Development of a Digestion Procedure Using Fe²⁺ ions for Electrochemical Detection of MnO₂ Particles in Drinking Water

Abstract

Developing methods for detection contaminants in drinking water is essential to ensuring that safe and acceptable quality drinking water is delivered to consumers. While manganese (Mn) was previously known only as a mere aesthetic issue, recent epidemiological data has shown to have negative neurological effects on humans, especially on children, prompting new health-based guidelines by Health Canada and the World Health Organization. In drinking water, Mn exists predominantly as Mn(II) and Mn(IV), and is regulated based on total Mn levels. Interestingly, measurement of Mn particulate using electroanalytical methods has not yet been reported in the literature. Herein, a digestion procedure for insoluble manganese dioxide (MnO₂) using ferrous (Fe²⁺) ions was optimized in preparation for Mn detection by cyclic voltammetry (CV). Digestion conditions including concentration of Fe²⁺ ions, pH and digestion time were explored and optimized. Digestion of MnO₂ was found to be successful in both perfect and imperfect stoichiometric ratios; however, digestion was shown to be most effective in perfect stoichiometric conditions. CV proved to be an effective technique for the detection of different particulate Mn concentrations with good reproducibility using glassy carbon electrodes. According to the CV data, the detection limits of 0.3 mmol·L^-1 and 0.1 mmol·L^-1 for MnO₂ were determined after the digestion time of 4.5 h and 24 h, respectively. The digestion method, in addition to CV detection, was found to be impacted by the presences of Cu²⁺ and Fe³⁺ ions.This interference suggests that this method may offer value as a multi-plexed technique. The Mn reduction signal was found to be enhanced in the presence of Mn²⁺, indicating that this method has the potential to be used to detect soluble and insoluble Mn species simultaneously. These digestion and detection methods are simple and reproducible methods which introduce the opportunity for total Mn detection in drinking water.

Keywords

Manganese / Drinking water / Cyclic voltammetry / Digestion / Manganese dioxide

Acknowledgements

Authors would like to thank financial support from the Natural Sciences and Engineering Research Council of Canada through the Discovery Grant program. Authors are also grateful for supports from the Department of Chemistry, the Department of Civil Engineering, and Beaty Water Research Centre.

Conflicts of Interest

The authors declare no conflicts of interest.

Data Availability

Data is provided within the manuscript.

Author Contributions

Sarah Jane Payne and Zhe She developed the initial concept and provided resources. Kayla Elliott conducted experiments, prepared the figures and wrote the main manuscript text. All authors reviewed the manuscript.

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