Key Cr species controlling Cr stability in contaminated soils before and chemical stabilization at a remediation engineering site

Abstract

Linking chromium (Cr) speciation with its stability in soils is vital because insoluble Cr(VI) and chemically adsorbed Cr(VI) could hinder the remediation efficiency and release Cr(VI) for a prolonged period of time. In this study, we investigated key Cr species to probe the mechanisms controlling the release of insoluble Cr(VI) at Cr-contaminated sites using synchrotron-based X-ray absorption near-edge structure (XANES) for the first time. Chromite, stichtite and Cr-silicate were predominant forms of Cr(III). Insoluble Cr(VI) was hosted by layered double hydroxides (LDHs) such as brownmilerite and hydrotalcite. Anion competition tests documented a substitution of absorbed Cr(VI) by SO42- and NO3-. Acid extraction released 6.7–25.7% more Cr(VI) than anion extraction, possibly attributing to the erosion of LDH and CaCrO4 in calcite rather than Cr-bearing minerals. Brown and red soils released maximally 62% and 44% of total Cr(VI) by 10 mol/(kg soil) and 2 mol/(kg soil) of H+, respectively. SO42-, H2O and H+ contributed to more release of total Cr(VI) in brown soils (22%, 33% and 7%) than red soils (25%, 17% and 2%). More crystalline Cr structures were found after chemical stabilization, indicating a higher Cr stability in chemically stabilized soils. Cr and Mn exhibited an overlapped distribution pattern in both contaminated and chemically stabilized soils, hinting at the re-oxidation of Cr(III). Insoluble Cr(VI) could be released by acidic rainfalls and soil organic matters, posing potential threats to Cr long-term stability in field-scale remediation.