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Phytoremediation of contaminated mine soils requires the use of fast-growing, deep-rooted, high-biomass, and metal-tolerant plants with the application of soil amendments that promote metal uptake by plants. A pot experiment was performed to evaluate the combined use of vetiver grass (Chrysopogon zizanioides) and humic acid for phytoremediation of Cu and Zn in mine soils. Vetiver plants were grown in soil samples collected from two mine sites of Spain mixed with a commercial humic acid derived from leonardite at doses of 0, 2, 10, and 20 g kg(-1). Plant metal concentrations and biomass were measured and metal bioavailability in soils was determined by a low molecular weight organic acid extraction. Results showed that humic acid addition decreased organic acid-extractable metals in soil. Although this extraction method is used to estimate bioavailability of metals, it was not a good estimator under these conditions due to competition with the strong chelators in the added humic acid. High doses of humic acid also promoted root growth and increased Cu concentrations in plants due to formation of soluble metal-organic complexes, which enhanced removal of this metal from soil and its accumulation in roots. Although humic acid was not able to improve Zn uptake, it managed to reduce translocation of Zn and Cu to aerial parts of plants. Vetiver resulted unsuitable for phytoextraction, but our study showed that the combined use of this species with humic acid at 10-20 g kg(-1) could be an effective strategy for phytostabilization of mine soils.

A one-step extraction procedure and a leaching column experiment were performed to assess the effects of citric and tartaric acids on Cu and Zn mobilization in naturally contaminated mine soils to facilitate assisted phytoextraction. A speciation modeling of the soil solution and the metal fractionation of soils were performed to elucidate the chemical processes that affected metal desorption by organic acids. Different extracting solutions were prepared, all of which contained 0.01 M KNO(3) and different concentrations of organic acids: control without organic acids, 0.5 mM citric, 0.5 mM tartaric, 10 mM citric, 10 mM tartaric, and 5 mM citric +5 mM tartaric. The results of the extraction procedure showed that higher concentrations of organic acids increased metal desorption, and citric acid was more effective at facilitating metal desorption than tartaric acid. Metal desorption was mainly influenced by the decreasing pH and the dissolution of Fe and Mn oxides, not by the formation of soluble metal-organic complexes as was predicted by the speciation modeling. The results of the column study reported that low concentrations of organic acids did not significantly increase metal mobilization and that higher doses were also not able to mobilize Zn. However, 5-10 mM citric acid significantly promoted Cu mobilization (from 1 mg kg(-1) in the control to 42 mg kg(-1) with 10 mM citric acid) and reduced the exchangeable (from 21 to 3 mg kg(-1)) and the Fe and Mn oxides (from 443 to 277 mg kg(-1)) fractions. Citric acid could efficiently facilitate assisted phytoextraction techniques., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

We studied the effects of commercial humic substances derived from leonardite at different rates (0, 0.25, 2, 10 g kg−1) and pH (4.5, 6.0, 8.0) on Cu and Zn mobility, to evaluate their use for remediation of metal contaminated mine soils and to optimize their application conditions. We conducted a single-step extraction experiment and analyzed extracts for metal concentrations, soluble organic carbon and their E4/E6 ratio (ratio of absorption at 465 to 665 nm). Metal speciation in a soil solution was simulated by the non-ideal competitive adsorption-Donnan (NICA-Donnan) model. Increasing the amount of humic substances and the pH caused higher release rates of soluble organic carbon with a lower humic/fulvic acids ratio. This led to a higher mobility of metals (up to 110 times Cu concentration in control and 12 times for Zn) due to the formation of soluble metal-humic complexes. Speciation modeling predicted that increasing rates of humic substances would result in a higher proportion of Cu and Zn associated with fulvic acids, more mobile than the humic acids fraction. Application of commercial leonardite humic substances at 2–10 g kg−1 and with pH levels similar to or below natural soil could be useful for assisted-phytoextraction of contaminated anthropogenic soils. High rates of humic substances in more alkaline conditions could entail a considerable risk of metal leaching to groundwater, toxicity and transfer to the trophic chain. [ABSTRACT FROM AUTHOR]