Louise J. Criscenti

Elucidating the Bimodal Acid-Base Behavior of the Water-Silica Interface from First Principles

Understanding the acid-base behavior of silica surfaces is critical for many nanoscience and bionano interface applications. Silanol groups (SiOH) on silica surfaces exhibit two acidity constants-one as acidic as vinegar-but their structural basis remains controversial. The atomic details of the more acidic silanol site govern not just the overall surface charge density at near neutral solution pH but also how ions and biomolecules interact with and bind to silica immersed in water. Using ab initio molecular dynamics simulations and multiple representative crystalline silica surfaces, we determine the deprotonation free energies of silanol groups with different structural motifs. We show that previously proposed motifs related to chemical connectivity or intersilanol hydrogen bonds do not yield high acidity. Instead, a plausible candiate for pK(a) = 4.5 silanol groups may be found in locally strained or defected regions with sparse silanol coverage. In the process, irreversible ring-opening reactions of strained silica trimer rings in contact with liquid water are observed.

A molecular dynamics study of alkaline earth metal-chloride complexation in aqueous solution.

The relative stability of alkaline earth metals (M2+ = Mg2+, Ca2+, Sr2+, and Ba2+) and their chloride complexes in aqueous solution is examined through molecular dynamics simulations using a flexible SPC water model with an internally consistent set of metal ion force field parameters. For each metal-chloride ion pair in aqueous solution, the free energy profile was calculated via potential of mean force simulations. The simulations provide detailed thermodynamic information regarding the relative stability of the different types of metal-chloride pairs. The free energy profiles indicate that the preference for contact ion pair formation increases with ionic radius and is closely related to the metal hydration free energies. The water residence times within the first hydration shells are in agreement with residence times reported in other computational studies. Calculated association constants suggest an increase in metal-chloride complexation with increasing cation radii that is inconsistent with experimentally observed trends. Possible explanations for this discrepancy are discussed.

Assessing conceptual models for subsurface reactive transport of inorganic contaminants

In many subsurface situations where human health and environmental quality are at risk (e.g., contaminant hydrogeology petroleum extraction, carbon sequestration, etc.),scientists and engineers are being asked by federal agency decision-makers to predict the fate of chemical species under conditions where both reactions and transport are processes of first-order importance. In 2002, a working group (WG) was formed by representatives of the U.S. Geological Survey, Environmental Protection Agency, Department of Energy Nuclear Regulatory Commission, Department of Agriculture, and Army Engineer Research and Development Center to assess the role of reactive transport modeling (RTM) in addressing these situations. Specifically the goals of the WG are to (1) evaluate the state of the art in conceptual model development and parameterization for RTM, as applied to soil,vadose zone, and groundwater systems, and (2) prioritize research directions that would enhance the practical utility of RTM.

Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of a robust surface complexation database to estimate alkaline earth sorption in the environment.

Molecular simulations of carbon dioxide and water: cation solvation.

Proposed carbon dioxide sequestration scenarios in sedimentary reservoirs require investigation into the interactions between supercritical carbon dioxide, brines, and the mineral phases found in the basin and overlying caprock. Molecular simulations can help to understand the partitioning of metal cations between aqueous solutions and supercritical carbon dioxide where limited experimental data exist. In this effort, we used classical molecular dynamics simulations to compare the solvation of alkali and alkaline-earth metal cations in water and liquid CO(2) at 300 K by combining a flexible simple point charge model for water and an accurate flexible force field for CO(2). Solvation energies for these cations are larger in water than in carbon dioxide, suggesting that they will partition preferentially into water. In both aqueous and CO(2) solutions, the solvation energies decrease with cation size and increase with cation charge. However, changes in solvation energy with ionic radii are smaller in CO(2) than in water suggesting that the partitioning of cations into CO(2) will increase with ion size. Simulations of the interface between aqueous solution and supercritical CO(2) support this suggestion in that some large cations (e.g., Cs(+) and K(+)) partition into the CO(2) phase, often with a partial solvation sphere of water molecules.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.

Predicting the acidity constant of a goethite hydroxyl group from first principles

Accurate predictions of the acid-base behavior of hydroxyl groups at mineral surfaces are critical for understanding the trapping of toxic and radioactive ions in soil samples. In this work, we apply ab initio molecular dynamics (AIMD) simulations and potential-of-mean-force techniques to calculate the pK(a) of a doubly protonated oxygen atom bonded to a single Fe atom (Fe(I)OH(2)) on the goethite (101) surface. Using formic acid as a reference system, pK(a) = 7.0 is predicted, suggesting that isolated, positively charged groups of this type are marginally stable at neutral pH. Similarities and differences between AIMD and the more empirical multi-site complexation methodology are highlighted, particularly with respect to the treatment of hydrogen bonding with water and proton sharing among surface hydroxyl groups. We also highlight the importance of an electronic structure method that can accurately predict transition metal ion properties for goethite pK(a) calculations.

Temperature effects on alkaline earth metal ions adsorption on gibbsite: approaches from macroscopic sorption experiments and molecular dynamics simulations.

Two approaches, macroscopic adsorption experiments and molecular dynamics simulations, were employed to study the effect of temperature on alkaline earth metals adsorption on gibbsite surfaces. Increased reaction temperature enhanced the extent of metal ion adsorption for all of the alkaline earth metals studied. Whereas Mg(2+) and Sr(2+) adsorption displayed dependence on ionic strength, Sr(2+) adsorption exhibited less dependence on background ionic strength regardless of temperature. The ionic strength dependence was attributed to outer-sphere complexation reactions. The ionic strength effect on metal ion removal decreased with increasing temperature for both metals. Ba(2+) removal by gibbsite, on the other hand, was not affected by ionic strength. Results from molecular dynamics simulations were in agreement with the findings of the experimental study. The amount of thermal energy required to remove waters of hydration from the metal cation and the ratio of outer-sphere to inner-sphere complexation decreased with increasing ionic radii. It was observed from both macroscopic and molecular approaches that the tendency to form inner-sphere complexes on gibbsite decreased in the order: Ba(2+)>Sr(2+)>Mg(2+) and that the common assumption that alkaline earth metal ions form outer-sphere complexes appears to be dependent on ionic radius and temperature.

Sulfate adsorption at the buried hematite/solution interface investigated using total internal reflection (TIR)-Raman spectroscopy.

Sulfate adsorption at buried mineral/solution interfaces is of great interest in geochemistry and atmospheric aerosol chemistry due to the sulfate anions environmental ubiquity and the wide role of physical and chemical phenomena that it impacts. Here we present the first application of total internal reflection-Raman (TIR-Raman) spectroscopy, a surface sensitive spectroscopy, to probe sulfate ion behavior at the buried hematite/solution interface. Hematite is the most thermodynamically stable iron oxide polymorph and as such is widely found in nature. Our results demonstrate the feasibility of a TIR-Raman approach to study simple, inorganic anion adsorption at buried interfaces. Moreover, our data suggest that inner-sphere sulfate adsorption proceeds in a bidentate fashion at the hematite surface. These results help clarify long-standing questions as to whether sulfate forms inner-sphere adsorption complexes at hematite surfaces in a mono- or bidentate fashion based on attenuated total reflection-infrared (ATR-IR) observations. Our results are discussed with perspective to this debate and the applicability of TIR-Raman spectroscopy to address ambiguities of ion adsorption to mineral surfaces.

Surface Structure and Stability of Partially Hydroxylated Silica Surfaces

Surface energies of silicates influence crack propagation during brittle fracture and decrease with surface relaxation caused by annealing and hydroxylation. Molecular-level simulations are particularly suited for the investigation of surface processes. In this work, classical MD simulations of silica surfaces are performed with two force fields (ClayFF and ReaxFF) to investigate the effect of force field reactivity on surface structure and energy as a function of surface hydroxylation. An unhydroxylated fracture surface energy of 5.1 J/m2 is calculated with the ClayFF force field, and 2.0 J/m2 is calculated for the ReaxFF force field. The ClayFF surface energies are consistent with the experimental results from double cantilever beam fracture tests (4.5 J/m2), whereas ReaxFF underestimated these surface energies. Surface relaxation via annealing and hydroxylation was performed by creating a low-energy equilibrium surface. Annealing condensed neighboring siloxane bonds increased the surface connectivity, and decreased the surface energies by 0.2 J/m2 for ClayFF and 0.8 J/m2 for ReaxFF. Posthydroxylation surface energies decreased further to 4.6 J/m2 with the ClayFF force field and to 0.2 J/m2 with the ReaxFF force field. Experimental equilibrium surface energies are ∼0.35 J/m2, consistent with the ReaxFF force field. Although neither force field was capable of replicating both the fracture and equilibrium surface energies reported from experiment, each was consistent with one of these conditions. Therefore, future computational investigations that rely on accurate surface energy values should consider the surface state of the system and select the appropriate force field.