Formation and Dissolution of Single and Mixed Zn and Ni Precipitates in Soil: Evidence from Column Experiments and Extended X-ray Absorption Fine Structure Spectroscopy

Abstract

The stability and the formation and dissolution kinetics of mixed trace metal precipitates in soils are currently unknown. The objective of this study was to investigate slow sorption and release processes of Zn and Ni in a loamy soil using a combination of soil column experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy. To investigate slow sorption processes, the soil material was packed into columns and leached with 5400 pore volumes of 10(-2) M CaCl2 solutions containing either ZnCl2 (5.2 x 10(-5) M) or NiCl2 (5.2 x 10(-5) M) or both ZnCl2 and NiCl2 (5.2 x 10(-5) M each). The Zn and Ni concentrations in the column effluents were monitored. The metal breakthrough curves showed that slow sorption processes lead to metal retention, whereby Zn was more strongly retained than Ni. In the experiment with both Zn and Ni present, amounts of Zn and Ni similar to those in the experiments with either Zn or Ni alone were retained. Analysis of soil samples by EXAFS spectroscopy showed that layered double hydroxide (LDH)-type precipitates had formed in all columns and that a mixed ZnNi-LDH had formed in the presence of both Zn and Ni. The dissolution of those precipitates under acidic conditions was assessed by subsequent leaching of the columns with a 10(-2) M CaCl2 solution at pH 3.0 (approximately 3000 pore volumes). When only Zn was present, 95% of the retained Zn was leached at pH 3. In contrast, only 23% of the retained Ni was leached in experiments with Ni alone. When Zn and Ni were present, 90% of the retained Zn and 87% of the retained Ni were released upon acidification. EXAFS analysis revealed that the LDH phases in the Zn experiment and the Zn-Ni experiment had been completely dissolved, while the LDH phase formed in the Ni experiment was still present. The higher resistance of Ni-LDH against dissolution at low pH could also be shown in dissolution studies with synthetic Zn-LDH, Ni-LDH, and ZnNi-LDH. Our results suggest that the individual rates at which Zn and Ni cations enter into the LDH structure determine the composition of the mixed ZnNi-LDH precipitate, and that the LDH composition determines the rate at which the LDH phase dissolves under acidic conditions.