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Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

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Abstract

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

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Acknowledgments

We thank Prof. Yuying Huang and Xiaohan Yu at the SSRF and Dr. Yidong Zhao at the BSRF for their kind help during these synchrotron experiments. This research was funded by the National Natural Science Foundation of China (21207114, 11179025); China Postdoctoral Science Foundation (2012M511375); Zhejiang Provincial Natural Science Foundation of China (R5110031); and Program for New Century Excellent Talents in University (NCET-11-0455). Cu L3,2-edge XANES and STXM measurements were performed at the SGM and Spectromicroscopy beamlines in CLS which was supported by NSERC, NRC, CIHR, the Province of Saskatchewan, WEDC, and the University of Saskatchewan.

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Correspondence to Jiyan Shi or John S. Tse.

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Responsible editor: Stuart Simpson

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Additional information as noted in text. This material is available via the Internet at http://www.sciencedirect.com.

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Yang, J., Liu, J., Dynes, J.J. et al. Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques. Environ Sci Pollut Res 21, 2943–2954 (2014). https://doi.org/10.1007/s11356-013-2214-8

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