John S. Loring

Rethinking Arsenate Coordination at the Surface of Goethite

A fundamental precept of geochemistry is that arsenate coordinates at mineral surfaces in a predominately bridging-bidentate fashion. We show that this is incorrect for the model system, arsenate adsorbed at the surface of goethite (alpha-FeOOH), using a combination of XRD, EXAFS, and IR spectroscopic results. We report the crystal structure of pentaamminecobalt(III) arsenate, which consists of monodentate-coordinated metal-arsenato complexes that have Co-As distances of only 3.25 A. This result implies that metal-arsenic distances are not diagnostic for the coordination mode of arsenate. We show that the K-edge EXAFS spectra of pentaamminecobalt(III) arsenate and arsenate-goethite surface complexes are strikingly similar, which suggests that arsenate could be coordinated at the goethite surface in a monodentate fashion. Refinements of the k(3)-weighted EXAFS spectra of arsenate adsorbed on goethite results in values of CN(As-Fe) between 0.8-1.1 (+/-0.7), and there is no evidence that the coordination mode of arsenate changes as a function of pH or arsenate surface coverage. We report IR spectra from the first simultaneous IR and potentiometric titration of arsenate adsorbed on deuterated goethite (alpha-FeOOD) in D(2)O, and we show for the first time the As-O stretching bands of arsenate-goethite surface complexes. We deduce that arsenate-goethite surface complexes are un-, singly, or doubly protonated, depending on pH, from a principal component analysis of the As-O stretching region and an interpretation of the Type-B OH stretching region. In summary, our cumulative results show that arsenate coordinates at the water-goethite interface in a predominately monodentate fashion. Furthermore, we find no evidence for bridging-bidentate coordination, which is a finding that impacts oxoanion bioavailability and challenges theories of mineral dissolution and surface complexation.

In Situ Molecular Spectroscopic Evidence for CO2 Intercalation into Montmorillonite in Supercritical Carbon Dioxide

The interaction of anhydrous supercritical CO(2) (scCO(2)) with both kaolinite and ~1W (i.e., close to but less than one layer of hydration) calcium-saturated montmorillonite was investigated under conditions relevant to geologic carbon sequestration (50 °C and 90 bar). The CO(2) molecular environment was probed in situ using a combination of three novel high-pressure techniques: X-ray diffraction, magic angle spinning nuclear magnetic resonance spectroscopy, and attenuated total reflection infrared spectroscopy. We report the first direct evidence that the expansion of montmorillonite under scCO(2) conditions is due to CO(2) migration into the interlayer. Intercalated CO(2) molecules are rotationally constrained and do not appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO(2) does not intercalate into kaolinite. The findings show that predicting the seal integrity of caprock will have complex dependence on clay mineralogy and hydration state.

In Situ Study of CO2 and H2O Partitioning between Na–Montmorillonite and Variably Wet Supercritical Carbon Dioxide

Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this study, in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy were used to investigate the swelling/shrinkage and H2O/CO2 sorption of Na(+)-exchanged montmorillonite, Na-SWy-2, as the clay is exposed to variably hydrated supercritical CO2 (scCO2) at 50 °C and 90 bar. Measured d001 values increased in stepwise fashion and sorbed H2O concentrations increased continuously with increasing percent H2O saturation in scCO2, closely following previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show H2O and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types of H2O and CO2 with distinct chemical environments. Based on the absorbance of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, the sorbed CO2 concentration increases dramatically at sorbed H2O concentrations from 0 to 4 mmol/g. Sorbed CO2 then sharply decreases as sorbed H2O increases from 4 to 10 mmol/g. With even higher sorbed H2O concentrations as saturation of H2O in scCO2 was approached, the concentration of sorbed CO2 decreased asymptotically. Two models, one involving space filling and the other a heterogeneous distribution of integral hydration states, are discussed as possible mechanisms for H2O and CO2 intercalations in montmorillonite. The swelling/shrinkage of montmorillonite could affect solid volume, porosity, and permeability of shales. Consequently, the results may aid predictions of shale caprock integrity in large-scale GCS as well as methane transmissivity in enhanced gas recovery operations.

Molecular Structures of Citrate and Tricarballylate Adsorbed on α-FeOOH Particles in Aqueous Suspensions

In this work, the adsorption of citric (2-hydroxypropane-1,2,3-tricarboxylic acid) and tricarballylic (propane-1,2,3-tricarboxylic acid) acids onto alpha-FeOOH (goethite) in aqueous suspensions was studied as a function of pH and total ligand concentration in 0.1 M NaCl at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The adsorption experiments were carried out as a series of batch experiments, and a newly developed simultaneous infrared and potentiometric titration technique was used to collect in situ infrared spectra with high signal-to-noise ratios. The high quality of the infrared spectra allowed analysis by means of two-dimensional correlation spectroscopy formalism that aided the resolution of pH-dependent spectral features. This has enabled the detection of two previously unidentified citrate-goethite surface complexes: one protonated species at low pH, and one inner sphere complex prevailing at high pH and coordinated via a combination of hydroxyl and carboxylate groups. In addition, an inner sphere complex involving only carboxylate coordination predominating at low pH and an outer sphere complex existing in the circumneutral pH region were identified. The behavior of tricarballylate parallels that of citrate, except no inner sphere surface complex is formed at high pH values, which is in accordance with the lack of an alpha-hydroxyl group. The comparison between citrate and tricarballylate reinforces previous observations showing that inner sphere surface complexes of pure carboxylates at water-iron oxide interfaces are suppressed at high pH values, where outer sphere species are relatively more predominant. It also shows that significant amounts of inner sphere surface complexes of carboxylates only seem to form in the basic pH region when the ligands contain complementary functional groups, such as the hydroxyl or amine groups.

A sniftirs study of the diffuse double layer at single crystal platinum electrodes in acetonitrile

Abstract In situ reflection infrared spectroscopy with electrochemical modulation has been used to investigate the structure of the double layer for the system: Pt(hkl)/acetonitrile. The electrolytes used were tetraethylammonium perchlorate and sodium perchlorate. It has been found that acetonitrile is preferentially chemisorbed on the surface either through the non-bonding electrons on the nitrogen atom at potentials positive of the point of zero charge, or on its side in a rehybridized form at negative potentials. The transition between these orientations can be followed by the present technique. The experiments were also used to study the accumulation of solvated cations in the double layer. The spectroscopic data are discussed with respect to the orientation of the solvent and location of the electrolyte ions in the double layer.

Adsorption, desorption, and surface-promoted hydrolysis of glucose-1-phosphate in aqueous goethite (α-FeOOH) suspensions.

Adsorption, desorption, and precipitation reactions at environmental interfaces govern the fate of phosphorus in terrestrial and aquatic environments. Typically, a substantial part of the total pool of phosphorus consists of organophosphate, and in this study we have focused on the interactions between glucose-1-phosphate (G1P) and goethite (α-FeOOH) particles. The adsorption and surface-promoted hydrolysis reactions have been studied at room temperature as a function of pH, time, and total concentration of G1P by means of quantitative batch experiments in combination with infrared spectroscopy. A novel simultaneous infrared and potentiometric titration (SIPT) technique has also been used to study the rates and mechanisms of desorption of the surface complexes. The results have shown that G1P adsorption occurs over a wide pH interval and at pH values above the isoelectric point of goethite (IEP(goethite) = 9.4), indicating a comparatively strong interaction with the particle surfaces. As evidenced by IR spectroscopy, G1P formed pH-dependent surface complexes on goethite, and investigations of both adsorption and desorption processes were consistent with a model including three types of surface complexes. These complexes interact monodentately with surface Fe but differ in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The apparent desorption rates were shown to be influenced by reaction pathways that include interconversion of surface species, which highlights the difficulty in determining the intrinsic desorption rates of individual surface complexes. Desorption results have also indicated that the molecular structures of surface complexes and the surface charge are two important determinants of G1P desorption rates. Finally, this study has shown that surface-promoted hydrolysis of G1P by goethite is base-catalyzed but that the extent of hydrolysis was small.

In situ infrared spectroscopic study of brucite carbonation in dry to water-saturated supercritical carbon dioxide.

In geologic carbon sequestration, whereas part of the injected carbon dioxide will dissolve into host brine, some will remain as neat to water saturated supercritical CO(2) (scCO(2)) near the well bore and at the caprock, especially in the short term life cycle of the sequestration site. Little is known about the reactivity of minerals with scCO(2) containing variable concentrations of water. In this study, we used high-pressure infrared spectroscopy to examine the carbonation of brucite (Mg(OH)(2)) in situ over a 24 h reaction period with scCO(2) containing water concentrations between 0% and 100% saturation, at temperatures of 35, 50, and 70 °C, and at a pressure of 100 bar. Little or no detectable carbonation was observed when brucite was reacted with neat scCO(2). Higher water concentrations and higher temperatures led to greater brucite carbonation rates and larger extents of conversion to magnesium carbonate products. The only observed carbonation product at 35 °C was nesquehonite (MgCO(3)·3H(2)O). Mixtures of nesquehonite and magnesite (MgCO(3)) were detected at 50 °C, but magnesite was more prevalent with increasing water concentration. Both an amorphous hydrated magnesium carbonate solid and magnesite were detected at 70 °C, but magnesite predominated with increasing water concentration. The identity of the magnesium carbonate products appears strongly linked to magnesium water exchange kinetics through temperature and water availability effects.

Highly mobile iron pool from a dissolution-readsorption process

Oxalate (C2O4 2-) acts synergistically on the dissolution of goethite (alpha-FeOOH) in the presence of siderophores that are secreted by plants and microorganisms to sequester iron. We report here the first in situ molecular-scale observations of synergistic ligand-promoted dissolution processes. We show that there are conditions under which oxalate promotes goethite dissolution, but dissolved Fe(III) concentrations do not increase because Fe(III)-oxalate complexes readsorb to the mineral surface. We demonstrate that these readsorbed Fe(III)-oxalate complexes are highly mobile, extremely reactive in the presence of uncomplexed siderophores, and responsible for the synergistic effects on the dissolution of goethite.

Rotor Design for High Pressure Magic Angle Spinning Nuclear Magnetic Resonance

High pressure magic angle spinning (MAS) nuclear magnetic resonance (NMR) with a sample spinning rate exceeding 2.1 kHz and pressure greater than 165 bar has never been realized. In this work, a new sample cell design is reported, suitable for constructing cells of different sizes. Using a 7.5 mm high pressure MAS rotor as an example, internal pressure as high as 200 bar at a sample spinning rate of 6 kHz is achieved. The new high pressure MAS rotor is re-usable and compatible with most commercial NMR set-ups, exhibiting low (1)H and (13)C NMR background and offering maximal NMR sensitivity. As an example of its many possible applications, this new capability is applied to determine reaction products associated with the carbonation reaction of a natural mineral, antigorite ((Mg,Fe(2+))(3)Si(2)O(5)(OH)(4)), in contact with liquid water in water-saturated supercritical CO(2) (scCO(2)) at 150 bar and 50°C. This mineral is relevant to the deep geologic disposal of CO(2), but its iron content results in too many sample spinning sidebands at low spinning rate. Hence, this chemical system is a good case study to demonstrate the utility of the higher sample spinning rates that can be achieved by our new rotor design. We expect this new capability will be useful for exploring solid-state, including interfacial, chemistry at new levels of high-pressure in a wide variety of fields.

Infrared spectra of phthalic acid, the hydrogen phthalate ion, and the phthalate ion in aqueous solution

The infrared spectra of a series of aqueous solutions containing phthalic acid (1,2-benzenedicarboxylic acid) and varying pH were examined using attenuated total reflection Fourier transform infrared spectroscopy and potentiometry. The basis spectra of phthalic acid, the hydrogen phthalate ion, and the phthalate ion were isolated using a factor analysis in which the absorbance of these species varies with pH and total phthalate concentration according to equilibrium and mass balance relations. Assignments of these basis spectra were made by comparison with spectra calculated ab initio. The conditional formation constants of phthalic acid and the hydrogen phthalate ion were determined at 25.0+/-0.1 degrees C in 0.6 M NaCl ionic media using infrared spectroscopy and in 1.5 M NaCl ionic media using both infrared spectroscopy and potentiometry.