Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf, Switzerland.
Environ Sci Technol. 2010 Dec 1;44(23):8983-8. doi: 10.1021/es100554v. Epub 2010 Nov 5.
Chromate is a toxic contaminant of potential concern, as it is quite soluble in the alkaline pH range and could be released to the environment. In cementitous systems, CrO4(2−) is thought to be incorporated as a solid solution with SO4(2−) in ettringite. The formation of a solid solution (SS) could lower the soluble CrO4(2−) concentrations. Ettringite containing SO4(2−) or CrO4(2−) and mixtures thereof have been synthesized. The resulting solids and their solubility after an equilibration time of 3 months have been characterized. For CrO4-ettringite at 25 °C, a solubility product log K(S0) of −40.2 ± 0.4 was calculated: log K(CrO4−ettringite) = 6log{Ca2+} + 2log{Al(OH)4(−)} + 3log{CrO4(2−)} + 4log{OH−} + 26log{H2O}. X-ray diffraction and the analysis of the solution indicated the formation of a regular solid solution between SO4- and CrO4-ettringite with a miscibility gap between 0.4 ≤ XCrO4 ≤ 0.6. The miscibility gap of the SO4- and CrO4-ettringite solid solution could be reproduced with a dimensionless Guggenheim fitting parameter (a0) of 2.03. The presence of a solid solution between SO4- and CrO4-ettringite results in a stabilization of the solids compared to the pure ettringites and thus in an increased uptake of CrO4(2−) in cementitious systems.
铬酸盐是一种潜在关注的有毒污染物,因为它在碱性 pH 范围内相当易溶,可能会释放到环境中。在水泥体系中,CrO4(2−)被认为是以固溶体的形式与 ettringite 中的 SO4(2−)结合的。固溶体的形成可能会降低可溶性 CrO4(2−)浓度。已经合成了含有 SO4(2−)或 CrO4(2−)的 ettringite 及其混合物。对 3 个月平衡时间后的固体及其溶解度进行了表征。对于 25°C 的 CrO4-ettringite,计算出溶解度积 log K(S0)为-40.2 ± 0.4:log K(CrO4−ettringite) = 6log{Ca2+} + 2log{Al(OH)4(−)} + 3log{CrO4(2−)} + 4log{OH−} + 26log{H2O}。X 射线衍射和溶液分析表明,SO4-和 CrO4-ettringite 之间形成了规则的固溶体,在 0.4 ≤ XCrO4 ≤ 0.6 之间存在混溶性间隙。SO4-和 CrO4-ettringite 固溶体的混溶性间隙可以用无量纲 Guggenheim 拟合参数(a0)为 2.03 来重现。SO4-和 CrO4-ettringite 之间存在固溶体,导致固体比纯 ettringite 更稳定,因此在水泥体系中更能吸收 CrO4(2−)。