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Adv."],"published-print":{"date-parts":[[2026,5,15]]},"abstract":"<jats:p>\n                    Declining nitrogen oxide (NO\n                    <jats:italic toggle=\"yes\">\n                      <jats:sub>x<\/jats:sub>\n                    <\/jats:italic>\n                    \u00a0=\u00a0NO + NO\n                    <jats:sub>2<\/jats:sub>\n                    ) emissions have transformed oxidation pathways in urban atmospheres, with implications for air quality. Organic peroxy radicals (RO\n                    <jats:sub>2<\/jats:sub>\n                    ), key intermediates in volatile organic compound oxidation, typically react with NO to form ozone (O\n                    <jats:sub>3<\/jats:sub>\n                    ). Under lower-NO conditions, alternative RO\n                    <jats:sub>2<\/jats:sub>\n                    fates, including isomerization forming highly oxidized organic molecules (HOMs), can enhance secondary organic aerosol (SOA) production. We combine aircraft observations over four major North American cities with geostationary satellite data to characterize isoprene-derived RO\n                    <jats:sub>2<\/jats:sub>\n                    fate across urban environments. We infer RO\n                    <jats:sub>2<\/jats:sub>\n                    bimolecular lifetimes (\u03c4\n                    <jats:sub>bi<\/jats:sub>\n                    ) as a proxy for isomerization potential, finding longer \u03c4\n                    <jats:sub>bi<\/jats:sub>\n                    (17\u00a0\u00b1\u00a011 seconds) in New York, Chicago, and Toronto compared to Los Angeles (7\u00a0\u00b1\u00a06 seconds). Satellite measurements reveal that long \u03c4\n                    <jats:sub>bi<\/jats:sub>\n                    is widespread across urban North America, suggesting that declining NO\n                    <jats:italic toggle=\"yes\">\n                      <jats:sub>x<\/jats:sub>\n                    <\/jats:italic>\n                    is likely to lead to greater HOM formation in urban regions. These findings indicate that atmospheric models omitting RO\n                    <jats:sub>2<\/jats:sub>\n                    isomerization chemistry may incorrectly simulate organic oxidation and the subsequent oxidation state of volatile organic compounds and SOA.\n                  <\/jats:p>","DOI":"10.1126\/sciadv.aea6509","type":"journal-article","created":{"date-parts":[[2026,5,13]],"date-time":"2026-05-13T18:00:56Z","timestamp":1778695256000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":3,"title":["Fate of isoprene peroxy radical constrains the urban photochemical regime"],"prefix":"10.1126","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0977-9148","authenticated-orcid":true,"given":"Michael A.","family":"Robinson","sequence":"first","affiliation":[{"name":"Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USA."},{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5763-1925","authenticated-orcid":true,"given":"Matthew M.","family":"Coggon","sequence":"additional","affiliation":[{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7544-9580","authenticated-orcid":true,"given":"Kelvin H.","family":"Bates","sequence":"additional","affiliation":[{"name":"Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USA."},{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9320-7101","authenticated-orcid":true,"given":"Jeff","family":"Peischl","sequence":"additional","affiliation":[{"name":"Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USA."},{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0302-5222","authenticated-orcid":true,"given":"Christopher M.","family":"Jernigan","sequence":"additional","affiliation":[{"name":"Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80305, USA."},{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4009-039X","authenticated-orcid":true,"given":"Gordon","family":"Novak","sequence":"additional","affiliation":[{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1733-9177","authenticated-orcid":true,"given":"Subi","family":"Thakali","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8485-8172","authenticated-orcid":true,"given":"James M.","family":"Roberts","sequence":"additional","affiliation":[{"name":"Chemical Sciences Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO 80305, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"J. 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