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TECHNICAL REPORTS

Heavy Metals in the Environment

Zinc Fractionation in Contaminated Soils by Sequential and Single Extractions: Influence of Soil Properties and Zinc Content

Soil Chemistry Group, Institute of Biogeochemistry and Pollutant Dynamics, ETH Zurich, ETH Zentrum CHN, CH-8092 Zürich, Switzerland

^* Corresponding author (voegelin{at}env.ethz.ch).

Received for publication June 19, 2007. We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH₄NO₃; F2: NH₄–acetate, pH 6; F3: NH₃OHCl, pH 6; F4: NH₄–EDTA, pH 4.6; F5: NH₄–oxalate, pH 3; F6: NH₄–oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0–7.3), organic C content (9.3–102 g kg^–1), and clay content (38–451 g kg^–1). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg^–1. In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH 6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.

Abbreviations: ECEC, effective cation exchange capacity • SEP, sequential extraction procedures • SSR, solution-to-soil ratio • XRF, X-ray fluorescence • Zn-HIM, Zn bound in the Al-hydroxy interlayers of clay minerals