Deciphering strontium sulfate precipitation via Ostwald's rule of stages: From prenucleation clusters to solution-mediated phase tranformation.

Multiple-step nucleation pathways have been observed during mineral formation in both inorganic and biomineral systems. These pathways can involve precursor aqueous species, amorphous intermediates, or metastable phases. Despite the widespread occurrence of these processes, elucidating the precise nucleation steps and the transformation mechanisms between each step remains a challenging task. Using a suite of potentiometric, microscopic, and spectroscopic tools, we studied the nucleation pathway of SrSO4 as a function of the physico-chemical solution parameters. Our observations reveal that below a threshold supersaturation, nucleation is driven by bound species, akin to the prenucleation cluster model, which directly leads to the formation of the stable phase celestine, SrSO4. At higher supersaturations, this situation is altered, with nucleation dominated by the consumption of free ions. Importantly, this change in nucleation mechanism is coupled to the formation of a hemihydrate metastable phase, SrSO4 · 1/2H2O, which eventually transforms into celestine, adhering to Ostwald's rule of stages. This transformation is a solution-mediated process, also occurring in the presence of a fluid film and is controlled by the physico-chemical parameters of the surrounding environment. It proceeds through the dissolution of the metastable phase and the de novo crystallization of the final phase. Overall, our results reveal that ion association taking place during the prenucleation stage dictates whether the nucleation pathway goes through an intermediate phase or not. This also underlines that although Ostwald's rule of stages is a common process, it is not a prerequisite for mineral formation-even in systems where it can occur.

Mineral sequestration of CO(2) by aqueous carbonation of coal combustion fly-ash.

The increasing CO(2) concentration in the Earth's atmosphere, mainly caused by fossil fuel combustion, has led to concerns about global warming. A technology that could possibly contribute to reducing carbon dioxide emissions is the in-situ mineral sequestration (long term geological storage) or the ex-situ mineral sequestration (controlled industrial reactors) of CO(2). In the present study, we propose to use coal combustion fly-ash, an industrial waste that contains about 4.1 wt.% of lime (CaO), to sequester carbon dioxide by aqueous carbonation. The carbonation reaction was carried out in two successive chemical reactions, first, the irreversible hydration of lime. second, the spontaneous carbonation of calcium hydroxide suspension. A significant CaO-CaCO(3) chemical transformation (approximately 82% of carbonation efficiency) was estimated by pressure-mass balance after 2h of reaction at 30 degrees C. In addition, the qualitative comparison of X-ray diffraction spectra for reactants and products revealed a complete CaO-CaCO(3) conversion. The carbonation efficiency of CaO was independent on the initial pressure of CO(2) (10, 20, 30 and 40 bar) and it was not significantly affected by reaction temperature (room temperature "20-25", 30 and 60 degrees C) and by fly-ash dose (50, 100, 150 g). The kinetic data demonstrated that the initial rate of CO(2) transfer was enhanced by carbonation process for our experiments. The precipitate calcium carbonate was characterized by isolated micrometric particles and micrometric agglomerates of calcite (SEM observations). Finally, the geochemical modelling using PHREEQC software indicated that the final solutions (i.e. after reaction) are supersaturated with respect to calcium carbonate (0.7 < or = saturation index < or = 1.1). This experimental study demonstrates that 1 ton of fly-ash could sequester up to 26 kg of CO(2), i.e. 38.18 ton of fly-ash per ton of CO(2) sequestered. This confirms the possibility to use this alkaline residue for CO(2) mitigation.

Arsenite and chromate sequestration onto ferrihydrite, siderite and goethite nanostructured minerals: Isotherms from flow-through reactor experiments and XAS measurements.

Sorption isotherms remain a major tool to describe and predict the mobility of pollutants in natural and anthropogenic environments, but they are typically determined by independent batch experiments. In the present study, the sequestration of As(III), Cr(VI) and competitive As(III)-Cr(VI) on/in 6L-ferrihydrite, siderite and goethite nanostructured minerals was reinvestigated using stirred flow-through reactor experiments. Herein, sorption isotherms were particularly determined from breakthrough curves for inert and reactive tracers monitored simultaneously in a single percolation experiment. In complement, X-ray absorption spectroscopy (XAS) was used to identify As sorption sites on 6L-ferrihydrite and goethite. As expected, the minerals have high potential to remove As and Cr from water (siderite = ferrihydrite (about 60 mg/g) > goethite (20 mg/g)). As and Cr sorption isotherms were modelled with a Langmuir model, and with a sigmoidal Hill model in the case of the competitive sorption. XAS measurements have revealed that As(III) was partially oxidized (up to 22%) in the competitive system with chromate oxyanion Cr(VI). As(III) sorbed on ferrihydrite and goethite adopted edge-sharing and corner sharing complex geometries. Nowadays, a new class of adsorbing phases is being developed for wastewater treatment, including engineered nanostructured materials and nanocomposites. The use of flow through reactor experiments as a high throughput method, combined with XAS, should be considered as efficient screening methods to test their sorbing properties on various contaminants.

A simplified method to estimate kinetic and thermodynamic parameters on the solid-liquid separation of pollutants.

The aim of the present study was to propose a simplified experimental-theoretical method for estimating the kinetic and thermodynamic parameters for the solid-liquid separation of pollutants by using kinetic studies with batch reactors, i.e., the removed quantity of dissolved ion as a function of time at different initial concentration. This method was applied to the removal of uranyl ion (UO(2+)(2)) from aqueous solutions onto synthetic manganese oxide (birnessite). The pseudo-second-order kinetics and one-site saturation models were proposed to fit the experimental and calculated data, the fitting parameters being estimated by nonlinear regression, using the least-squares method. For initial concentration range 0.2-11.8 microM, the results showed that the uranyl removal process in dispersed batch reactors can be efficiently modeled by the proposed models. Then, several kinetic and thermodynamic parameters were calculated, such as maximal removed quantity of uranyl, q(r,max), half-removal time, t(1/2), initial rate of uranyl-ion removal, v(0), initial uranyl-removal coefficient, K, maximal rate of uranyl removal, v(0,max), mass transfer coefficient, D(transfer), equilibrium Langmuir constant, K(L), and constant separation factor, K(s). These parameters make it possible to demonstrate that the removal of U onto birnessite is favorable, and that the maximum surface coverage of the uranyl ions represents about 3% of vacant sites in the Mn layer.

Synthesis of a red iron oxide/montmorillonite pigment in a CO2-rich brine solution.

The homoionic calcium-montmorillonite was used to synthesize a red iron oxide/clay pigment in a CO2-rich brine solution (0.5 M of NaCl) by using an agitated batch-reactor (engineer autoclave). The operating conditions were 15 days of reaction, 200 bars of pressure and 150 degrees C of temperature. SEM/EDS, STEM/EDS, XRD and Infrared Spectrometry were performed to characterize before and after reaction the solid phase. The results showed the precipitation of spherical nanoparticles (50-500 nm) of iron oxide (Fe2O3) dispersed and/or coagulated in the clay-matrix. Evidently, this oxide produced red coloration in the final product. For this case, the Fe3+ cation was provided to the aqueous solution by the dissolution of Ca-montmorillonite, particularly, the dissolution of most fine particles contained in the starting clay material. The cation exchange process and precipitation of polymorph silica were also observed.

Removal of oxyanions from synthetic wastewater via carbonation process of calcium hydroxide: applied and fundamental aspects.

Removal of oxyanions (selenite, selenate, arsenate, phosphate and nitrate) during calcite formation was experimentally studied using aqueous carbonation of calcium hydroxide under moderate pressure (P(CO2) congruent with 20 bar) and temperature (30 degrees C). The effects of Ca(OH)(2) dose (10 and 20 g), Ca(OH)(2) source (commercial pure material or alkaline paper mill waste) and oxyanion initial concentration (from 0 to 70 mg atom/L) were investigated for this anisobaric gas-liquid-solid system. The Ca(OH)(2) carbonation reaction allowed successfully the removal of selenite (>90%), arsenate (>78%) and phosphate (congruent with 100%) from synthetic solutions. Conversely, nitrate and selenate had not any physicochemical affinity/effect during calcite formation. The rate of CO(2) transfer during calcite formation in presence of oxyanions was equal or slower than for an oxyanion-free system, allowing to define a retarding kinetic factor RF that can vary between 0 (no retarding effect) to 1 (total inhibition). For selenite and phosphate RF was quite high, close to 0.3. A small retarding effect was detected for arsenate (RF approximately 0.05) and no retarding effect was detected for selenate and nitrate (RF approximately 0). In general, RF depends on the oxyanion initial concentration, oxyanion nature and Ca(OH)(2) dose. The presence of oxyanions could also influence the crystal morphology and aggregation/agglomeration process. For example, a c-axis elongation of calcite crystals was clearly observed at the equilibrium, for calcite formation in presence of selenite and phosphate. The oxyanions removal process proposed herein was inspired on the common physicochemical treatment of wastewater using calcium hydroxide (Ca(OH)(2)). The particularity, for this novel method is the simultaneous calcium hydroxide carbonation with compressed carbon dioxide in order to stabilise the solid matter. This economical and ecological method could allow the removal of various oxyanions as well as the ex situ mineral sequestration of CO(2); particularly, when the Ca(OH)(2) source comes from alkaline solid waste.