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Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol
Secondary organic aerosol (SOA) is a complex mixture of hundreds of semi-volatile to extremely low-volatility organic compounds that are chemically processed in the atmosphere, including via heterogeneous oxidation by gas-phase radicals. Relative humidity (RH) has a substantial impact on particle ph...
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Published in: | Atmospheric chemistry and physics 2018-10, Vol.18 (19), p.14585-14608 |
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creator | Li, Ziyue Smith, Katherine A Cappa, Christopher D |
description | Secondary organic aerosol (SOA) is a complex mixture of hundreds of
semi-volatile to extremely low-volatility organic compounds that are
chemically processed in the atmosphere, including via heterogeneous
oxidation by gas-phase radicals. Relative humidity (RH) has a substantial
impact on particle phase, which can affect how SOA evolves in the
atmosphere. In this study, SOA from dark α-pinene ozonolysis is
heterogeneously aged by OH radicals in a flow tube at low and high RH. At
high RH (RH =89 %) there is substantial loss of particle volume
(∼60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH =25 %) there is little mass loss
( |
doi_str_mv | 10.5194/acp-18-14585-2018 |
format | article |
fullrecord | <record><control><sourceid>gale_doaj_</sourceid><recordid>TN_cdi_doaj_primary_oai_doaj_org_article_d3ca838f4ec24e169b4816b6e2add4c8</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><galeid>A557795760</galeid><doaj_id>oai_doaj_org_article_d3ca838f4ec24e169b4816b6e2add4c8</doaj_id><sourcerecordid>A557795760</sourcerecordid><originalsourceid>FETCH-LOGICAL-c576t-139ec0e2d3407e084195454203adceb74e379ebcad7d50fd3db6954366f2a4b53</originalsourceid><addsrcrecordid>eNptkktr3DAQx01poWnaD9CbaU89ONXoYcnHEPpYCAT6uPQiZGm8q2XX2kpySL99J9kQulB0kGb0m5f0b5q3wC4UDPKj84cOTAdSGdVxBuZZcwa9YZ0WXD7_5_yyeVXKljGuGMiz5tdqnnYLzh7bNLUZd67GW2w3yz6GWP-0aW7rhmysmNMaZ0xLadNdDMTRHcUU9GkOLhOb126OvnWElrR73byY3K7gm8f9vPn5-dOPq6_d9c2X1dXldeeV7msHYkDPkAchmUZmJAxKKsmZcMHjqCUKPeDoXdBBsSmIMPZEiL6fuJOjEufN6pg3JLe1hxz31IxNLtoHB3VlXa7R79AG4Z0RZpLouUToh1Ea6MceuQtBekO53h1zpVKjLT5W9Buab0ZfLUitQQBB74_QIaffC5Zqt2nJM81oOYA2XBjq74laO6oc5ynV7Pw-Fm8vldJ6oOkZURf_oWgF3EcqjFMk_0nAh5MAYire1bVbSrGr799OWTiynj6kZJyeXgeYvZeNJdlYMPZBNvZeNuIvEBSz2Q</addsrcrecordid><sourcetype>Open Website</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2117823854</pqid></control><display><type>article</type><title>Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol</title><source>Publicly Available Content Database</source><source>DOAJ Directory of Open Access Journals</source><source>Alma/SFX Local Collection</source><creator>Li, Ziyue ; Smith, Katherine A ; Cappa, Christopher D</creator><creatorcontrib>Li, Ziyue ; Smith, Katherine A ; Cappa, Christopher D</creatorcontrib><description>Secondary organic aerosol (SOA) is a complex mixture of hundreds of
semi-volatile to extremely low-volatility organic compounds that are
chemically processed in the atmosphere, including via heterogeneous
oxidation by gas-phase radicals. Relative humidity (RH) has a substantial
impact on particle phase, which can affect how SOA evolves in the
atmosphere. In this study, SOA from dark α-pinene ozonolysis is
heterogeneously aged by OH radicals in a flow tube at low and high RH. At
high RH (RH =89 %) there is substantial loss of particle volume
(∼60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH =25 %) there is little mass loss
(<20 %) at the same OH exposure. Mass spectra of the SOA
particles were measured as a function of OH exposure using a vacuum
ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra
observed at low RH overall exhibit minor changes with oxidation and
negligible further changes above an OH exposure =2×1012 molecule cm−3 s
suggesting limited impact of oxidation on the particle
composition. In contrast, the mass spectra observed at high RH exhibit
substantial and continuous changes as a function of OH exposure. Further, at
high RH clusters of peaks in the mass spectra exhibit unique decay patterns,
suggesting different responses of various species to oxidation. A model of
heterogeneous oxidation has been developed to understand the origin of the
difference in aging between the low- and high-RH experiments. Differences in
diffusivity of the SOA between the low- and high-RH experiments alone can
explain the difference in compositional change but cannot explain the
difference in mass loss. Instead, the difference in mass loss is
attributable to RH-dependent differences in the OH uptake coefficient
and/or the net probability of fragmentation, with either or both larger at
high RH compared to low RH. These results illustrate the important impact of
relative humidity on the fate of SOA in the atmosphere.</description><identifier>ISSN: 1680-7324</identifier><identifier>ISSN: 1680-7316</identifier><identifier>EISSN: 1680-7324</identifier><identifier>DOI: 10.5194/acp-18-14585-2018</identifier><language>eng</language><publisher>Katlenburg-Lindau: Copernicus GmbH</publisher><subject>Aerosols ; Ageing ; Aging ; Atmosphere ; Chemical properties ; Continuity (mathematics) ; Environmental aspects ; Exposure ; Free radicals ; Humidity ; Mass ; Mass spectra ; Mass spectrometry ; Mass spectroscopy ; Observations ; Organic chemistry ; Organic compounds ; Oxidation ; Oxidation-reduction reactions ; Ozonolysis ; Particle composition ; Probability theory ; Radicals ; Relative humidity ; Secondary aerosols ; Spectra ; Uptake ; Vacuum ; Volatility ; α-Pinene</subject><ispartof>Atmospheric chemistry and physics, 2018-10, Vol.18 (19), p.14585-14608</ispartof><rights>COPYRIGHT 2018 Copernicus GmbH</rights><rights>2018. This work is published under https://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c576t-139ec0e2d3407e084195454203adceb74e379ebcad7d50fd3db6954366f2a4b53</citedby><cites>FETCH-LOGICAL-c576t-139ec0e2d3407e084195454203adceb74e379ebcad7d50fd3db6954366f2a4b53</cites><orcidid>0000-0001-9101-7737 ; 0000-0002-3528-3368 ; 0000000235283368 ; 0000000191017737</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.proquest.com/docview/2117823854/fulltextPDF?pq-origsite=primo$$EPDF$$P50$$Gproquest$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.proquest.com/docview/2117823854?pq-origsite=primo$$EHTML$$P50$$Gproquest$$Hfree_for_read</linktohtml><link.rule.ids>230,314,780,784,864,885,2100,25752,27923,27924,37011,44589,74897</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1477131$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Li, Ziyue</creatorcontrib><creatorcontrib>Smith, Katherine A</creatorcontrib><creatorcontrib>Cappa, Christopher D</creatorcontrib><title>Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol</title><title>Atmospheric chemistry and physics</title><description>Secondary organic aerosol (SOA) is a complex mixture of hundreds of
semi-volatile to extremely low-volatility organic compounds that are
chemically processed in the atmosphere, including via heterogeneous
oxidation by gas-phase radicals. Relative humidity (RH) has a substantial
impact on particle phase, which can affect how SOA evolves in the
atmosphere. In this study, SOA from dark α-pinene ozonolysis is
heterogeneously aged by OH radicals in a flow tube at low and high RH. At
high RH (RH =89 %) there is substantial loss of particle volume
(∼60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH =25 %) there is little mass loss
(<20 %) at the same OH exposure. Mass spectra of the SOA
particles were measured as a function of OH exposure using a vacuum
ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra
observed at low RH overall exhibit minor changes with oxidation and
negligible further changes above an OH exposure =2×1012 molecule cm−3 s
suggesting limited impact of oxidation on the particle
composition. In contrast, the mass spectra observed at high RH exhibit
substantial and continuous changes as a function of OH exposure. Further, at
high RH clusters of peaks in the mass spectra exhibit unique decay patterns,
suggesting different responses of various species to oxidation. A model of
heterogeneous oxidation has been developed to understand the origin of the
difference in aging between the low- and high-RH experiments. Differences in
diffusivity of the SOA between the low- and high-RH experiments alone can
explain the difference in compositional change but cannot explain the
difference in mass loss. Instead, the difference in mass loss is
attributable to RH-dependent differences in the OH uptake coefficient
and/or the net probability of fragmentation, with either or both larger at
high RH compared to low RH. These results illustrate the important impact of
relative humidity on the fate of SOA in the atmosphere.</description><subject>Aerosols</subject><subject>Ageing</subject><subject>Aging</subject><subject>Atmosphere</subject><subject>Chemical properties</subject><subject>Continuity (mathematics)</subject><subject>Environmental aspects</subject><subject>Exposure</subject><subject>Free radicals</subject><subject>Humidity</subject><subject>Mass</subject><subject>Mass spectra</subject><subject>Mass spectrometry</subject><subject>Mass spectroscopy</subject><subject>Observations</subject><subject>Organic chemistry</subject><subject>Organic compounds</subject><subject>Oxidation</subject><subject>Oxidation-reduction reactions</subject><subject>Ozonolysis</subject><subject>Particle composition</subject><subject>Probability theory</subject><subject>Radicals</subject><subject>Relative humidity</subject><subject>Secondary aerosols</subject><subject>Spectra</subject><subject>Uptake</subject><subject>Vacuum</subject><subject>Volatility</subject><subject>α-Pinene</subject><issn>1680-7324</issn><issn>1680-7316</issn><issn>1680-7324</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><sourceid>PIMPY</sourceid><sourceid>DOA</sourceid><recordid>eNptkktr3DAQx01poWnaD9CbaU89ONXoYcnHEPpYCAT6uPQiZGm8q2XX2kpySL99J9kQulB0kGb0m5f0b5q3wC4UDPKj84cOTAdSGdVxBuZZcwa9YZ0WXD7_5_yyeVXKljGuGMiz5tdqnnYLzh7bNLUZd67GW2w3yz6GWP-0aW7rhmysmNMaZ0xLadNdDMTRHcUU9GkOLhOb126OvnWElrR73byY3K7gm8f9vPn5-dOPq6_d9c2X1dXldeeV7msHYkDPkAchmUZmJAxKKsmZcMHjqCUKPeDoXdBBsSmIMPZEiL6fuJOjEufN6pg3JLe1hxz31IxNLtoHB3VlXa7R79AG4Z0RZpLouUToh1Ea6MceuQtBekO53h1zpVKjLT5W9Buab0ZfLUitQQBB74_QIaffC5Zqt2nJM81oOYA2XBjq74laO6oc5ynV7Pw-Fm8vldJ6oOkZURf_oWgF3EcqjFMk_0nAh5MAYire1bVbSrGr799OWTiynj6kZJyeXgeYvZeNJdlYMPZBNvZeNuIvEBSz2Q</recordid><startdate>20181011</startdate><enddate>20181011</enddate><creator>Li, Ziyue</creator><creator>Smith, Katherine A</creator><creator>Cappa, Christopher D</creator><general>Copernicus GmbH</general><general>Copernicus Publications, EGU</general><general>Copernicus Publications</general><scope>AAYXX</scope><scope>CITATION</scope><scope>ISR</scope><scope>7QH</scope><scope>7TG</scope><scope>7TN</scope><scope>7UA</scope><scope>8FD</scope><scope>8FE</scope><scope>8FG</scope><scope>ABUWG</scope><scope>AEUYN</scope><scope>AFKRA</scope><scope>ARAPS</scope><scope>ATCPS</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BFMQW</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>BKSAR</scope><scope>C1K</scope><scope>CCPQU</scope><scope>DWQXO</scope><scope>F1W</scope><scope>GNUQQ</scope><scope>H8D</scope><scope>H96</scope><scope>HCIFZ</scope><scope>KL.</scope><scope>L.G</scope><scope>L7M</scope><scope>P5Z</scope><scope>P62</scope><scope>PATMY</scope><scope>PCBAR</scope><scope>PIMPY</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>PYCSY</scope><scope>OTOTI</scope><scope>DOA</scope><orcidid>https://orcid.org/0000-0001-9101-7737</orcidid><orcidid>https://orcid.org/0000-0002-3528-3368</orcidid><orcidid>https://orcid.org/0000000235283368</orcidid><orcidid>https://orcid.org/0000000191017737</orcidid></search><sort><creationdate>20181011</creationdate><title>Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol</title><author>Li, Ziyue ; Smith, Katherine A ; Cappa, Christopher D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c576t-139ec0e2d3407e084195454203adceb74e379ebcad7d50fd3db6954366f2a4b53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Aerosols</topic><topic>Ageing</topic><topic>Aging</topic><topic>Atmosphere</topic><topic>Chemical properties</topic><topic>Continuity (mathematics)</topic><topic>Environmental aspects</topic><topic>Exposure</topic><topic>Free radicals</topic><topic>Humidity</topic><topic>Mass</topic><topic>Mass spectra</topic><topic>Mass spectrometry</topic><topic>Mass spectroscopy</topic><topic>Observations</topic><topic>Organic chemistry</topic><topic>Organic compounds</topic><topic>Oxidation</topic><topic>Oxidation-reduction reactions</topic><topic>Ozonolysis</topic><topic>Particle composition</topic><topic>Probability theory</topic><topic>Radicals</topic><topic>Relative humidity</topic><topic>Secondary aerosols</topic><topic>Spectra</topic><topic>Uptake</topic><topic>Vacuum</topic><topic>Volatility</topic><topic>α-Pinene</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Li, Ziyue</creatorcontrib><creatorcontrib>Smith, Katherine A</creatorcontrib><creatorcontrib>Cappa, Christopher D</creatorcontrib><collection>CrossRef</collection><collection>Gale In Context: Science</collection><collection>Aqualine</collection><collection>Meteorological & Geoastrophysical Abstracts</collection><collection>Oceanic Abstracts</collection><collection>Water Resources Abstracts</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest One Sustainability</collection><collection>ProQuest Central UK/Ireland</collection><collection>Advanced Technologies & Aerospace Collection</collection><collection>Agricultural & Environmental Science Collection</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Continental Europe Database</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>Earth, Atmospheric & Aquatic Science Collection</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ProQuest One Community College</collection><collection>ProQuest Central Korea</collection><collection>ASFA: Aquatic Sciences and Fisheries Abstracts</collection><collection>ProQuest Central Student</collection><collection>Aerospace Database</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) 2: Ocean Technology, Policy & Non-Living Resources</collection><collection>SciTech Premium Collection</collection><collection>Meteorological & Geoastrophysical Abstracts - Academic</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) Professional</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Advanced Technologies & Aerospace Database</collection><collection>ProQuest Advanced Technologies & Aerospace Collection</collection><collection>Environmental Science Database</collection><collection>Earth, Atmospheric & Aquatic Science Database</collection><collection>Publicly Available Content Database</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>Environmental Science Collection</collection><collection>OSTI.GOV</collection><collection>DOAJ Directory of Open Access Journals</collection><jtitle>Atmospheric chemistry and physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Li, Ziyue</au><au>Smith, Katherine A</au><au>Cappa, Christopher D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol</atitle><jtitle>Atmospheric chemistry and physics</jtitle><date>2018-10-11</date><risdate>2018</risdate><volume>18</volume><issue>19</issue><spage>14585</spage><epage>14608</epage><pages>14585-14608</pages><issn>1680-7324</issn><issn>1680-7316</issn><eissn>1680-7324</eissn><abstract>Secondary organic aerosol (SOA) is a complex mixture of hundreds of
semi-volatile to extremely low-volatility organic compounds that are
chemically processed in the atmosphere, including via heterogeneous
oxidation by gas-phase radicals. Relative humidity (RH) has a substantial
impact on particle phase, which can affect how SOA evolves in the
atmosphere. In this study, SOA from dark α-pinene ozonolysis is
heterogeneously aged by OH radicals in a flow tube at low and high RH. At
high RH (RH =89 %) there is substantial loss of particle volume
(∼60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH =25 %) there is little mass loss
(<20 %) at the same OH exposure. Mass spectra of the SOA
particles were measured as a function of OH exposure using a vacuum
ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra
observed at low RH overall exhibit minor changes with oxidation and
negligible further changes above an OH exposure =2×1012 molecule cm−3 s
suggesting limited impact of oxidation on the particle
composition. In contrast, the mass spectra observed at high RH exhibit
substantial and continuous changes as a function of OH exposure. Further, at
high RH clusters of peaks in the mass spectra exhibit unique decay patterns,
suggesting different responses of various species to oxidation. A model of
heterogeneous oxidation has been developed to understand the origin of the
difference in aging between the low- and high-RH experiments. Differences in
diffusivity of the SOA between the low- and high-RH experiments alone can
explain the difference in compositional change but cannot explain the
difference in mass loss. Instead, the difference in mass loss is
attributable to RH-dependent differences in the OH uptake coefficient
and/or the net probability of fragmentation, with either or both larger at
high RH compared to low RH. These results illustrate the important impact of
relative humidity on the fate of SOA in the atmosphere.</abstract><cop>Katlenburg-Lindau</cop><pub>Copernicus GmbH</pub><doi>10.5194/acp-18-14585-2018</doi><tpages>24</tpages><orcidid>https://orcid.org/0000-0001-9101-7737</orcidid><orcidid>https://orcid.org/0000-0002-3528-3368</orcidid><orcidid>https://orcid.org/0000000235283368</orcidid><orcidid>https://orcid.org/0000000191017737</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Aerosols Ageing Aging Atmosphere Chemical properties Continuity (mathematics) Environmental aspects Exposure Free radicals Humidity Mass Mass spectra Mass spectrometry Mass spectroscopy Observations Organic chemistry Organic compounds Oxidation Oxidation-reduction reactions Ozonolysis Particle composition Probability theory Radicals Relative humidity Secondary aerosols Spectra Uptake Vacuum Volatility α-Pinene |
title | Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol |
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