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The feasibility of a novel EDTA-based soil heap leaching method with treatment and reuse of extractants in a closed process loop was evaluated on a laboratory scale. Ozone and UV irradiation were used for oxidative decomposition of EDTA-metal complexes in extractants from Pb (1243 mg kg(-1)) and Zn (1190 mg kg(-1)) contaminated soil. Released metals were absorbed in a commercial metal absorbent Slovakite. Six-consecutive additions of 2.5 mmol kg(-1) EDTA (total 15 mmol kg(-1) EDTA) removed 49.6 +/- 0.6% and 19.7 +/- 1.7% of initial total Pb and Zn from soil (4.6 kg) packed in 22 cm high columns. The efficiency of extraction was similar to small-scale simulations of heap leaching (15 0 g of soil), where EDTA used in the same manner removed 49.7 +/- 1.0% and 13.7 +/- 0.4% of Pb and Zn. The new heap leaching method produced discharge extractant with fairly low final concentrations of Pb, Zn and EDTA (1.98 +/- 2.17 mg l(-1), 4.55 +/- 2.36 mg l(-1), and 0.05 +/- 0.04 mM, respectively), which could presumably be reduced even further with continuation of treatment. The results of our study indicate that for soils contaminated primarily with Pb, treating the EDTA extractants with ozone/UV and reuse of extractants enables efficient soil heap leaching with very little or no wastewater generation, easy control over emissions, and lowers the requirements for process water.

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.