed in this work outperformed the other mechanisms on average when compared to the experimental chamber data, having the lowest fractional gross error for 8 out of the 14 DMS oxidation products studied. A box model of a marine boundary layer was also run, demonstrating that the deviations in the mechanisms seen when comparing them against chamber data are also prominent under more atmospherically relevant conditions.</p>
<p>Although this work demonstrates the need for further experimental work, the mechanism developed in this work has been evaluated against a range of experiments, which validate the mechanism and reduce the bias from individual experiments. Our mechanism provides a good basis for a near-explicit DMS oxidation mechanism that would include other initiation reactions (e.g. halogens) and can be used to compare the performance of reduced mechanisms used in global models.</p> |
| first_indexed | 2024-04-24T22:55:23Z |
| format | Article |
| id | doaj.art-dca87eea7896412296341a06fa22999b |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-24T22:55:23Z |
| publishDate | 2024-03-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-dca87eea7896412296341a06fa22999b2024-03-18T08:57:30ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242024-03-01243329334710.5194/acp-24-3329-2024Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 frameworkL. S. D. Jacob0C. Giorio1A. T. Archibald2A. T. Archibald3Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UKYusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UKYusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UKNational Centre for Atmospheric Science, Cambridge, CB2 1EW, UK<p>Understanding dimethyl sulfide (DMS) oxidation can help us constrain its contribution to Earth's radiative balance. Following the discovery of hydroperoxymethyl thioformate (HPMTF) as a DMS oxidation product, a range of new experimental chamber studies have since improved our knowledge of the oxidation mechanism of DMS and delivered detailed chemical mechanisms. However, these mechanisms have not undergone formal intercomparisons to evaluate their performance.</p> <p>This study aimed to synthesise the recent experimental studies and develop a new, near-explicit, DMS mechanism, through a thorough literature review. A simple box model was then used with the mechanism to simulate a series of chamber experiments and evaluated through comparison with four published mechanisms. Our modelling shows that the mechanism developed in this work outperformed the other mechanisms on average when compared to the experimental chamber data, having the lowest fractional gross error for 8 out of the 14 DMS oxidation products studied. A box model of a marine boundary layer was also run, demonstrating that the deviations in the mechanisms seen when comparing them against chamber data are also prominent under more atmospherically relevant conditions.</p> <p>Although this work demonstrates the need for further experimental work, the mechanism developed in this work has been evaluated against a range of experiments, which validate the mechanism and reduce the bias from individual experiments. Our mechanism provides a good basis for a near-explicit DMS oxidation mechanism that would include other initiation reactions (e.g. halogens) and can be used to compare the performance of reduced mechanisms used in global models.</p>https://acp.copernicus.org/articles/24/3329/2024/acp-24-3329-2024.pdf |
| spellingShingle | L. S. D. Jacob C. Giorio A. T. Archibald A. T. Archibald Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework Atmospheric Chemistry and Physics |
| title | Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework |
| title_full | Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework |
| title_fullStr | Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework |
| title_full_unstemmed | Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework |
| title_short | Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework |
| title_sort | extension development and evaluation of the representation of the oh initiated dimethyl sulfide dms oxidation mechanism in the master chemical mechanism mcm v3 3 1 framework |
| url | https://acp.copernicus.org/articles/24/3329/2024/acp-24-3329-2024.pdf |
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