Search

The growth of lepidocrocite (γ-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104) surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology. [ABSTRACT FROM AUTHOR]

X-ray scattering techniques [in situ resonant anomalous X-ray reflectivity (RAXR) and specular crystal truncation rods (CTR)] were used to compare muscovite (001) surfaces in contact with solutions containing either 0.1 mM plutonyl(VI) or 1 mM uranyl(VI) at pH = 3.2 ± 0.2, I(NaCl) = 0.1 M, as well as in situ grazing-incidence X-ray absorption near-edge structure (GI XANES) spectroscopy and ex situ alpha spectrometry. Details of the surface coverage are found to be very different. In the case of Pu, alpha spectrometry finds a surface coverage of 8.3 Pu/AUC (AUC = 46.72 Ų, the unit cell area), far in excess of the 0.5 Pu/AUC expected for ionic adsorption of PuO22+. GI XANES results show that Pu is predominantly tetravalent on the surface, and the CTR/RAXR results show that the adsorbed Pu is broadly distributed. Taken together with previous findings, the results are consistent with adsorption of Pu in the form of Pu(IV)-oxo-nanoparticles. In contrast, uranyl shows only negligible, if any, adsorption according to all methods applied. These results are discussed and compared within the context of known Pu and U redox chemistry. [ABSTRACT FROM AUTHOR]

The formation of Al (oxy)hydroxide on the basal surface of muscovite mica was investigated to understand how the structure of the substrate controls the nucleation and growth of secondary phases. Atomic force microscopy images showed that solid phases nucleated on the surface initially as two-dimensional islands that were ≤10 Å in height and ≤200 Å in diameter after 16-50 h of reaction in a 100 μM AlCl3 solution at pH 4.2 at room temperature. High-resolution X-ray reflectivity data indicated that these islands were gibbsite layers whose basic unit is composed of a plane of Al ions octahedrally coordinated to oxygen or hydroxyl groups. The formation of gibbsite layers is likely favored because of the structural similarity between its basal plane and the underlying mica surface. After 700-2000 h of reaction, a thicker and continuous film had formed on top of the initial gibbsite layers. X-ray diffraction data showed that this film was composed of diaspore that grew predominantly with its [040] and [140] crystallographic directions oriented along the muscovite [001] direction. These results show the structural characteristics of the muscovite (001) and Al (oxy)hydroxide film interface where presumed epitaxy had facilitated nucleation of metastable gibbsite layers which acted as a structural anchor for the subsequent growth of thermodynamically stable diaspore grown from a mildly acidic and Al-rich solution. [ABSTRACT FROM AUTHOR]

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 Cu2+, Zn2+, and Pb2+ 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 Hg2+, Sr2+, and Ba2+ 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 (Ba2+ ≈ Sr2+ < Pb2+ < Hg2+). This trend is associated with differences in the sorption mechanism: Ba2+ and Sr2+ sorbed in the outer portion of the FA film whereas Pb2+ and Hg2+ complexed with FA effectively throughout the film. The more strongly hydrated Cu2+ and Zn2+ 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. [ABSTRACT FROM AUTHOR]

Evidence is increasing for the mobility and bioavailability of aqueous mercury(II) species being related to the interactions of mercury with dissolved organic matter (DOM). Here, we assess the relative roles of the mineral surface and DOM in controlling mercury(II) uptake at the muscovite (001)—solution interface using interface-specific X-ray reflectivity combined with element-specific resonant anomalous X-ray reflectivity. Experiments were performed with single crystals of muscovite and solutions of 100 mg/kg Elliott Soil Fulvic Acid II and 0.5-1 × 10-3 mol/kg Hg(NO3)2 at pH 2-12. Mercury(II) adsorbed from a 1 × 10-3 mol/kg Hg(II) solution at pH 2 without fulvic acid (FA) as inner- and outer-sphere complexes that compensated 55(4)% of the permanent negative charge of the muscovite surface. The remaining charge presumably was compensated by hydronium. The enhanced uptake of Hg(II) (compensating 128% of the muscovite surface charge) and FA (43% more adsorbed compared to the amount from a similar solution without Hg), along with a broader distribution of Hg(II) at the interface, occurred by adsorption from a premixed solution of 1 × 10-3 mol/kg Hg(NO3)2 and 100 mg/kg FA at pH 2. Adsorption of Hg(II) and FA, likely as complexes, decreased significantly as pH increased from 3.7 to 12 in solutions of 0.5 × 10-3 mol/kg Hg(NO3)2 and 100 mg/kg FA. Preadsorbed FA molecules provide different binding environments and stability for Hg(II) than dissolved FA, which may be attributed to conformational differences, fractionation, or kinetic effects in the presence of the mineral surface, at least at these relatively high concentrations of aqueous Hg(II). [ABSTRACT FROM AUTHOR]

Interfacial structures of the basal surface of muscovite mica in 100 mg kg −1Elliott 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 ≤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 Å as pH increased from 2 to 3.7 to 6, respectively. At pH ≥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. [ABSTRACT FROM AUTHOR]