Association of cadmium, zinc, copper, and nickel with components in naturally heavy metal‐rich soils studied by parallel and sequential extractions

Abstract

In this study, a new parallel and sequential extraction procedure was proposed to investigate the solubility of metals [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] and their association with soil components in naturally metal‐rich soils of Norway. Two different soils, alum shale (clay loam) and moraine (loam), developed on alum shale minerals were used. Each soil had two pH levels. For parallel and successive extractions, H2O, 0.1M NH4OAc (soil pH), 0.3M NH4OAc (soil pH), 1M NH4OAc (soil pH), and 1M NH4OAc (pH 5.0) were used. A significant amount of Cd was extracted by NH4O Ac related to concentration of NH4OAc in the extracting solution. The amounts of Zn, Cu, and Ni extracted by these reagents were almost negligible except with 1M NH4OAc (pH 5.0). Thus these metals were strongly bound to soil components. A seven step sequential extraction procedure was applied to evaluate the association of metals with soil constituents. The extractions were performed sequentially by extracting the soil with reagents having an increasing dissolution strength: 1M NH4OAc (soil pH), 1M NH4OAc (pH 5.0), 1M NH2OH.HCl (in 25% HOAc), 1M NH2OH.HCl (in 0.1M HNO3), 30% H2O2 (in 0.1M HNO3), 30% H2O2 (1M HNO3), and aqua regia. In both soils at both pH levels investigated, appreciable percentages of total Cd (20–50%) were found associated with the NH4OAc extractable fraction (mobile fraction). For Zn, Cu, and Ni, the percentage of total metal extracted with NH4OAc was low (<4%), but it increased significantly by introducing a reducing agent (NH2OH.HCl). The NH2OH.HCl‐extractable fraction was the greatest fraction (>60%) for all four metals examined. These results suggest that among the metals studied, only Cd was easily desorbed from soil and should be considered mobile and potentially bioavailable. Other metals (Zn, Cu, and Ni) were strongly associated with the soil components and should be considered less available to plants. Using the sequential fractionation technique as a measure of availability, mobility and potential bioavailability of these four metals in the alum shale soils were: Cd>Zn>Ni>Cu.