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The speciation of copper in the early stage of the electrokinetic remediation (EKR) process has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy in the present work. By in-situ EXAFS, we found that copper in a contaminated soil possessed a Cu-O bond distance of 1.98 Å with a coordination number (CN) of 5.8. In the second shell, the bond distance of Cu-(O)-Cu was 2.87 Å with a CN of 6.4. However, possibly due to the fact that incompact copper atoms in the outer shells were distorted by EKR, the Cu-(O)-Cu (2nd shell) bond distance and the CN of copper in the contaminated soil decreased by 0.08 Å and 5.4, respectively in the early stage of the EKR process. Interestingly, after prolonging the contact time to about 80 minutes, the 1st-shell copper atoms were also perturbed by EKR. This work is an example of usefulness of the in-situ EXAFS spectroscopy for detailed studies of the speciation of copper in the contaminated soil during EKR process.

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