Oxidation of Organic Compounds in Water by Unactivated Peroxymonosulfate

Yi Yang, Gourab Banerjee, Gary W Brudvig, Jae Hong Kim, Joseph J. Pignatello

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Peroxymonosulfate (HSO5 - and PMS) is an optional bulk oxidant in advanced oxidation processes (AOPs) for treating wastewaters. Normally, PMS is activated by the input of energy or reducing agent to generate sulfate or hydroxyl radicals or both. This study shows that PMS without explicit activation undergoes direct reaction with a variety of compounds, including antibiotics, pharmaceuticals, phenolics, and commonly used singlet-oxygen (1O2) traps and quenchers, specifically furfuryl alcohol (FFA), azide, and histidine. Reaction time frames varied from minutes to a few hours at pH 9. With the use of a test compound with intermediate reactivity (FFA), electron paramagnetic resonance (EPR) and scavenging experiments ruled out sulfate and hydroxyl radicals. Although 1O2 was detected by EPR and is produced stoichiometrically through PMS self-decomposition, 1O2 plays only a minor role due to its efficient quenching by water, as confirmed by experiments manipulating the 1O2 formation rate (addition of H2O2) or lifetime (deuterium solvent isotope effect). Direct reactions with PMS are highly pH- and ionic-strength-sensitive and can be accelerated by (bi)carbonate, borate, and pyrophosphate (although not phosphate) via non-radical pathways. The findings indicate that direct reaction with PMS may steer degradation pathways and must be considered in AOPs and other applications. They also signal caution to researchers when choosing buffers as well as 1O2 traps and quenchers.

Original languageEnglish
Pages (from-to)5911-5919
Number of pages9
JournalEnvironmental Science and Technology
Volume52
Issue number10
DOIs
Publication statusPublished - May 15 2018

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electron spin resonance
hydroxyl radical
Organic compounds
Hydroxyl Radical
Paramagnetic resonance
alcohol
organic compound
sulfate
oxidation
Oxidation
Singlet Oxygen
Borates
Azides
borate
Water
Deuterium
Carbonates
Reducing Agents
Scavenging
deuterium

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Oxidation of Organic Compounds in Water by Unactivated Peroxymonosulfate. / Yang, Yi; Banerjee, Gourab; Brudvig, Gary W; Kim, Jae Hong; Pignatello, Joseph J.

In: Environmental Science and Technology, Vol. 52, No. 10, 15.05.2018, p. 5911-5919.

Research output: Contribution to journalArticle

Yang, Yi ; Banerjee, Gourab ; Brudvig, Gary W ; Kim, Jae Hong ; Pignatello, Joseph J. / Oxidation of Organic Compounds in Water by Unactivated Peroxymonosulfate. In: Environmental Science and Technology. 2018 ; Vol. 52, No. 10. pp. 5911-5919.
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