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

Abstract

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.

Keywords: Analysis bias; Cr(Ⅵ)-contaminated soils; Iron ions; Method 3060a; Sulfide.