Spectroscopic evaluation of UVI–cement mineral interactions: ettringite and hydrotalcite

Portland cement based grouts used for radioactive waste immobilization contain high replacement levels of supplementary cementitious materials, including blast-furnace slag and fly ash. The minerals formed upon hydration of these cements may have capacity for binding actinide elements present in radioactive waste. In this work, the minerals ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)·26H(2)O) and hydro­talcite (Mg(6)Al(2)(OH)(16)CO(3)·4H(2)O) were selected to investigate the importance of minor cement hydrate phases in sequestering and immobilizing U(VI) from radioactive waste streams. U L (III)-edge X-ray absorption spectroscopy (XAS) was used to probe the U(VI) coordination environment in contact with these minerals. For the first time, solid-state (27)Al magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy was applied to probe the Al coordination environment in these U(VI)-contacted minerals and make inferences on the U(VI) coordination, in conjunction with the X-ray spectroscopy analyses. The U L (III)-edge XAS analysis of the U(VI)-contacted ettringite phases found them to be similar (>∼70%) to the uranyl oxyhydroxides present in a mixed becquerelite/metaschoepite mineral. Fitting of the EXAFS region, in combination with (27)Al NMR analysis, indicated that a disordered Ca- or Al-bearing U(VI) secondary phase also formed. For the U(VI)-contacted hydro­talcite phases, the XAS and (27)Al NMR data were interpreted as being similar to uranyl carbonate, that was likely Mg-containing

Sustainable iron-rich cements:raw material sources and binder types

Abstract The bulk of the cement industry’s environmental burden is from the calcareous source. Calcium is mostly available naturally as limestone (CaCO₃), where almost half of the mass is eventually released as CO₂ during clinker manufacture. Iron (Fe) is the fourth most common element in the Earth’s crust surpassed only by oxygen, silicon, and aluminium; therefore, potential raw materials for alternative cements can contain significant amounts of iron. This review paper discusses in detail the most abundantly available Fe-rich natural resources and industrial by-products and residues, establishing symbiotic supply chains from various sectors. The discussion then focusses on the impact of high iron content in clinker and on ferrite (thermo)chemistry, as well as the importance of iron speciation on its involvement in the reactions as supplementary cementitious material or alkali-activated materials, and the technical quality that can be achieved from sustainable Fe-rich cements