Evaluation of remediation of Cr(VI)-contaminated soils by calcium polysulfide: Long-term stabilization and mechanism studies.

In the remediation of Cr(VI)-contaminated soils, the effectiveness and long-term stability are critical qualities for the selection of a reductant. In current engineering practices, iron-based materials and sulfides are the most prevalent reductants, and calcium polysulfide (CaS4) is considered as the one with the highest effectiveness and strongest long-term stabilization ability. But this opinion is questioned by the high interference ability of CaS4 to soil Cr(VI) analysis. This study provides a pretreatment method to eliminate the interference of residual ferrous and sulfides to soil Cr(VI) analysis. By this pretreatment method and comparing with FeSO4 and Na2S, the mechanisms of the false high effectiveness and strong long-term stabilization ability of CaS4 is revealed. In the remediation process, CaS4 produces much elemental sulfur (S0) which remains in the soils. During the alkaline digestion, the S0 generates polysulfide which reduces the extracted Cr(VI), inducing serious negative analysis bias. When this negative bias is eliminated by pretreatment method, analysis results show that CaS4 exhibits lowest effectiveness. The S0 cannot be leached away from soils and oxidized by oxygen under natural conditions, this makes CaS4 exhibit a persistent interference ability, which is mistaken for a strong long-term stabilization ability.

Interference of sulfide with iron ions to the analysis of Cr(â ¥) by Method 3060a & Method 7196a.

When Cr(Ⅵ)-contaminated soil was remediated with sulfide, due to incomplete reaction and overdose, excess sulfide could remain in the soil inducing unacceptable underestimation of residual Cr(Ⅵ) analysis, which would get worse when iron ions were introduced in. Unfortunately, the quality control policy of Method 3060a cannot distinguish the difference between real zero and false zero residual Cr(Ⅵ) when their spike recoveries are zero. This paper systematically investigated the sulfide-induced Cr(Ⅵ) reduction in Cr(Ⅵ) analysis by Method 3060a & Method 7196a. Experimental results indicate that the sulfide-Cr(Ⅵ) reaction mainly occurs during alkaline digestion and pH adjustment processes, and iron ions as an electron transfer carrier between sulfide and Cr(Ⅵ) can catalyze the redox reaction during alkaline digestion. Besides, the high temperature in alkaline digestion significantly accelerates the redox reaction which usually is negligible at room temperature. Sulfur of high concentrations in remediated soils can also cause unacceptable underestimation of Cr(Ⅵ) due to the production of sulfide ions by disproportionation reaction in alkaline digestion. This paper also provides a method to eliminate sulfide ions from alkaline digestion solution before pH adjustment and suggests some possible solutions to the ferrous or sulfide-induced Cr(Ⅵ) analysis bias.