Publications

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In this work, solubility measurements regarding boracite [Mg₃B₇O₁₃Cl(cr)] and aksaite [MgB₆O₇(OH)₆·2H₂O(cr)] from the direction of supersaturation were conducted at 22.5 ± 0.5 °C. The equilibrium constant (log₁₀K⁰) for boracite in terms of the following reaction, Mg₃B₇O₁₃Cl(cr) + 15H₂O(l) ⇌ 3Mg²⁺ + 7B(OH)₄^– + Cl^– + 2H⁺ is determined as -29.49 ± 0.39 (2σ) in this study. The equilibrium constant for aksaite according to the following reaction, MgB₆O₇(OH)₆•2H₂O(cr) + 9H₂O(l) ⇌ Mg²⁺ + 6B(OH)₄^– + 4H⁺ is determined as -44.41 ± 0.41 (2σ) in this work. This work recommends a set of thermodynamic properties for aksaite at 25 °C and 1 bar as follows: ΔH$0\atop{f}$ =-6063.70 ± 4.85 kJ·mol^-1, ΔG =-5492.55 ± 2.32 kJ·mol^-1, and S⁰ = 344.62 ± 1.85 J·mol^-1·K^-1. Among them, ΔG$0\atop{f}$ is derived from the equilibrium constant for aksaite determined by this study; ΔH$0\atop{f}$ is from the literature, determined by calorimetry; and S⁰ is computed in the present work from ΔG$0\atop{f}$ and ΔH$0\atop{f}$. This investigation also recommends a set of thermodynamic properties for boracite at 25 °C and 1 bar as follows: ΔH$0\atop{f}$ =-6575.02 ± 2.25 kJ·mol^-1, ΔG$0\atop{f}$ =-6178.35 ± 2.25 kJ·mol^-1, and S⁰ = 253.6 ± 0.5 J·mol^-1·K^-1. Among them, ΔG$0\atop{f}$ is derived from the equilibrium constant for boracite determined by this study; S⁰ is from the literature, determined by calorimetry; and ΔH$0\atop{f}$ is computed in this work from ΔG$0\atop{f}$ and S⁰. The thermodynamic properties determined in this study can find applications in many fields. For instance, in the field of material science, boracite has many useful properties including ferroelectric and ferroelastic properties. The equilibrium constant of boracite determined in this work will provide guidance for economic synthesis of boracite in an aqueous medium. Similarly, in the field of nuclear waste management, iodide boracite [Mg₃B₇O₁₃I(cr)] is proposed as a waste form for radioactive ¹²⁹I. Therefore, the solubility constant for chloride boracite [Mg₃B₇O₁₃Cl(cr)] will provide the guidance for the performance of iodide boracite in geological repositories. Boracite/aksaite themselves in geological repositories in salt formations may be solubility-controlling phase(s) for borate. Finally, solubility constants of boracite and aksaite will enable researchers to predict borate concentrations in equilibrium with boracite/aksaite in salt formations.

Radionuclides and heavy metals easily sorb onto colloids. This phenomenon can have a beneficial impact on environmental clean-up activities if one is trying to scavenge hazardous elements from soil for example. On the other hand, it can have a negative impact in cases where one is trying to immobilize these hazardous elements and keep them isolated from the public. Such is the case in the field of radioactive waste disposal. Colloids in the aqueous phase in a radioactive waste repository could facilitate transport of contaminants including radioactive nuclides. Salt formations have been recommended for nuclear waste isolation since the 1950's by the U.S. National Academy of Science. In this capacity, salt formations are ideal for isolation of radioactive waste. However, salt formations contain brine (the aqueous phase), and colloids could possibly be present. If present in the brines associated with salt formations, colloids are highly relevant to the isolation safety concept for radioactive waste. The Waste Isolation Pilot Plant (WIPP) in southeast New Mexico is a premier example where a salt formation is being used as the primary isolation barrier for radioactive waste. WIPP is a U.S. Department of Energy geological repository for the permanent disposal of defenserelated transuranic (TRU) waste. In addition to the geological barrier that the bedded salt formation provides, an engineered barrier of MgO added to the disposal rooms is used in WIPP. Industrial-grade MgO, consisting mainly of the mineral periclase, is in fact the only engineered barrier certified by the U.S. Environmental Protection Agency (EPA) for emplacement in the WIPP. Of interest, an Mg(OH)2-based engineered barrier consisting mainly of the mineral brucite is to be employed in the Asse repository in Germany. The Asse repository is located in a domal salt formation and is another example of using salt formations for disposal of radioactive waste. Should colloids be present in salt formations, they would facilitate transport of contaminants including actinides. In the case of colloids derived from emplaced MgO, it is the hydration and carbonation products that are of interest. These colloids could possibly form under conditions relevant in particular to the WIPP. In this chapter, we report a systematic experimental study performed at Sandia National Laboratories in Carlsbad, New Mexico, related to the WIPP engineered barrier, MgO. The aim of this work is to confirm the presence or absence of mineral fragment colloids related to MgO in high ionic strength solutions (brines). The results from such a study provides information about the stability of colloids in high ionic strength solutions in general, not just for the WIPP. We evaluated the possible formation of mineral fragment colloids using two approaches. The first approach is an analysis of long-term MgO hydration and carbonation experiments performed at Sandia National Laboratories (SNL) as a function of equivalent pore sizes. The MgO hydration products include Mg(OH)2 (brucite) and Mg3 Cl(OH)5•4H2O (phase 5), and the carbonation product includes Mg5(CO3)4(OH)2•4H2O (hydromagnesite). All these phases contain magnesium. Therefore, if mineral fragment colloids of these hydration and carbonation products were formed in the SNL experiments mentioned above, magnesium concentrations in the filtrate from the experiments would show a dependence on ultrafiltration. In other words, there would be a decrease in magnesium concentrations as a function of ultrafiltration with decreasing molecular weight (MW) cut-offs for the filtration. Therefore, we performed ultrafiltration on solution samples from the SNL hydration and carbonation experiments as a function of equivalent pore size. We filtered solutions using a series of MW cut-off filters at 100 kD, 50 kD, 30 kD and 10 kD. Our results demonstrate that the magnesium concentrations remain constant with decreasing MW cutoffs, implying the absence of mineral fragment colloids. The second approach uses spiked Cs+ to indicate the possible presence of mineral fragment colloids. Cs+ is easily absorbed by colloids. Therefore, we added Cs+ to a subset of SNL MgO hydration and carbonation experiments. Again, we filtered the solutions with a series of MW cut-off filters at 100 kD, 50 kD, 30 kD and 10 kD. This time we measured the concentrations of Cs. 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 the absence of mineral fragment colloids from MgO hydration and carbonation products. Based on our experimental results, we acknowledge that mineral fragment colloids were not formed in the SNL MgO hydration and carbonation experiments, and we further conclude that high ionic strength solutions associated with salt formations prevent the formation of mineral fragment colloids. This is due to the fact that the high ionic strength solutions associated with salt formations have high concentrations of both monovalent and divalent metal ions that are orders of magnitude higher than the critical coagulation concentrations for mineral fragment colloids. The absence of mineral fragment colloids in high ionic strength solutions implies that contributions from mineral fragment colloids to the total mobile source term of radionuclides in a salt repository are minimal.

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In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH)₃(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH)₃(micro cr), avoiding the possibility of phase change.

Here, a solubility model is presented for ferrous iron hydroxide (Fe(OH)₂(s)), hibbingite (Fe₂Cl(OH)₃(s)), siderite (FeCO₃(s)), and chukanovite (Fe₂CO₃(OH)₂(s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH)₂(s) was observed in the experiments that were initiated with Fe₂Cl(OH)₃(s) in Na₂SO₄ solution. Coexistence of siderite and chukanovite was observed in the experiments in Na₂CO₃ + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH)₂(s) and Fe₂Cl(OH)₃(s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO₃)₂^–2. Five Pitzer interaction parameters were derived in this paper: β⁽⁰⁾, β⁽¹⁾, and C^φ parameters for the species pair Fe⁺²/SO₄^–2; β⁽⁰⁾ and β⁽¹⁾ parameters for the species pair Na+/Fe(CO3)2–2. Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10^–91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).

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In this study, solubility measurements were conducted for sodium polyborates in MgCl2 solutions at 22.5 ± 0.5 °C. According to solution chemistry and XRD patterns, di-sodium tetraborate decahydrate (borax) dissolves congruently, and is the sole solubility-controlling phase, in a 0.01 mol/kg MgCl2 solution: {equation presented} However, in a 0.1 mol/kg MgCl2 solution borax dissolves incongruently and is in equilibrium with di-sodium hexaborate tetrahydrate: {equation presented} In this study, the equilibrium constant (log K0) for Reaction 2 at 25 °C and infinite dilution was determined to be -16.44 ± 0.13 (2σ) based on the experimental data and the Pitzer model for calculations of activity coefficients of aqueous species. In accordance with the log K0 for Reaction 1 from a previous publication from this research group, and log K0 for Reaction 2 from this study, the equilibrium constant for dissolution of di-sodium hexaborate tetrahydrate at 25 °C and at infinite dilution, {equation presented} was derived to be -45.42 ± 0.16 (2σ). The equilibrium constants determined in this study can find applications in many fields. For example, in the field of nuclear waste management, the formation of di-sodium hexaborate tetrahydrate in brines containing magnesium will decrease borate concentrations, making less borate available for interactions with Am(III). In the field of experimental investigations, based on the equilibrium constant for Reaction 2, the experimental systems can be controlled in terms of acidity around neutral pH by using the equilibrium assemblage of borax and di-sodium hexaborate tetrahydrate at 25 °C. As salt lakes and natural brines contain both borate and magnesium as well as sodium, the formation of sodium hexaborate tetrahydrate may influence the chemical evolution of salt lakes and natural brines. Di-sodium hexaborate tetrahydrate is a polymorph of the mineral ameghinite [chemical formula Na2B6O10·4H2O; structural formula NaB3O3(OH)4 or Na2B6O6(OH)8]. Di-sodium hexaborate tetrahydrate could be a precursor of ameghinite and could be transformed when borate deposits are subject to diagenesis.

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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.

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