Evidence for arsenic-driven redox chemistry in a wetland system: a field voltammetric study

L. Haffert; S. G. Sander; K. A. Hunter; D. Craw

doi:10.1071/EN10019

RESEARCH ARTICLE

Previous Contents Vol 7(4)

Evidence for arsenic-driven redox chemistry in a wetland system: a field voltammetric study

L. Haffert ^A , S. G. Sander ^B , K. A. Hunter ^B and D. Craw ^A ^C

+ Author Affiliations

- Author Affiliations

^A Geology Department, University of Otago, PO Box 56, Dunedin, New Zealand.

^B Chemistry Department, University of Otago, PO Box 56, Dunedin, New Zealand.

^C Corresponding author. Email: dave.craw@stonebow.otago.ac.nz

Environmental Chemistry 7(4) 386-397 https://doi.org/10.1071/EN10019
Submitted: 9 March 2010 Accepted: 4 June 2010 Published: 20 August 2010

Environmental context. The speciation of the toxic element arsenic directly controls its environmental mobility and toxicity. The current study took place on site in an historic mine processing environment that is extremely arsenic-rich and comparatively sulfur-deficient. When arsenic is one of the major chemical components, redox state and pH of the chemical system are closely linked to arsenic speciation.

Abstract. This study investigates the chemistry of the As^III–As^V redox couple in association with As-rich processing residues (up to 40 wt%) from a historic gold mine in New Zealand. The site provides a unique natural laboratory of a sulfide-free chemical system driven by arsenolite dissolution. Field based cathodic stripping voltammetry, which circumvents post-sampling preservation issues, was successfully applied to analyse the As^III to the microgram level. The As^III–As^V redox couple, in particular the oxidation of As^III, was found to have a noticeable influence on system pH and E_H. The As redox pair itself is controlled by a range of processes, which were identified for the varying aqueous environments present on the studied site.

Additional keywords: arsenic speciation, cathodic stripping voltammetry.

Acknowledgements

We thank FRST for financial support and EcoChemie BV, the Netherlands, for the donation of a μAutolab III. We are grateful to David Barr for the analysis of auxiliary data. Department of Conservation kindly gave permission for sampling on historic sites, and provided logistical support. Discussions with James Pope were helpful at various stages of this study. We thank G. Pekrovski and other anonymous reviewers for their constructive comments on this paper.

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Evidence for arsenic-driven redox chemistry in a wetland system: a field voltammetric study

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