Multilayer composite soil chamber was proposed to extract the Cr of contaminated site soil and insight into transformation of Cr fractionation associated with valence states. The variations of current, soil pH and moisture content were explored, as well as the migration of Cr fractionation and redistribution of Cr. Results indicated that duration of half peak current could be used to adjust treatment time and it varied among different composite ways. Moreover, extraction efficiency of Cr in soil near cathode was relatively higher and reached 60% when citric acid was used. Citric acid could promote the transformation between different Cr fractionations or different valence states. It could also improve the desorption of Cr, and could prevent excessive fluctuations of moisture content at the same time. Cr redistributed acrossed the soil chamber after extraction. When deionized water was used, Cr(VI) significantly migrated toward anode mainly in the form of exchangeable fractionation (EXC) while Fe-Mn oxides fractionation (Fe-Mn) which may be in the form of cationic Cr(III) hydroxides migrated toward cathode. When using citric acid, fractionations that were difficult to migrate of Cr, especially for Fe-Mn in site soils could be activated and became EXC and carbonate fractionation (CAR), then migrated to the anode or cathode. The migration of exchangeable Cr(III) was dramatically enhanced. But the use of citric acid could cause Cr(VI) transformation to Cr(III) near anode. In addition, during the migration process, EXC could go back to Fe-Mn again or transform to residue fractionation (RES).
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