While conducting siderite (FeCO3) solubility experiments in NaCl-Na2CO3 brines, evidence for a second phase was detected. Experiments, in which synthesized siderite was reacted with high ionic strength (0.18 - 7.5 m) solutions at room temperature and high pH (>10), were conducted in a glovebox. As the aging time of siderite-bearing experiments increased, the pH of the solution decreased, signaling formation of a hydroxyl-bearing phase. Decreasing pH values are interpreted to indicate that a hydroxyl-bearing phase, such as chukanovite, is the reaction controlling solid in the solid assemblage. Chukanovite was tentatively identified by XRD analysis. We set out, therefore, to determine the thermodynamic stability of chukanovite under the experimental conditions. Aqueous thermodynamic model parameters were determined with experimentally analyzed Fe(II) solubility data, and subsequently yielded a proposed formation free energy of chukanovite (-1149.8 kJ/mol).
ANS IHLRWM 2017 - 16th International High-Level Radioactive Waste Management Conference: Creating a Safe and Secure Energy Future for Generations to Come - Driving Toward Long-Term Storage and Disposal
The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy geological repository for the permanent disposal of defense-related transuranic (TRU) waste. Industrial-grade MgO consisting mainly of the mineral periclase is the only engineered barrier certified by U.S. EPA for emplacement in the WIPP in the U.S. An Mg(OH)2-based engineered barrier consisting mainly of the mineral brucite is to be employed in the Asse repository in Germany. The WIPP is located in a bedded salt formation, and the Asse repository is located in a domal salt formation. Colloids would facilitate transport of contaminants including actinides. The regulator for the WIPP, U.S. Environmental Protection Agency (EPA), expressed its interest that possible formation of mineral colloids by MgO and its hydration and carbonation products under the WIPP-relevant conditions be evaluated. In this presentation, we report a systematic experimental study to address U.S. EPA's interest. We evaluated the possible formation of mineral colloids by using two approaches. In the first approach, as the hydration products, Mg(OH)2 (brucite), and(Mg)3Cl(OH)5′4H2O (phase 5), and the carbonation product, (Mg)5(CO3)4(OH)2•4H2O (hydromagnesite), contain magnesium, should mineral fragment colloids exist, magnesium concentrations in solution samples from MgO hydration and carbonation experiments would show a dependence on ultrafiltration, i.e., a decrease in magnesium concentrations as a function of ultrafiltration with decreasing molecular weight (MW) cut-offs. Therefore, we investigated magnesium concentrations from solutions samples in hydration and carbonation experiments as a function of ultrafiltration. We ultrafiltered solutions with a series of MW cut-off filters at 100 κD, 50 κD, 30 κD and 10 κD. Our results demonstrate that the magnesium concentrations remain constant with decreasing MW cut-offs, implying the absence of mineral fragment colloids. In the second approach, because Cs+ is easily absorbed by colloids, we spiked MgO hydration and carbonation experiments under the WIPP-relevant conditions with Cs+. Then, we ultra-filtered solutions with a series of MW cut-off filters at 100 κD, 50 κD, 30 κD and 10 κD. The concentrations of Cs do not change as a function of MW cut-offs, indicating the absence of colloids from MgO hydration and carbonation products. Therefore, both approaches demonstrate that the absence of mineral fragment colloids from MgO hydration and carbonation products.