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  4. Hydrogen Peroxide Formation during Ozonation of Olefins and Phenol: Mechanistic Insights from Oxygen Isotope Signatures
 
research article

Hydrogen Peroxide Formation during Ozonation of Olefins and Phenol: Mechanistic Insights from Oxygen Isotope Signatures

Houska, Joanna
•
Stocco, Laura
•
Hofstetter, Thomas B.
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May 8, 2023
Environmental Science & Technology

Mitigation of undesired byproducts from ozonation of dissolved organic matter (DOM) such as aldehydes and ketones is currently hampered by limited knowledge of their precursors and formation pathways. Here, the stable oxygen isotope composition of H2O2 formed simultaneously with these byproducts was studied to determine if it can reveal this missing information. A newly developed procedure, which quantitatively transforms H2O2 to O2 for subsequent 18O/16O ratio analysis, was used to determine the 618O of H2O2 generated from ozonated model compounds (olefins and phenol, pH 3-8). A constant enrichment of 18O in H2O2 with a 618O value of similar to 59%o implies that 16O-16O bonds are cleaved preferentially in the intermediate Criegee ozonide, which is commonly formed from olefins. H2O2 from the ozonation of acrylic acid and phenol at pH 7 resulted in lower 18O enrichment (618O = 47-49%o). For acrylic acid, enhancement of one of the two pathways followed by a carbonyl-H2O2 equilibrium was responsible for the smaller 618O of H2O2. During phenol ozonation at pH 7, various competing reactions leading to H2O2 via an intermediate ozone adduct are hypothesized to cause lower 618O in H2O2. These insights provide a first step toward supporting pH -dependent H2O2 precursor elucidation in DOM.

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Type
research article
DOI
10.1021/acs.est.3c00788
Web of Science ID

WOS:000985957500001

Author(s)
Houska, Joanna
Stocco, Laura
Hofstetter, Thomas B.
von Gunten, Urs  
Date Issued

2023-05-08

Publisher

AMER CHEMICAL SOC

Published in
Environmental Science & Technology
Subjects

Engineering, Environmental

•

Environmental Sciences

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Engineering

•

Environmental Sciences & Ecology

•

ozonation

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hydrogen peroxide

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reaction mechanisms

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olefins

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phenol

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oxygen isotopes

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isotope ratio mass spectrometry

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dissolved organic-matter

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n-nitrosodimethylamine

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advanced oxidation

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ozone reactions

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water

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radicals

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chlorine

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chloramination

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fractionation

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decomposition

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LTQE  
Available on Infoscience
June 5, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/198010
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