Calcite-water Interface Research Articles

Experimental-Theoretical Approach to the Adsorption Mechanisms for Anionic, Cationic, and Zwitterionic Surfactants at the Calcite-Water Interface.

The adsorption of surfactants (DTAB, SDS, and CAPB) at the calcite-water interface was studied through surface zeta potential measurements and multiscale molecular dynamics. The ground-state polarization of surfactants proved to be a key factor for the observed behavior; correlation was found between adsorption and the hard or soft charge distribution of the amphiphile. SDS exhibits a steep aggregation profile, reaching saturation and showing classic ionic-surfactant behavior. In contrast, DTAB and CAPB featured diversified adsorption profiles, suggesting interplay between supramolecular aggregation and desorption from the solid surface and alleviating charge buildup at the carbonate surface when bulk concentration approaches CMC. This manifests as an adsorption profile with a fast initial step, followed by a metastable plateau and finalizing with a sharp decrease and stabilization of surface charge. Suggesting this competition of equilibria, elicited at the CaCO3 surface, this study provides atomistic insight into the adsorption mechanism for ionic surfactants on calcite, which is in accordance with experimental evidence and which is a relevant criterion for developing enhanced oil recovery processes.

Influence of surface conductivity on the apparent zeta potential of calcite

Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz–Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength⩽0.01M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite–water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model.

Visualizing Organophosphate Precipitation at the Calcite-Water Interface by in Situ Atomic-Force Microscopy.

Esters of phosphoric acid constitute a large fraction of the total organic phosphorus (OP) in the soil environment and, thus, play an important role in the global phosphorus cycle. These esters, such as glucose-6-phosphate (G6P), exhibit unusual reactivity toward various mineral particles in soils, especially those containing calcite. Many important processes of OP transformation, including adsorption, hydrolysis, and precipitation, occur primarily at mineral-fluid interfaces, which ultimately governs the fate of organophosphates in the environment. However, little is known about the kinetics of specific mineral-surface-induced adsorption and precipitation of organophosphates. Here, by using in situ atomic-force microscopy (AFM) to visualize the dissolution of calcite (1014) faces, we show that the presence of G6P results in morphology changes of etch pits from the typical rhombohedral to a fan-shaped form. This can be explained by a site-selective mechanism of G6P-calcite surface interactions that stabilize the energetically unfavorable (0001) or (0112) faces through step-specific adsorption of G6P. Continuous dissolution at calcite (1014)-water interfaces caused a boundary layer at the calcite-water interface to become supersaturated with respect to a G6P-Ca phase that then drives the nucleation and growth of a G6P-Ca precipitate. Furthermore, after the introduction of the enzyme alkaline phosphatase (AP), the precipitates were observed to contain a mixture of components associated with G6P-Ca, amorphous calcium phosphate (ACP)-hydroxyapatite (HAP) and dicalcium phosphate dihydrate (DCPD). These direct dynamic observations of the transformation of adsorption- and complexation-surface precipitation and enzyme-mediated pathways may improve the mechanistic understanding of the mineral-interface-induced organophosphate sequestration in the soil environment.

Mechanism of atomic force microscopy imaging of three-dimensional hydration structures at a solid-liquid interface

Here we present both subnanometer imaging of three-dimensional (3D) hydration structures using atomic force microscopy (AFM) and molecular dynamics simulations of the calcite-water interface. In AFM, by scanning the 3D interfacial space in pure water and recording the force on the tip, a 3D force image can be produced, which can then be directly compared to the simulated 3D water density and forces on a model tip. Analyzing in depth the resemblance between experiment and simulation as a function of the tip-sample distance allowed us to clarify the contrast mechanism in the force images and the reason for their agreement with water density distributions. This work aims to form the theoretical basis for AFM imaging of hydration structures and enables its application to future studies on important interfacial processes at the molecular scale.

A Weeks–Chandler–Andersen based potential fitting procedure for molecular dynamics simulations of the calcite–water interface

We propose a standardized potential fitting procedure capable of producing cross-term parameters required by classical molecular dynamic (MD) simulations of aqueous-mineral systems where pure species parameters for water, solutes and mineral are known. Unlike other approaches, our technique keeps the original pure-species partial charges intact and provides the short-range part of potential in cases when direct application of standard combination rules is not feasible. The procedure is based on Weeks–Chandler–Andersen potential splitting method with Barker–Henderson integration and yields effective hard-sphere diameter used as one of the fitting criteria. A set of water-calcite interaction parameters was produced and applied to model behaviour of water near 101¯4 calcite surface by means of MD. The water structure was compared to both high-resolution XR data [1,2] and previous MD studies using various force fields [3–6]. Our simulations featuring fitted cross term parameters were found to be in general agreement with experimental data and proven more successful in matching water density profiles and ordering than previously utilized force field due to Hwang et al. [4,3].

Thin-film-induced morphological instabilities over calcite surfaces.

Precipitation of calcium carbonate from water films generates fascinating calcite morphologies that have attracted scientific interest over past centuries. Nowadays, speleothems are no longer known only for their beauty but they are also recognized to be precious records of past climatic conditions, and research aims to unveil and understand the mechanisms responsible for their morphological evolution. In this paper, we focus on crenulations, a widely observed ripple-like instability of the the calcite-water interface that develops orthogonally to the film flow. We expand a previous work providing new insights about the chemical and physical mechanisms that drive the formation of crenulations. In particular, we demonstrate the marginal role played by carbon dioxide transport in generating crenulation patterns, which are indeed induced by the hydrodynamic response of the free surface of the water film. Furthermore, we investigate the role of different environmental parameters, such as temperature, concentration of dissolved ions and wall slope. We also assess the convective/absolute nature of the crenulation instability. Finally, the possibility of using crenulation wavelength as a proxy of past flows is briefly discussed from a theoretical point of view.

Electrolyte layering at the calcite(104)-water interface indicated by Rb(+)- and Se(VI) K-edge resonant interface diffraction.

Calcite-water interface reactions are of major importance in various environmental settings as well as in industrial applications. Here we present resonant interface diffraction results on the calcite(104)-aqueous solution interface, measured in solutions containing either 10 mmol L(-1) RbCl or 0.5 mmol L(-1) Se(VI). Results indicate that Rb(+) ions enter the surface adsorbed water layers and adsorb at the calcite(104)-water interface in an inner-sphere fashion. A detailed analysis based on specular and off-specular resonant interface diffraction data reveals three distinct Rb(+) adsorption species: one 1.2 Å above the surface, the second associated with surface adsorbed water molecules 3.2 Å above the surface, and the third adsorbed in an outer-sphere fashion 5.6 Å above the surface. A peak in resonant amplitude between L = 1.5 and L = 3.0 is interpreted as signal from a layered electrolyte structure. The presence of a layered electrolyte structure seems to be confirmed by data measured in the presence of Se(VI).

Adsorption of Aerosol-OT at the calcite/water interface – Comparison of the sodium and calcium salts

The adsorption of the surfactant Aerosol-OT (AOT) at the calcite–water interface has been investigated using batch adsorption isotherms and neutron reflection. The adsorption isotherms showed that NaAOT adsorption followed S-type adsorption behaviour with a maximum surface excess of 2.5mgm−2 but the method could not be used for the investigation of Ca(AOT)2 adsorption owing to the changes in the bulk phase behaviour of the solution. The surface excess, determined by neutron reflection at the critical micelle concentration (CMC), was 2.5mgm−2 for Ca(AOT)2 and 1.8mgm−2 for NaAOT. The time dependence of the NaAOT adsorption suggests a slow conversion from the sodium to the calcium salt of AOT at the calcite–water interface by binding calcium ions released from the slightly soluble calcite. The layer thickness in both cases was 35Å which indicates adsorption as bilayers or distorted micelles. At higher concentrations of NaAOT (∼10× CMC) adsorption of an AOT lamellar phase was evident from Bragg peaks in the specular reflection.To our knowledge, this is the first time that adsorption of a surfactant at the calcite–water interface has been investigated by neutron reflection. The technique provided significant new insight into the adsorption behaviour of AOT which would not have been accessible using traditional techniques.

The influence of kinetics on the oxygen isotope composition of calcium carbonate

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3−, CO32− and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite–water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Chemistry of the calcite/water interface: Influence of sulfate ions and consequences in terms of cohesion forces

Calcite suspensions are used to mimic the behavior of more complex cementitious systems. Therefore the characterization of calcite–water interface in strong alkaline conditions, through ionic adsorption, electrokinetic measurements, static rheology and atomic force microscopy is a prerequisite. Calcium, a potential determining ion for calcite, adsorbs specifically onto the weakly positively charged calcite surface in water. This leads to an increase of the repulsive electric double layer force and thus weakens the particle cohesion. Sulfate adsorption, made at constant calcium concentration and ionic strength, significantly increases the attractive interactions between the calcite particles despite its very low adsorption. This is attributed to a lowering of the electrostatic repulsion in connection with the evolution of the zeta potential. The linear relationship found between the yield stress and ζ2 proves that the classical DLVO theory applies for these systems, contrary to what was previously observed with C–S–H particles under the same conditions.

Is the Calcite–Water Interface Understood? Direct Comparisons of Molecular Dynamics Simulations with Specular X-ray Reflectivity Data

New insights into the understanding of calcite–water interface structure are obtained through direct comparisons of multiple classical molecular dynamics (MD) simulations with high-resolution specular X-ray reflectivity (XR) data. This set of comparisons, with four different state-of-the-art force fields (including two nonpolarizable, one polarizable, and one reactive force field), reveal new insights into the absolute accuracy of the simulated structures and the uniqueness of the XR-derived structural results. These four simulations, though qualitatively similar, have visibly distinct interfacial structures and are distinguished through a quantitative comparison of the XR signals calculated from these simulations with experimental XR data. The results demonstrate that the simulated calcite–water interface structures, taken as a whole, are not consistent with the XR data (i.e., within the precision and accuracy of the XR data). This disagreement is largely due to the simulated calcite interfacial structure. The simulated interfacial water profiles show a higher level of consistency with the XR data, but with substantially different levels of agreement, with the rigid-ion model (RIM) simulations showing semiquantitative agreement. Further comparisons of the structural parameters that describe the interfacial structure (derived from both the MD simulations and the XR data) provide further insight into the sources of differences between these two approaches. Using the new insights from the RIM simulations, new structures of the calcite–water interface consistent with both the experimental data and the simulation are identified and compared to recent results.

Direct Visualization of Single Ions in the Stern Layer of Calcite

Calcite is among the most abundant minerals on earth and plays a central role in many environmental and geochemical processes. Here we used amplitude modulation atomic force microscopy (AFM) operated in a particular regime to visualize single ions close to the (1014) surface of calcite in solution. The results were acquired at equilibrium, in aqueous solution containing different concentrations of NaCl, RbCl, and CaCl(2). The AFM images provide a direct and atomic-level picture of the different cations adsorbed preferentially at certain locations of the calcite-water interface. Highly ordered water layers at the calcite surface prevent the hydrated ions from directly interacting with calcite due to the energy penalty incurred by the necessary restructuring of the ions' solvation shells. Controlled removal of the adsorbed ions from the interface by the AFM tip provides indications about the stability of the adsorption site. The AFM results show the familiar "row pairing" of the carbonate oxygen atoms, with the adsorbed monovalent cations located adjacent to the most prominent oxygen atoms. The location of adsorbed cations near the surface appears better defined for monovalent ions than for Ca(2+), consistent with the idea that Ca(2+) ions remain further away from the surface of calcite due to their larger hydration shell. The precise distance between the different hydrated ions and the surface of calcite is quantified using MD simulation. The preferential adsorption sites found by MD as well as the ion residence times close to the surface support the AFM findings, with Na(+) ions dwelling substantially longer and closer to the calcite surface than Ca(2+). The results also bring new insights into the problem of the Stern and electrostatic double layer at the surface of calcite, showing that parameters such as the thickness of the Stern layer can be highly ion dependent.

Posner's cluster revisited: direct imaging of nucleation and growth of nanoscale calcium phosphate clusters at the calcite-water interface

Although many in vitro studies have looked at calcium phosphate (Ca–P) mineralization, they have not emphasized the earliest events and the pathway of crystallization from solvated ions to the final apatitic mineral phase. Only recently has it become possible to unravel experimentally the processes of Ca–P formation through a cluster-growth model. Here we use mineral replacement reactions by the interaction of phosphate-bearing solutions with calcite surfaces in a fluid cell of an atomic force microscope (AFM) and reveal that the mineral surface-induced formation of an apatitic phase proceeds through the nucleation and aggregation of nanosized clusters with dimensions similar to those of Posner's clusters, which subsequently form stable amorphous calcium phosphate (ACP) plates prior to the transformation to the final crystalline phase. Our direct AFM observations provide evidence for the existence of stable Posner's clusters even though no organic template is applied.

Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite–water interface

Calcite-water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity. Firstly, we employ classical Molecular Dynamics simulations of calcite surfaces containing an etch pit and a growth terrace, to show that the local environment in water around structurally different surface sites is distinct. In addition to observing the expected formation of more calcium-water interactions and hydrogen-bonds at lower-coordinated sites, we also observed subtle differences in hydrogen bonding around acute versus obtuse edges and corners. We subsequently used this information to refine the protonation constants for the calcite surface sites, according to the Charge Distribution MUltiSite Ion Complexation (CD-MUSIC) approach. The subtle differences in hydrogen bonding translate into markedly different charging behaviour versus pH, in particular for acute versus obtuse corner sites. The results show quantitatively that calcite surface reactivity is directly related to surface topography. The information obtained in this study is not only crucial for the improvement of existing macroscopic surface models of the reactivity of calcite towards contaminants, but also improves our atomic-level understanding of mineral-water interactions.

Probing adsorption of sodium poly(acrylate) at the calcite–water interface by ellipsometry

Null ellipsometry was used to investigate the adsorption of poly(acrylic acid) (PAA) in the form of sodium poly(acrylate) (NaPA) on polished calcite crystals in aqueous electrolytes at pH 9. The ellipsometric angles were converted into adsorbed mass with an optical layer model, which treats the surface roughness by introducing an additional surface layer. One finds that the adsorbed mass saturates near 4 mg/m 2. Higher values of specific adsorbed mass were also observed, and they can be explained with the precipitation of polyelectrolyte with calcium ions.

Formation of a ternary neptunyl(V) biscarbonato inner-sphere sorption complex inhibits calcite growth rate

Neptunyl, Np(V)O 2 +, along with the other actinyl ions U(VI)O 2 2+ and Pu(V,VI)O 2 (+,2+), is considered to be highly mobile in the geosphere, while interaction with mineral surfaces (inner- or outer-sphere adsorption, ion-exchange, and coprecipitation/structural incorporation) may retard its migration. Detailed information about the exact interaction mechanisms including the structure and stoichiometry of the adsorption complexes is crucial to predict the retention behavior in diverse geochemical environments. Here, we investigated the structure of the neptunyl adsorption complex at the calcite–water interface at pH 8.3 in equilibrium with air by means of low-temperature (15 K) EXAFS spectroscopy at the Np-L III edge. The coordination environment of neptunyl consists of two axial oxygen atoms at 1.87(± 0.01) Å, and an equatorial oxygen shell of six atoms at 2.51(± 0.01) Å. Two oxygen backscatterers at 3.50(± 0.04) Å along with calcium backscatterers at 3.95(± 0.03) Å suggest that neptunyl is linked to the calcite surface through two monodentate bonds towards carbonate groups of the calcite surface. Two additional carbon backscatterers at 2.94(± 0.02) Å are attributed to two carbonate ions in bidentate coordination. This structural environment is conclusively interpreted as a ternary surface complex, where a neptunyl biscarbonato complex sorbs through two monodentate carbonate bonds to steps at the calcite (104) face, while the two bidentately coordinated carbonate groups point away from the surface. This structural information is further supported by Mixed Flow Reactor (MFR) experiments. They show a significant decrease of the calcite growth rate in the presence of neptunyl(V), in line with blockage of the most active crystal growth sites, step and kink sites, by adsorption of neptunyl. Formation of this sorption complex constitutes an important retention mechanism for neptunyl in calcite-rich environments.

Structure and reactivity of the calcite–water interface

The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO 2 partial pressure. Changes in pH have only a weak effect in non-equilibrium solutions. The surface structure of (1 0 4)-faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ∼4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 ± 0.05 Å above surface calcium ions and the second layer at 3.24 ± 0.06 Å above the surface associated with surface carbonate ions. A Basic-Stern surface complexation model is developed to model observed zetapotentials, while only considering outer-sphere complexes of ions other than protons and hydroxide. The Basic-Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results.

Structure and reactivity of the dolomite (104)–water interface: New insights into the dolomite problem

The structure and reactivity of the dolomite (104)–water interface was probed in situ with high resolution X-ray reflectivity and surface force microscopy at room temperature. Measurements in stoichiometric solutions alternating between saturated and supersaturated (log IAP/K = 2.3) conditions show that the dolomite surface termination readily changes in response to solution composition, but these changes are self-limiting and partially irreversible. The freshly cleaved dolomite (104) surface in contact with the saturated solution has a stoichiometric termination, a distinct surface hydration layer and small surface structural displacements, similar to those observed previously at the calcite–water interface. After reaction with supersaturated solutions dolomite is terminated by a two-layer thick Ca-rich film with substantial structural displacements of the cations. With subsequent exposure to a saturated solution this surface was transformed to an interfacial structure different from the freshly cleaved surface, having a reduced density of the outermost surface layer and a Ca-rich second layer. These results provide new insight into the lack of dolomite growth in modern carbonate environments (i.e., the “dolomite problem”), suggesting that this behavior is associated with a combination of thermodynamic and kinetic factors, including (1) growth of compositionally modified epitaxial Ca X Mg 2− X (CO 3) 2 layers having thicknesses limited by lattice strain, (2) slow incorporation of Mg during layer growth, and (3) partial irreversibility of surface reactions.

Alginic acid conformations and the calcite–water interface

Alginic acid conformations and the calcite–water interface

The influence of pH on the kinetics, reversibility and mechanisms of Pb(II) sorption at the calcite-water interface

Pb(II) sorption experiments with calcite powders were conducted in suspensions equilibrated at atmospheric PCO 2(g) and ambient temperature at pH 7.3, 8.2 and 9.4. Pb fractional sorption was low at pH 7.3 and 9.4 relative to pH 8.2, and correlated well with PbCO 3 0 (aq) speciation. Desorption experiments conducted for initial sorption times ranging from 0.5 h to 12 d reveal an almost completely reversible process at pH 8.2, attributed to the dominance of an adsorption mechanism, with slight and pronounced irreversibility at pH 7.3 and 9.4 respectively. Similarities in X-ray absorption near edge spectra (XANES) for 24 h and 12 d pH 7.3 and 9.4 sorption samples indicate no effect of initial sorption time. Results from linear combination (LC) fits of XANES spectra for samples sorbed at pH 9.4 confirm ∼75% adsorbed and ∼25% coprecipitated components. The coprecipitated fraction was attributed to the non-exchangeable metal observed in desorption experiments. At pH 7.3, ∼95% adsorbed and ∼5% coprecipitated components were obtained. A comparison of results from desorption experiments and LC-XANES alludes to an irreversibly bound adsorbed component for the pH 9.4 12 d sorption sample. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis of pH 7.3 and 9.4 12 d sorption samples confirms the presence of both adsorbed and coprecipitated metal. At pH 7.3 a first-shell Pb-O bond length of 2.38 Å is intermediate between that of adsorbed (2.34 Å) and coprecipitated (2.51 Å) Pb. At pH 9.4, two first-shell Pb-O distances at 2.35 Å and 2.51 Å were obtained, indicative of the occurrence of both adsorption and coprecipitation and a larger coprecipitated fraction relative to that at pH 7.3, consistent with LC-XANES results. We propose that the disparity in the fraction of coprecipitated metal with pH may be linked to the ability of sorbed Pb to inhibit near-surface dynamic exchange of Ca and CO 3 species, which dictates step advance and retreat. Less effective inhibition of step motion at pH 9.4, due to lower fractional sorption, combined with highest rates of dynamic exchange results in a significant fraction of coprecipitated Pb at this pH. At low pH, though fractional sorption is also low, lower rates of exchange prohibit significant coprecipitation. At pH 8.2, effective inhibition of surface processes due to higher fractional sorption and lower rates of exchange compared to pH 7.3 and 9.4 preclude detectable coprecipitation. Other factors such as changes in surface speciation and solubility of the Pb-Ca solid solution with pH may also come into play. Overall, this study presents evidence for the influence of pH on Pb sorption mechanisms, and addresses the efficiency of Pb immobilization in calcitic systems.