Volume 44 - Issue 2 - April 1996
Research Article
K Transfer during Burial Diagenesis in the Mahakam Delta Basin (Kalimantan, Indonesia)
- Sylvie Furlan, Norbert Clauer, Sam Chaudhuri, Frédéric Sommer
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- 28 February 2024, pp. 157-169
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Progressively buried sandstones and shales of the Mahakam Delta Basin in Indonesia were studied. Mineralogical, morphological and K-Ar isotopic data were obtained for clay, mica and feldspar minerals. The data indicate that K necessary for the illitization of illite/smectite mixed-layer minerals was supplied mainly from K-feldspar alteration within the sandstones and from mica within the shales. Most of the K-feldspar alteration for both the shale and sandstone samples were observed outside the main zone of illitization, which is restricted to the upper 2000 m of sediment. The feldspar grains were altered below this depth for both lithologies. Therefore, illitization requires an open sedimentary system. This is in contrast to the illitization model for deeply buried shales of the Gulf Coast. That system is commonly assumed to be a closed K system.
Interaction of Trialkyl Phosphites with Montmorillonites
- G. Dios Cancela, E. Romero Taboada, F. J. Huertas, A. Hernández Laguna, F. Sánchez Rasero
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- 28 February 2024, pp. 170-180
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Complexes formed between montmorillonite, saturated in Li+, Na+, Mg2+, Ca2+, Co2+, Fe3+, Cu2+ and Zn2+, and trimethyl phosphites (TMP) and triethyl phosphites (TEP) were studied. In all of the cases, phosphites penetrate into the interlayer space of the montmorillonite and produce solvates whose basal spacing varies depending on the characteristics of the exchangeable cation. All the complexes with low basal spacing (Li+, Na+, Mg2+, Co2+ and Zn2+) are stable in vacuum, whereas those with high basal spacing, formed by the Ca2+ sample with TMP, and Ca2+ and Fe3+ samples with TEP are transformed into low basal spacing complexes in vacuum. The complexes with high basal spacing (Cu2+ sample with TMP and TEP) are stable in vacuum.
The TMP and TEP complexes stable in vacuum with low spacing are thermally destroyed in one or two stages with two loss maxima, as a result of partial burning of phosphite molecules. Those with high spacing (Cu2+) are destroyed in two stages; the first is probably the result of the transformation process from high to low spacing, as a consequence of the structural reorganization of the molecules which remain in the interlayer space, and the second, could be associated with the destruction of low spacing complexes.
The IR spectra show that the molecule and the cation are linked by the P of the phosphite, which produces a reinforcement of the other bonds in the molecule, caused by an inductive effect. The phosphite intercalation is accompanied by a partial isomerization of phosphite to phosphonate.
The heat of adsorption of phosphites shows that the molecule-cation bond is ion-dipole. In the Cu sample with trimethyl phosphite, this bond seems to be reinforced by retrodonation of electrons from copper to ligand. Finally, the possible disposition of phosphite molecules in the interlayer space is considered. For this purpose, ab initio calculations have been performed on the different conformers of the TMP molecule at 6–31G* and 6–31+G* basis sets.
Structural Transformations of Interstratified Illite-Smectites from Dolná Ves Hydrothermal Deposits: Dynamics and Mechanisms
- V. A. Drits, A. L. Salyn, V. Šucha
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- 28 February 2024, pp. 181-190
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Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.
Why Does Halloysite Roll?—A New Model
- Balbir Singh
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- 28 February 2024, pp. 191-196
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A model is presented to explain why tubular halloysite rolls in preference to tetrahedral rotation to correct misfit of the octahedral and tetrahedral sheets. It is shown that the rolling mechanism operates as it encounters significantly less resistance from Si-Si repulsion in comparison to tetrahedral rotation to correct the same amount of misfit. The model explains the observed and experimental rolling of planar kaolinites to form tubular halloysite upon hydration and exfoliation.
Study of a Commercial SiO2 Sol and Gel By Small Angle X-Ray Scattering: Effect of Sample Thickness and Interpretation by Means of Smoluchowski Scheme
- Yingnian Xu, Pang L. Hiew, Matthew Akira Kuppenstein, Yoshikata Koga
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- 28 February 2024, pp. 197-213
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Ludox HS SiO2 sols at high concentrations show a peak in small angle x-ray scattering (SAXS) reminiscent to a “structure.” The appearance of such a peak was found to depend crucially on the thickness of the sample cell used for SAXS measurements. The thinner the cell used, the more prominent the peak. When the thickness was larger than 2 mm, it was no longer observable. When sols were treated with activated charcoal powders (in order to remove a surfactant) the peak became less prominent.
For the cases where clear features for structure were absent (thick sample regime), the Smoluchowski scheme was utilized to study the nature of sols. Namely, the distribution of the Smoluchowski species were estimated by numerically calculating the size distribution of particles directly from SAXS data. The distribution was found basically bimodal, and the main distribution peak, particularly for dilute sols (less than 5 wt%), was consistent with primary particles of SiO2. The second distribution peak was strongly dependent on the concentration of SiO2 particles. The observed trend was that the higher the concentration of SiO2 particles, the more prominent the second distribution peak and the locus of the maximum tended to move toward a smaller value in diameter. This behavior of the second distribution peak of the Smoluchowski species is no doubt a manifestation of the interparticle correlation. The observation of such behavior may provide a convenient means to characterize sols with interparticle correlation. This method was also applied for characterizing gels formed when the pH values were altered.
57Fe Mössbauer Effect Study of Al-Substituted Lepidocrocites
- E. De Grave, G. M. da Costa, L. H. Bowen, U. Schwertmann, R. E. Vandenberghe
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- 28 February 2024, pp. 214-219
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Seven Al-containing lepidocrocite samples, γ-Fe1−xAlxOOH, prepared from FeCl2/Al(N03)3 solutions with initial Al/(Al + Fe) mole ratios Ci of 0.0025, 0.01, 0.025, 0.05, 0.075, 0.10 and 0.15 mol/mol, were examined by means of Mössbauer spectroscopy at room temperature (RT) and at various temperatures in the range of 8 to 80 K. The spectra at RT and 80°K consist of broadened quadrupole doublets and were analyzed in terms of a single doublet and of a model-independent quadrupole-splitting distribution, the latter yielding the best fit. The observed variations of the quadrupole-splitting parameters with increasing Ci are inconclusive as to whether the Al cations are substituting into the structure. The temperature at which the onset of magnetic ordering is reflected in the spectra, was measured by the thermoscan method with zero source velocity. A gradual shift from 50 K for Ci = 0.0025 mol/mol to 44 K for Ci = 0.10 mol/mol was observed for that temperature. As compared to earlier studies of Al-free γ-FeOOH samples with similar morphological characteristics, the fractional doublet area in the mixed sextet-doublet spectra at 35 K is significantly higher for the present lepidocrocites. This observation is ascribed to the substitution of Al cations into the lepidocrocite structure. A similar conclusion is inferred from the variation with Ci of the maximum-probability hyperfine field derived from the spectra recorded at 8 K and fitted with a model-independent hyperfine-field distribution. The magnetic results suggest that for the sample corresponding to Ci = 0.15 mol/mol, not all of the initially present Al has been incorporated into the structure.
Sorption Mechanisms of Lanthanum on Oxide Minerals
- Scott Fendorf, Mark Fendorf
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- 28 February 2024, pp. 220-227
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The retention of hazardous species, including many of the lanthanides, on soils and sediments is vital for maintaining environmental quality. In this study, high-resolution transmission electron microscopy (HRTEM) was used to identify surface precipitates of La and their degree of atomic ordering on oxides of Mn (birnessite), Fe (goethite) and Ti (rutile) over a pH range of 3 to 8. At pH >5.5, the aqueous concentration of La was fully depleted by all three metal-oxides. On birnessite, surface precipitation of La-hydroxide occurred at pH = 5 and appears to be the dominant sorption mechanism on this mineral. Surface precipitation was not observed on rutile or goethite until much higher pH values, 6.5 for rutile and 8.0 for goethite. Precipitation is thus correlated with the points of zero charge (PZC) of the minerals, 6.3 for rutile and 7.8 for goethite, and in each case was observed only at pH values above the PZC. Although La sorption was extensive on all of the minerals at the higher pHs, the depletion of La from solution by rutile and goethite at pH values well below the PZC indicates that the sorption mechanism differs from that on birnessite. While surface precipitation was found to be the dominant sorption mechanism of La on birnessite, surface complexation of monomelic or small multinuclear species appears to predominate in La retention on rutile and goethite at most commonly encountered pH values.
Dissolution of Hectorite in Inorganic Acids
- P. Komadel, J. Madejová, M. Janek, W. P. Gates, R. J. Kirkpatrick, J. W. Stucki
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- 28 February 2024, pp. 228-236
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The effect of acid type and concentration on the reaction rate and products of dissolution of hectorite in inorganic acids was investigated. The dissolution of hectorite in hydrochloric (HCl), nitric (HNO3) and sulphuric (H2SO4) acids was characterized using quantitative chemical analysis, infrared (IR) and multinuclear MAS NMR spectroscopies. The rate of dissolution increased with acid concentration and decreased in the order HCl ≥ HNO3 = H2SO4 at the same molar concentration. No differences were found in the reaction products of hectorite treated with the three acids. The rate of Li dissolution was slightly greater than that of Mg at lesser acid concentrations (0.25 M), indicating that protons preferentially attack Li octahedra. The gradual changes in the Si-O IR bands reflects the extent of hectorite dissolution. The analysis of 29Si MAS NMR spectra relative peak intensities with dissolution time and acid concentration provided direct dissolution rates for tetrahedral (Q3) Si. After acid dissolution, most Si was bound in a three dimensional framework site (Q4), but a substantial part also occurred in the Si(OSi)3OH (Q31OH) and Si(OSi)2(OH)2 (Q220H) environments. These three sites probably occur in a hydrous amorphous silica phase. Both AlJV and AlVt rapidly disappeared from 27Al MAS NMR spectra of the dissolution products with acid treatment. The changes in IR and MAS NMR spectra of hectorite due to acid dissolution are similar to those of montmorillonite.
Study of Nanocomposites Obtained by Carbonization of Different Organic Precursors within Taeniolite Matrices
- Teresa J. Bandosz, Karol Putyera, Jacek Jagiełło, James A. Schwarz
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- 28 February 2024, pp. 237-243
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The lithium form of taeniolite served as the molecular template for carbon nanocomposites. It was intercalated with hydroxy aluminum and hydroxy aluminum-zirconium cations. Aliquots of the inorganic matrices were saturated by furfuryl alcohol followed by its interlayer polymerization. The structures were heated at 973 K in nitrogen to carbonize the polymeric precursor. Additional materials were mixed with polypropylene glycol which was then carbonized within the mineral layers. The surface properties of the nanocomposites were studied by X-ray diffraction (XRD), DTA, SEM and sorption experiments (sorption of nitrogen). The results showed that structural properties of the derived materials depend on the inorganic matrix and organic precursor. The carbon-taeniolite nanocomposites derived from polyfurfuryl alcohol as a precursor were characterized by high carbon content and a high percentage of its surface area in micropores. A broad spectrum of surface characteristics of the final products were found, depending on the history of the sample.
Weathering of Chlorite in a Quartz-Chlorite Schist: I. Mineralogical and Chemical Changes
- Takashi Murakami, Hiroshi Isobe, Tsutomu Sato, Toshihiko Ohnuki
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- 28 February 2024, pp. 244-256
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The weathering of chlorite, one of the major minerals of the host rock in the uranium ore deposit at Koongarra, Australia, was examined by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), electron microprobe analysis, and transmission electron microscopy (TEM). The conversion sequence of chlorite weathering is: (1) chlorite; (2) chlorite/vermiculite intergrade (showing XRD responses to various treatments intermediate between those of chlorite and vermiculite); (3) interstratified chlorite and vermiculite; (4) vermiculite; and (5) kaolinite. This sequence may be more simply expressed as chlorite ⤒ vermiculite ⤒ kaolinite. The weathering finally changed chlorite into sub-micrometer to micrometer sized Fe minerals and kaolinite. The transformation of chlorite to vermiculite is chemically characterized by an Fe and Mg loss with a slight decrease in the Al/Si ratio. Mg continues to be released throughout the weathering. Fe minerals formed through chlorite weathering are located between chlorite and vermiculite domains (a few μm in size) at first, and then accumulated between grain boundaries, occasionally forming veins. The distribution of Fe minerals is suggestive of preferential pathways of water movement. The time-dependent nature of mineral alteration demonstrated in the present study must be taken into account for the quantitative estimation of radionuclide migration.
Tem Observations of Coherent Stacking Relations in Smectite, I/S and Illite of Shales: Evidence for MacEwan Crystallites and Dominance of 2M1 Polytypism
- Hailiang Dong, Donald R. Peacor
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- 28 February 2024, pp. 257-275
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TEM characterization of stacking relations in I/S of expanded shale samples from the Gulf Coast and Michigan Basin was carried out to address the issues of the degree of coherency and the nature of layer stacking sequences in smectite, I/S and illite. The two-dimensional lattice fringe images obtained from this study show that cross fringes are commonly observed to be continuous over at least 3–4 layers for smectite, 6–7 layers for ordered I/S and 9–10 layers for illite-rich I/S. This demonstrates that such sequences are coherent, or at least semi-coherent (in smectite) units (MacEwan crystallites). The observations demonstrate that so-called fundamental particles are fragments of MacEwan crystallites formed primarily as a result of disaggregation along weakly-bonded smectite interlayers. However, both 0k1 and h01 reflections may coexist in selected area electron diffraction (SAED) patterns. The frequency of occurrence of the coexistence in SAED patterns decreases in the order smectite, I/S and illite for Gulf Coast samples. This is consistent with the presence of turbostratically-related interfaces in packets of all of these materials. Therefore, any given layer sequence in smectite, ordered I/S and illite may have both turbostratic and coherent interfaces. The proportion of coherently-related layers increases with increasing proportion of illite-like layers. The concept of fundamental or elementary particles is not related to layer sequences in non-disaggregated, original rocks. Indeed, it implies relations that are not valid.
The lattice fringe images, SAED and optical diffraction patterns demonstrate that where layers are coherently-related, 2M1 is the dominant polytypic sequence in all samples. However, this periodic 2M1 stacking is so frequently interrupted by stacking faults in smectite that it gives rise to apparent lMd polytypism. The degree to which the periodic 2M1 sequences are interrupted by stacking faults decreases with increasing proportion of illite-like layers. The SAED patterns of I/S and illite unmodified since its formation are diffuse parallel to c* and have poorly-defined, non-periodic reflections for indices k ≠ 3N as a measure of local ordering superimposed on poorly-ordered coherent sequences with a turbostratic component. X-ray diffraction (XRD) patterns, as integrated over domains with a range of heterogeneous stacking relations, do not represent simple mixtures of discrete IM and 2M1 polytypes.
The observations of this study imply that dissolution-crystallization is a dominant mechanism for the smectite-to-illite transition. The semi-coherent stacking of smectite-like layers in smectite-rich samples implies that either a dissolution-crystallization process took place subsequent to deposition of detrital smectite or that Gulf Coast smectite is an in-situ alteration product of volcanic ash.
Exchange Reactions in the Ca-Mg-Na-Montmorillonite System
- Giora Rytwo, Amos Banin, Shlomo Nir
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- 28 February 2024, pp. 276-285
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The exchange reactions of Na, Ca and Mg on montmorillonite are revisited employing recently developed analytical and theoretical approaches. The fractional adsorption of the cations has been determined by displacing them from the adsorbed state in one step, using a low concentration of an organic cation of large binding affinity. The analysis of displaced and solution cations employed inductively coupled plasma emission spectrometry. An adsorption model was employed in the analysis of the data. The procedure consists of solving the electrostatic Gouy-Chapman equations and calculating adsorbed amounts of the cations as the sum of the cations residing in the double layer region, and the cations chemically bound to the surface, in a closed system. The model also accounts explicitly for cation complexation in solution. Thus the calculations also considered the adsorption of CaCl+ and MgCl+, which eliminated the apparent increase of the cation exchange capacity (CEC) with divalent cation concentration. The model could explain and yield predictions for our measured adsorbed amounts as well as previously published data, in the binary and ternary systems of Ca/Mg/Na, provided that the fraction of surface sites occupied by calcium did not exceed 0.4. For a larger coverage of surface sites by calcium, a fit of the experimental data required an order of magnitude increase in the binding coefficients of the divalent cations in the binary system Ca/Na and in the ternary system Ca/Mg/Na.
Goethite Dispersibility in Solutions of Variable Ionic Strength and Soluble Organic Matter Content
- A. C. Herrera Ramos, M. B. McBride
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- 28 February 2024, pp. 286-296
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The degree of flocculation of aqueous suspensions of microcrystalline goethite was measured in salts of monovalent, divalent and trivalent cations at pH 6.0–6.5 over a range of ionic strengths using light scattering measurements at 650 nm. Varying concentrations of soluble humic material as well as the organic ligands, salicylate and citrate, were tested for their effect on flocculation. It was found that KCl and NaCl induced flocculation at lower ionic strength than CaCl2, while AlCl3 favored dispersion at all ionic strengths tested. The simple organic ligands promoted flocculation at low concentration, with citrate having a more pronounced effect than salicylate. At higher concentrations, these ligands reversed their effect, inducing a more dispersed state of the oxide. The organic ligand effect on dispersibility was modified by the particular metal cation present, with Ca2+ being more conducive to flocculation than K+. Soluble humic materials affected goethite flocculation in a qualitatively similar way to that of the simple organic ligands, that is low concentrations favored flocculation while high concentrations induced dispersion. This dispersing effect was partially suppressed by the presence of Ca2+, and completely suppressed by Al3+. Thus, soluble humic substances at relatively high concentrations appear to have a marked dispersing effect on goethite in the absence of polyvalent cations, and a strongly flocculating effect in their presence.
The results can be explained qualitatively by a simple oxide surface charge model, in which chemi-sorption of multivalent cations or organic ligands alters the surface charge. Reactions that increase the magnitude of positive or negative surface charge favor dispersion, while those that reduce the magnitude of charge favor flocculation.