ZINC MOBILITY AND SPECIATION IN SOIL COVERED BY CONTAMINATED DREDGED SEDIMENT USING MICROMETER-SCALE AND BULK-AVERAGING X-RAY FLUORESCENCE, ABSORPTION AND DIFFRACTION TECHNIQUES

Abstract

The mobility and solid-state speciation of zinc in a pseudogley soil (pH = 8.2–8.3) before and after contamination by land-disposition of a dredged sediment ([Zn] = 6600 mg kg−1) affected by smelter operations were studied in a 50 m2 pilot-scale test site and the laboratory using state-of-the-art synchrotron-based techniques. Sediment disposition on land caused the migration of micrometer-sized, smelter-related, sphalerite (ZnS) and franklinite (ZnFe2O4) grains and dissolved Zn from the sediment downwards to a soil depth of 20 cm over a period of 18 months. Gravitational movement of fine-grained metal contaminants probably occurred continuously, while peaks of Zn leaching were observed in the summer when the oxidative dissolution of ZnS was favored by non-flooding conditions. The Zn concentration in the <50 μm soil fraction increased from ~61 ppm to ~94 ppm in the first 12 months at 0–10 cm depth, and to ~269 ppm in the first 15 months following the sediment deposition. Higher Zn concentrations and enrichments were observed in the fine (<2 μm) and very fine (<0.2 μm) fractions after 15 months (480 mg kg−1 and 1000 mg kg−1, respectively), compared to 200 mg kg−1 in the <2 μm fraction of the initial soil. In total, 1.2% of the Zn initially present in the sediment was released to the environment after 15 months, representing an integrated quantity of ∼4 kg Zn over an area of 50 m2. Microfocused X-ray fluorescence (XRF), diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques were used to image chemical associations of Zn with Fe and Mn, and to identify mineral and Zn species in selected points-of-interest in the uncontaminated and contaminated soil. Bulk average powder EXAFS spectroscopy was used to quantify the proportion of each Zn species in the soil. In the uncontaminated soil, Zn is largely speciated as Zn-containing phyllosilicate, and to a minor extent as zincochromite (ZnCr2O4), IVZn-sorbed turbostratic birnessite (δ-MnO2), and Zn-substituted goethite. In the upper 0–10 cm of the contaminated soil, ~60 ± 10% of total Zn is present as ZnS inherited from the overlying sediment. Poorly-crystalline Zn-sorbed Fe (oxyhydr)oxides and zinciferous phyllosilicate amount to ~20–30 ± 10% each and, therefore, make up most of the remaining Zn. Smaller amounts of franklinite (ZnFe2O4), Zn-birnessite and Zn-goethite were also detected. Further solubilization of the Zn inventory in the sediment, and also remobilization of Zn from the poorly-crystalline neoformed Fe (oxyhydr)oxide precipitates, are expected over time. This study shows that land deposition of contaminated dredged sediments is a source of Zn for the covered soil and, consequently, presents environmental hazards. Remediation technologies should be devised to either sequester Zn into sparingly soluble crystalline phases, or remove Zn by collecting leachates beneath the sediment.