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Arsenic Oxidation by Flavin-Derived Reactive Species under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence.

Abstract

Flavins are ubiquitous redox-active compounds capable of producing reactive oxygen (O2•-, •OH, and H2O2) and flavin radical species in natural environments, yet their roles in the redox transformations of environmental contaminants, such as arsenic (As), remain to be investigated. Here, we show that reduced flavins can be a source of effective oxidants for As(III) under both oxic and anoxic conditions. For instance, in the presence of 15 μM reduced riboflavin (RBFH2), 22% of 30 μM As(III) is oxidized in aerated solution at pH 7.0. The co-oxidation of As(III) with RBFH2 is pH-dependent, with a faster reaction rate under mildly acidic relative to alkaline conditions. Quencher tests with 2-propanol (for •OH) and catalase (for H2O2) indicate that As(III) oxidation under oxic conditions is likely controlled by flavin-derived •OH at pH 5.2 and 7.0, and by H2O2 at pH 9.0. Kinetic modeling further implies that flavin-derived reactive oxygen species are mainly responsible for As(III) oxidation under oxic conditions, whereas oxidation of As(III) under anoxic conditions at pH 9.0 is attributed to riboflavin radicals (RBFH•) generated from co-existing oxidized and reduced riboflavin. The demonstrated ability of flavins to catalyze As(III) oxidation has potential implications for As redox cycling in the environment.

Authors+Show Affiliations

Ecohydrology Research Group, Department of Earth and Environmental Sciences & Water Institute , University of Waterloo , N2L 3G1 Waterloo , Canada.Amphos 21 Consulting S.L. , C/Venecuela, 103 , 08019 Barcelona , Spain.State Key Laboratory of Biogeology and Environmental Geology , China University of Geosciences , 430074 Wuhan , China.Ecohydrology Research Group, Department of Earth and Environmental Sciences & Water Institute , University of Waterloo , N2L 3G1 Waterloo , Canada.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31419125

Citation

Pi, Kunfu, et al. "Arsenic Oxidation By Flavin-Derived Reactive Species Under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence." Environmental Science & Technology, 2019.
Pi K, Markelova E, Zhang P, et al. Arsenic Oxidation by Flavin-Derived Reactive Species under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence. Environ Sci Technol. 2019.
Pi, K., Markelova, E., Zhang, P., & Van Cappellen, P. (2019). Arsenic Oxidation by Flavin-Derived Reactive Species under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence. Environmental Science & Technology, doi:10.1021/acs.est.9b03188.
Pi K, et al. Arsenic Oxidation By Flavin-Derived Reactive Species Under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence. Environ Sci Technol. 2019 Aug 28; PubMed PMID: 31419125.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Arsenic Oxidation by Flavin-Derived Reactive Species under Oxic and Anoxic Conditions: Oxidant Formation and pH Dependence. AU - Pi,Kunfu, AU - Markelova,Ekaterina, AU - Zhang,Peng, AU - Van Cappellen,Philippe, Y1 - 2019/08/28/ PY - 2019/8/17/pubmed PY - 2019/8/17/medline PY - 2019/8/17/entrez JF - Environmental science & technology JO - Environ. Sci. Technol. N2 - Flavins are ubiquitous redox-active compounds capable of producing reactive oxygen (O2•-, •OH, and H2O2) and flavin radical species in natural environments, yet their roles in the redox transformations of environmental contaminants, such as arsenic (As), remain to be investigated. Here, we show that reduced flavins can be a source of effective oxidants for As(III) under both oxic and anoxic conditions. For instance, in the presence of 15 μM reduced riboflavin (RBFH2), 22% of 30 μM As(III) is oxidized in aerated solution at pH 7.0. The co-oxidation of As(III) with RBFH2 is pH-dependent, with a faster reaction rate under mildly acidic relative to alkaline conditions. Quencher tests with 2-propanol (for •OH) and catalase (for H2O2) indicate that As(III) oxidation under oxic conditions is likely controlled by flavin-derived •OH at pH 5.2 and 7.0, and by H2O2 at pH 9.0. Kinetic modeling further implies that flavin-derived reactive oxygen species are mainly responsible for As(III) oxidation under oxic conditions, whereas oxidation of As(III) under anoxic conditions at pH 9.0 is attributed to riboflavin radicals (RBFH•) generated from co-existing oxidized and reduced riboflavin. The demonstrated ability of flavins to catalyze As(III) oxidation has potential implications for As redox cycling in the environment. SN - 1520-5851 UR - https://www.unboundmedicine.com/medline/citation/31419125/Arsenic_oxidation_by_flavin-derived_reactive_species_under_oxic_and_anoxic_conditions:_Oxidant_formation_and_pH_dependence L2 - https://dx.doi.org/10.1021/acs.est.9b03188 DB - PRIME DP - Unbound Medicine ER -