Volume 40 - Issue 1 - February 1992
Research Article
Site Occupancy in Nontronite Studied by Acid Dissolution and Mössbauer Spectroscopy
- Vittorio Luca, Dugald J. MacLachlan
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- 28 February 2024, pp. 1-7
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The dissolution of two Ca2+-exchanged nontronite samples has been studied in 10% HCl. Early acid-dissolution studies (Osthaus, 1954) have indicated that after two hours of dissolution most of the octahedral Fe3+ (VIFe3+) would be removed leaving mainly tetrahedral Fe3+ (IVFe3+) in the nontronite structure. In the present study, 57Fe Mössbauer spectra of acid-treated samples were recorded and fitted with two octahedral Fe3+ (2 × VIFe3+) and two octahedral and one tetrahedral (2 × VIFe3+, 1 × IVFe3+) doublet models. The Mössbauer spectra of acid-treated Garfield nontronite samples could be adequately fitted with two-doublet models but acid-treated Hohen Hagen nontronite samples could not. Isomer shift and quadrupole splitting values obtained from the two-doublet models corresponded to VIFe3+ and not IVFe3+, as was suggested by the Osthaus (1954) experiment. When an IVFe3+ doublet was included in the model used to fit the Mössbauer spectra of acid-treated Garfield nontronite samples, a slight increase in the intensity of the IVFe3+ doublet occurred with increasing dissolution, but this was much lower than indicated by Osthaus (1954). No trend in the intensity of the IVFe3+ doublet was observed for acid-treated Hohen Hagen nontronite. Therefore, acid treatment appears to remove VIFe3+ and IVFe3+ from the nontronite structure at about the same rate. Mössbauer spectroscopy, infrared spectroscopy and X-ray powder diffraction data indicate that the nontronite that remains undissolved following acid treatment is structurally similar to the untreated nontronite.
Influence of Climate on the Iron Oxide Mineralogy of Terra Rossa
- Valter Boero, Alessandra Premoli, Pietro Melis, Elisabetta Barberis, Enza Arduino
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- 28 February 2024, pp. 8-13
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Terra rossa samples were taken from the B horizons of soil profiles and from cracks within limestone in Italy. The average annual temperature (AAT) of the sites ranged from 8.4 to 20.3°C and the average annual precipitation (AAP) from 511 to 3113 mm, with either a 5–6 month water deficit or a large water surplus. Goethite and hematite were identified in all the samples. Under a moist (> 1700 mm AAP) and cool (13°C AAT) climate, a xeric, hematitic pedoenvironment was preserved by the well-litified carbonate rock. Hematite occurred in trace amounts, even with an AAT of 8.4°C and an AAP of 3300 mm, confirming the specific role of the hard limestone on the pedoclimate of terra rossa. The lowest mean crystallite dimension of goethite and hematite was found in the samples from the wettest sites, and in these samples hematite was nearly free of Al substitution. Rubification in terra rossa appeared to be due to the specific pedoenvironment. The hematite cannot be considered a relict phase formed under another climate. Illite and kaolinite were the main clay minerals in samples from xeric sites whereas more weathered clays, such as Al-interlayered vermiculite, occurred in cool, moist sites. We postulate that the processes of rubification and vermiculitization could have taken place at the same time.
Fast and Slow Phosphate Sorption by Goethite-Rich Natural Materials
- J. Torrent, U. Schwertmann, V. Barrón
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- 28 February 2024, pp. 14-21
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Although phosphate sorption by goethite and other less-abundant Fe oxides strongly influences the concentration of this anion in the soil solution and aquatic environments, relatively little is known on the P-sorption characteristics of natural goethites. For this reason, we examined the P-sorption capacity and time course of P sorption of 10 goethite-rich soil, ferricrete and lake ore samples, in which the content and nature of mineral impurities were unlikely to affect P sorption significantly. Phosphate sorption could be adequately described by a modified Freundlich equation including a time term. The amount of P sorbed after 1 day of equilibration at a concentration of 1 mg P/liter ranged widely (0.36–2.04 /μmol P/m2). The total P sorbed after 75 days of equilibration varied less, in relative terms (1.62–3.18 μmol P/m2), i.e., a higher slow sorption tended to compensate for a lower initial (fast) sorption. Total sorbed P (X̄ = 2.62, SD = 0.52 μmol P/m2) was similar to the sorption capacity of synthetic goethites, suggesting a common sorption mechanism and the predominance of one type of crystal face, which, according to previous transmission electron microscope observations, might be the (110).
The extent of the slow reaction correlated to the ratio between micropore surface area and total surface area, as well as to oxalate-extractable Fe, which is an estimation of the ferrihydrite content. Ferrihydrite impurities might affect the slow reaction by contributing to the microporosity of some samples. Silicate adsorbed on the surface of the goethites was readily desorbed during phosphate sorption and did not significantly affect the extent of the slow sorption process.
Saponite and Vermiculite in Amygdales of the Granby Basaltic Tuff, Connecticut Valley
- Richard H. April, Dianne M. Keller
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- 28 February 2024, pp. 22-31
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Clay of apparent hydrothermal origin that fills amygdales in the Granby Basaltic Tuff (Lower Jurassic) of the Connecticut Valley was analyzed and found to consist of two exceptionally well-crystallized Fe-rich, trioctahedral 2:1 layer expandable phyllosilicates. Based on chemical and XRD analyses, the minerals were tentatively identified as saponite and vermiculite. The saponite exists predominately in the two-water hydration state, but also displays one- and three-water layer hydration states, which suggests heterogeneous layer charge distribution—a phenomenon not uncommon in smectites. The identity of the second clay remains equivocal, but XRD analyses, especially with regard to the swelling properties of the clay, indicate that it is a vermiculite. The well-crystallized nature of the Granby clay and the large size of the clay flakes (up to 1 mm) allowed us to use SEM/EDS X-ray imaging and spot analysis techniques in an attempt to detect chemical differences between the saponite and vermiculite. Results showed that the chemistry of individual crystals, within and among amygdales, was essentially uniform. This suggests that the saponite and vermiculite are chemically similar and that variations in their swelling properties result from other factors, such as crystal size, layer charge density, or charge localization within the unit layers. Crystal size differences in the Granby clay were observed with both the petrographic and scanning electron microscope. Changes in layer charge density or charge localization within unit layers could have been affected by the oxidation of Fe2+ to Fe3+, a transformation inferred from the green-to-brown color changes observed in the larger amygdales. The Granby clay is of special importance, because it is one of the few examples of a naturally occurring mixture of two well-crystallized, Fe-rich trioctahedral 2:1 layer expandable phyllosilicates with crystallochemical and swelling properties that appear to bridge the operational definitions for the smectite and vermiculite groups.
Occluded Mica in Hydroxy-Interlayered Vermiculite Grains from a Highly-Weathered Soil
- W. G. Harris, A. A. Morrone, S. E. Coleman
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- 28 February 2024, pp. 32-39
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Hydroxy-interlayered vermiculite (HIV) is a ubiquitous phyllosilicate in the <0.05-mm fraction of sandy soils on the U.S. southeastern coastal plain. Extensive areas of soils with abundant HIV (i.e., peninsular Florida) have no detectable mica; yet the coarseness, platy habit, and nonexchangeable K associated with HIV grains suggest a mica precursor. The objectives of this study were: (1) to probe for mica zones (1.0-nm) within HIV grains, using high-resolution transmission electron microscopy (HRTEM), and (2) to determine intragrain elemental distributions via electron microprobe analysis (EMA). HIV grains from a Quartzipsamment medium-silt fraction, which contained no detectable mica by X-ray diffraction (XRD), were concentrated via high-density liquid separation. EMA transects and X-ray dot maps showed zonation or trends of K depletion near edges of some grains, with K2O contents ranging from trace levels to >40 g kg-1. Elemental oxide data indicated a dioctahedral phyllosilicate structure, with some octahedral substitution of Fe and Mg for Al. Intermittent 1.0-nm lattice-fringe images obtained by HRTEM supported the presence of mica zones within grains. There were no detectable 1.4-nm fringes, despite the dominance of a 1.4-nm XRD peak, indicating the instability of the HIV specimen under the electron beam. Results support a transformational link between mica and HIV in these soils. Rapid incursion and polymerization of Al following loss of K from mica may limit the extent of the vermiculite intermediate. The latter idea is consistent with the paucity of vermiculite in Florida soils. Traces of occluded mica may be the last remnants of the precursor grain. A sand-sized mica precursor would likely have weathered in place during the period when colloidal components such as kaolinite illuviated to deeper zones. Thus, the transformation product (HIV) would comprise a significant proportion of the <0.05-mm fraction persisting in sandy eluvial horizons.
Characterization of the End of Smectite-to-Illite Transformation: Decomposition of X-Ray Patterns
- Bruno Lanson, Gérard Besson
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- 28 February 2024, pp. 40-52
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Complex X-ray diffraction (XRD) profiles are described crystallographically by simulating XRD peaks for each phase, and adding the various elementary patterns to fit the experimental X-ray pattern. X-ray patterns of a ground muscovite and three polyphasic diagenetic I/S samples are fitted with this powerful, but time-consuming, technique. In the 6°–10°2θ CuKα range, the asymmetry of the muscovite peak is related to a very broad coherent scattering domain size (CSDS) distribution; for the I/S samples the even greater asymmetry is due to the presence of several phases with close, but distinct crystallographic characteristics (I/S, illite, and detrital mica).
A simulation-decomposition approach for modelling XRD patterns is introduced to describe quickly and accurately the various clay minerals (essentially mixed-layer illite/smectite and illite) present in a sedimentary series, and to follow their individual evolution during diagenesis. The theory for these simulations is described briefly. The influence of mixed-layer heterogeneity (the distribution of CSDS, and the distribution of smectite content) on the shape of X-ray peaks is shown theoretically to be minimal. Indeed, for both CSDS and smectite content, the important parameter for peak shape appears to be the mean value of the distribution and not its width and/or its shape. The theoretical limitations of the decomposition method are presented. Minor experimental limitations (reproducibility, experimental peak shape, discrimination) make this method a powerful and reliable tool to describe X-ray patterns. The method is used to show the simultaneous occurrence of three “illitic” phases in a sedimentary series from the Paris Basin. The respective evolution of the three phases is clearly evidenced by using this decomposition method. However, the precise identification of these different phases remains difficult to determine because of the difference in peak width between simulated and experimental X-ray patterns.
Smectite-to-Illite Conversion in a Geothermally and Lithologically Complex Permian Sedimentary Sequence
- C. Bühmann
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- 28 February 2024, pp. 53-64
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The <0.5-μm fraction of 120 samples from a lithologically complex Permian sedimentary sequence, underlying dolerite intrusive sheets, has been characterized by means of X-ray diffraction to establish I/S compositions as a function of temperature, lithology and time duration. Illitization has been active over the entire 210 m depth range and the clay data reflect both the local pattern of contact metamorphism and the more regional trend of heat flow during burial. A continuum exists in the illite proportions of the illite/smectite interstratifications with increasing distance from the intrusive sheet ranging from R = 3 with less than 5% smectite via R = 2 and R = 1 to R = 0 with up to 70% smectite. In the mixed-lithology section, individual component layers in the I/S within similar distance levels, but between contrasting lithologies, appear to vary only within a very restricted compositional range. In the massive mudstone strata, however, more silty parts contain I/S of a higher degree of ordering and lower expandability. Calcite contents are reflected in a higher rate of chlorite formation, but not in the I/S composition. A satisfactory inverse correlation was found between percent smectite in I/S and vitrinite reflectance in the lithologically complex section. R = 1 interstratifications are associated with a maximum vitrinite reflectance of 1.07–1.29 and R > 1 phases with 1.93–2.7, indicating that time duration is not a controlling factor in the illitization process in this facies. R = 0 interstratifications are present in a massive mudstone/siltstone sequence situated furthest from the igneous intrusives, and display vitrinite reflectance values of 1.42–1.52. No satisfactory explanations for this finding can be offered.
Smectite-Illite Transition in Barbados Accretionary Wedge Sediments: Tem and Aem Evidence for Dissolution/Crystallization at Low Temperature
- Martine D. Buatier, Donald R. Peacor, James R. O'Neil
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- 28 February 2024, pp. 65-80
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Sediments from depths to 670 m in the Barbados accretionary complex and transecting the décollement zone have been studied by transmission and analytical electron microscopy (TEM/AEM). The sediments consist of claystone and mudstone intercalated with layers of volcanic ash. Smectite comprises the bulk of the noncalcareous sediments and forms a continuous matrix enveloping sparse, irregular, large grains of illite, chlorite, kaolinite and mixed-layer illite/chlorite of detrital origin at all depths. The detrital origin of illite is implied by illite-smectite textural relations, well-ordered 2M polytypism, and a muscovite-like composition. K is the dominant interlayer cation in smectite at all depths, in contrast to the Na and Ca that are normally present in similar rocks.
Deeper samples associated with the décollement zone contain small (up to 100 Å thick) illite packets included within still-dominant subparallel layers of contiguous smectite. AEM analyses of these packets imply illite-like compositions. Selected area electron diffraction (SAED) patterns show that this illite is the 1Md polytype. Packets display step-like terminations like those seen in illite of hydrothermal origin. The data collectively demonstrate that smectite transforms progressively to illite via a dissolution-recrystallization process within a depleting matrix of smectite, and not by a mechanism of layer replacement. This illite seems to form at depths as shallow as 500 m and temperatures of 20°-30°C, which is in marked contrast to the much higher temperature conditions normally assumed for this transformation. This implies that the high water/rock ratios associated with the décollement zone are significant in promoting reaction.
Far-Infrared Study of the Interlayer Torsional-Vibrational Mode of Mixed-Layer Illite/Smectites
- Paul A. Schroeder
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- 28 February 2024, pp. 81-91
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Investigation of mixed-layer illite/smectites with far-infrared (FIR) spectroscopy indicates the presence of torsional mode absorption bands associated with interlayer fixed-K sites. By contrast, hydrated montmorillonitic interlayer cation sites are transparent in the far IR. The presence or absence of bands for interlayer cation sites appears to be related to both the magnitude and site of negative layer charge within the 2:1 layer structure. The bimodal nature of illite/smectite spectra leads to the suggestion that two different fixed-K environments occur within illite/smectite structures. These two environments are controlled by the composition of the octahedral sheet. The torsional modes at 112 and 89 cm-1 represent fixed-K sites influenced, respectively, by an Al-rich, high-charge dioctahedral layer and a heterogeneous Al-Fe-Mg-bearing, low-charge layer. A general trend of increasing absorption of the 112 cm-1 band, relative to the 89 cm-1 band, is observed in a typical diagenetic illite/smectite sequence of Miocene shales from the Gulf of Mexico sedimentary basin. The absorbance strength of both torsional bands is also seen to increase with increasing degree of illitization and the amount of fixed potassium in the illite/smectite. These observations are consistent with the concept of shales undergoing illitization during burial diagenesis by both the collapse of high-charge smectite layers to form illite layers (i.e., transformation) and the formation of new high-charge (-0.9) illite layers at the expense of smectite layers (i.e., dissolution/ neoformation).
FTIR Study of Deuterated Montmorillonites: Structural Features Relevant to Pillared Clay Stability
- Krishna Bukka, J. D. Miller, Joseph Shabtai
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- 28 February 2024, pp. 92-102
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FTIR studies of six partially-deuterated montmorillonites (MS) reveal the presence of two O-D stretching bands, one between 2702–2728 cm-1 and another near 2680 cm-1. For homoionic (Li, Na, Mg, Ca, or La) Wyoming-type MS, the position of the higher frequency band, designated as (O-D)h, is between 2714–2728 cm-1, whereas for homoionic Cheto-type MS it is between 2702–2706 cm-1. The lower frequency band, designated as (O-D)1, is in the narrow range of 2674–2684 cm-1. Resolution of two corresponding O-H bands, appearing near 3670 and 3635 cm-1, was observed only after partial dehydroxylation of the smectites. The changes in the relative intensities of the two O-D stretching bands as a function of the smectite type and of the Lewis acidity (charge density) of the exchangeable ion were determined. For Wyoming-type MS, the intensity of the (O-D)h band is much lower than that of the (O-D)l band, whereas for Cheto-type MS, the intensity of the (O-D)h band is about equal or slightly higher than that of the (O-D)l band. The observed resolution can be ascribed tentatively to the presence of (at least) two types of octahedral OH groups in the smectites, the (O-D)h band being assigned to AlMgOH and the (O-D)1 band to AlAlOH groups. Pillaring of Cheto-type MS with hydroxy-Al13 oligocations resulted in products showing much higher thermal stability between 400–600°C compared to that of identically pillared Wyoming-type MS. Compositional and other factors, e.g., CEC values and mode of pillaring, may cause this difference in stability.
Effects of Layer Charge, Charge Location, and Energy Change on Expansion Properties of Dioctahedral Smectites
- Tsutomu Sato, Takashi Watanabe, Ryohei Otsuka
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- 28 February 2024, pp. 103-113
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Expansion properties often homoionic smectites that differed in amount and location of layer charge were examined by X-ray powder diffraction analysis at various relative humidities, or after glycerol or ethylene glycol solvations. Except for K-samples with glycerol solvation, and Na- and Ca-samples with ethylene glycol, differences in the basal spacings are observed in samples having similar layer charge. These results show that the basal spacings are larger when the layer charge is located in octahedral sites than when it is in tetrahedral sites. This suggests that expansion is due to the combined effects of the charge location and amount.
The effects of layer charge magnitude and location on expansion were represented by an energy change (expansion energy: ΔEr) during the hydration and solvation processes. Plots of basal spacings versus ΔEr show a reasonable relationship; the spacings generally decrease stepwise as the value of ΔEr increases. The basal spacings of K-samples with glycerol solvation, Na-saturated and K-saturated samples at 100% RH are apt to contract stepwise with increasing value of ΔEr. For these samples, the figures showing the relationship between each expanded phase and the charge characteristics are obtained from the isoquants of ΔEr, given the boundary of the expanded phases. A behavior test using these figures may be combined with the Greene-Kelly test to estimate the amount and the location of the layer charge of common smectites.
Microtopography of Regularly-Interstratified Mica and Smectite
- Ryuji Kitagawa, Toshihiko Matsuda
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- 28 February 2024, pp. 114-121
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The gold decoration technique of electron microscopy was used to observe the microtopography of natural (001) surfaces of 1:1 regularly-interstratified mica/smectite minerals (expandable layer: 40–45%) collected from four different pyrophyllite deposits in Japan. The specimens are characterized by parallel growth steps of malformed, circular or polygonal forms with varying step separations. Many particles exhibit paired steps that seem to show spiral growth. Microtopographic observations suggest that the growth of regular interstratification (at least for the specimens investigated in this study) normally takes place by an interlacing of paired steps. If the height of a single step corresponds to that of a mica or a smectite layer, the particles are estimated to be normally 40–300 Å in thickness. If the particles on which a spiral center is observed are single crystals of interstratified mica and smectite, then some crystals investigated in this study are far thicker than fundamental particles. The results of this study are interpreted to suggest that these regularly-interstratified mica/smectites were formed by hydrothermal metasomatism from their respective host rocks.
Structural Water in Volcanic Glass
- Kazue Tazaki, T. Tiba, M. Aratani, M. Miyachi
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- 28 February 2024, pp. 122-127
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High-resolution transmission electron microscopy has revealed spherical and hemispherical structures on the surface of partly hydrated volcanic and synthetic glasses. These structures contrast with the bulk of the glass in showing lattice-fringe images indicative of the early stages of crystallization. Heavy-ion Rutherford scattering analysis of the noncrystalline volcanic glass indicates a structural water with hydrogen and deuterium. Depth profiles show that the glass grains contain structural water without adsorbed water on the surface. The presence of structural water in volcanic glass must be of interest to the formation of primitive clays. The spherical and hemispherical structures favor production of clay precursors in the presence of water.