Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

Zeng, Meirong; Wilson, Kevin R.

doi:10.1021/acs.est.4c02590

Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

Journal Article · Thu Jun 20 00:00:00 EDT 2024 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.4c02590· OSTI ID:2499765

Zeng, Meirong ^[1]; ^[2]

Shanghai Jiao Tong Univ. (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Organic molecules in the environment oxidatively degrade by a variety of free radical, microbial, and biogeochemical pathways. A significant pathway is heterogeneous autoxidation, in which degradation occurs via a network of carbon and oxygen centered free radicals. Recently, we found evidence for a new heterogeneous autoxidation mechanism of squalene that is initiated by hydroxyl (OH) radical addition to a carbon–carbon double bond and apparently propagated through pathways involving Criegee Intermediates (CI) produced from β-hydroxy peroxy radicals (β-OH-RO₂•). It remains unclear, however, exactly how CI are formed from β-OH-RO₂•, which could occur by a unimolecular or bimolecular pathway. Combining kinetic models and multiphase OH oxidation measurements of squalene, we evaluate the kinetic viability of three mechanistic scenarios. Scenario 1 assumes that CI are formed by the unimolecular bond scission of β-OH-RO₂•, whereas Scenarios 2 and 3 test bimolecular pathways of β-OH-RO₂• to yield CI. Scenario 1 best replicates the entire experimental data set, which includes effective uptake coefficients vs [OH] as well as the formation kinetics of the major products (i.e., aldehydes and secondary ozonides). Finally, although the unimolecular pathway appears to be kinetically viable, future high-level theory is needed to fully explain the mechanistic relationship between CI and β-OH-RO₂• in the condensed phase.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2499765

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 26 Vol. 58; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Evaluating Possible Formation Mechanisms of Criegee Intermediates during the Heterogeneous Autoxidation of Squalene

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