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Fiałkiewicz-Kozieł, Barbara
Adam Mickiewicz University in Poznań
in Cooperation with on an Cooperation-Score of 37%
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article
Self-stabilization of Zn, Pb, Cd, and As in smelter-impacted organic-rich soil: The effect of hydrous Fe oxides and ZnCd sulfide coprecipitation
Abstract
Soil constitutes a direct sink for elements mobilized due to mining and smelting activities. One of the desiredpathways for reducing the bioavailability and toxicity of the contaminants is their transformation into sparinglysoluble solid phases. Here, we report the formation of secondary mineral phases in extremely contaminated (upto 210 g Zn kg 1,102 g Pb kg 1, 5.7 g Cd kg 1, and 6.4 g As kg 1, respectively) organic-rich soil. Combiningmineralogical techniques (SEM, XRD), a nonspecific sequential extraction (CISED) with M¨ossbauer and X-rayphotoelectron (XPS) spectroscopies evidenced two poorly crystalline goethite components differing in crystallitesize and As, Zn, Pb, Ca, Al, P substitutions and minor magnetite associated with plant roots (mainly Deschampsiacaespitosa, Equisetum palustre, and Carex rostrate) directly below a layer of smelter-derived particles depositedinto the soil. SEM was the only method that unambiguously documented the occurrence of ZnCd sulfidemicrosize aggregates incrusting plant roots and located in between the (hydrous) Fe oxides. Sequential extractionconfirmed a complete As immobilization by goethite, while Cd forms a solid solution with ZnS and is lacking inthe Fe hydroxides. The partitioning of Zn and Pb between the goethite and sulfide phases depends on soil watersaturation. It is proposed that the coexistence of hydrous Fe oxides and nonferrous metal sulfides in the soilsubsurface is possible because of redox heterogeneity of the rhizosphere and the decoupling of sulfur and ironcycles. Low mobility of biogenic sulfide ions and the protecting role of organic matter limits goethite sulfidation.The system remains active, adapting to the seasonally changeable plant roots ecology and fluctuations in watersaturation. The obtained results are of value in remediation and managing strategies for contaminated soils andin reconstructing processes related to the formation and/or transformation of low-temperature sulfide deposits.