Release and mobilization of Ni, Co, and Cr under dynamic redox changes in a geogenic contaminated soil: Assessing the potential risk in serpentine paddy environments

Abstract

The release dynamics and mobilization of geogenic Ni, Co, and Cr in serpentine paddy soils under fluctuating redox conditions have not yet been well studied. Here we investigated the release dynamics of Cr, Co, and Ni and controlling factors (e.g., Fe, Mn, Mg, Cl^-, PO₄^3-, SO₄^2-, and dissolved organic carbon (DOC)) in a geogenic-contaminated serpentine soil under wide range of redox potential (E_H) changes. The effects of re-oxidation process have been also investigated. The soil was incubated for 28 days and E_H was controlled from oxidation (+200 mV) to reduction (-200 mV) and re-oxidation (+240 mV) using a microcosm setup in duplicates. The slurry pH increased, along with decreasing E_H. The average concentration of dissolved Co (17.1-23.6 μg L^-1) decreased under low E_H/high pH and vice versa. The average concentration of dissolved Cr decreased sharply from 624 μg L^-1 to 54.4 μg L^-1 with decreasing E_H from +200 mV to 0 mV and the associated increase of pH from 7.8 to 8.5; then, it was constant around 24.5 μg L^-1. Concentration of dissolved Ni was lower (73.5-84.6 μg L^-1) under high E_H at the first week of incubation; then, increased to 108.5 μg L^-1 under low E_H (-200 mV); thereafter, increased more at the end up to 124.5 μg L^-1 at high E_H (+240 mV), because of the pH decrease. A factor analysis identified that Cr and Co formed one group with Mn and Mg, while Ni was clustered together with Cl^-, DOC, and SO₄^2-. This indicates that the redox-induced release dynamic of Cr and Co was mainly governed by MnMg compounds, while the release of Ni was mainly affected by the aliphatic compounds of DOC and the redox chemistry of chlorides and sulfur in this soil. The re-oxidation increased the mobilization of Ni and Co and did not affect the release of Cr. These findings suggest that the redox-induced mobilization of geogenic Co, Ni, and Cr from soil to water in serpentine rice soils should be considered due to the high solubility and thus the associated bioavailability and potential environmental and human health risks, when such metal-enriched soils will be used for agricultural flood-dry cycle systems.

Keywords: Groundwater; Heavy metals; Paddy environments; Redox chemistry; Serpentine rice soils.