Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb2+ Solutions.

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb2+ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb2+ concentrations ([Pb2+] = 0 to 5 × 10-2 M) and flow velocities (v = 1.67-53.3 mm s-1). Calcite (104) surface dissolution rates decreased with increasing [Pb2+]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb2+] ≥ 5 × 10-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.

Ion correlations drive charge overscreening and heterogeneous nucleation at solid-aqueous electrolyte interfaces.

Classical electrical double layer (EDL) models are foundational to the representation of atomistic structure and reactivity at charged interfaces. An important limitation to these models is their dependence on a mean-field approximation that is strictly valid for dilute aqueous solutions. Theoretical efforts to overcome this limitation are severely impeded by the lack of visualization of the structure over a wide range of ion concentration. Here, we report the salinity-dependent evolution of EDL structure at negatively charged mica-water interfaces, revealing transition from the Langmuir-type charge compensation in dilute salt solutions to nonclassical charge overscreening in highly concentrated solutions. The EDL structure in this overcharging regime is characterized by the development of both lateral positional correlation between adsorbed ions and vertical layering of alternating cations and anions reminiscent of the structures of strongly correlated ionic liquids. These EDL ions can spontaneously grow into nanocrystalline nuclei of ionic compounds at threshold ion concentrations that are significantly lower than the bulk solubility limit. These results shed light on the impact of ion cooperativity that drives heterogeneous nonclassical behaviors of the EDL in high-salinity conditions.

Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite-Water Interface by Adsorption of Rb+ and Halides (Cl- , Br- , I- ) at High Salinity.

Classical electric double layer (EDL) models have been widely used to describe ion distributions at charged solid-water interfaces in dilute electrolytes. However, the chemistry of EDLs remains poorly constrained at high ionic strength where ion-ion correlations control non-classical behavior such as overcharging, i. e., the accumulation of counter-ions in amounts exceeding the substrate's surface charge. Here, we provide direct experimental observations of correlated cation and anion distributions adsorbed at the muscovite (001)-aqueous electrolyte interface as a function of dissolved RbBr concentration ([RbBr]=0.01-5.8 M) using resonant anomalous X-ray reflectivity. Our results show alternating cation-anion layers in the EDL when [RbBr]≳100 mM, whose spatial extension (i. e., ~20 Šfrom the surface) far exceeds the dimension of the classical Stern layer. Comparison to RbCl and RbI electrolytes indicates that these behaviors are sensitive to the choice of co-ion. This new in-depth molecular-scale understanding of the EDL structure during transition from classical to non-classical regimes supports the development of realistic EDL models for technologies operating at high salinity such as water purification applications or modern electrochemical storage.

Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite-Water Interface by Adsorption of Rb+ and Halides (Cl- , Br- , I- ) at High Salinity.

The front cover artwork is provided by Argonne National Laboratory. The image shows the arrangement of correlated cations and anions at a charged solid surface in contact with highly concentrated electrolyte solutions. Read the full text of the Research Article at 10.1002/cphc.202300545.

Carbonate Coprecipitation for Cd and Zn Treatment and Evaluation of Heavy Metal Stability Under Acidic Conditions.

Mining wastes or combustion ash are materials of high carbon sequestration potential but are also known for their toxicity in terms of heavy metal content. To utilize such waste materials for engineered carbon mineralization purposes, there is a need to investigate the fate and mobility of toxic metals. This is a study of the coprecipitation of metals with calcium carbonate for environmental heavy metal mitigation. The study also examines the stability of precipitated phases under environmentally relevant acid conditions. For a wide range of cadmium (Cd) and zinc (Zn) concentrations (10 to 5000 mg/L), induced coprecipitation led to greater than 99% uptake from water. The calcium carbonate phases were found to contain amounts as high as 9.9 wt % (Cd) and 17 wt % (Zn), as determined by novel synchrotron techniques, including X-ray fluorescence element mapping and three-dimensional (3D) nanotransmission X-ray microscopy (TXM). TXM imaging revealed first-of-a-kind observations of chemical gradients and internal nanoporosity within particles. These observations provided new insights into the mechanisms leading to the retention of coprecipitated heavy metals during the dissolution of calcite in acidic (pH 4) solutions. These observations highlight the feasibility of utilizing carbonate coprecipitation as an engineered approach to the durable sequestration of toxic metals.

Y(III) Sorption at the Orthoclase (001) Surface Measured by X-ray Reflectivity.

Interactions of heavy metals with charged mineral surfaces control their mobility in the environment. Here, we investigate the adsorption of Y(III) onto the orthoclase (001) basal plane, the former as a representative of rare earth elements and an analogue of trivalent actinides and the latter as a representative of naturally abundant K-feldspar minerals. We apply in situ high-resolution X-ray reflectivity to determine the sorption capacity and molecular distribution of adsorbed Y species as a function of the Y3+ concentration, [Y3+], at pH 7 and 5. With [Y3+] ≥ 1 mM at pH 7, we observe an inner-sphere (IS) sorption complex at a distance of ∼1.5 Å from the surface and an outer-sphere (OS) complex at 3-4 Å. Based on the adsorption height of the IS complex, a bidentate, binuclear binding mode, in which Y3+ binds to two terminal oxygens, is proposed. In contrast, mostly OS sorption is observed at pH 5. The observed maximum Y coverage is ∼1.3 Y3+/AUC (AUC: area of the unit cell = 111.4 Å2) for all the investigated pH values and Y concentrations, which is in the expected range based on the estimated surface charge of orthoclase (001).

Synergistic Enhancement of Lead and Selenate Uptake at the Barite (001)-Water Interface.

The interactions of heavy metals with minerals influence the mobility and bioavailability of toxic elements in natural aqueous environments. The sorption of heavy metals on covalently bonded minerals is generally well described by surface complexation models (SCMs). However, understanding sorption on sparingly soluble minerals is challenging because of the dynamically evolving chemistry of sorbent surfaces. The interpretation can be even more complicated when multiple metal ions compete for sorption. In the present study, we observed synergistically enhanced uptake of lead and selenate on the barite (001) surface through two sorption mechanisms: lattice incorporation that dominates at lower coverages and two-dimensional monolayer growth that dominates at higher coverages. We also observed a systematic increase in the sorption affinity with increasing co-sorbed ion coverages, different from the assumption of invariant binding constants for individual adsorption processes in classical SCMs. Computational simulations showed thermodynamically favorable co-incorporation of lead and selenate by simultaneously substituting for barium and sulfate in neighboring sites, resulting in the formation of molecular clusters that locally match the net dimension of the substrate lattice. These results emphasize the importance of ion-ion interactions at mineral-water interfaces that control the fate and transport of contaminants in the environment.

Structural analysis of the initial lithiation of NiO thin film electrodes.

Observations of the initial lithiation of NiO electrodes demonstrate how to seed conversion reactions using interfaces in a thin film Ni/NiO bilayer architecture. Operando X-ray reflectivity (XRR) reveals that structural changes in a NiO film begin at potentials near the theoretical reduction potential (1.8-2.0 V) with detectable lithiation of both the buried Ni/NiO interface and the outer NiO surface that occur prior to the reaction of the NiO film. This initial conversion reaction is most pronounced in ultrathin NiO films (∼20 Å) with only small changes to the NiO film surface for thicker films (∼67 Å). The limited reactivity of thicker NiO films probed using operando grazing incidence small-angle X-ray scattering (GISAXS) shows the growth of nanoparticles at the electrode/electrolyte interface during initial lithium ion insertion, with a 16-20 Å average radius. Ex situ X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning transmission electron microscopy/electron energy loss spectroscopy (STEM/EELS) confirm our conclusions about the morphological changes accompanying initial stage of lithiation in these conversion reaction electrodes. The present study reveals the interconnected challenges of solid-solid transitions, overpotentials, interfacial nucleation and kinetics, and transition metal dissolution in conversion-type electrodes that are critical for their use as electrodes in lithium-ion batteries.

Lithiation of multilayer Ni/NiO electrodes: criticality of nickel layer thicknesses on conversion reaction kinetics.

X-ray reflectivity and transmission electron microscopy (TEM) were used to characterize the morphological changes in thin film electrodes with alternating Ni and NiO layers during lithiation as a function of the Ni buffer layer thickness. Complete lithiation of the active NiO layers occurs only when the thickness of the Ni/NiO bilayers are less than 75 Å - a threshold value that is determined by the sum of the Ni quantity in the Ni/NiO bilayer of the multilayer stack. Thicker Ni/NiO bilayers present a kinetic barrier for lithium ion diffusion inside the stack resulting in partial lithiation of the multilayer electrodes in which only the top NiO layer lithiates. Lithiation of NiO layers in a multilayer stack also leads to an interface-specific reaction that is observed to increase the thicknesses of adjacent Ni layers by 3-4 Å and is associated with the formation of a low-density Li2O layer, corresponding to an interfacially-driven phase separation of the NiO. Rate dependent cyclic voltammetry studies reveal a linear relation between the peak current and scan rate suggesting that the lithiation kinetics are controlled by charge transfer resistance at the liquid-solid interface.

Structural Characterization of Aluminum (Oxy)hydroxide Films at the Muscovite (001)-Water Interface.

The formation of Al (oxy)hydroxide on the basal surface of muscovite mica was investigated to understand how the structure of the substrate controls the nucleation and growth of secondary phases. Atomic force microscopy images showed that solid phases nucleated on the surface initially as two-dimensional islands that were ≤10 Å in height and ≤200 Å in diameter after 16-50 h of reaction in a 100 µM AlCl3 solution at pH 4.2 at room temperature. High-resolution X-ray reflectivity data indicated that these islands were gibbsite layers whose basic unit is composed of a plane of Al ions octahedrally coordinated to oxygen or hydroxyl groups. The formation of gibbsite layers is likely favored because of the structural similarity between its basal plane and the underlying mica surface. After 700-2000 h of reaction, a thicker and continuous film had formed on top of the initial gibbsite layers. X-ray diffraction data showed that this film was composed of diaspore that grew predominantly with its [040] and [140] crystallographic directions oriented along the muscovite [001] direction. These results show the structural characteristics of the muscovite (001) and Al (oxy)hydroxide film interface where presumed epitaxy had facilitated nucleation of metastable gibbsite layers which acted as a structural anchor for the subsequent growth of thermodynamically stable diaspore grown from a mildly acidic and Al-rich solution.

A Comparison of Adsorption, Reduction, and Polymerization of the Plutonyl(VI) and Uranyl(VI) Ions from Solution onto the Muscovite Basal Plane.

X-ray scattering techniques [in situ resonant anomalous X-ray reflectivity (RAXR) and specular crystal truncation rods (CTR)] were used to compare muscovite (001) surfaces in contact with solutions containing either 0.1 mM plutonyl(VI) or 1 mM uranyl(VI) at pH = 3.2 ± 0.2, I(NaCl) = 0.1 M, as well as in situ grazing-incidence X-ray absorption near-edge structure (GI XANES) spectroscopy and ex situ alpha spectrometry. Details of the surface coverage are found to be very different. In the case of Pu, alpha spectrometry finds a surface coverage of 8.3 Pu/AUC (AUC = 46.72 Å2, the unit cell area), far in excess of the 0.5 Pu/AUC expected for ionic adsorption of PuO22+. GI XANES results show that Pu is predominantly tetravalent on the surface, and the CTR/RAXR results show that the adsorbed Pu is broadly distributed. Taken together with previous findings, the results are consistent with adsorption of Pu in the form of Pu(IV)-oxo-nanoparticles. In contrast, uranyl shows only negligible, if any, adsorption according to all methods applied. These results are discussed and compared within the context of known Pu and U redox chemistry.

Replacement of Calcite (CaCO3) by Cerussite (PbCO3).

The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here, we report a study of the bulk transformation of single-crystal calcite (CaCO3) into polycrystalline cerussite (PbCO3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development of ∼100 nm wide pores parallel to calcite c-glide or (12̅0) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.

Full-field X-ray reflection microscopy of epitaxial thin-films.

Novel X-ray imaging of structural domains in a ferroelectric epitaxial thin film using diffraction contrast is presented. The full-field hard X-ray microscope uses the surface scattering signal, in a reflectivity or diffraction experiment, to spatially resolve the local structure with 70 nm lateral spatial resolution and sub-nanometer height sensitivity. Sub-second X-ray exposures can be used to acquire a 14 µm × 14 µm image with an effective pixel size of 20 nm on the sample. The optical configuration and various engineering considerations that are necessary to achieve optimal imaging resolution and contrast in this type of microscopy are discussed.

Incorporation of Pb at the calcite (104)-water interface.

Lead (Pb) is a common environmental pollutant, and its transport in surface waters and groundwater is controlled in part by sorption and precipitation reactions at mineral surfaces. Using in situ specular and resonant anomalous X-ray reflectivity measurements, we investigated the interaction of the calcite (104) surface with a dilute Pb- and EDTA-bearing solution that is slightly undersaturated with respect to calcite. The X-ray results reveal Pb coherently substituting for Ca in the near-surface layers of strained calcite with Pb/(Pb + Ca) atom fractions as high as 0.28 in the outermost layer. The larger ionic radius of Pb(2+) relative to Ca(2+) is accommodated in calcite by vertical displacements of Pb relative to the Ca site. In situ atomic force microscopy images obtained during the reaction suggest that Pb incorporation below the surface occurs after initial dissolution followed by regrowth of a strained epitaxial Pb-rich calcite solid-solution at the calcite (104)-water interface. This process could produce a widespread host phase for Pb in groundwater aquifers and soil pore fluids.

Unraveling pH-Dependent Changes in Adsorption Structure of Uranyl on Alumina (012).

Mitigating uranium transport in groundwater is imperative for ensuring access to clean water across the globe. Here, in situ resonant anomalous X-ray reflectivity is used to investigate the adsorption of uranyl on alumina (012) in acidic aqueous solutions, representing typical UVI concentrations of contaminated water near mining sites. The analyses reveal that UVI adsorbs at two distinct heights of 2.4-3.2 and 5-5.3 Å from the surface terminal oxygens. The former is interpreted as the mixture of inner-sphere and outer-sphere complexes that adsorb closest to the surface. The latter is interpreted as an outer-sphere complex that shares one equatorial H2O with the terminal surface oxygen. With increasing pH, we observe an increasing prevalence of these outer-sphere complexes, indicating the enhanced role of the hydrogen bond that stabilizes adsorbed uranyl species. The presented work provides a molecular-scale understanding of sorption of uranyl on Al-based-oxide surfaces that has implications for environmental chemistry and materials science.

Visualizing the Internal Nanocrystallinity of Calcite Due to Nonclassical Crystallization by 3D Coherent X-Ray Diffraction Imaging.

The internal crystallinity of calcite is investigated for samples synthesized using two approaches: precipitation from solution and the ammonium carbonate diffusion method. Scanning electron microscopy (SEM) analyses reveal that the calcite products precipitated using both approaches have a well-defined rhombohedron shape, consistent with the euhedral crystal habit of the mineral. The internal structure of these calcite crystals is characterized using Bragg coherent diffraction imaging (BCDI) to determine the 3D electron density and the atomic displacement field. BCDI reconstructions for crystals synthesized using the ammonium carbonate diffusion approach have the expected euhedral shape, with internal strain fields and few internal defects. In contrast, the crystals synthesized by precipitation from solution have very complex external shapes and defective internal structures, presenting null electron density regions and pronounced displacement field distributions. These heterogeneities are interpreted as multiple crystalline domains, created by a nonclassical crystallization mechanism, where smaller nanoparticles coalescence into the final euhedral particles. The combined use of SEM, X-ray diffraction (XRD), and BCDI allows for structurally differentiating calcite crystals grown with different approaches, opening new opportunities to understand how grain boundaries and internal defects alter calcite reactivity.

Optimizing a flow-through X-ray transmission cell for studies of temporal and spatial variations of ion distributions at mineral-water interfaces.

The optimization of an X-ray transmission-cell design for high-resolution X-ray reflectivity measurements of the kinetics and thermodynamics of reactions at mineral-solution interfaces is presented. The transmission cell is equipped with a liquid flow system consisting of a pair of automated syringe pumps whose relative flow rates control the composition of a solution injected into the cell with ∼1% precision. The reflectivity measurements from the muscovite-(001)-solution interface at photon energies of 15-16.5 keV show that the cell is useful for probing interfacial ion adsorption-desorption experiments at a time scale of several seconds or slower. The time resolution is achieved with a small-volume (∼0.22 ml) reaction chamber to facilitate fast solution exchange. Additional reductions in reaction chamber volume will improve both the data quality by reducing X-ray absorption through the solution and the time resolution by increasing the solution exchange rate in the cell.

Systematic observations of enhanced oil recovery and associated changes at carbonate-brine and carbonate-petroleum interfaces.

Enhanced oil recovery (EOR) from carbonates is obtained by injection of controlled ionic strength brines containing "active ions" (e.g., SO42-, Mg2+, Ca2+). It is generally believed that this occurs through the interaction of the active ions at the carbonate-brine interface (e.g., within a thin brine layer separating the petroleum and the carbonate phases). Here, in-situ observations show how one active ion, SO42-, alters behavior at the carbonate-petroleum interface. Displacement of petroleum from initially oil-wet carbonate rocks using brines with variable SO4 concentrations systematically changes oil recovery, in situ contact angles, and connectivity of the oil phase, confirming that the active ion alters interactions at the oil/brine/carbonate interface, as expected. Measurements of model calcite-fluid interfaces show that there is no measurable sorption of SO4 to carbonate-brine interfaces but reveals that the carbonate-petroleum interface is altered by previous exposure to SO4-containing brines. These results suggest that EOR in carbonates is controlled indirectly by active ions. We propose that this may be due to a reduced oleophilicity of the carbonate caused by chemical complexation between the active ion and petroleum's acidic and basic functional groups. This mechanism explains how both anions and cations act as active ions for EOR in carbonates.

Monovalent ion adsorption at the muscovite (001)-solution interface: relationships among ion coverage and speciation, interfacial water structure, and substrate relaxation.

The interfacial structure between the muscovite (001) surface and aqueous solutions containing monovalent cations (3 × 10(-3) m Li(+), Na(+), H(3)O(+), K(+), Rb(+), or Cs(+), or 3 × 10(-2) m Li(+) or Na(+)) was measured using in situ specular X-ray reflectivity. The element-specific distribution of Rb(+) was also obtained with resonant anomalous X-ray reflectivity. The results demonstrate complex interdependencies among adsorbed cation coverage and speciation, interfacial hydration structure, and muscovite surface relaxation. Electron-density profiles of the solution near the surface varied systematically and distinctly with each adsorbed cation. Observations include a broad profile for H(3)O(+), a more structured profile for Li(+) and Na(+), and increasing electron density near the surface because of the inner-sphere adsorption of K(+), Rb(+), and Cs(+) at 1.91 ± 0.12, 1.97 ± 0.01, and 2.26 ± 0.01 Å, respectively. Estimated inner-sphere coverages increased from ~0.6 to 0.78 ± 0.01 to ~0.9 per unit cell area with decreasing cation hydration strength for K(+), Rb(+), and Cs(+), respectively. Between 7 and 12% of the Rb(+) coverage occurred as an outer-sphere species. Systematic trends in the vertical displacement of the muscovite lattice were observed within ~40 Å of the surface. These include a <0.1 Å shift of the interlayer K(+) toward the interface that decays into the crystal and an expansion of the tetrahedral-octahedral-tetrahedral layers except for the top layer in contact with solution. The distortion of the top tetrahedral sheet depends on the adsorbed cation, ranging from an expansion (by ~0.05 Å vertically) in 3 × 10(-3)m H(3)O(+) to a contraction (by ~0.1 Å) in 3 × 10(-3) m Cs(+). The tetrahedral tilting angle in the top sheet increases by 1 to 4° in 3 × 10(-3) m Li(+) or Na(+), which is similar to that in deionized water where the adsorbed cation coverages are insufficient for full charge compensation.

Water Adsorption on Mica Surfaces with Hydrophilicity Tuned by Counterion Types (Na, K, and Cs) and Structural Fluorination.

The stability of adsorbed water films on mineral surfaces has far-reaching implications in the Earth, environmental, and materials sciences. Here, we use the basal plane of phlogopite mica, an atomically smooth surface of a natural mineral, to investigate water film structure and stability as a function of two features that modulate surface hydrophilicity: the type of adsorbed counterions (Na, K, and Cs) and the substitution of structural OH groups by F atoms. We use molecular dynamics simulations combined with in situ high-resolution X-ray reflectivity to examine surface hydration over a range of water loadings, from the adsorption of isolated water molecules to the formation of clusters and films. We identify four regimes characterized by distinct adsorption energetics and different sensitivities to cation type and mineral fluorination: from 0 to 0.5 monolayer film thickness, the hydration of adsorbed ions; from 0.5 to 1 monolayer, the hydration of uncharged regions of the siloxane surface; from 1 to 1.5 monolayer, the attachment of isolated water molecules on the surface of the first monolayer; and for >1.5 monolayer, the formation of an incipient electrical double layer at the mineral-water interface.