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Density functional theory (DFT) investigation of the oxidative degradation of NaAsO2 via hydroxyl radical

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Abstract

Arsenic is an environmentally ubiquitous health hazard due to its toxicity combined with its natural abundance and heavy industrial applications. Due to its role in cardiovascular disease, neurotoxicity, and various cancers, it is important to understand environmental fate of arsenic-containing compounds to take steps towards remediation. Sodium arsenite (NaAsO2) is one such compound that has been used worldwide as an herbicide, rodenticide, and insecticide. It is also toxic by ingestion, inhalation, and skin absorption. In aqueous environments, arsenite (As(III))-containing compounds can be oxidized to the less-toxic arsenate (As(V)) form. We have investigated the oxidation of sodium arsenite in water solution at the density functional theory level using the Minnesota 06 hybrid (M06-2X) functional and Pople basis sets (6-31G(d,p) and 6-311G(d,p)) with polarizable continuum model (PCM) solvation approach. Our computational results indicate that the oxidation mechanism of NaAsO2 by hydroxyl radical proceeds via sequential addition reactions where sodium arsenite (III) converts to sodium arsenate (V) via an arsenic (IV) intermediate.

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The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors would like to thank Dr. Caitlin Bresnahan and Dr. Robert Lamb for providing feedback and guidance on the reaction mechanism calculations. The use of trade, product, or firm names in this report is for descriptive purposes only and does not imply endorsement by the U.S. Government. The tests described and the resulting data presented herein, unless otherwise noted, were obtained from research funded under the Installations and Operational Environments, Office of the Technical Director of the United States Army Corps of Engineers, and the Environmental Security Technology Certification Program of the Department of Defense by the USAERDC. Permission was granted by the Chief of Engineers to publish this information. The findings of this report are not to be considered as an official Department of the Army position unless so designated by other authorized documents. This work was supported by a grant of computer time from the DoD High Performance Computing Modernization Program at ERDC, Vicksburg, MS. This document has been approved for public release (Distribution Statement A) by the Engineer Research and Development Center.

Funding

This research was funded under the Installations and Operational Environments, Office of the Technical Director of the US Army Corps of Engineers.

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Authors and Affiliations

  1. Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN, 37830, USA

    Ashlyn M. Koval

  2. Simetri, Inc, 7005 University Blvd, Winter Park, FL, 32792, USA

    Ashlyn M. Koval

  3. Environmental Laboratory, US Army Engineer Research and Development Center, 3909 Halls Ferry Road, Vicksburg, MS, 39180, USA

    Harley McAlexander, Christa M. Woodley & Manoj K. Shukla

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  1. Ashlyn M. Koval
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All authors contributed to the study conception and design. Computations, data collection, and analysis were performed by AMK. The first draft of the manuscript was written by AMK, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Manoj K. Shukla.

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Koval, A.M., McAlexander, H., Woodley, C.M. et al. Density functional theory (DFT) investigation of the oxidative degradation of NaAsO2 via hydroxyl radical. Struct Chem 33, 625–630 (2022). https://doi.org/10.1007/s11224-022-01884-5

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