Atomistic simulations of calcium aluminosilicate interfaced with liquid water.

The dissolution behavior of calcium aluminosilicate based glass fibers, such as stone wool fibers, is an important consideration in mineral wool applications for both the longevity of the mineral wool products in humid environments and limiting the health impacts of released and inhaled fibers from the mineral wool product. Balancing these factors requires a molecular-level understanding of calcium aluminosilicate glass dissolution mechanisms, details that are challenging to resolve with experiment alone. Molecular dynamics simulations are a powerful tool capable of providing complementary atomistic insights regarding dissolution; however, they require force fields capable of describing not-only the calcium aluminosilicate surface structure but also the interactions relevant to dissolution phenomena. Here, a new force field capable of describing amorphous calcium aluminosilicate surfaces interfaced with liquid water is developed by fitting parameters to experimental and first principles simulation data of the relevant oxide-water interfaces, including ab initio molecular dynamics simulations performed for this work for the wüstite and periclase interfaces. Simulations of a calcium aluminosilicate surface interfaced with liquid water were used to test this new force field, suggesting moderate ingress of water into the porous glass interface. This design of the force field opens a new avenue for the further study of calcium and network-modifier dissolution phenomena in calcium aluminosilicate glasses and stone wool fibers at liquid water interfaces.

First-principles prediction of critical micellar concentrations for ionic and nonionic surfactants.

The concentration of surfactant in solution for which micelles start to form, also known as critical micelle concentration is a key property in formulation design. The critical micelle concentration can be determined experimentally with a tensiometer by measuring the surface tension of a concentration series. In analogy with experiments, in-silico predictions can be achieved through interfacial tension calculations. We present a newly developed method, which employs first principles-based interfacial tension calculations rooted in COSMO-RS theory, for the prediction of the critical micelle concentration of a set of nonionic, cationic, anionic, and zwitterionic surfactants in water. Our approach consists of a combination of two prediction strategies for modelling two different phenomena involving the removal of the surfactant hydrophobic tail from contact with water. The two strategies are based on regular micelle formation and thermodynamic phase separation of the surfactant from water and both are required to take into account a wide range of polarity in the hydrophilic headgroup. Our method yields accurate predictions for the critical micellar concentration, within one log unit from experiments, for a wide range of surfactant types and introduces possibilities for first-principles based prediction of formulation properties for more complex compositions.

First-Principles Prediction of Surface Wetting.

We have developed a method for predicting the solvation contribution to solid-liquid interfacial tension (IFT) based on density functional theory and the implicit solvent model COSMO-RS. Our method can be used to predict wetting behavior for a solid surface in contact with two liquids. We benchmarked our method against measurements of contact angle from water-in-oil on silica wafers and a range of self-assembled monolayers (SAMs) with different compositions, ranging from oil-wet to water-wet. We also compared our predictions to literature data for wetting of a polydimethylsilane surface. By explicitly including deprotonation for silica surfaces and carboxylic acid SAMs, very good agreement was obtained with experimental data for nearly all surfaces. Poor agreement was found for amine-terminated SAMs, which could be the result of both method and model insufficiencies and impurities known to be present for such surfaces. Solid-liquid IFT cannot be measured directly, making predictions such as from our method all the more important.

Unstable, Super Critical CO2-Water Displacement in Fine Grained Porous Media under Geologic Carbon Sequestration Conditions.

In this study we investigated fluid displacement water with supercritical (sc) CO2 in chalk under conditions close to those used for geologic CO2 sequestration (GCS), to answer two main questions: How much volume is available for scCO2 injection? And what is the main mechanism of displacement over a range of temperatures? Characterization of immiscible scCO2 displacement, at the pore scale in the complex microstructure in chalk reservoirs, offers a pathway to better understand the macroscopic processes at the continuum scale. Fluid behavior was simulated by solving the Navier-Stokes equations, using finite-volume methods within a pore network. The pore network was extracted from a high resolution 3D image of chalk, obtained using X-ray nanotomography. Viscous fingering dominates scCO2 infiltration and pores remain only partially saturated. The unstable front, developed with high capillary number, causes filling of pores aligned with the flow direction, reaching a maximum of 70% scCO2 saturation. The saturation rate increases with temperature but the final saturation state is the same for all investigated temperatures. The higher the saturation rate, the higher the dynamic capillary pressure coefficient. A higher dynamic capillary pressure coefficient indicates that scCO2 needs more time to reach capillary equilibrium in the porous medium.

The mechanisms of crystal growth inhibition by organic and inorganic inhibitors.

Understanding mineral growth mechanism is a key to understanding biomineralisation, fossilisation and diagenesis. The presence of trace compounds affect the growth and dissolution rates and the form of the crystals produced. Organisms use ions and organic molecules to control the growth of hard parts by inhibition and enhancement. Calcite growth in the presence of Mg2+ is a good example. Its inhibiting role in biomineralisation is well known, but the controlling mechanisms are still debated. Here, we use a microkinetic model for a series of inorganic and organic inhibitors of calcite growth. With one, single, nonempirical parameter per inhibitor, i.e. its adsorption energy, we can quantitatively reproduce the experimental data and unambiguously establish the inhibition mechanism(s) for each inhibitor. Our results provide molecular scale insight into the processes of crystal growth and biomineralisation, and open the door for logical design of mineral growth inhibitors through computational methods.

The effect of solvation and temperature on the adsorption of small organic molecules on calcite.

We performed density functional theory calculations to investigate the effect of solvation and temperature on the adsorption of small organic molecules on calcite. The Conductor like Screening Model for Real Solvents (COSMO-RS) solvation model was used to describe a multicomponent mixture consisting of both hydrophobic and hydrophilic phases. The results demonstrate that the combination of solvation and temperature significantly influences adsorption, with the effect of temperature dominating over the effect of solvation. At 25 °C, carboxylic acids and methanol are stable on calcite with free energy of adsorption <0 in the hydrophobic phase. None of the molecules considered in this study remain on the surface in the hydrophilic phase.

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl- adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl- ions will co-adsorb, thereby changing the observed ordered surface structure.

Elements of Eoarchean life trapped in mineral inclusions.

Metasedimentary rocks from Isua, West Greenland (over 3,700 million years old) contain 13C-depleted carbonaceous compounds, with isotopic ratios that are compatible with a biogenic origin. Metamorphic garnet crystals in these rocks contain trails of carbonaceous inclusions that are contiguous with carbon-rich sedimentary beds in the host rock, where carbon is fully graphitized. Previous studies have not been able to document other elements of life (mainly hydrogen, oxygen, nitrogen and phosphorus) structurally bound to this carbonaceous material. Here we study carbonaceous inclusions armoured within garnet porphyroblasts, by in situ infrared absorption on approximately 10-21 m3 domains within these inclusions. We show that the absorption spectra are consistent with carbon bonded to nitrogen and oxygen, and probably also to phosphate. The levels of C-H or O-H bonds were found to be low. These results are consistent with biogenic organic material isolated for billions of years and thermally matured at temperatures of around 500 °C. They therefore provide spatial characterization for potentially the oldest biogenic carbon relics in Earth's geological record. The preservation of Eoarchean organic residues within sedimentary material corroborates earlier claims for the biogenic origins of carbon in Isua metasediments.

Predicting CO2-H2O Interfacial Tension Using COSMO-RS.

Knowledge about the interaction between fluids and solids and the interfacial tension (IFT) that results is important for predicting behavior and properties in industrial systems and in nature, such as in rock formations before, during, and after CO2 injection for long-term storage. Many authors have studied the effect of the environmental variables on the IFT in the CO2-H2O system. However, experimental measurements above CO2 supercritical conditions are scarce and sometimes contradictory. Molecular modeling is a valuable tool for complementing experimental IFT determination, and it can help us interpret results and gain insight under conditions where experiments are difficult or impossible. Here, we report predictions for CO2-water interfacial tension performed using density functional theory (DFT) combined with the COSMO-RS implicit solvent model. We predicted the IFT dependence as a function of pressure (0-50 MPa), temperature (273-383 K), and salinity (0-5 M NaCl). The results agree well with literature data, within the estimated uncertainty for experiments and for molecular dynamics (MD) simulations, suggesting that the model can be used as a fast alternative to time-consuming computational approaches for predicting the CO2-water IFT over a range of pressures, temperatures, and salinities.

A Microkinetic Model of Calcite Step Growth.

In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis.

Density functional theory with modified dispersion correction for metals applied to molecular adsorption on Pt(111).

We have performed density functional theory calculations using our modified DFT-D2 dispersion correction for metals to investigate adsorption of a range of molecules on Pt(111). The agreement between our calculations and experimental adsorption energies ranging from 0 to 3 eV was excellent with a mean absolute deviation of 0.19 eV and a maximum deviation of 0.37 eV. Our results show that the DFT-D2 semiempirical dispersion correction can provide accurate results also for describing adsorption on metals, provided that relevant physical properties of the system are taken into account, such as shorter ranged dispersion because of screening by the conducting electrons and a lower polarizability of the core electrons in metals compared to isolated atoms.

Modelling how incorporation of divalent cations affects calcite wettability-implications for biomineralisation and oil recovery.

Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

Specific ion effects on the hydrophobic interaction of benzene self-assembled monolayers.

The interaction of aromatic compounds with various ions in aqueous solutions plays a role in a number of fields, as diverse as protein folding and enhanced oil recovery, among others. Therefore, we have investigated the effect of the four electrolytes, KCl, NaCl, MgCl2 and CaCl2, on the hydrophobic interaction of benzene self-assembled monolayers. Using the jump to contact phenomenon of an atomic force microscope (AFM) tip as an indicator of attractive forces between the surfaces of a sample and the tip, we discovered lower frequencies in the snap in as well as narrower distributions for the snap in distance for the monovalent ions, especially for K(+), compared with the behaviour for the divalent ions. These observations are explained by the accumulation of charge at the surface by cation-π interactions and an influence of the ions on the formation of capillaries that bridge the tip to the surface. Bridging capillaries, i.e. nanometre scale gas bubbles, are some of the factors contributing to the long range hydrophobic interaction. The results demonstrate how ions influence the attraction of hydrophobic entities in aqueous solutions.

The effect of ionic strength on oil adhesion in sandstone--the search for the low salinity mechanism.

Core flood and field tests have demonstrated that decreasing injection water salinity increases oil recovery from sandstone reservoirs. However, the microscopic mechanism behind the effect is still under debate. One hypothesis is that as salinity decreases, expansion of the electrical double layer decreases attraction between organic molecules and pore surfaces. We have developed a method that uses atomic force microscopy (AFM) in chemical force mapping (CFM) mode to explore the relationship between wettability and salinity. We functionalised AFM tips with alkanes and used them to represent tiny nonpolar oil droplets. In repeated measurements, we brought our "oil" close to the surface of sand grains taken from core plugs and we measured the adhesion between the tip and sample. Adhesion was constant in high salinity solutions but below a threshold of 5,000 to 8,000 ppm, adhesion decreased as salinity decreased, rendering the surface less oil wet. The effect was consistent, reproducible and reversible. The threshold for the onset of low salinity response fits remarkably well with observations from core plug experiments and field tests. The results demonstrate that the electric double layer force always contributes at least in part to the low salinity effect, decreasing oil wettability when salinity is low.

Adhesion of alkane as a functional group on muscovite and quartz: dependence on pH and contact time.

The interactions between mineral surfaces and organic molecules in water control many processes in nature and in the production of modern materials. To improve the understanding of fluid-surface interactions, we investigated the interface behavior of quartz and muscovite, a model for clay minerals, in aqueous solutions where the pH and composition were controlled. We used atomic force microscopy (AFM) in chemical force mapping (CFM) mode to measure adhesion using tips functionalized with alkyl, -CH3. By combining adhesion forces measured as a function of pH, with data from streaming potential experiments and DLVO calculations, we were able to determine the surface charge density. We observed increased adhesion between the mineral surface and the hydrophobic tips as the contact time increased from 7 ms to ∼2 s. The diffusion of dissolved ions takes time, and density functional theory (DFT) calculations did not indicate a strong hydration of the mineral surfaces. Therefore, we interpret that the loss of ions from the confined space between the tip and sample is a likely explanation of the correlation between the dwell time and adhesion. The maximum adhesion increase with dwell time for muscovite, i.e., 400 ± 77 pN, was considerably larger than for quartz, 84 ± 15 pN, which fits with the different surface structure and composition of the two minerals. We propose two mechanisms to explain these results: (1) cations that are structured in the solution and on the surface remain associated at the tip-sample interface initially but diffuse away during extended contact time and (2) adventitious carbon, the organic material that comes spontaneously from air and solution, can diffuse to the tip-sample interface during contact. This material decreases the surface energy by aggregating near the alkyl tip and increases adhesion between the tip and sample.

Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths--do we observe the mineral surface?

We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

Incorporation of monovalent cations in sulfate green rust.

Green rust is a naturally occurring layered mixed-valent ferrous-ferric hydroxide, which can react with a range of redox-active compounds. Sulfate-bearing green rust is generally thought to have interlayers composed of sulfate and water. Here, we provide evidence that the interlayers also contain monovalent cations, using X-ray photoelectron spectroscopy and synchrotron X-ray scattering. For material synthesized with Na(+), K(+), Rb(+), or Cs(+), interlayer thickness derived from basal plane spacings correlates with the radius of the monovalent cation. In addition, sequential washing of the materials with water showed that Na(+) and K(+) were structurally fixed in the interlayer, whereas Rb(+) and Cs(+) could be removed, resulting in a decrease in the basal layer spacing. The incorporation of cations in the interlayer opens up new possibilities for the use of sulfate green rust for exchange reactions with both anions and cations: e.g., radioactive Cs.

Strontium, nickel, cadmium, and lead substitution into calcite, studied by density functional theory.

We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid interface, and into the second layer of the solid. This information can be used as an indicator for cation substitution in the bulk phase, such as for the uptake of toxic metals from the environment and the growth of secondary phases. In both the surface and in the second layer, Ni(2+), Cd(2+), and Pb(2+) substitute exothermically and Sr(2+) substitutes endothermically. Our results agree with published experimental data that demonstrate trace metal coprecipitation with calcite as a sink for Ni(2+), Cd(2+), and Pb(2+), whereas Sr(2+) has a distribution constant significantly smaller than 1. Ni(2+) substitution is favored at the mineral-fluid interface compared with bulk substitution, which also agrees with experimental data. Our results predict that Ni(2+), Cd(2+), and Pb(2+) form a stable solid solution with calcite. Successful prediction of the experimental results gives us confidence in our ability to predict the divalent cation preference for surfaces rather than for sites within the bulk crystal structure, which cannot be directly derived from experiment.

Predicting the pKa and stability of organic acids and bases at an oil-water interface.

We have used density functional theory and the implicit solvent model, COSMO-RS, to investigate how the acidity constant, pKa, of organic acids and bases adsorbed at the organic compound-aqueous solution interface changes, compared to its value in the aqueous phase. The pKa determine the surface charge density of the molecules that accumulate at the fluid-fluid interface. We have estimated the pKa by comparing the stability of the protonated and unprotonated forms of a series of molecules in the bulk aqueous solution and at an interface where parts of each molecule reside in the hydrophobic phase and the rest remains in the hydrophilic phase. We found that the pKa for acids is shifted by ∼1 pH unit to higher values compared to the bulk water pKa, whereas they are shifted to lower values by a similar amount for bases. Because this pKa shift is similar in magnitude for each of the molecules studied, we propose that the pKa for molecules at a water-organic compound interface can easily be predicted by adding a small shift to the aqueous pKa. This shift is general and correlates with the functional group. We also found that the relative composition of molecules at the fluid-fluid interface is not the same as in the bulk. For example, species such as carboxylic acids are enriched at the interface, where they can dominate surface properties, even when they are a modest component in the bulk fluid. For high surface concentrations of carboxylic acid groups at an interface, such as a self-assembled monolayer, we have demonstrated that the pKa depends on the degree of deprotonation through direct hydrogen bonding between protonated and deprotonated acidic headgroups.

First-Principles Prediction of Liquid/Liquid Interfacial Tension.

The interfacial tension between two liquids is the free energy per unit surface area required to create that interface. Interfacial tension is a determining factor for two-phase liquid behavior in a wide variety of systems ranging from water flooding in oil recovery processes and remediation of groundwater aquifers contaminated by chlorinated solvents to drug delivery and a host of industrial processes. Here, we present a model for predicting interfacial tension from first principles using density functional theory calculations. Our model requires no experimental input and is applicable to liquid/liquid systems of arbitrary compositions. The consistency of the predictions with experimental data is significant for binary, ternary, and multicomponent water/organic compound systems, which offers confidence in using the model to predict behavior where no data exists. The method is fast and can be used as a screening technique as well as to extend experimental data into conditions where measurements are technically too difficult, time consuming, or impossible.