Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

Velivetskaya, T. A.; Ignatiev, A. V.; Budnitskiy, Sergey Y.; Yakovenko, V. V.; Vysotskiy, S. V.

doi:10.1016/j.gca.2016.08.008

Cited by 10 publications

(2 citation statements)

References 52 publications

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“…In a typical sample matrix, the δ 18 O values of these H 2 O 2 standards were 22.2 ± 1.0‰ ( n = 20) and thus identical within uncertainty (Figure S9b). All measured values coincide with the range of measured δ 18 O of H 2 O 2 standards examined previously of 21.4–25.8‰. , These O isotope signatures are confined to an amazingly narrow range of approximately 5‰, presumably because commercially available H 2 O 2 is almost exclusively produced by the anthraquinone process . The agreement of the measurement with previous data for δ 18 O of H 2 O 2 further underscores the accuracy of the presented analytical procedure.…”

Section: Resultssupporting

confidence: 86%

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

Houska,

Stocco,

Hofstetter

et al. 2023

Environ. Sci. Technol.

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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 H 2 O 2 formed simultaneously with these byproducts was studied to determine if it can reveal this missing information. A newly developed procedure, which quantitatively transforms H 2 O 2 to O 2 for subsequent 18 O/ 16 O ratio analysis, was used to determine the δ 18 O of H 2 O 2 generated from ozonated model compounds (olefins and phenol, pH 3−8). A constant enrichment of 18 O in H 2 O 2 with a δ 18 O value of ∼59‰ implies that 16 O− 16 O bonds are cleaved preferentially in the intermediate Criegee ozonide, which is commonly formed from olefins. H 2 O 2 from the ozonation of acrylic acid and phenol at pH 7 resulted in lower 18 O enrichment (δ 18 O = 47−49‰). For acrylic acid, enhancement of one of the two pathways followed by a carbonyl−H 2 O 2 equilibrium was responsible for the smaller δ 18 O of H 2 O 2 . During phenol ozonation at pH 7, various competing reactions leading to H 2 O 2 via an intermediate ozone adduct are hypothesized to cause lower δ 18 O in H 2 O 2 . These insights provide a first step toward supporting pHdependent H 2 O 2 precursor elucidation in DOM.

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Section: Resultssupporting

confidence: 86%

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

Houska,

Stocco,

Hofstetter

et al. 2023

Environ. Sci. Technol.

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“…Oxygen stable isotopes of the bulk hydrogen peroxide reagent (30% w/w) were measured by pyrolysis using a Thermo Finnigan TC/EA coupled to a Thermo Finnigan Delta V IRMS via a Thermo Finnigan Conflo III device. Measurement of the peroxide oxygen in the reagent was conducted following procedures modified from previous experiments. , Solutions of hydrogen peroxide and potassium permanganate (diluted to 0.05 g/mL and acidified to pH 1 with H 2 SO 4 ) were frozen under liquid nitrogen and evacuated to remove any oxygen gas impurities. The hydrogen peroxide solution was then thawed and injected into a vacuum flask containing the still frozen KMnO 4 solution.…”

Section: Methodsmentioning

confidence: 99%

Fractionation of Oxygen Isotopes in Uranium Oxides during Peroxide Precipitation and Dry Air Calcination

Klosterman

Oerter

Chakraborty

et al. 2021

ACS Earth Space Chem.

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The interaction between uranium and oxygen-containing substrates is nearly ubiquitous within the nuclear fuel cycle. Given the well-known and predictable oxygen stable isotope compositions of atmospheric oxygen and meteoric waters around the world, the use of these isotopes as a potential geolocation or processing signature of uranium compounds has been of interest within the nuclear safeguards community. This study focuses on measuring the oxygen-stable isotope composition of synthetically produced uranium oxides to determine the mechanism and extent of fractionation during materials processing relevant to the nuclear fuel cycle. Metastudtite [UO2O2(H2O)2] samples were first produced using water and hydrogen peroxide of a known oxygen isotope composition. This starting material was calcined in dry air at temperatures ranging from 300 °C to 1000 °C for 20 h producing oxides ranging in composition from UO3 +x (0 ≤ x ≤ 0.5) to U3O8. In addition, calcinations between 500 and 800 °C were performed at different time intervals to evaluate the rate of isotopic equilibration. The δ18O values of water bound to metastudtite were measured by thermogravimetric analysis coupled to isotope ratio infrared spectroscopy (TGA–IRIS). A redesigned fluorination manifold was constructed at the University of Utah and was used to extract the bulk oxygen from precipitated and calcined products using bromine pentafluoride (BrF5). Mineralization water on metastudtite (measured by TGA–IRIS) was closely associated with the aqueous environment of precipitation with a fractionation of +3.5 ± 0.6‰. In contrast, bulk oxygen from metastudtite (measured by fluorination and gas chromatography combined with isotope ratio mass spectrometry) was found to have an inconsistent fractionation with precipitation water. Samples calcined in dry air exhibited a wide range of oxygen isotope compositions which increased from δ18O = +1.4 ± 0.9‰ at 300 °C to +17.3 ± 0.9‰ at 1000 °C. This variation in δ18O values was a result of oxygen exchange with atmospheric O2 and was found to be rapid at calcination temperatures greater than 600°Cwith equilibration occurring in less than 2 h. These results provide insights into the incorporation and exchange of oxygen isotopes during precipitation and calcination processes comparable to those employed within the nuclear fuel cycle and establish a foundation for future investigations to build upon.

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Mass-independent fractionation processes in the atmosphere

Hemingway,

Claire

2025

Treatise on Geochemistry

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Mass-independent fractionation of oxygen isotopes during H2O2 formation by gas-phase discharge from water vapour

Cited by 10 publications

References 52 publications

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

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

Fractionation of Oxygen Isotopes in Uranium Oxides during Peroxide Precipitation and Dry Air Calcination

Mass-independent fractionation processes in the atmosphere

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