Hypersaline brines can be solidified and stabilized via the hydraulic and pozzolanic reactions between fly ash(es) and calcium-based additives. Although recent work has examined fly ash reactivity in single-salt ("simple") hypersaline brines (ionic strength, Im > 1 mol/L), the effects of mixed-salt solutions on fly ash reactivity remain unclear. Herein, the reactivity of a Class C (calcium oxide [CaO]-rich) or Class F (CaO-poor) fly ash mixture with calcium hydroxide is reacted in solutions bearing sodium chloride (NaCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), sodium sulfate (Na2SO4), or combinations thereof for 1.5 ≤ Im ≤ 2.25 mol/L, from 1 week until 24 weeks. Expectedly, sulfate anions promote the formation of sulfate phases (i.e., ettringite, monosulfoaluminate, U-phase), while chloride anions induce the formation of Cl-AFm compounds (i.e., Kuzel's and Friedel's salt). Although the Class C fly ash's reactivity is similar across different anions (for a fixed cation and Im), Class F fly ash shows a small change in reactivity depending on the anion present. NaCl suppresses (Class C and Class F) fly ash reactivity by up to 30 % as compared to neat CaCl2 and MgCl2-based brines. Thermodynamic modeling reveals that NaCl induces a considerable increase in pH-up to 13.7, where many hydrated phases of interest cease to be the major phase expected-as compared to CaCl2 and MgCl2 brines (pH < 13). In mixed-salt brines, anion immobilization is competitive: Sulfate achieves a greater level of incorporation into the hydrates, as compared to chloride. These results offer new understanding of how the brine composition affects solidification and stabilization and thereby yield new insight into improved approaches for wastewater disposal.

The disposal of highly concentrated brines from coal power generation can be effectively accomplished by physical solidification and chemical stabilization (S&S) processes that utilize fly ashes as a reactant. Herein, pozzolanic fly ashes are typically combined with calcium-based additives to achieve S&S. While the reactions of fly ash-(cement)-water systems have been extensively studied, the reactivity of fly ashes in hypersaline brines (ionic strength, Im > 1 mol/L) is comparatively less understood. Therefore, the interactions of a Class C (Ca-rich) fly ash and a Class F (Ca-poor) fly ash were examined in the presence of Ca(OH)2, and their thermodynamic phase equilibria were modeled on contact with NaCl or CaCl2 brines for 0 ≤ Im ≤ 7.5 mol/L. At low ionic strengths (<0.3 mol/L), reactivity and stable phase assemblages remain effectively unaltered. However, at high(er) ionic strengths (>0.5 mol/L), the phase assemblage shows a particular abundance of Cl-AFm compounds (i.e., Kuzel's and Friedel's salts). Although formation of Kuzel's and Friedel's salts enhances the Class F fly ash reactions in both NaCl and CaCl2 brines, NaCl brines compromise Class C fly ash reactivity substantially, while CaCl2 results in the reactivity remaining essentially unchanged. Thermodynamic modeling that accounts for the fractional and noncongruent dissolution of the fly ashes indicates that their differences in reaction behavior are provoked by differences in the prevalent pore solution pH, which affects phase stability. The outcomes offer new insights for matching fly ashes, Ca additives, and brines, and accounting for and controlling fly ash-brine interactions as relevant to optimizing physical solidification and chemical stabilization applications.

The “U-phase,” a sodium-containing (alumino-ferrite-monosubstituent) AFm phase, has been observed to form in sodium-enriched highly alkaline cementitious systems, for example, of relevance to nuclear waste, and saline industrial brine management. But, minimal information is available of the U-phase's (e.g., solubility or thermodynamic properties) due to its limited stability and its tendency to transform into ettringite or monosulfoaluminate. Herein, the U-phase was systematically synthesized at four temperatures (5, 15, 25, and 50°C) and fully characterized in terms of its thermochemical properties. The average composition of the synthesized U-phase (4CaO·Al2O3·1.85SO3·0.85Na2O·12H2O) deviates slightly from typical disclosures in the literature. The solubility product of the U-phase formation was measured from conditions of oversaturation. The measured thermodynamic data accurately predicted experimental observations of U-phase formation in cementitious environments. In general, it was noted that the U-phase forms and persists (i.e., remains stable) at pH > 13.7 and [Na+] concentrations superior to 1 mol/L.

The pozzolanic reaction of fly ashes with calcium-based additives can be effectively used to solidify and chemically stabilize (S&S process) highly concentrated brines inside a cementitious matrix. However, complex interactions between the fly ash, the additive, and the brine typically affect the phases formed at equilibrium, and the resulting solid capacity to successfully encapsulate the brine and its contaminants. Here, the performances of two types of fly ash (a Class C and Class F fly ash) are assessed when combined with different additives (two types of cement, or lime with and without NaAlO₂), and two types of brine (NaCl or CaCl₂) over a range of concentrations (0 ≤ [Cl^-] ≤ 2 M). The best performing matrices - i.e., the matrices with the highest Cl-containing phases content - were identified using XRD and TGA. The experimental results were then combined with thermodynamic modeling to dissociate the contribution of the fly ash from that of the additives. All results were implemented in a machine learning model that showed good accuracy at predicting the fly ash degree of reaction, allowing for the robust prediction of extended systems performance when combined with thermodynamic modeling.

Layered double hydroxide (LDH) phases that form during cement hydration can incorporate a variety of interlayer anions in their interlayer positions. Here, a range of phases of general formula [MII(1−x)MIII(x)(OH)2][An−]x/n·zH2O were synthesized, where MII = Mg2+ (hydrotalcite) or Ca2+ (AFm), MIII = Al3+ such that [MII/Al] = 2 (Ca and Mg, atomic units) or 3 (Mg only), and A = Cl−, Br−, or I−. All the synthesized phases were characterized to assess their composition, density, and crystal structure. By approach from undersaturation, the solubility data of these compounds was measured at 5, 25, and 60°C. This thermochemical data was used to successfully model their formation using thermodynamic modeling and to infer the fields of stability of these compounds for conditions of relevance to cementitious systems. It is seen that halide-containing hydrotalcite phases strongly compete with hydroxide-containing hydrotalcite, with the latter prevailing at high pH. In contrast, halide-containing AFm compounds are more stable compared with hydroxide-containing AFm compositions.