Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms
<p>Organonitrates (ONs) are key components of secondary organic aerosols (SOAs) with potential environmental and climate effects. However, ON formation from limonene, a major monoterpene with unique structure, and its sensitivity to oxidation pathways remain insufficiently explored due to the...
Saved in:
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2025-08-01
|
| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/25/9249/2025/acp-25-9249-2025.pdf |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1849224464690053120 |
|---|---|
| author | Q. Guo H. Zhang B. Long L. Cui Y. Sun H. Liu Y. Liu Y. Xiao P. Fu J. Zhu |
| author_facet | Q. Guo H. Zhang B. Long L. Cui Y. Sun H. Liu Y. Liu Y. Xiao P. Fu J. Zhu |
| author_sort | Q. Guo |
| collection | DOAJ |
| description | <p>Organonitrates (ONs) are key components of secondary organic aerosols (SOAs) with potential environmental and climate effects. However, ON formation from limonene, a major monoterpene with unique structure, and its sensitivity to oxidation pathways remain insufficiently explored due to the absence of models with explicit chemical mechanisms. This study advances the representation of limonene-derived ON formation by incorporating 90 gas-phase reactions and 39 intermediates across three oxidation pathways (<span class="inline-formula">O<sub>3</sub></span>, OH, <span class="inline-formula">NO<sub>3</sub></span>) into both a chemical box model and a global model. Box model sensitivity experiments revealed that competition among major oxidation pathways, coupled with the high yield of limonene-derived ON from <span class="inline-formula">O<sub>3</sub></span>-initiated oxidation, leads to increased limonene-derived ON production when the <span class="inline-formula">O<sub>3</sub></span>-initiated pathway is enhanced, whereas strengthening the OH- or <span class="inline-formula">NO<sub>3</sub></span>-initiated pathways reduces ON formation. Compared to the box model, the global simulation exhibits stronger nonlinear responses and great spatiotemporal variability in limonene-derived ON formation across different oxidation pathways. This is primarily driven by the complex distribution of precursors and oxidants, as well as the change in dominate chemical pathways under various meteorological conditions. In the presence of the other two pathways, increasing the <span class="inline-formula">O<sub>3</sub></span>- or <span class="inline-formula">NO<sub>3</sub></span>-initiated oxidation pathway reduces the global limonene-derived ON burden by 19.9 % and 17.3 %, respectively, whereas enhancing the OH-initiated pathway increases it by 44.7 %. Limonene-derived ON chemistry developed in this study not only enhances the global model's ability to simulate ON formation evaluated through comparison with observations but also demonstrates an approach based on explicit chemical mechanisms that establishes a methodological framework for simulating the chemical formation processes of SOA.</p> |
| format | Article |
| id | doaj-art-baba96df00a445e1a694781903acd995 |
| institution | Kabale University |
| issn | 1680-7316 1680-7324 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj-art-baba96df00a445e1a694781903acd9952025-08-25T09:56:26ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242025-08-01259249926210.5194/acp-25-9249-2025Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanismsQ. Guo0H. Zhang1B. Long2L. Cui3Y. Sun4H. Liu5Y. Liu6Y. Xiao7P. Fu8J. Zhu9Institute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaDepartment of Chemistry, University of California, Riverside, California 92521, USACollege of Materials Science and Engineering, Guizhou Minzu University, Guiyang 550025, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, ChinaInstitute of Surface-Earth System Science, School of Earth System Science, Tianjin University, Tianjin 300072, China<p>Organonitrates (ONs) are key components of secondary organic aerosols (SOAs) with potential environmental and climate effects. However, ON formation from limonene, a major monoterpene with unique structure, and its sensitivity to oxidation pathways remain insufficiently explored due to the absence of models with explicit chemical mechanisms. This study advances the representation of limonene-derived ON formation by incorporating 90 gas-phase reactions and 39 intermediates across three oxidation pathways (<span class="inline-formula">O<sub>3</sub></span>, OH, <span class="inline-formula">NO<sub>3</sub></span>) into both a chemical box model and a global model. Box model sensitivity experiments revealed that competition among major oxidation pathways, coupled with the high yield of limonene-derived ON from <span class="inline-formula">O<sub>3</sub></span>-initiated oxidation, leads to increased limonene-derived ON production when the <span class="inline-formula">O<sub>3</sub></span>-initiated pathway is enhanced, whereas strengthening the OH- or <span class="inline-formula">NO<sub>3</sub></span>-initiated pathways reduces ON formation. Compared to the box model, the global simulation exhibits stronger nonlinear responses and great spatiotemporal variability in limonene-derived ON formation across different oxidation pathways. This is primarily driven by the complex distribution of precursors and oxidants, as well as the change in dominate chemical pathways under various meteorological conditions. In the presence of the other two pathways, increasing the <span class="inline-formula">O<sub>3</sub></span>- or <span class="inline-formula">NO<sub>3</sub></span>-initiated oxidation pathway reduces the global limonene-derived ON burden by 19.9 % and 17.3 %, respectively, whereas enhancing the OH-initiated pathway increases it by 44.7 %. Limonene-derived ON chemistry developed in this study not only enhances the global model's ability to simulate ON formation evaluated through comparison with observations but also demonstrates an approach based on explicit chemical mechanisms that establishes a methodological framework for simulating the chemical formation processes of SOA.</p>https://acp.copernicus.org/articles/25/9249/2025/acp-25-9249-2025.pdf |
| spellingShingle | Q. Guo H. Zhang B. Long L. Cui Y. Sun H. Liu Y. Liu Y. Xiao P. Fu J. Zhu Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms Atmospheric Chemistry and Physics |
| title | Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms |
| title_full | Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms |
| title_fullStr | Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms |
| title_full_unstemmed | Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms |
| title_short | Competing multiple oxidation pathways shape atmospheric limonene-derived organonitrates simulated with updated explicit chemical mechanisms |
| title_sort | competing multiple oxidation pathways shape atmospheric limonene derived organonitrates simulated with updated explicit chemical mechanisms |
| url | https://acp.copernicus.org/articles/25/9249/2025/acp-25-9249-2025.pdf |
| work_keys_str_mv | AT qguo competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT hzhang competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT blong competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT lcui competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT ysun competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT hliu competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT yliu competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT yxiao competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT pfu competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms AT jzhu competingmultipleoxidationpathwaysshapeatmosphericlimonenederivedorganonitratessimulatedwithupdatedexplicitchemicalmechanisms |