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At least 19 records

Lattice-scale variations in viscosity are correlated with solution structure at mineral-water interfaces

At solid-liquid interfaces, the viscosity increases markedly from the bulk due to the collective interactions of ions and water molecules, influencing phenomena relevant to nanofluidics, colloidal dynamics, and electrochemistry. Here, in this study, we investigated dissipative forces at the boehmite-water interface using 3D atomic force microscopy. We observed an increase in interfacial solution viscosity, η, by 10-100-fold as the nanoprobe approached the surface in normal direction, with up to four oscillatory features showing average peaks of η/η bulk = 44-71. Moreover, the viscosity showed sub-nanometer variations within 0.5 nm from the interface, templated by the underlying crystal lattice and correlated with the interfacial solution structure. Beyond a near-wall region of approximately 1.2 nm, the dissipative response was comparable to that in bulk solution. Molecular dynamics simulations, along with statistical mechanical analyses, provided details on hydrodynamic structures near the interface. Specifically, the lattice-dependent dissipative responses are correlated with extensive hydrogen bonding by interfacial water molecules, which increased friction, particularly along the [001] direction. These results demonstrate how solution viscosity at mineral-water interfaces is anisotropic and correlated with the local solution structure, providing insights into the dynamics of nanocrystal attachment.

Viscosity↗

Variation in Cation Adsorption Mechanism Controlled by Chemical and Structural Heterogeneities at the Quartz (101)–Water Interface

Mineral–water interfacial reactions are central to chemical processes that control the fate of nutrients and contaminants in natural environments. Mineral surfaces commonly have complex structures and compositions whose impact on interfacial reactivity is poorly understood. Here, in this work, we investigated the effects of surface heterogeneities on Rb + sorption at the quartz (101)–10 mM RbCl solution interface at pH 9.8 using in situ high-resolution X-ray reflectivity. Two surface locales (i.e., Spots A and B) having distinct interfacial structures were chosen: Spot A was characterized by its low defect density (≤20% topmost Si vacancies) and Rb + adsorption occurred predominantly as an inner-sphere complex. In comparison, Spot B had a higher defect density (~50% vacancies) and was covered with poorly crystalline SiO 2 . A substantially larger Rb + uptake (i.e., 7-times higher coverage) was observed on this defective surface where Rb + incorporated in the vacancy sites (confirmed by density functional tight binding-based molecular dynamics simulations) or adsorbed directly on the disordered film. These results provide a direct quantification of how surface heterogeneity influences the geochemical behavior of mineral–water interfaces, in particular highlighting the important role of chemical and structural defects on the sorbate speciation and coverage at silicate mineral surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric Field Effects on Water and Ion Structure and Diffusion at the Orthoclase (001)–Water Interface

Understanding the electrochemical properties of mineral–water interfaces tends to rely upon electrical double layer (EDL) models, but these models are based on the assumption that electrostatic equilibrium is constantly maintained. In reality, interfacial reactions, ion diffusion, and their electrochemical signatures are based in nonequilibrium conditions of locally or globally imbalanced electrical fields where current EDL models have limited purview. In this work, we performed molecular dynamics (MD) simulations of the orthoclase (001) surface in contact with a 1 M NaCl aqueous solution under various electric fields, to explore the interplay between EDL structure and dynamics when perturbed by electric fields of different direction and strength, by confinement, and by different distributions of structural surface charge. The simulations showed that confinement between two opposing (001) surfaces led to the development of an induced field when the applied field was perpendicular to the surfaces and, as a result, to ionic diffusion coefficients that were independent of electric field strength. In contrast, when the applied field was parallel to the surfaces, confinement resulted in ionic diffusion coefficients that were more strongly dependent on the magnitude of the electric field than in bulk water. Differences in the density and distribution of aluminol groups on the two surfaces had a significant impact on how the interfacial structure and dynamics varied in the presence of an electric field. Notably, these differences resulted in an electro-osmotic flow with opposite directions at the two surfaces under parallel applied electric field. Overall, the MD simulations highlighted the importance of considering atomic-level structure and heterogeneities when developing models of the electrochemical properties of mineral–water interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BioGeoChemistry at Interfaces (LLNL SFA OBER FY22 Program Management and Performance Report)

The focus of the BioGeoChemistry at Interfaces SFA is to identify and quantify the biogeochemical processes and the underlying mechanisms that control actinide mobility in an effort to reliably predict and control the cycling and migration of actinides in the environment. The research approach includes: (1) Field Studies that capture actinide behavior on the timescale of decades (Research Thrust 1), and (2) Fundamental Laboratory Studies that isolate specific biogeochemical processes observed in the field (Research Thrust 2). These Research Thrusts are underpinned by the unique capabilities and staff expertise at Lawrence Livermore National Laboratory, allowing the BioGeoChemistry at Interfaces SFA to advance our understanding of actinide migration behavior in the environment, and serve as an resource for environmental radiochemistry research internationally. In the past year, our greater focus on transient redox gradients across stratified waters, sediment-water interfaces, and mineral-water interfaces extended our research beyond actinides to address processes controlling cycling of redox-sensitive metals more broadly. Nevertheless, Research Thrusts 1 and 2 are guided by the following broad central hypotheses that were developed during our last program review held at the end of FY18: Thrust 1 Hypothesis: Biogeochemical processes occurring on the timescale of years to decades lead to greater actinide recalcitrance in sediments and limits their migration in surface and groundwater. Thrust 2 Hypothesis: Long-term biogeochemical processes include mineral and surface alteration, which leads to stabilization of actinide surface associations or incorporation into mineral precipitates. Our strategic goal is to use the knowledge gained from our Science Plan to advance our understanding of the behavior of actinides and other radionuclides (e.g. Cs) and provide DOE with the scientific basis for remediation and long-term stewardship of DOE’s legacy sites. More broadly, we will enhance our understanding of transport phenomena in environmental systems sciences with a particular emphasis on environmentally relevant (long-term) timescales. While we retain our focus on actinide biogeochemistry, our increased focus on overall biogeochemical processes occurring at unique Test Bed locations associated with this SFA provides fundamental information on abiotic and biotic redox processes that control the cycling of redox sensitive metals under dynamic and transient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LLNL SFA OBER FY23 Program Management and Performance Report: BioGeoChemistry at Interfaces

The focus of the BioGeoChemistry at Interfaces SFA has been to identify and quantify the biogeochemical processes and the underlying mechanisms that control actinide mobility in an effort to reliably predict and control the cycling and migration of actinides in the environment. The research approach has included: (1) Field Studies that capture actinide behavior on the timescale of decades (Research Thrust 1), and (2) Fundamental Laboratory Studies that isolate specific biogeochemical processes observed in the field (Research Thrust 2). These Research Thrusts are underpinned by the unique capabilities and staff expertise at Lawrence Livermore National Laboratory, allowing the BioGeoChemistry at Interfaces SFA to advance our understanding of actinide migration behavior in the environment, and serve as a resource for environmental radiochemistry research internationally (Figure 1). In FY23, our SFA research focused on transient redox gradients across stratified waters, sediment-water interfaces, and mineral-water interfaces to address processes controlling cycling of redox-sensitive metals. Nevertheless, Research Thrusts 1 and 2 are guided by the following broad central hypotheses that were developed during our last program review held at the end of FY18: Thrust 1 Hypothesis: Biogeochemical processes occurring on the timescale of years to decades lead to greater actinide recalcitrance in sediments and limits their migration in surface and groundwater. Thrust 2 Hypothesis: Long-term biogeochemical processes include mineral and surface alteration, which leads to stabilization of actinide surface associations or incorporation into mineral precipitates. Our strategic goal is to use the knowledge gained from our Science Plan to advance our understanding of the behavior of actinides and other radionuclides (e.g. Cs) and provide DOE with the scientific basis for remediation and long-term stewardship of DOE’s legacy sites. More broadly, we are improving our understanding of transport phenomena in environmental systems sciences with a particular emphasis on environmentally relevant (long-term) timescales. While we retained some of our historical focus on actinide biogeochemistry this past fiscal year, biogeochemical processes occurring at unique Test Bed locations associated with this SFA provide fundamental information on abiotic and biotic redox processes that control the cycling of redox sensitive metals under dynamic and transient conditions. Furthermore, in collaboration with SFA teams at Argonne National Laboratory, our SFA has begun to transition away from the current research focus and develop a new research program in terrestrial wetland systems. The Terrestrial Wetland Function and Resilience SFA program plan will be delivered to the Environmental System Science (ESS) program within BER at the end of FY23.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Structure and Dynamics in Geochemical Systems

Neutron scattering is a powerful tool to elucidate the structure and dynamics of systems that are important to geochemists, including ion association in complex aqueous solutions, solvent-exchange reactions at mineral–water interfaces, and reaction and transport of fluids in nanoporous materials. This article focusses on three techniques: neutron diffraction, which can reveal the atomic-level structure of aqueous solutions and solids; quasi-elastic neutron scattering, which measures the diffusional dynamics at mineral–water interfaces; and small-angle neutron scattering, which can show how properties of nanoporous systems change during gas, liquid, and solute imbibition and reaction. Furthermore, the usefulness and applicability of the experimental results are extended by rigorous comparison to computational simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights

Despite decades of work on aqueous lead (Pb) adsorption on a-Fe2O3 (hematite) and a-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experimental for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001),(012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parametrized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experiment insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).

lead contamination↗

Distribution of nickel(II) ions adsorbed at the muscovite mica (001)-water interface determined by in-situ resonant anomalous X-ray reflectivity

Mineral-water interfaces mediate adsorption, ion exchange, and secondary mineral formation that control element mobility in natural and engineered systems. Reliable prediction and control of these processes require a fundamental understanding of the interfacial structure that links adsorbed ion speciation to macroscopic sorption capacity and strength. Here, we determine atomic-scale changes in hydration and distribution of Ni(II) at the muscovite mica (001)-water interface using in situ high-resolution X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR) at 1 mM NiCl2 and pH 5.7. XR reveals reorganization of the primary hydration structure relative to that in deionized water: the water layer adsorbed in the cavity sites at a height of ~1.3 Å disappears, while distinct solution layers emerge at ~2.3, ~4.1, and ~5.6 Å above the basal oxygen plane. RAXR resolves three interfacial Ni(II) species: a dominant outer-sphere complex at 3.65 Å (~80% of the total coverage), a minor inner-sphere complex at 0.75 Å, and a low-coverage, more distant outer-sphere species at 5.63 Å. These three adsorbed Ni(II) species account for a total Ni(II) coverage of 0.54 ± 0.02 ion per unit cell area that compensates for the surface charge. These results highlight the role of interfacial hydration in controlling the speciation and stability of adsorbate cations on the negatively charged mica surface, providing quantitative insight into predicting the geochemical behavior of divalent metal cations in the aqueous environments.

Lee, Sang Soo↗

Reactive force fields for aqueous and interfacial magnesium carbonate formation

Here we develop Mg/C/O/H ReaxFF parameter sets for two environments: an aqueous force field for magnesium ions in solution and an interfacial force field for minerals and mineral–water interfaces. Since magnesium is highly ionic, we choose to fix the magnesium charge and model its interaction with C/O/H through Coulomb, Lennard-Jones, and Buckingham potentials. We parameterize the forcefields against several crystal structures, including brucite, magnesite, magnesia, magnesium hydride, and magnesium carbide, as well as Mg 2+ water binding energies for the aqueous forcefield. Then, we test the forcefield for other magnesium-containing crystals, solvent separated and contact ion-pairs and single-molecule/multilayer water adsorption energies on mineral surfaces. We also apply the forcefield to the forsterite–water and brucite–water interface that contains a bicarbonate ion. We observe that a long-range proton transfer mechanism deprotonates the bicarbonate ion to carbonate at the interface. Free energy calculations show that carbonate can attach to the magnesium surface with an energy barrier of about 0.22 eV, consistent with the free energy required for aqueous Mg–CO 3 ion pairing. Also, the diffusion constant of the hydroxide ions in the water layers formed on the forsterite surface are shown to be anisotropic and heterogeneous. These findings can help explain the experimentally observed fast nucleation and growth of magnesite at low temperature at the mineral–water–CO 2 interface in water-poor conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of Electric Polarization and Relaxation of Ions at Humid Calcite Surfaces

Mobile ions at mineral surfaces can respond to an applied electric field, adopting a new distribution that effectively represents polarization of the electrical double layer. When the field is released, the ions relax to their equilibrium distribution. In both cases, the dynamics are characteristic of the interface. However, current models of electrokinetic phenomena are not sufficiently robust to accurately predict collective ion dynamics at structurally and chemically specific mineral–water interfaces. Here, in this study, we use electrostatic force microscopy (EFM) to investigate the dynamics of ion relaxation at hydrated calcite (104) surfaces at controlled relative humidity (RH). Electrically biased probes are used to polarize the distributions of calcium and carbonate ions that are intrinsic to this interface across a range of RH values. Polarization kinetics are tracked by monitoring the tip–sample force gradient during charging, and EFM imaging is used to characterize the spatial relaxation dynamics after the applied field is released. Electrostatic finite element modeling of the sample/probe system across length-scales from nanometers to millimeters reproduces the observed stretched exponential charging response. Together, these results allow us to estimate the ion diffusivities at the interface across a wide range of RH values. These diffusivities increase by roughly 5 orders of magnitude as the RH is increased from 5 to 90%, highlighting the critical role of adsorbed water for surface ion solvation that enables ion mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

dynamics of organic-mineral interactions at the metal oxide-solution interface as studied via binding energetics (Final report)

This project focused on addressing longstanding fundamental and experimental uncertainties on how dissolved organic substances (DOS) interact with metal oxide surface under environmentally relevant conditions. By leveraging a custom-built real-time, in-tandem flow adsorption microcalorimetry-UV-Vis/fluorescence spectroscopy platform, we characterized the binding energetics, kinetics and mechanistic pathways driving DOS-metal oxide interactions at temporal resolution on the order of 1-5 seconds. We studied a diverse suite of model organic compounds/substances – including monocarboxylates (e.g. acetate and benzoate), di-carboxylates (oxalate and succinate), amino acids, amino-based nanparticles and natural organic matter – interacting at the mineral-water interface of structurally- and/or chemically distinct metal oxides (including SiO2, boehmite, ferrihydrite, and γ-Al2O3). Our results indicated that DOS-metal oxide interactions are governed by multi-step reaction pathways, often switching between distinct, resolvable enthalpy- and entropy-driven non-electrostatic or electrostatic configurations. To quantify these interactions, we developed and implemented an analytical workflow that integrates peak deconvolution and Monte-Carlo based error propagation to determine site-specific thermodynamic and kinetic parameters for individual binding/debinding events. In addition to resolving apparent first-order rate constants of each event, we were able to quantify associated apparent equilibrium constants as well as free energy, enthalpy and entropy contribution to the activation and subsequent progression of the binding/debinding process across compounds, compound class and metal oxide surfaces. The kinetic-thermodynamic data produced in this study captured how the interplay between oxide surface reactivity and DOS molecular structure jointly drives binding-debinding dynamics. Notably, that at pH below PZC of the oxide surface, neutral species were heavily involved in monocarboxylate binding, while anionic species drove dicarboxylate binding. Also, that among amino acids 1) positional isomers show distinctive binding characteristics to each other while enantiomers show no significant differences in binding characteristics, 2) molecules that bind via outer-sphere complexation show a larger entropic shift between binding and debinding with no impact on oxide surface while 3) inner-sphere interactions increased anion exchange capacity of the oxide surface. The new insights and data from this work has great potential for improving predictive modeling of carbon dynamics and specifically organic-mineral interactions in environmental and industrial systems.

54 ENVIRONMENTAL SCIENCES↗

Facet‐dependent Heterogeneous Fenton Reaction Mechanisms on Hematite Nanoparticles for (Photo)catalytic Degradation of Organic Dyes

Although heterogeneous photo‐Fenton reactions on nanoparticulate iron oxides effectively degrade organic pollutants, the underlying surface mechanisms remain debated. Here, we demonstrate how these pathways are modulated by specific hematite crystal facets. To investigate the influence of particle surface structure, methylene blue (MB) adsorption and photodegradation kinetics are examined using facet‐engineered hematite nanoparticles with distinct exposed facets. The results reveal that MB photodegradation strongly depends on both pH and facet orientation. When normalized by surface area, (116) facet shows higher photodegradation activity than those with (104) or (001) facets. This enhanced activity is attributed to favorable electronic structure and surface characteristics, including a smaller optical bandgap, faster charge transfer, and superior H 2 O 2 decomposition. In contrast, the photodegradation capacity follows (104) 〉 (116) 〉 (001), primarily due to the higher density of surface‐active sites on the (104) facet. These sites promote coupled MB adsorption and degradation, enabling removal of a greater overall quantity of MB. Additionally, under high pH conditions, hematite can degrade MB in the dark, with capacities following (001) ≫ (116) 〉 (104). These findings underscore the critical catalytic role of specific hematite surfaces and advance the understanding of facet‐dependent photoinduced redox chemistry at mineral–water interfaces.

(photo)catalytic degradation↗

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. Further, 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.

54 ENVIRONMENTAL SCIENCES↗

Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling Evidence

The simultaneous sorption of cations and anions at the mineral–water interface can substantially alter their individual sorption characteristics; however, this phenomenon lacks a mechanistic understanding. Our study provides direct spectroscopic and modeling evidence of the molecular cosorption mechanisms of the cadmium ion (Cd 2+ ) and phosphate (P) on goethite and layered manganese (Mn) oxide of birnessite, through in situ attenuated total reflection Fourier-transform infrared (ATR-FTIR), P K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and surface complexation modeling. Phosphate synergistically cosorbed with Cd on goethite predominantly through P-bridged ternary complexes (≡Fe–P–Cd) and electrostatic interactions at wide pH conditions. Likewise, P and Cd exhibited synergistic cosorption on birnessite by forming P-bridged ternary complexes (≡Mn–P–Cd) and weak competitive sorption at the layer edge sites. As pH and Cd loading increased, the surface P species transitioned from a binary complex to a ternary complex and/or Cd 3 (PO 4 ) 2 precipitate for both goethite and birnessite. Compared to that in solution at pH 8, the formation of Cd 3 (PO 4 ) 2 was inhibited by the presence of goethite and birnessite, ascribed to the specific adsorption of P and Cd, more pronounced in birnessite due to the stronger sorption of Cd at its vacant sites. Finally, the discovered cosorption mechanisms of P and Cd have important implications for understanding and predicting their mobility and availability in Cd-contaminated settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and Dynamics of Aqueous Electrolytes at Quartz (001) and (101) Surfaces

Here, understanding and describing reactivity at mineral-water interfaces such as ion adsorption, the kinetics of dissolution, or surface charge development depends on our ability to improve the accuracy of electrical double layer (EDL) models. While molecular dynamics (MD) simulations are routinely used to investigate the structure and energetics of adsorbed ions comprising the EDL, less attention is paid to their self-diffusion dynamics, which can uniquely inform on coupling to interfacial reactions. Here we use MD to investigate both the organization and diffusion dynamics of water and electrolyte ions (NaCl, KCl, CaCl 2 ) at hydroxylated quartz (001) and (101) surfaces, a comparison which allowed us to assess surface structural effects of corrugation and silanol density. We found that inner- versus outer-sphere complex formation depends on cation size and charge but not necessarily hydration energies. Participation of surface silanols in the hydration spheres of Na + and K + generally indicated their preference for inner-sphere complexation, but this depends strongly on the orientation of the surface considered through its influence over the organization and dynamics of adsorbed water layers. In particular, surface orientation substantially affects the diffusive behavior of the near-surface water. Na + was found to decrease the mobility of water in the first layer, consistent with an increasing frequency of hydrolysis implied by faster quartz dissolution rates observed in experiments via the well known salt effect. Our results are also in good agreement with the observed dissolution rate of quartz vs. surface adsorption strength measure by Dove and Nix. This study sets the stage for a forthcoming paper examining how the dynamics at quartz/electrolyte interfaces are influenced by externally applied electric fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inorganic Hydrogeochemistry in the 21st Century

Abstract Chemical and isotopic processes occur in every segment of the hydrological cycle. Hydrogeochemistry—the subdiscipline that studies these processes—has seen a transformation from “witch's brew” to credible science since 2000. Going forward, hydrogeochemical research and applications are critical to meeting urgent societal needs of climate change mitigation and clean energy, such as (1) removing CO 2 from the atmosphere and storing gigatons of CO 2 in soils and aquifers to achieve net‐zero emissions, (2) securing critical minerals in support of the transition from fossil fuels to renewable energies, and (3) protecting water resources by adapting to a warming climate. In the last two decades, we have seen extensive activity and progress in four research areas of hydrogeochemistry related to water‐rock interactions: arsenic contamination of groundwater; the use of isotopic and chemical tracers to quantify groundwater recharge and submarine groundwater discharge; the kinetics of chemical reactions and the mineral‐water interface's control of contaminant fate and transport; and the transformation of geochemical modeling from an expert‐only exercise to a widely accessible tool. In the future, embracing technological advances in machine learning, cyberinfrastructure, and isotope analytical tools will allow breakthrough research and expand the role of hydrogeochemistry in meeting society's needs for climate change mitigation and the transition from fossil fuels to renewable energies.

Zhu, Chen (ORCID:0000000153746787)↗

Interfacial X-Ray Scattering from Small Surfaces: Adapting Mineral-Fluid Structure Methods for Microcrystalline Materials

Crystal truncation rod (CTR) X-ray diffraction is an invaluable tool for measuring mineral surface and adsorbate structures, and has been applied to several environmentally and geochemically important systems. Traditionally, the method has been restricted to single crystals with lateral dimensions >3 mm. Minerals that meet this size criterion represent a minute fraction of those that are relevant to interfacial geochemistry questions, however. Crystal screening, data collection, and CTR measurement methods have been developed for crystals of <0.3 mm in lateral size using the manganese oxide mineral chalcophanite (ZnMn 3 O 7 •3H 2 O) as a case study. Furthermore, this work demonstrates the feasibility of applying the CTR technique to previously inaccessible surfaces, opening up a large suite of candidate substrates for future study.

58 GEOSCIENCES↗

Nickel hydroxide–nickel carbonate competitive growth on carbonate surfaces

The thermodynamic and kinetic factors controlling the competitive heterogeneous nucleation and growth of ubiquitous metal carbonate and hydroxide phases are poorly understood. In this work, calcite (CaCO 3 ) and magnesite (MgCO 3 ) powders were reacted with NiCl 2 (0–600 μM) for 7 days at 22 °C and 5 °C. The reacted powders were analyzed with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to characterize the Ni surface precipitates formed. Evidence from these techniques pointed to the formation of mixed Ni carbonate-Ni hydroxide amorphous surface precipitates. On calcite, XPS detected primarily Ni(OH) 2 despite the initial solutions being more supersaturated with respect to gaspéite (NiCO 3 ) than to theophrastite (Ni(OH) 2 ) by a factor of 17–18. In contrast, NiCO 3 was the dominant component detected by XPS on magnesite in the same conditions. Decreasing the temperature had the effect of increasing the proportion of NiCO 3 to the detriment of Ni(OH) 2 . The experimental observations were consistent with low lattice/cation size mismatch favoring NiCO 3 nucleation and temperature most influencing Ni(OH) 2 nucleation. Comparison to previous work on Co-reacted powders indicated the differences in lattice/cation size mismatch and/or water exchange rate impacted the composition of the surface precipitates more than the relative thermodynamic stabilities of the competing minerals. This work explored the heterogeneous growth regime of Ni carbonate and hydroxide phases on carbonate surfaces and shed light on the factors that control the competition between surface precipitates when mineral surfaces are in contact with aqueous solutions supersaturated with respect to multiple mineral phases. In conclusion, these results contribute to geochemists’ efforts toward interpreting data from geochemical systems with elevated Ni concentrations, improving Ni environmental remediation and recovery strategies, and predicting the fate and transport of Ni in geochemical systems.

Heterogeneous nucleation↗