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dc.contributor.author
Schmitt, Markus
dc.contributor.author
Moor, Kyle J.
dc.contributor.author
Erickson, Paul R.
dc.contributor.author
McNeill, Kristopher
dc.date.accessioned
2019-08-07T09:00:50Z
dc.date.available
2019-08-06T02:56:49Z
dc.date.available
2019-08-07T09:00:50Z
dc.date.issued
2019-07-16
dc.identifier.issn
0013-936X
dc.identifier.issn
1520-5851
dc.identifier.other
10.1021/acs.est.9b01789
en_US
dc.identifier.uri
http://hdl.handle.net/20.500.11850/356719
dc.identifier.doi
10.3929/ethz-b-000356719
dc.description.abstract
Sorbic acid (2,4-hexadienoic acid; HDA) isomerization is frequently used to probe triplet-state dissolved organic matter (3CDOM*) reactivity, but there remain open questions about the reaction kinetics of 3CDOM* with HDA due to the difficulties of directly measuring 3CDOM* quenching rate constants. Using our recently developed approach based on observing the radical cation of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) formed through oxidation of TMPD by 3CDOM*, we studied 3CDOM* quenching kinetics with HDA monitored via transient absorption spectroscopy. A competition kinetics-based approach utilizing formation yields of TMPD•+ was developed, validated with model sensitizers, and used to determine bimolecular rate constants between 3CDOM* oxidants and HDA for diverse DOM isolates and natural waters samples, yielding values in the range of (2.4–7.7) × 108 M–1 s–1. The unquenchable fraction of TMPD-oxidizing triplets showed that, on average, 41% of 3CDOM* oxidants cannot be quenched by HDA. Conversely, cycloheptatriene quenched nearly all TMPD•+-forming triplets in CDOM, suggesting that most 3CDOM* oxidants possess energies greater than 150 kJ mol–1. Comparing results with our companion study, we found slight, but noticeable differences in the 3CDOM* quenching rate constants by HDA and unquenchable triplet fractions determined by oxidation of TMPD and energy transfer to O2 (1O2 formation) methods.
en_US
dc.format
application/pdf
en_US
dc.language.iso
en
en_US
dc.publisher
American Chemical Society
en_US
dc.rights.uri
http://creativecommons.org/licenses/by/4.0/
dc.title
Sorbic Acid as a Triplet Probe: Reactivity of Oxidizing Triplets in Dissolved Organic Matter by Direct Observation of Aromatic Amine Oxidation
en_US
dc.type
Journal Article
dc.rights.license
Creative Commons Attribution 4.0 International
dc.date.published
2019-06-20
ethz.journal.title
Environmental Science & Technology
ethz.journal.volume
53
en_US
ethz.journal.issue
14
en_US
ethz.journal.abbreviated
Environ. Sci. Technol.
ethz.pages.start
8087
en_US
ethz.pages.end
8096
en_US
ethz.version.deposit
publishedVersion
en_US
ethz.grant
Electron transfer properties of photoexcited natural organic matter
en_US
ethz.identifier.wos
ethz.identifier.scopus
ethz.publication.place
Washington, DC
en_US
ethz.publication.status
published
en_US
ethz.leitzahl
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02350 - Dep. Umweltsystemwissenschaften / Dep. of Environmental Systems Science::02721 - Inst. f. Biogeochemie u. Schadstoffdyn. / Inst. Biogeochem. and Pollutant Dynamics::03850 - McNeill, Kristopher / McNeill, Kristopher
ethz.leitzahl.certified
ETH Zürich::00002 - ETH Zürich::00012 - Lehre und Forschung::00007 - Departemente::02350 - Dep. Umweltsystemwissenschaften / Dep. of Environmental Systems Science::02721 - Inst. f. Biogeochemie u. Schadstoffdyn. / Inst. Biogeochem. and Pollutant Dynamics::03850 - McNeill, Kristopher / McNeill, Kristopher
ethz.grant.agreementno
156198
ethz.grant.fundername
SNF
ethz.grant.funderDoi
10.13039/501100001711
ethz.grant.program
Projekte MINT
ethz.date.deposited
2019-08-06T02:57:03Z
ethz.source
SCOPUS
ethz.eth
yes
en_US
ethz.availability
Open access
en_US
ethz.rosetta.installDate
2019-08-07T09:01:00Z
ethz.rosetta.lastUpdated
2022-03-28T23:25:55Z
ethz.rosetta.versionExported
true
ethz.COinS
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