The sorption of selenite and selenate to ettringite (3CaO x Al2O3 x 3CaSO4 x 32H2O), "monosulfate" (3CaO x Al2O3 x CaSO4 x 12H2O), and calcium silicate hydrate (C-S-H) was investigated in order to understand Se immobilization by cement in hazardous wastes. Sorption kinetics were fast with equilibrium between the minerals and Se species reached within 1 d. Selenite is suggested to sorb by surface reactions, and for ettringite, a sorption maximum of 0.03 mol kg(-1) was determined. Distribution ratios (Rd) for selenite were 0.18, 0.38, and 0.21 m3 kg(-1) for ettringite, monosulfate, and C-S-H, respectively. At high selenite additions, CaSeO3 was precipitated with a solubility product of Kso = 10(-7.27) (I = 0, 25 degrees C). Selenate sorbed only weakly to ettringite (Rd = 0.03), and no significant sorption to C-S-H was found. In contrast, sorption to monosulfate was strong (Rd = 2.06). With increasing selenate addition, XRD analyses revealed changes in the interlayer distance of monosulfate, in parallel with an increase of the ettringite fraction. Substitution of sulfate is suggested to be the relevant process. This indicates that selenate is sorbed more efficiently by monosulfate-rich cement, while the cement composition is of minor importance for selenite sorption.
The factors controlling leachate composition of cement stabilized air pollution control (APC) residues (41% APC residues, 22% cement, 3% Na2CO3, and 32% water, w/w) have been investigated both in the laboratory and in a pilot landfill. Batch leaching and tank leaching tests were carried out in the laboratory in order to determine solubility controlling phases and diffusion controlled species. The major species Ca, SO4, Al, and Si could be partially modeled by assuming calcium silicate hydrate (C-S-H), portlandite, and ettringite to be the solubility controlling phases both in field and laboratory. There were obviously additional minerals that could not be taken into account in calculations because of the lack of data. The determined effective diffusion coefficients (De) for Na and K (2.18e-12 and 5.43e-12 m2s-1) were used to model field concentrations. Agreement with field data was good. Heavy metal concentrations were in the range of 10(-8) mol dm-1 (Cd, Co, Cu, Mn, Ni) to 10(-6) mol dm-1 (Mo, Pb, W, Zn) in all experiments and often lower in the field leachate than expected from batch experiments. In laboratory experiments, the solubility of Mo and W was most probably controlled by their calcium metalates, Cu by CuO, Ni by Ni(OH)2, and Zn probably by a Zn containing C-S-H phase. In the field, diffusion seems to control Mo and W leachability, with calculated De values of 3.49e-14 and 1.35e-15 m2s-1.
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