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Aqueous Phase Photo-oxidation of Brown Carbon Nitrophenols: Reaction Kinetics, Mechanism, and Evolution of Light Absorption

2018· article· en· W2783619428 on OpenAlexafffund
Rachel F. Hems, Jonathan P. D. Abbatt

Bibliographic record

VenueACS Earth and Space Chemistry · 2018
Typearticle
Languageen
FieldEarth and Planetary Sciences
TopicAtmospheric chemistry and aerosols
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsChemistryAqueous solutionPhotochemistryAbsorption (acoustics)PhotodissociationReaction rate constantAerosolRadicalCarbon fibersInorganic chemistryKineticsOrganic chemistryMaterials science

Abstract

fetched live from OpenAlex

Light absorbing organic aerosol particles, referred to as brown carbon, are geographically widespread and can have an important climate impact through the absorption of solar radiation. Recent studies, both in the laboratory and the field, have shown that brown carbon aerosols can be bleached of their color by direct photolysis and photo-oxidation reactions on the time scale of hours to days. However, the photo-oxidation of nitrophenol molecules, which are colored compounds often associated with biomass burning organic aerosol, show an enhancement in light absorption before the color is lost. This study investigates the mechanism of color enhancement and the fate of three nitrophenol compounds, specifically nitrocatechol, nitroguaiacol, and dinitrophenol, in the aqueous phase using online aerosol chemical ionization mass spectrometry (aerosol-CIMS). The second-order rate constants for the three nitrophenols with OH radicals in the aqueous phase at pH 7 (298 K), were determined to be 5 × 109 M–1 s–1, 5.2 × 109 M–1 s–1, and 3.7 × 109 M–1 s–1 for nitrocatechol, nitroguaiacol, and dinitrophenol, respectively. For a representative aqueous OH concentration, these rate constants correspond to an aqueous lifetime with respect to OH on the order of hours. While the nitrophenol molecules react rapidly with OH, the initial products, which are functionalized by additional electron-donating OH groups, likely lead to the observed absorption increase in the visible range. Further photo-oxidation fragments the aromatic structure to produce smaller, highly oxygenated molecules which no longer absorb strongly at visible wavelengths. These products include furoic acid, glyoxylic acid, malonic acid, oxalic acid, and isocyanic acid. All three nitrophenols investigated formed similar products during photo-oxidation, suggesting that these results could be generalized to this larger class of compounds.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.003
Threshold uncertainty score0.482

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.007
GPT teacher head0.197
Teacher spread0.190 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations205
Published2018
Admission routes2
Has abstractyes

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