Redox Transformations and Sulfur Speciation in Flue Gas Desulferization Sludge

Abstract

Changes in redox potential (Eh), major sulfur species and the solubility of selenium and boron in reduced flue gas desulfurization (FGD) sludge, when exposed to atmosphere were studied in laboratory experiments. Also the effect of organic carbon and temperature on reduction of FGD sludge and changes in concentration of major S species was studied. Stable isotopic ratios of sulfur and carbon compounds were used to investigate the possible pathways of S transformation in FGD sludge disposal site. Oxidation of reduced sludge appears to be a two step process, a fast step of chemical oxidation followed by a slow step of biological oxidation and is significantly affected by moisture content and mixing of the sludge. With the addition of organic carbon Eh of the FGD sludge dropped exponentially and reduction of sulfate initiated at Eh of about -75 mV and was maximum in the range of -265 to -320 mV. Temperatur8e of the profile and organic carbon appear to be the key factors affecting the rate and extent of reduction in flooded FGD sludge. Selenium solubility decreased four times as Eh dropped from 215 mV to -350 mV while boron solubility was unchanged in this range of Eh. Stable isotopic ratio of sulfate and sulfide are typical of bacterial reduction and suggest that only aqueous sulfate was being reduced. The low δ³⁴S values of CaSO₄ from the upper layers of profile indicate the production and upward movement of hydrogen sulfide gas in the FGD sludge.