Average chemical properties and potential formation pathways of highly oxidized organic aerosol
Measurements of ambient organic aerosol indicate that a substantial fraction is highly oxidized and low in volatility, but this fraction is generally not reproduced well in either laboratory studies or models. Here we describe a new approach for constraining the viable precursors and formation pathw...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2014
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| Online Access: | http://hdl.handle.net/1721.1/90983 https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 |
| _version_ | 1826189147517222912 |
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| author | Kessler, Sean Herbert Daumit, Kelly Elizabeth Kroll, Jesse |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Kessler, Sean Herbert Daumit, Kelly Elizabeth Kroll, Jesse |
| author_sort | Kessler, Sean Herbert |
| collection | MIT |
| description | Measurements of ambient organic aerosol indicate that a substantial fraction is highly oxidized and low in volatility, but this fraction is generally not reproduced well in either laboratory studies or models. Here we describe a new approach for constraining the viable precursors and formation pathways of highly oxidized organic aerosol, by starting with the oxidized product and considering the possible reverse reactions, using a set of simple chemical rules. The focus of this work is low-volatility oxidized organic aerosol (LV-OOA), determined from factor analysis of aerosol mass spectrometer data. The elemental composition and volatility of the aerosol enable the determination of its position in a three-dimensional chemical space (defined by H/C, O/C, and carbon number) and thus its average chemical formula. Consideration of possible back-reactions then defines the movement taken through this chemical space, constraining potential reaction pathways and precursors. This approach is taken for two highly oxidized aerosol types, an average of LV-OOA factors from ten field campaigns (average formula C[subscript 10.5]H[subscript 13.4]O[subscript 7.3]), and extremely oxidized LV-OOA (from Mexico City, average formula C[subscript 10]H[subscript 12.1]O[subscript 8.4]). Results suggest that potential formation pathways include functionalization reactions that add multiple functional groups per oxidation step, oligomerization of highly oxidized precursors, and, in some cases, fragmentation reactions that involve the loss of small, reduced fragments. |
| first_indexed | 2024-09-23T08:10:16Z |
| format | Article |
| id | mit-1721.1/90983 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:10:16Z |
| publishDate | 2014 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/909832022-09-23T11:22:49Z Average chemical properties and potential formation pathways of highly oxidized organic aerosol Kessler, Sean Herbert Daumit, Kelly Elizabeth Kroll, Jesse Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Daumit, Kelly Elizabeth Kessler, Sean Herbert Kroll, Jesse Measurements of ambient organic aerosol indicate that a substantial fraction is highly oxidized and low in volatility, but this fraction is generally not reproduced well in either laboratory studies or models. Here we describe a new approach for constraining the viable precursors and formation pathways of highly oxidized organic aerosol, by starting with the oxidized product and considering the possible reverse reactions, using a set of simple chemical rules. The focus of this work is low-volatility oxidized organic aerosol (LV-OOA), determined from factor analysis of aerosol mass spectrometer data. The elemental composition and volatility of the aerosol enable the determination of its position in a three-dimensional chemical space (defined by H/C, O/C, and carbon number) and thus its average chemical formula. Consideration of possible back-reactions then defines the movement taken through this chemical space, constraining potential reaction pathways and precursors. This approach is taken for two highly oxidized aerosol types, an average of LV-OOA factors from ten field campaigns (average formula C[subscript 10.5]H[subscript 13.4]O[subscript 7.3]), and extremely oxidized LV-OOA (from Mexico City, average formula C[subscript 10]H[subscript 12.1]O[subscript 8.4]). Results suggest that potential formation pathways include functionalization reactions that add multiple functional groups per oxidation step, oligomerization of highly oxidized precursors, and, in some cases, fragmentation reactions that involve the loss of small, reduced fragments. National Science Foundation (U.S.) (Grant CHE-1012809) National Science Foundation (U.S.) (Grant AGS-1056225) 2014-10-20T14:17:57Z 2014-10-20T14:17:57Z 2013-05 2013-03 Article http://purl.org/eprint/type/JournalArticle 1359-6640 1364-5498 http://hdl.handle.net/1721.1/90983 Daumit, Kelly E., Sean H. Kessler, and Jesse H. Kroll. “Average Chemical Properties and Potential Formation Pathways of Highly Oxidized Organic Aerosol.” Faraday Discussions 165 (2013): 181. © Royal Society of Chemistry https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 en_US http://dx.doi.org/10.1039/C3FD00045A Faraday Discussions Creative Commons Attribution-Noncommercial http://creativecommons.org/licenses/by-nc/3.0/ application/pdf Royal Society of Chemistry RSC |
| spellingShingle | Kessler, Sean Herbert Daumit, Kelly Elizabeth Kroll, Jesse Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title | Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title_full | Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title_fullStr | Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title_full_unstemmed | Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title_short | Average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| title_sort | average chemical properties and potential formation pathways of highly oxidized organic aerosol |
| url | http://hdl.handle.net/1721.1/90983 https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 |
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