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

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.