Changyong Park

Structure of the orthoclase (001)- and (010)-water interfaces by high-resolution x-ray reflectivity.

High-resolution in situ X-ray specular reflectivity was used to measure the structures of orthoclase (001) and (010) cleavage surfaces in contact with deionized water at 25°C. X-ray reflectivity data demonstrate a high degree of structural similarity between these two orthoclase-water interfaces. Both interfacial structures include cleavage along the plane of minimal bond breakage resulting in surfaces terminated by non-bridging oxygens; structured water within 5 A of the orthoclase surface (consisting of adsorbed species at the surface and layered water above the surface), with a featureless water profile beyond 5 A; substitution of outermost K+ ions by an oxygen containing species (presumably H3O+); and small structural displacements of the near surface atoms. The interfacial water structure, in comparison with recent results for other mineral-water interfaces, is intermediate between the minimal structure found at calcite-, barite-, and quartz-water interfaces and the more extensive structure found at the muscovite-water interface.

Orthoclase dissolution kinetics probed by in situ X-ray reflectivity: Effects of temperature, pH, and crystal orientation

Initial dissolution kinetics at orthoclase (001) and (010) cleavage surfaces were measured for ∼2 to 7 monolayers as a function of temperature using in situ X-ray reflectivity. The sensitivity of X-ray reflectivity to probe mineral dissolution is discussed, including the applicability of this approach for different dissolution processes and the range of dissolution rates (∼10−12 to 10−6 mol/m2/sec) that can be measured. Measurements were performed at pH 12.9 for the (001) surface and at pH 1.1 for the (001) and (010) surfaces at temperatures between 46 and 83°C. Dissolution at pH 12.9 showed a temperature-invariant process with an apparent activation energy of 65 ± 7 kJ/mol for the (001) cleavage surface consistent with previous powder dissolution results. Dissolution at pH 1.1 of the (001) and (010) surfaces revealed a similar process for both surfaces, with apparent activation energies of 87 ± 7 and 41 ± 7 kJ/mol, respectively, but with systematic differences in the dissolution process as a function of temperature. Longer-term measurements (five monolayers) show that the initial rates reported here at acidic pH are greater than steady-state rates by a factor of 2. Apparent activation energies at acidic pH differ substantially from powder dissolution results for K-feldspar; the present results bracket the value derived from powder dissolution measurements. The difference in apparent activation energies for the (001) and (010) faces at pH 1.1 reveals an anisotropy in dissolution kinetics that depends strongly on temperature. Our results imply a projected ∼25-fold change in the ratio of dissolution rates for the (001) and (010) surfaces between 25 and 90°C. The dissolution rate of the (001) surface is higher than that of the (010) surface above 51°C and is projected to be lower below this temperature. These results indicate clearly that the kinetics and energetics of orthoclase dissolution at acidic pH depend on crystal orientation. This dependence may reflect the different manifestation of the Al-Si ordering between the T1 and T2 tetrahedral sites at these two crystal faces and can be rationalized in terms of recent theoretical models of mineral dissolution.

Phasing of resonant anomalous X-ray reflectivity spectra and direct Fourier synthesis of element-specific partial structures at buried interfaces

A formalism for model-independent determination of element-specific partial structures at buried interfaces using the phase-dependent behavior of resonant anomalous X-ray reflectivity (RAXR) data is described. Each RAXR spectrum (i.e. reflectivity versus energy at a fixed momentum transfer near the absorption edge of interest) is uniquely constrained by the amplitude and phase of the resonant partial structure factor with pre-determined non-resonant total structure factor and anomalous dispersion corrections of the resonant species. The element-specific partial density distribution is then imaged by discrete Fourier synthesis with the partial structure factor. The utility of this approach is demonstrated in the comparison of Rb+ and Sr2+ distributions at muscovite (001)–aqueous solution interfaces derived by model-independent and model-dependent approaches. This imaging method is useful for rapid determination of complex buried interfacial structures where element-specific atomic distributions are poorly constrained by conventional X-ray reflectivity analysis.

Thermodynamics, interfacial structure, and pH hysteresis of Rb+ and Sr2+ adsorption at the muscovite (001)-solution interface.

The coverage and average height of adsorbed Rb+ and Sr2+ at the muscovite (001)-solution interface were measured with resonant anomalous X-ray reflectivity (RAXR) as a function of cation concentration (10-8 < [Sr2+] < 10(-1) m, 10-6 < [Rb+] < 10(-1) m at pH 5.5 and 3.5) and pH (1.5 to 5.5 at [Me(n+)] = 10(-3) m) without background electrolyte. At pH 5.5, Rb+ uptake approximately follows a Langmuir isotherm with deltaG(Rb)(o) = -23.5 +/- 4.0 kJ x mol(-1) and a saturation coverage of Tmax = 0.94 +/- 0.06 Rb+ per unit cell area, Auc = 46.72 A2, compensating the nominal surface charge density (1 e-/Auc). The Sr2+ isotherm has a saturation coverage of 0.47 +/- 0.05 Sr2+/Auc that also compensates the muscovites charge, but the adsorption edge is both more abrupt and shifted significantly to lower concentration than that for Rb+. The uptake of Sr2+ is consistent with a Frumkin isotherm with an intrinsic adsorption constant, deltaG(Sr)(o) = -28.8 +/- 6.0 kJ x mol(-1) and a correlation energy, gamma(Sr) = -7.2 +/- 3.7 kJ x mol(-1). The average height of each adsorbed cation, corresponding to inner-sphere dominant Rb+ and coexisting inner- and outer-sphere Sr2+ distributions, was independent of ion coverage at pH 5.5. At pH 3.5, the adsorption edges of both ions shift to higher cation concentration, indicating competition with hydronium, and the shifts are accompanied by an irreversible reduction in the saturation coverage. The inner-sphere dominant mode of Rb+ adsorption did not change at pH 3.5, while that of Sr2+ changed to an outer-sphere dominant distribution. Hysteresis in both the amount and height of the adsorbed ion was observed as a function of the direction in which pH was changed, indicating that the intrinsic surface charge density decreased after reaction with acidic solutions. These results suggest new and unexpected interrelationships among the distribution of adsorbed ions, competitive adsorption of hydronium, and surface charge density at the mineral-solution interface.

Structure of the fluorapatite (100)-water interface by high-resolution X-ray reflectivity

Abstract A complete understanding of the surface chemistry of the apatite-water system requires direct observation of the interfacial structure at the molecular scale. We report results for the structure of the apatite (100)-water interface obtained with high-resolution specular X-ray reflectivity from a natural growth surface of Durango fluorapatite. A uniform termination at the crystallographic unit-cell boundary was determined. An atomistic model of the interfacial structure is compared to the experimental results and optimized through non-linear least-squares fitting in which the structural parameters were selected to be both physically and chemically plausible. The best-fit structure includes a Ca- and/or F-deficient outermost surface, minimal structural relaxations of the near-surface apatite crystal, and the presence of a layered interfacial water structure exhibiting two distinct water layers. The height of the first water layer is 2.64(9) Å relative to the relaxed surface with 3.5(1.3) water molecules per surface unit-cell area (64.9 Å2). A second layer of adsorbed water is found 1.53(5) Å above the first layer, followed by a nearly featureless profile of the bulk liquid water. The layered structure of water is interpreted as being due to hydrogen bonding at the solid-water interface. The interfacial structure shows a strong similarity with the octacalcium phosphate structure projected along a surface normal direction.

Heavy Metal Sorption at the Muscovite (001)–Fulvic Acid Interface

The role of fulvic acid (FA) in modifying the adsorption mode and sorption capacity of divalent metal cations on the muscovite (001) surface was evaluated by measuring the uptake of Cu(2+), Zn(2+), and Pb(2+) from 0.01 m solutions at pH 3.7 with FA using in situ resonant anomalous X-ray reflectivity. The molecular-scale distributions of these cations combined with those previously observed for Hg(2+), Sr(2+), and Ba(2+) indicate metal uptake patterns controlled by cation-FA binding strength and cation hydration enthalpy. For weakly hydrated cations the presence of FA increased metal uptake by approximately 60-140%. Greater uptake corresponded with increasing cation-FA affinity (Ba(2+) ≈ Sr(2+) < Pb(2+) < Hg(2+)). This trend is associated with differences in the sorption mechanism: Ba(2+) and Sr(2+) sorbed in the outer portion of the FA film whereas Pb(2+) and Hg(2+) complexed with FA effectively throughout the film. The more strongly hydrated Cu(2+) and Zn(2+) adsorbed as two distinct outer-sphere complexes on the muscovite surface, with minimal change from their distribution without FA, indicating that their strong hydration impedes additional binding to the FA film despite their relatively strong affinity for FA.

Image contrast in X-ray reflection interface microscopy: comparison of data with model calculations and simulations

The contrast mechanism for imaging molecular-scale features on solid surfaces is described for X-ray reflection interface microscopy (XRIM) through comparison of experimental images with model calculations and simulated measurements. Images of elementary steps show that image contrast is controlled by changes in the incident angle of the X-ray beam with respect to the sample surface. Systematic changes in the magnitude and sign of image contrast are asymmetric for angular deviations of the sample from the specular reflection condition. No changes in image contrast are observed when defocusing the condenser or objective lenses. These data are explained with model structure-factor calculations that reproduce all of the qualitative features observed in the experimental data. These results provide new insights into the image contrast mechanism, including contrast reversal as a function of incident angle, the sensitivity of image contrast to step direction (i.e. up versus down), and the ability to maximize image contrast at almost any scattering condition defined by the vertical momentum transfer, Q(z). The full surface topography can then, in principle, be recovered by a series of images as a function of incident angle at fixed momentum transfer. Inclusion of relevant experimental details shows that the image contrast magnitude is controlled by the intersection of the reciprocal-space resolution function (i.e. controlled by numerical aperture of the condenser and objective lenses) and the spatially resolved interfacial structure factor of the object being imaged. Together these factors reduce the nominal contrast for a step near the specular reflection condition to a value similar to that observed experimentally. This formalism demonstrates that the XRIM images derive from limited aperture contrast, and explains how non-zero image contrast can be obtained when imaging a pure phase object corresponding to the interfacial topography.

Rb+ and Sr2+ Adsorption at the TiO2 (110)―Electrolyte Interface Observed with Resonant Anomalous X-ray Reflectivity

We report the vertical density profiles of Rb(+) and Sr(2+) at the rutile TiO(2)(110)-electrolyte interface for the following bulk electrolyte conditions, [Rb(+)] = 1 mM at pH 11 and [Sr(2+)] = 0.1 mM at pH 10.3, using X-ray reflectivity and resonant anomalous X-ray reflectivity. We find that Rb(+) specifically adsorbs with a coverage of 0.080 +/- 0.003 monolayer (ML) and a height of 3.72 +/- 0.03 A above the surface Ti-O plane. In comparison, Sr(2+) adsorbs with a coverage of 0.40 +/- 0.07 ML and an average height of 3.05 +/- 0.16 A, but with a significant vertical distribution width (0.35 +/- 0.02 A). The Sr(2+) distribution in the presence of a background electrolyte ([Na(+)] = 30 mM) was also investigated, and it is found that, while the ion height and coverage are unchanged within the uncertainties of the measurements, the width of the distribution is apparently increased in the presence of Na(+). Comparison is made with previous results, including XR and X-ray standing waves (XSW) measurements, and molecular dynamics simulations. Our results are in excellent agreement with a recently proposed multisite adsorption mechanism that suggests simultaneous adsorption in two inner-sphere adsorption geometries, the tetradentate and the bidentate sites.

Fulvic acid sorption on muscovite mica as a function of pH and time using in situ X-ray reflectivity.

Interfacial structures of the basal surface of muscovite mica in 100 mg kg (-1) Elliott Soil Fulvic Acid II solutions were investigated using in situ X-ray reflectivity. Molecular-scale variations in the thickness and internal structure of the fulvic acid (FA) film were observed and quantified as a function of pH (2-12) and reaction time (3-500 h at pH 3.7). At pH < or =6, the electron-density profile of the FA layer sorbed on the muscovite surface was composed of one near-surface peak followed by a broad peak that diminished in electron density with distance from the surface. The presence of the near-surface peak is attributed to condensation of FA molecules during sorption. The apparent thickness of the FA layer decreased from 12.3 to 7.2 to 6.4 A as pH increased from 2 to 3.7 to 6, respectively. At pH > or =8.5, a distinct interfacial structure was observed, consisting of sharper peaks similar to those previously observed for muscovite in the absence of FA. These peaks are most likely composed of smaller aqueous species, such as H 2O molecules, metal ion impurities from FA, and Na (+) from NaOH. The FA sorbed on the muscovite surface at pH 3.7 maintained a relatively constant thickness after 3 hours. However, the electron density of the near-surface FA peak increased by about 24% from 3 to 12 hours, and remained relatively constant from 12 to 500 hours. The electron density of the more distant part of the sorbed FA layer increased slightly after 12-50 hours of reaction but then decreased, and the broad peak flattened by 500 hours. Internal structural changes are possibly due to the slow sorption rate of FA molecules, or a fractionation effect, i.e., continuous subsitution of smaller FA molecules by larger FA molecules.

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

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