Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals
The immense complexity inherent in the formation of secondary organic aerosol (SOA)—due primarily to the large number of oxidation steps and reaction pathways involved—has limited the detailed understanding of its underlying chemistry. As a means of simplifying such complexity, here we demonstrate t...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/72399 https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 https://orcid.org/0000-0002-9259-1869 |
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| author | Kessler, Sean Herbert Nah, Theodora Carrasquillo, Anthony Joseph Jayne, John T. Worsnop, Douglas R. Wilson, Kevin R. Kroll, Jesse |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Kessler, Sean Herbert Nah, Theodora Carrasquillo, Anthony Joseph Jayne, John T. Worsnop, Douglas R. Wilson, Kevin R. Kroll, Jesse |
| author_sort | Kessler, Sean Herbert |
| collection | MIT |
| description | The immense complexity inherent in the formation of secondary organic aerosol (SOA)—due primarily to the large number of oxidation steps and reaction pathways involved—has limited the detailed understanding of its underlying chemistry. As a means of simplifying such complexity, here we demonstrate the formation of SOA through the photolysis of gas-phase alkyl iodides, which generates organic peroxy radicals of known structure. In contrast to standard OH-initiated oxidation experiments, photolytically initiated oxidation forms a limited number of products via a single reactive step. As is typical for SOA, the yields of aerosol generated from the photolysis of alkyl iodides depend on aerosol loading, indicating the semivolatile nature of the particulate species. However, the aerosol was observed to be higher in volatility and less oxidized than in previous multigenerational studies of alkane oxidation, suggesting that additional oxidative steps are necessary to produce oxidized semivolatile material in the atmosphere. Despite the relative simplicity of this chemical system, the SOA mass spectra are still quite complex, underscoring the wide range of products present in SOA. |
| first_indexed | 2024-09-23T14:04:53Z |
| format | Article |
| id | mit-1721.1/72399 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:04:53Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/723992022-09-28T18:15:23Z Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals Kessler, Sean Herbert Nah, Theodora Carrasquillo, Anthony Joseph Jayne, John T. Worsnop, Douglas R. Wilson, Kevin R. Kroll, Jesse Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Kroll, Jesse Kessler, Sean Herbert Carrasquillo, Anthony Joseph Kroll, Jesse The immense complexity inherent in the formation of secondary organic aerosol (SOA)—due primarily to the large number of oxidation steps and reaction pathways involved—has limited the detailed understanding of its underlying chemistry. As a means of simplifying such complexity, here we demonstrate the formation of SOA through the photolysis of gas-phase alkyl iodides, which generates organic peroxy radicals of known structure. In contrast to standard OH-initiated oxidation experiments, photolytically initiated oxidation forms a limited number of products via a single reactive step. As is typical for SOA, the yields of aerosol generated from the photolysis of alkyl iodides depend on aerosol loading, indicating the semivolatile nature of the particulate species. However, the aerosol was observed to be higher in volatility and less oxidized than in previous multigenerational studies of alkane oxidation, suggesting that additional oxidative steps are necessary to produce oxidized semivolatile material in the atmosphere. Despite the relative simplicity of this chemical system, the SOA mass spectra are still quite complex, underscoring the wide range of products present in SOA. National Science Foundation (U.S.) (CHE-1012809) American Chemical Society Petroleum Research Fund (50341-DNI4) United States. Dept. of Energy (Director, Office of Energy Research, Office of Basic Energy Sciences, and Chemical Sciences Division of the US DOE (contract no. DE-AC02-05CH11231)) 2012-08-28T20:35:33Z 2012-08-28T20:35:33Z 2011-05 2011-03 Article http://purl.org/eprint/type/JournalArticle 1948-7185 http://hdl.handle.net/1721.1/72399 Kessler, Sean H. et al. “Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals.” The Journal of Physical Chemistry Letters 2.11 (2011): 1295–1300. Web. https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 https://orcid.org/0000-0002-9259-1869 en_US http://dx.doi.org/10.1021/jz200432n Journal of Physical Chemistry Letters Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Jesse Kroll |
| spellingShingle | Kessler, Sean Herbert Nah, Theodora Carrasquillo, Anthony Joseph Jayne, John T. Worsnop, Douglas R. Wilson, Kevin R. Kroll, Jesse Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title | Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title_full | Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title_fullStr | Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title_full_unstemmed | Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title_short | Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals |
| title_sort | formation of secondary organic aerosol from the direct photolytic generation of organic radicals |
| url | http://hdl.handle.net/1721.1/72399 https://orcid.org/0000-0002-6275-521X https://orcid.org/0000-0003-1627-5618 https://orcid.org/0000-0002-9259-1869 |
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