title: Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.
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.
authors.affiliation: Department of Environmental Engineering, Zhejiang University, 866 Yuhangtang Road, Hangzhou, Zhejiang, 310058, People's Republic of China.
authors.forename: Jianjun
authors.initials: J
authors.lastname: Yang
authors.forename: Jin
authors.initials: J
authors.lastname: Liu
authors.forename: James J
authors.initials: JJ
authors.lastname: Dynes
authors.forename: Derek
authors.initials: D
authors.lastname: Peak
authors.forename: Tom
authors.initials: T
authors.lastname: Regier
authors.forename: Jian
authors.initials: J
authors.lastname: Wang
authors.forename: Shenhai
authors.initials: S
authors.lastname: Zhu
authors.forename: Jiyan
authors.initials: J
authors.lastname: Shi
authors.forename: John S
authors.initials: JS
authors.lastname: Tse
mesh_terms: D000327:Adsorption; D002681:China; D003300:Copper / Q000032:analysis* / Q000737:chemistry; D004784:Environmental Monitoring; D058085:Iron Compounds / Q000737:chemistry; D008853:Microscopy / Q000379:methods; D008903:Minerals / Q000737:chemistry; D008906:Mining; D012987:Soil / Q000737:chemistry; D012989:Soil Pollutants / Q000032:analysis* / Q000737:chemistry; D017356:Synchrotrons; D056928:X-Ray Absorption Spectroscopy
chemical_list: D058085:Iron Compounds; D008903:Minerals; D012987:Soil; D012989:Soil Pollutants; C094886:goethite; D003300:Copper