Metal release and speciation changes during wet aging of coal fly ashes

Introduction of coal fly ash into aquatic systems poses a potential environmental hazard because of its heavy metal content. Here we investigate the relationship between solid phase transformations, fluid composition, and metal release and speciation during prolonged wet aging of a class C and class F coal fly ash. The class C ash causes rapid alkalinization of water that is neutralized over time by CO(2) uptake from air and calcite precipitation. The resulting aqueous metal concentrations are below regulatory limits with the exception of Cr; solubility constraints suggest this is released as chromate. Limited As release is accompanied by no change in solid-phase speciation, but up to 35% of the Zn in the ash dissolves and reprecipitates in secondary phases. Similar processes inhibit Ba and Cu release. In contrast, the class F ash causes rapid acidification of water and initially releases substantial quantities of As, Se, Cr, Cu, Zn, and Ba. Arsenic concentrations decline during aging because of adsorption to the iron oxide-rich ash; this is aided by As(III) oxidation. Precipitation processes lower Ba and Cr concentrations during aging. Se, Cu, and Zn concentrations remain elevated during wet aging and solid-phase Zn speciation is not affected by ash-water reactions. Total metal contents were poor predictors of metal release, which is predominantly controlled by metal speciation and the effects of ash-water reactions on fluid pH. While contact with atmospheric gases has little effect on class F ash, carbonation of class C ash inhibits metal release and neutralizes the alkalinity produced by the ash.