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Long-term batch leaching studies of composites of lignite combustion and gasification ashes with a calcium-based scrubber waste have shown the prominent formation of an ettringite structure phase, accompanied by reductions in solution concentrations of potentially hazardous elements such as boron and selenium. The possibility that oxyanions such as arsenate, borate, chromate, molybdate, selenate and vanadate might substitute for sulfate in the ettringite structure has been explored. There are literature reports of fully substituted borate, chromate and selenate [ettringites]*, and of two minerals with partial borate for sulfate substitution. X-ray diffraction phase pure products with chromate and selenate, substituted completely for the sulfate in ettringite, and with arsenate, borate and vanadate partially substituted for sulfate, have been synthesized at room temperature by mixing soluble Ca, Al and sulfate sources and maintaining a pH> 12 with NaOH additions. Attempts to substitute substantial amount of molybdate for sulfate were unsuccessful. The resulting phases were characterized chemically by ICAP spectrometry, ion chromatography and thermal analysis, and for phase purity and unit cell size by XRD. The speciation of the oxyanions in the substituted [ettringite] were confirmed by FTIR spectrometry. In solid solutions, the sulfate/oxyanion ratio was greater in the precipitated solid than in the synthesis solution. Chemical analyses of the [ettringites] did not give simple stoichiometries analogous to Ca6Al2(SO4)(OH)12 ·26H2O. Because nonstoichiometry can be attributed to numerous possibilities for charge balance and defects, structural formulae of the oxyanion substituted [ettringites] could not be established.

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Recent results on synthesis, crystal chemistry, structure and stability of ettringite*, with specific reference to use of this material in hazardous waste immobilization, are presented. Ettringites with selenate, chromate, borate, sulfite and carbonate replacing sulfate have been synthesized and characterized by XRD for phase purity and structure. In X-ray powder diffractograms, selenate and chromate etringites have the normal trigonal P31cettringite structure, whereas the borate, sulfite and carbonate ettringites can be indexed on a hexagonal unit cell with a halved c parameter. In excess of 95% of the Se and B in solutions spiked with various concentrations of these elements has been removed by precipitation of ettringite. Ettringites appear to be unstable in solutions outside of the approximate pH range 11.0-12.5, and there is a potential for some oxyanion exchange between ettringites and oxyanion-containing solutions. Buffering of pH, and dissolved Ca, Al and sulfate activities by other components of ettringite-based hazardous waste forms, combined with low-reactivity C-S-H matrices, could largely mitigate these concerns.

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