Simultaneous reduction and immobilization of Cr(VI) in seasonally frozen areas: Remediation mechanisms and the role of ageing

Abstract

Among the toxic metals, hexavalent chromium [Cr(VI)] has attracted much attention due to its high mobility and toxicity, rendering considerable challenges for long-term remediation. In this study, the soil was collected from a dichromate contaminated industrial site in Liaoning Province, a seasonally frozen area in northern China, and subjected to frequent freeze-thaw cycles. Three additives, including (i) ferrous sulfate; (ii) calcium polysulfide; and (iii) combined biochar and calcium polysulfide were applied to reduce and immobilize Cr(VI) in the soils. The samples underwent 28 days of incubation followed by 16 freeze-thaw cycles. The toxicity characteristic leaching procedure (TCLP) and simulated acid rain leaching were adopted to test the remediation performances. It was observed that all three treatments can significantly reduce and immobilize Cr(VI) after short-term incubation, while biochar with abundant functional groups could adsorb and reduce Cr(VI) effectively. Notably, the concentration of Cr(VI) in TCLP leachates after incubation in combined treatment decreased by 67.87% and 37.27%, respectively, compared with the application of ferrous sulfate or calcium polysulfide alone. Freeze-thaw cycles induced the disintegration of soil particles and increased the risk of contaminant mobilization. Conversely, biochar particles has become finer and even produced nanoparticles with ageing, accompanied by the increase in oxygen-containing surface functional groups. Additionally, the specific surface area increased with the pyrolysis of biochar, which further enhanced the retention of soil colloidal particles and suppressed the migration of contaminants. Therefore, the cumulative release of Cr(VI) in the combined treatment (i.e., 10.97 ~ 32.97 mg/kg) was much lower than that of the other two treatments after freeze-thaw ageing. Overall, the combination of biochar and calcium polysulfide displayed advantages in the reduction and immobilization of Cr(VI), and offered a long-term, effective strategy for the remediation of Cr(VI) contaminated soils in cold regions.

Keywords: Accelerated ageing; Biochar; Freeze-thaw cycles; Hexavalent chromium; Long-term effectiveness; Sustainable remediation.