Baur Isabel, Johnson C Annette
Swiss Federal Institute for Environmental Science and Technology (EAWAG), Box 611, Ueberlandstrasse 133, CH-8600 Dübendorf, Switzerland.
Environ Sci Technol. 2003 Aug 1;37(15):3442-7. doi: 10.1021/es020148d.
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.
为了解水泥对危险废物中硒的固定作用,研究了亚硒酸盐和硒酸盐在钙矾石(3CaO·Al₂O₃·3CaSO₄·32H₂O)、“单硫酸盐”(3CaO·Al₂O₃·CaSO₄·12H₂O)和硅酸钙水化物(C-S-H)上的吸附情况。吸附动力学很快,1天内矿物与硒物种之间就达到了平衡。亚硒酸盐被认为是通过表面反应进行吸附,对于钙矾石,测定的最大吸附量为0.03 mol kg⁻¹。钙矾石、单硫酸盐和C-S-H对亚硒酸盐的分配系数(Rd)分别为0.18、0.38和0.21 m³ kg⁻¹。在高亚硒酸盐添加量下,CaSeO₃沉淀析出,其溶度积Kso = 10⁻⁷·²⁷(I = 0,25℃)。硒酸盐仅微弱吸附于钙矾石(Rd = 0.03),未发现对C-S-H有显著吸附。相比之下,对单硫酸盐的吸附很强(Rd = 2.06)。随着硒酸盐添加量的增加,XRD分析表明单硫酸盐的层间距离发生变化,同时钙矾石含量增加。硫酸盐的替代被认为是相关过程。这表明富含单硫酸盐的水泥对硒酸盐的吸附更有效,而水泥组成对亚硒酸盐吸附的重要性较小。