Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)
Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicro...
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Copernicus Publications
2016-09-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/16/11563/2016/acp-16-11563-2016.pdf |
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| author | W. Hu W. Hu B. B. Palm B. B. Palm D. A. Day D. A. Day P. Campuzano-Jost P. Campuzano-Jost J. E. Krechmer J. E. Krechmer Z. Peng Z. Peng S. S. de Sá S. T. Martin S. T. Martin M. L. Alexander K. Baumann L. Hacker A. Kiendler-Scharr A. R. Koss A. R. Koss A. R. Koss J. A. de Gouw J. A. de Gouw J. A. de Gouw A. H. Goldstein A. H. Goldstein R. Seco S. J. Sjostedt J.-H. Park A. B. Guenther S. Kim F. Canonaco A. S. H. Prévôt W. H. Brune J. L. Jimenez J. L. Jimenez |
| author_facet | W. Hu W. Hu B. B. Palm B. B. Palm D. A. Day D. A. Day P. Campuzano-Jost P. Campuzano-Jost J. E. Krechmer J. E. Krechmer Z. Peng Z. Peng S. S. de Sá S. T. Martin S. T. Martin M. L. Alexander K. Baumann L. Hacker A. Kiendler-Scharr A. R. Koss A. R. Koss A. R. Koss J. A. de Gouw J. A. de Gouw J. A. de Gouw A. H. Goldstein A. H. Goldstein R. Seco S. J. Sjostedt J.-H. Park A. B. Guenther S. Kim F. Canonaco A. S. H. Prévôt W. H. Brune J. L. Jimenez J. L. Jimenez |
| author_sort | W. Hu |
| collection | DOAJ |
| description | Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can
contribute substantially to organic aerosol (OA) concentrations in forested
areas under low NO conditions, hence significantly influencing the regional
and global OA budgets, accounting, for example, for 16–36 % of the submicron
OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a
thermodenuder show that the volatility of ambient IEPOX-SOA is lower than
that of bulk OA and also much lower than that of known monomer IEPOX-SOA
tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers
in the aerosol phase. The OH aging process of ambient IEPOX-SOA was
investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation
in the reactor was negligible, as the OFR does not accelerate processes such
as aerosol uptake and reactions that do not scale with OH. Simulation
results indicate that adding ∼ 100 µg m<sup>−3</sup> of
pure H<sub>2</sub>SO<sub>4</sub> to the ambient air allows IEPOX-SOA to be efficiently formed
in the reactor. The heterogeneous reaction rate coefficient of ambient
IEPOX-SOA with OH radical (<i>k</i><sub>OH</sub>) was estimated as 4.0 ± 2.0 × 10<sup>−13</sup> cm<sup>3</sup> molec<sup>−1</sup> s<sup>−1</sup>, which is
equivalent to more than a 2-week lifetime. A similar <i>k</i><sub>OH</sub> was
found for measurements of OH oxidation of ambient Amazon forest air in an
OFR. At higher OH exposures in the reactor (> 1 × 10<sup>12</sup> molec cm<sup>−3</sup> s), the mass loss of IEPOX-SOA due to
heterogeneous reaction was mainly due to revolatilization of fragmented
reaction products. We report, for the first time, OH reactive uptake
coefficients (<i>γ</i><sub>OH</sub> = 0.59 ± 0.33 in SE US and <i>γ</i><sub>OH</sub> = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A
relative humidity dependence of <i>k</i><sub>OH</sub> and <i>γ</i><sub>OH</sub> was
observed, consistent with surface-area-limited OH uptake. No decrease of
<i>k</i><sub>OH</sub> was observed as OH concentrations increased. These
observations of physicochemical properties of IEPOX-SOA can help to constrain
OA impact on air quality and climate. |
| first_indexed | 2024-04-12T00:14:45Z |
| format | Article |
| id | doaj.art-4bcac1047f7e4729a7adeec6369c0f2e |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-12T00:14:45Z |
| publishDate | 2016-09-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-4bcac1047f7e4729a7adeec6369c0f2e2022-12-22T03:55:52ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242016-09-0116115631158010.5194/acp-16-11563-2016Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)W. Hu0W. Hu1B. B. Palm2B. B. Palm3D. A. Day4D. A. Day5P. Campuzano-Jost6P. Campuzano-Jost7J. E. Krechmer8J. E. Krechmer9Z. Peng10Z. Peng11S. S. de Sá12S. T. Martin13S. T. Martin14M. L. Alexander15K. Baumann16L. Hacker17A. Kiendler-Scharr18A. R. Koss19A. R. Koss20A. R. Koss21J. A. de Gouw22J. A. de Gouw23J. A. de Gouw24A. H. Goldstein25A. H. Goldstein26R. Seco27S. J. Sjostedt28J.-H. Park29A. B. Guenther30S. Kim31F. Canonaco32A. S. H. Prévôt33W. H. Brune34J. L. Jimenez35J. L. Jimenez36Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USAJohn A. Paulson School of Engineering and Applied Sciences Harvard University, Cambridge, MA 01742, USAJohn A. Paulson School of Engineering and Applied Sciences Harvard University, Cambridge, MA 01742, USADepartment of Earth and Planetary Sciences, Harvard University, Cambridge, MA 01742, USAEnvironmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352, USAAtmospheric Research and Analysis Inc., Morrisville, NC 27560, USAInstitute for Energy and Climate Research – Troposphere (IEK-8), Forschungszentrum Jülich, 52425 Jülich, GermanyInstitute for Energy and Climate Research – Troposphere (IEK-8), Forschungszentrum Jülich, 52425 Jülich, GermanyCooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USAEarth System Research Laboratory, NOAA, Boulder, CO 80305, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USAEarth System Research Laboratory, NOAA, Boulder, CO 80305, USADepartment of Environmental Science, Policy, and Management, University of California, Berkeley, CA 94720, USADepartment of Civil and Environmental Engineering, University of California, Berkeley, CA 94720, USADepartment of Earth System Science, University of California, Irvine, CA 92697, USAEarth System Research Laboratory, NOAA, Boulder, CO 80305, USANational Institute of Environmental Research, Incheon 22689, Republic of KoreaDepartment of Earth System Science, University of California, Irvine, CA 92697, USADepartment of Earth System Science, University of California, Irvine, CA 92697, USALaboratory of Atmospheric Chemistry, Paul Scherrer Institute (PSI), 5232 Villigen, SwitzerlandLaboratory of Atmospheric Chemistry, Paul Scherrer Institute (PSI), 5232 Villigen, SwitzerlandDepartment of Meteorology, Pennsylvania State University, University Park, PA 16802, USACooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USADepartment of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USAIsoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100 µg m<sup>−3</sup> of pure H<sub>2</sub>SO<sub>4</sub> to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (<i>k</i><sub>OH</sub>) was estimated as 4.0 ± 2.0 × 10<sup>−13</sup> cm<sup>3</sup> molec<sup>−1</sup> s<sup>−1</sup>, which is equivalent to more than a 2-week lifetime. A similar <i>k</i><sub>OH</sub> was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10<sup>12</sup> molec cm<sup>−3</sup> s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (<i>γ</i><sub>OH</sub> = 0.59 ± 0.33 in SE US and <i>γ</i><sub>OH</sub> = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of <i>k</i><sub>OH</sub> and <i>γ</i><sub>OH</sub> was observed, consistent with surface-area-limited OH uptake. No decrease of <i>k</i><sub>OH</sub> was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.https://www.atmos-chem-phys.net/16/11563/2016/acp-16-11563-2016.pdf |
| spellingShingle | W. Hu W. Hu B. B. Palm B. B. Palm D. A. Day D. A. Day P. Campuzano-Jost P. Campuzano-Jost J. E. Krechmer J. E. Krechmer Z. Peng Z. Peng S. S. de Sá S. T. Martin S. T. Martin M. L. Alexander K. Baumann L. Hacker A. Kiendler-Scharr A. R. Koss A. R. Koss A. R. Koss J. A. de Gouw J. A. de Gouw J. A. de Gouw A. H. Goldstein A. H. Goldstein R. Seco S. J. Sjostedt J.-H. Park A. B. Guenther S. Kim F. Canonaco A. S. H. Prévôt W. H. Brune J. L. Jimenez J. L. Jimenez Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) Atmospheric Chemistry and Physics |
| title | Volatility and lifetime against OH heterogeneous reaction of ambient
isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) |
| title_full | Volatility and lifetime against OH heterogeneous reaction of ambient
isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) |
| title_fullStr | Volatility and lifetime against OH heterogeneous reaction of ambient
isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) |
| title_full_unstemmed | Volatility and lifetime against OH heterogeneous reaction of ambient
isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) |
| title_short | Volatility and lifetime against OH heterogeneous reaction of ambient
isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) |
| title_sort | volatility and lifetime against oh heterogeneous reaction of ambient isoprene epoxydiols derived secondary organic aerosol iepox soa |
| url | https://www.atmos-chem-phys.net/16/11563/2016/acp-16-11563-2016.pdf |
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