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At least 883 records · Page 49

Mineral carbonate dissolution with increasing CO 2 pressure measured by underwater laser induced breakdown spectroscopy and its application in carbon sequestration

In this study, the ability of laser-induced breakdown spectroscopy (LIBS) to measure the in situ aqueous dissolution of various mineral carbonates with increasing CO 2 pressure was examined. Dissolution experiments included four geologically common mineral carbonates (CaCO 3 , MgCO 3 , MnCO 3 , SrCO 3 ) and the CO 2 pressure ranged from ambient to 250 bar. The ensuing plasma emission was spectrally analyzed, and the intensities of Ca, Mg, Mn, and Sr emission lines were used to monitor the respective metal cations released to the aqueous solution. The strong emission lines of Ca (Ca II 393.36, Ca II 396.84, Ca I 422.67 nm), Mg (unresolved magnesium doublet: Mg I 383.230, Mg I 383.829 nm), Mn (unresolved manganese triplet: Mn I 403.076, Mn I 403.307, Mn I 403.449 nm), and Sr (Sr II 407.77, Sr II 421.55, Sr I 460.73 nm) were identified in the spectra. The amounts of metals released from their respective carbonates were estimated at different time intervals following the CO 2 injection (5 m, 1, 2, 3, 4, 24 h) and at different pressures (50, 100, 150, 200, 250 bar) using calibration models developed at corresponding pressure settings. The results demonstrated that the pressure-induced dissolution of all carbonates was consistent with their expected and selective pH-dependent solubility. The dissolution rate of CaCO 3 , MgCO 3 , and SrCO 3 was found to be higher than that of MnCO 3 . The dissolution of constituents in a Mt. Simon sandstone associated with a deep saline reservoir at elevated CO 2 pressure was also studied and Ca release was quantified. The results demonstrated that real-time monitoring of carbonate dissolution by LIBS may provide a useful indirect detection system indicative of CO 2 leakage from geologic carbon storage sites.

58 GEOSCIENCES↗

Thermodynamics and dehydration/hydration behaviors of Na-sulfate, -borate, and -bicarbonate minerals

Here, detailed thermal experiments using relative humidity- (RH) and temperature-controlled X-ray diffraction (XRD) and H 2 O adsorption/desorption measurements were applied to understand the dehydration/hydration behaviors of thenardite/mirabilite (Na 2 SO 4 /Na 2 SO 4 ·10H 2 O), tincalconite/borax (Na 2 B 4 O 7 ·5H 2 O/Na 2 B 4 O 7 ·10H 2 O), nahcolite (NaHCO 3 ), and qilianshanite (NaH 4 (BO 3 ) (CO 3 )·2H 2 O or NaHCO 3 ·H 3 BO 3 ·2H 2 O). The thermal behaviors of thenardite/mirabilite and tincalconite/borax were evaluated at room temperature as a function of RH. Hydration of thenardite to mirabilite is very sluggish and does not begin until at least 85 % RH, whereas dehydration of mirabilite to thenardite occurs at ~76 % RH. The reactions are accessible in the solid state and were not completely reversible on the time scale of these measurements. Qilianshanite appears stable under room conditions, as long as the RH is >20 %, supported by 2.5 months of observation during exposure to room air of known RH. Qilianshanite persists metastably for at least two days when exposed to both wet and 0% RH atmospheres at room temperature, observed during environment-controlled XRD. Below 20 % RH, qilianshanite sluggishly reacts to form tincalconite and nahcolite. When heated, qilianshanite broke down at 70 °C based on XRD results, and thermogravimetric analysis (TGA) confirmed a dehydration temperature of ~75 °C. Tincalconite hydrated to borax at 80 % RH, and dehydration from borax to tincalconite occurred at 40–50 % RH, illustrating the effective reversibility of the reaction under room conditions. The minor phase nahcolite originally in qilianshanite remained in the residue of decomposed qilianshanite after heating to 125 °C, demonstrated by continuous XRD measurements, whereas nahcolite was largely dehydrated when heated to ~100 °C during TGA. The difference can be attributed to the slower reaction kinetics in the environmental XRD. These results shed considerable light on the behavior of these minerals in the environment, particularly in evaporite deposits in Antarctica, where all of these minerals are reacting with the atmosphere on a diurnal-to-seasonal basis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pore-scale modelling of multiphase reactive flow: application to mineral dissolution with production of CO 2

A micro-continuum approach is proposed to simulate the dissolution of solid minerals at the pore scale in the presence of multiple fluid phases. The approach employs an extended Darcy–Brinkman–Stokes formulation that accounts for the interfacial tension between the two immiscible fluid phases and the moving contact line at the mineral surface. The simulation framework is validated using an experimental microfluidic device that provides time-lapse images of the dissolution dynamics. The set-up involves a single-calcite crystal and the subsequent generation of CO 2 bubbles in the domain. The dissolution of the calcite crystal and the production of gas during the acidizing process are analysed. We then show that the production of CO 2 bubbles during the injection of acid in a carbonate formation may limit the overall dissolution rate and prevent the emergence of wormholes.

bio-inspired, mechanical behavior, carbon sequestr↗

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion–mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ~10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41–92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (~1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO 3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. Finally, these roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

54 ENVIRONMENTAL SCIENCES↗

Mineral Scaling in 3D Interfacial Solar Evaporators–A Challenge for Brine Treatment and Lithium Recovery

In this work, we analyzed the effects of mineral scaling on the performance of a 3D interfacial solar evaporator, with a focus on the cations relevant to lithium recovery from brackish water. The field has been rapidly moving toward resource recovery applications from brines with higher cation concentrations. However, the potential complications caused by common minerals in these brines other than NaCl have been largely overlooked. Therefore, in this study, we thoroughly examined the effects of two common cations (calcium and magnesium) on the long-term solar evaporation performance of a 3D graphene oxide stalk. The 3D stalk can achieve an evaporation flux as high as 17.8 kg m –2 h –1 under one-sun illumination, and accumulation of NaCl on the stalk surface has no impact. However, the presence of CaCl 2 and MgCl 2 significantly reduces the evaporative flux even in solutions lacking scale-forming anions. A close examination of scale formation during long-term evaporation experiments revealed that CaCl 2 and MgCl 2 tend to precipitate out within the stalk, thus blocking water transport through the stalk and significantly dropping the evaporation rates. These findings imply that research attention is needed to modify and optimize the internal water transport channels for 3D evaporators. Additionally, we emphasize the importance of testing realistic mixtures–including prominent divalent cations– and testing long-term operations in interfacial solar evaporation research and investigating approaches to mitigate the negative impacts of divalent cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wellbore Cement Porosity Evolution in Response to Mineral Alteration during CO 2 Flooding

Mineral reactions during CO 2 sequestration will change the pore-size distribution and pore surface characteristics, complicating permeability and storage security predictions. In this study, we report a small/wide angle scattering study of wellbore cement that has been exposed to carbon dioxide for three decades. We have constructed detailed contour maps that describe local porosity distributions and the mineralogy of the sample and relate these quantities to the carbon dioxide reaction front on the cement. We find that the initial bimodal distribution of pores in the cement, 1–2 and 10–20 nm, is affected differently during the course of carbonation reactions. Initial dissolution of cement phases occurs in the 10–20 nm pores and leads to the development of new pore spaces that are eventually sealed by CaCO 3 precipitation, leading to a loss of gel and capillary nanopores, smoother pore surfaces, and reduced porosity. This suggests that during extensive carbonation of wellbore cement, the cement becomes less permeable because of carbonate mineral precipitation within the pore space. Additionally, the loss of gel and capillary nanoporosities will reduce the reactivity of cement with CO 2 due to reactive surface area loss. Finally, this work demonstrates the importance of understanding not only changes in total porosity but also how the distribution of porosity evolves with reaction that affects permeability.

54 ENVIRONMENTAL SCIENCES↗

Phenazine-1-Carboxylic Acid-Producing Bacteria Enhance the Reactivity of Iron Minerals in Dryland and Irrigated Wheat Rhizospheres

Phenazine-1-carboxylic acid (PCA) is a broad-spectrum antibiotic produced by rhizobacteria in the dryland wheat fields of the Columbia Plateau. PCA and other phenazines reductively dissolve Fe and Mn oxyhydroxides in bacterial culture systems, but the impact of PCA upon Fe and Mn cycling in the rhizosphere is unknown. Here, concentrations of dithionite-extractable and poorly crystalline Fe were approximately 10% and 30–40% higher, respectively, in dryland and irrigated rhizospheres inoculated with the PCA-producing (PCA + ) strain Pseudomonas synxantha 2–79 than in rhizospheres inoculated with a PCA-deficient mutant. Yet, rhizosphere concentrations of Fe(II) and Mn did not differ significantly, indicating that PCA-mediated redox transformations of Fe and Mn were transient or were masked by competing processes. Total Fe and Mn uptake into wheat biomass also did not differ significantly, but the PCA + strain significantly altered Fe translocation into shoots. X-ray absorption near edge spectroscopy revealed an abundance of Fe-bearing oxyhydroxides and phyllosilicates in all rhizospheres. These findings indicate that the PCA + strain enhanced the reactivity and mobility of Fe derived from soil minerals without producing parallel changes in plant Fe uptake. This is the first report that directly links significant alterations of Fe-bearing minerals in the rhizosphere to a single bacterial trait.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopic Properties of Americium(III) in Mineral Acid Media

We report the preparation and optical characterization of three solutions of Am(III) in common aqueous (aq.) mineral acids (HCl, HNO 3 and HBr), including absorption, emission, and Raman vibrational analyses. To our knowledge, this study provides the first detailed absorption spectra of Am(III) spanning the entire UV/Vis/NIR region in these mineral acids reported since the 1960s. Here, using this high-resolution absorption data, provided in an open access format for the broader field, we build on prior work by Carnall and others to provide detailed optical analysis including all transition assignments. This work also includes the first reported absorption spectrum of Am(III) in aq. HBr. Characteristic Am(III) luminescence could be detected from all three samples. These are the first reports of emission from Am(III) in these acid systems, which build on prior emission reports collected from aq. HClO 4 solutions. The acquired emission spectra display anion-dependent shifting of the visible-region transitions by up to 21 nm from their predicted positions, akin to the nephelauxetic effect. The shift magnitude trends linearly according to the acid p K a and more generally according to the transition metal spectrochemical series. These ligand field effects, coupled with luminescence lifetime experiments, indicate that weak Am-X interactions persist in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excitation Wavelength-Dependent Emission from Americium(III) in Mineral Acid Solutions

The photoluminescence behavior of trivalent americium, Am(III), in mineral acid solutions is reported under direct-metal excitation at seven high-energy wavelengths in the ultraviolet and visible regions (378-512 nm). This study revealed a dependence of the Am(III)-based visible emission profile on the chosen excitation wavelength. For example, excitation at the more common wavelength of 504 nm produces the two expected emission bands: one at approximately 600 nm (5D1' to 7F0') and another at 690 nm (5D1' to 7F1'). When the excitation wavelength is shifted to 398 nm (targeting the 5D3', 5H7' from 7F0' transitions), the emission occurs almost exclusively at 600 nm. This behavior is unexpected and potentially highlights fundamental knowledge gaps in the current understanding of the intraconfigurational 5f-5f electronic transitions that give rise to Am(III) photoluminescence. Although a full interpretation of these results is limited by the incomplete understanding of Am(III) speciation in mineral acid systems, this study explores several potential explanations for the observed behavior and challenges the widely held assumption of a single emissive Am(III) species.

Americium↗

Optical and Chemical Characterization of Uranium Dioxide (UO 2 ) and Uraninite Mineral: Calculation of the Fundamental Optical Constants

Quantitative infrared single-angle reflectance spectroscopic measurements using a calibrated Fourier transform infrared spectrometer were performed on synthetic uranium dioxide (UO2), high-purity crystalline uraninite, and massive uraninite mineral. The massive uraninite mineral was found to contain not only UO2 but also large amounts of calcite and silicates. From the experimentally measured reflectance spectra across two spectral domains (the far- and mid-infrared) the fundamental optical constants n and k were calculated using the Kramers-Kronig transformation for each species. We discuss both the derived n and k results for these species as well as the careful sample preparation needed in order to mount, polish, and measure such samples through a wide spectral range using modern instrumentation and data processing techniques. Our results for the optical constants n and k of synthetic UO2 differ significantly from previously published literature values. This is attributed to both improved spectroscopic resolution but also to a better understanding of potential surface oxidation effects on the measured reflectance values, and hence the calculated optical constants.

DeVetter, Brent M.↗

Radiation-Induced Changes in Single Crystal Calcite and Dolomite: Mineral Analogues of Light Water Reactor, Nuclear Power Plant Concrete Aggregates

Two analogues of aggregates (calcite and dolomite) found in nuclear power plant (NPP) concrete have been neutron irradiated to fluences up to 2 × 10 20 n/cm 2 at 52 °C and 4 × 10 19 n/cm 2 at 95 °C (E > 0.1 MeV). X-ray diffraction studies showed that these aging conditions affected crystallography of both calcite and dolomite, with both showing a growth in their unit cells compared to that of the unirradiated samples. Only dolomite samples showed a continuous increase of its lattice parameters with the increase in irradiation. In calcites, the lattice growth with irradiation dissipated after a fluence of 5 × 10 18 n/cm 2 . Radiation-induced disordering of the crystal structure was observed in both materials, while a healing effect of irradiation temperature was mainly observed in calcites. Dislocation densities calculated by using XRD data also supported these observations. Insights made into the unit cells of both minerals by using Fourier synthesis showed that the Mg sites are more prone to the neutron irradiation than the Ca sites, resulting in larger radiation effects and higher disruption in the crystal structure of dolomite than that of calcite. Furthermore, other than the polycrystalline characteristics observed by using TEM, these minerals did not show complete amorphization or significant structural decomposition at the studied irradiation fluences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for a montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.

36 MATERIALS SCIENCE↗

Competitive Sorption of H 2 O and CO 2 in Clay Mineral Interlayers

The first-reported competitive CO 2 –H 2 O sorption isotherms on a naturally occurring expandable clay mineral (saponite) exchanged with Na, K, and Cs at near ambient CO 2 concentrations (1% CO 2 ) are reported by combining ATR-FTIR spectroscopy with gravimetric sorption methods. Little CO 2 sorption was observed at high relative humidity (RH) but increased significantly at low RH. Unlike prior work where CO 2 sorption was reported on samples that were previously subjected to heating and/or evacuation treatment to remove sorbed H 2 O, this study manipulated CO 2 sorption by controlling RH. CO 2 sorption increased in the order Cs- > K- > Na-exchanged saponite and was anticorrelated with the Gibbs energy of hydration of the exchangeable cation. As expected, H 2 O sorption followed the opposite trend, with increased H 2 O sorption occurring in the order Na > K > Cs. The amount of CO 2 sorbed using 1 atm CO 2 (p/p o = 1.0) ranged from 50 to 30 mg CO 2 /g clay and from 1.25 to 0.8 mg CO2 /g clay for 1% CO 2 (p/p o = 0.01) in N 2 . The sensitivity of the ATR-FTIR measurements is demonstrated by detecting the CO 2 stretch of adsorbed CO 2 from air containing 500 ppmv CO 2 . The spectral features of sorbed CO 2 were minimally affected by the nature of the exchangeable cation or variations in H 2 O content. However, the position of the HOH bending band shifted significantly from 1638 to 1610 cm –1 as H 2 O content decreased, reflecting changes in intermolecular hydrogen bonding between H 2 O molecules in the saponite interlayer. The shift in position of the HOH bending band to lower energy was coincident with increased CO 2 sorption. CO 2 sorption in clay mineral interlayers is consistent with sorption on weakly hydrated partially hydrophobic sites found on low charge density smectites and is enhanced by lower RH and by the presence of weakly hydrated exchangeable cations like Cs + or K + . In conclusion, the greatest CO 2 sorption occurs on Cs-saponite because this is the least hydrated cation of the three used in the study and indicates that CO2 sorption occurs on the neutral portion of the siloxane surface.

Johnston, Cliff T. [Purdue Univ., West Lafayette, ↗

Surface-Catalyzed Oxygen Exchange during Mineral Carbonation in Nanoscale Water Films

Properties of nanoconfined adsorbed H2O on mineral surfaces are distinct from those of bulk H2O, and this can lead to significant differences in reactivity. Here, we investigate how O-exchange between H2O and CO2 depends on the thickness of H2O films on the mineral, forsterite (Mg2SiO4), which is reactive towards carbonation. Rates of O-exchange measured using O-isotopic tracers and infrared spectroscopy increase with adsorbed H2O concentration and are two orders of magnitude faster than for the previously studied inert substrate, fumed silica (SiO2). Theoretical calculations demonstrate that O exchange can be catalyzed through interactions with active Mg2+ sites that lower the barrier for carbonic acid formation. These active metal centers exist as =Mg-bicarbonate surface complexes or dissolved Mg2+ with predominantly bicarbonate counter ions, as evidenced by infrared and nuclear magnetic resonance spectroscopies. Intermolecular proton hopping to bicarbonate can form a carbonic acid complex that readily decomposes to CO2 and H2O, leading to O-isotope scrambling. Unlike fumed silica, we find no evidence that adsorbed H2O film structure dictates O-exchange rates. On the contrary, it is mainly =Mg-bicarbonate surface complexes that are the key players in metal-center catalyzed O-isotope scrambling.

Miller, Quin RS↗

Nucleation of Salt Crystals in Clay Minerals: Molecular Dynamics Simulation

Nucleation of salt crystals in confined media occurs in many processes of high importance, such as injection of CO 2 in geological formations for its sequestration. Specifically, salt precipitation in clays, a main component of sedimentary rock, is an important phenomenon. The crystals precipitate on the pores’ surface, modify the pore space morphology, and reduce its flow and transport properties. Despite numerous efforts to understand the mechanisms of nucleation of salt crystals in confined media, the effect of the clay’s chemistry on the growth, distribution, and properties of the crystals is not well understood. We discuss the results of extensive molecular dynamics simulation of nucleation and growth of NaCl crystals in a clay pore using molecular models of two types of clay minerals, Na-montmorillonite and kaolinite. Clear evidence is introduced for the nucleation of the salt crystals that indicates that the molecular structure of clay minerals affects their spatial distribution, although the nucleation mechanism is the same in both types of clays.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Transition States during the Hydration of Clay Minerals

A molecular-scale understanding of the transition between hydration states in clay minerals remains a challenging problem due to the very fast stepwise swelling process observed from Xray diffraction (XRD) experiments. XRD profile modeling assumes the coexistence of multiple hydration states in a clay sample to fit the experimental XRD pattern obtained under humid conditions. While XRD profile modeling provides a macroscopic understanding of the heterogeneous hydration structure of clay minerals, a microscopic model of the transition between hydration states is still missing. Here, for the first time, we use molecular dynamics simulation to investigate the transition states between a dry interlayer, one-layer hydrate, and two-layer hydrate. We find that the hydrogen bonds that form across the interlayer at the clay particle edge make an important contribution to the energy barrier to interlayer hydration, especially for initial hydration.

58 GEOSCIENCES↗

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide

Aluminum hydroxide, an abundant mineral found in nature, exists in four polymorphs: gibbsite, bayerite, nordstrandite, and doyleite. Among these polymorphs gibbsite, bayerite, and commercially synthesized amorphous aluminum hydroxide have been investigated as sorbent materials for lithium extraction from sulfate solutions. The amorphous form of Al(OH) 3 exhibits a reactivity higher than that of the naturally occurring crystalline polymorphs in terms of extracting Li + ions. This study employed high-temperature oxide melt solution calorimetry to explore the energetics of the sorbent polymorphs. The enthalpic stability order was measured to be gibbsite > bayerite > amorphous Al(OH) 3 . The least stable form, amorphous Al(OH) 3 , undergoes a spontaneous reaction with lithium, resulting in the formation of a stable layered double hydroxide phase. Consequently, amorphous Al(OH) 3 shows promise as a sorbent material for selectively extracting lithium from clay mineral leachate solutions. Further, this research demonstrates the selective direct extraction of Li + ions using amorphous aluminum hydroxide through a liquid–solid lithiation reaction, followed by acid-free delithiation and relithiation processes, achieving an extraction efficiency of 86%, and the maximum capacity was 37.86 mg·g –1 in a single step during lithiation. With high selectivity during lithiation and nearly complete recoverability of the sorbent material during delithiation, this method presents a circular economy model. Furthermore, a life cycle analysis was conducted to illustrate the environmental advantages of replacing the conventional soda ash-based precipitation process with this method, along with a simple operational cost analysis to evaluate reagent and fuel expenses.

25 ENERGY STORAGE↗