Javier Cuadros

EXPERIMENTAL KINETIC STUDY OF THE SMECTITE-TO-ILLITE TRANSFORMATION

The 1. The activation energy of the process is ∼7 kcal mol−1, suggesting a solid transformation mechanism. Based on these results, smectite seems to offer a safe barrier for nuclear waste.

Dehydration of Ca-montmorillonite at the crystal scale. Part I: Structure evolution

Abstract The dehydration dynamics of the of the Ca-saturated <1 μm size fraction of SWy-1 (low-charge montmorillonite) were studied at the crystal scale under isothermal conditions using X-ray diffraction with a position-sensitive detector (XRD-PSD) in the 30.170 °C temperature range. A total of 630 XRD patterns were modeled between 30 and 125 °C using a trial-and-error approach based on the direct comparison of experimental and calculated XRD patterns. The proportion of layers with different hydration states (bihydrated, mono-hydrated, and dehydrated) were determined in the temperature-time space as well as small variations of layer thickness within each hydration state. The results showed that dehydration produces complex structures with heterogeneous hydration states, some of which are stable (not transient) and remain at the end of the experiment. The evolution of other structural parameters (interlayer water content, layer thickness fluctuation) was consistent with previous reports of smectite hydration. For bihydrated layers, the amount of water molecules per interlayer cation indicated the presence of water molecules both coordinated and non-coordinated to the interlayer cation. The transition from bi- to mono-hydrated layers produced the maximum structural heterogeneity, with (1) strong interlayer thickness fluctuation (in individual layers), and (2) the presence of several elementary mixed-layer structures. In contrast, the transition from mono-hydrated to dehydrated layers occurs homogeneously within layers. Finally, the decrease in thickness of mono-hydrated layers only implied the removal of some water molecules forming the hydration shell of the interlayer cation.

Saline lake diagenesis as revealed by coupled mineralogy and geochemistry of multiple ultrafine clay phases: Pliocene Olduvai Gorge, Tanzania

Mineralogical and geochemical analyses of ultrafine (<0.1μm) extracts of Pliocene clays from Olduvai Gorge reveal the complexities of clay diagenesis in saline, alkaline paleo-waters. Multiple authigenic phases are routinely present; these may be distinguished and quantified by decomposition of XRD (060) peaks coupled with geochemical (microprobe, HRTEM-AEM) and crystallographic (IR) investigation. By assigning geochemistry based on XRD results, we identify three principal phases by octahedral composition: dioctahedral Al-rich, dioctahedral relatively Fe-rich, and Mg-rich with a trioctahedral component. Average octahedral formulae are Al1.30 Fe0.57 Mg0.13 (Al-rich), Al0.56 Fe0.80 Mg0.62 (Fe-rich), and Al0.09 Fe0.23 Mg2.09 (Mg-rich) per half formula unit. IR analyses support these octahedral structures. The Mg-rich phase either has coexisting dioctahedral and trioctahedral domains within individual sheets, or a homogeneous octahedral sheet of intermediate composition. This is, to our knowledge, the first report of an intermediate octahedral occupancy in a 2:1 phyllosilicate. HRTEM observations indicate both solid state octahedral and illitization reactions and dissolution-precipitation. Layer charge and interlayer cations suggest that during illitization, layer charge increase was due to interaction with Na-rich brines, but later K uptake may have been with either saline or fresher fluids with higher K/Na ratios. All three phases occur throughout the basin; relative proportions and octahedral compositions vary. Total Mg content of “bulk” <0.1μm clay fractions, (a paleochemical indicator in this and other basins) is the product of both the relative abundance and the Mg content of the Mg-rich phase. In addition to shedding light on the crystal chemistry of authigenic 2:1 phyllosilicates, these results demonstrate the paleolimnologic importance of discriminating the presence of multiple authigenic clay phases in lacustrine deposits.

Interstratified kaolinite-smectite : Nature of the layers and mechanism of smectite kaolinization

Abstract This study aims to contribute to a better understanding of the nature and evolution mechanism of interstratified clay minerals. We examined the <2 μm or <0.2 μm size fraction of interstratified kaolinite- smectite (K-S) formed by hydrothermal and hydrogenic alteration of volcanogenic material from a Tortonian clay deposit (Almería, Spain), a weathered Eocene volcanic ash (Yucatan, Mexico), and a weathered Jurassic bentonite (Northamptonshire, England). The methods used were X-ray diffraction analysis (XRD) of random and oriented preparations, thermogravimetry, chemical analysis, and 29Si MAS nuclear magnetic resonance. The proportions of kaolinite and smectite in K-S (%K) were determined by fitting the XRD patterns of ethylene-glycol-saturated samples with patterns calculated with the NEWMOD computer program. The obtained range of compositions is 0.85%K. A comparison of the results from the various techniques showed non-linear relationships, indicating that the layers in K-S are complex and hybrid in nature. The smectite-to-kaolinite reaction is a solid-state transformation proceeding through formation of kaolinite-like patches within the smectite layers. The process consists of several non-simultaneous stages: (1) removal of parts of the tetrahedral sheet, resulting in formation of kaolinite-like patches; (2) layer collapse to ~7 Å where the kaolinite-like patches are sufficiently large; (3) Al for Mg substitution in the octahedral sheet, simultaneous or slightly delayed with respect to layer collapse, causing a layer-charge decrease and loss of interlayer cations; (4) Si for Al replacement in the tetrahedral sheet and further loss of interlayer cations. Iron remains in the kaolinite or is lost at the latest stages of the process.

A reinvestigation of smectite illitization in experimental hydrothermal conditions: Results from X-ray diffraction and transmission electron microscopy

Abstract The hydrothermal reactivity of the <1 μm fraction, K-saturated SWy-2 Wyoming low-charge montmorillonite was studied in the 250-400 °C temperature range with reactions lasting between 5 and 120 days, with a solid/solution mass ratio of 1:10, and in 1 mol/L KCl solution. From X-ray diffraction (XRD) profile modeling results on K-saturated and ethylene-glycol solvated samples the illitization process appears to occur as a progressive replacement of expandable layers by layers with illitic behavior, in a single illite-smectite phase. However this treatment overestimates the amount of illite layers because of the presence of smectitic non-expandable layers. This was revealed by calcium exchange of the products, which causes re-expansion of the apparent illite layers. The illitization model then obtained consists of four phases with increasing illite content: discrete smectite, a randomly interstratified mixed-layered mineral (MLM) and two ordered MLMs that progressively replace the phases with less illite content. This polyphase model is consistent with results from transmission electron microscopy and chemical microanalysis, which show several types of particle morphology with different interlayer K content and Al-for-Si substitution that seem to correspond to the several phases detected by XRD. Thus, the actual illitization mechanism of smectite in our experiments is not a progressive reaction but a dissolution-precipitation process following the Ostwald step rule in which metastable smectite transforms into illite through a series of metastable illite-smectite phases.

Low-temperature illitization of smectite in the late eocene and early oligocene of the Isle of wight (Hampshire basin), U.K

Abstract Variegated palaeosols, which formed from weathering of clays, silts, and brackish to freshwater limestones, are present in the late Eocene-early Oligocene Solent Group of the Hampshire Basin, southern U.K. The detrital clay mineral suite is dominated by illite and illite-smectite with minor kaolinite and chlorite. In pedogenically modified (palaeosol) and evaporitic lacustrine clay-rich sediments, the proportion of illite in the illite-smectite is greater than in the non-pedogenically modified sediments, and where alteration is most intense, kaolinite and chlorite are absent. The smectite to illite transition has been investigated in the <0.5 μm fraction by XRD analysis (powder and oriented mounts), thermogravimetry (TG), analytical SEM, and chemical analysis of Fe2+. Modeling of XRD data reveals that the illite-smectite is a mixture of compositions (overall 60.95% illite), R0, with high rotational stacking disorder. Dehydroxylation occurs mainly at 500 °C, but also at higher temperatures, indicating heterogeneous octahedral cation composition. Analytical SEM and chemical analysis of Fe2+ indicate that the illite to smectite transition occurs through Fe reduction in octahedral sites leading to increased layer charge, coupled with K fixation. The driving mechanism for what appears to be irreversible Fe3+ reduction is wetting (reducing) and drying (oxidizing) cycles in gley soil, in which reoxidation of reduced Fe is never complete.

Dehydration of Ca-montmorillonite at the crystal scale. Part 2. Mechanisms and kinetics

Abstract A kinetic study of Ca-montmorillonite dehydration was performed based on information derived from X-ray diffraction (Ferrage et al. 2007, this issue) and, thus, focusing on interlayer water only. The dehydration was quantified following the two processes that were observed in the X-ray pattern modeling: the transitions between the different hydration states and small thickness decrease observed in the bi- and mono-hydrated layers. The thickness decrease of bihydrated layers with dehydration (activation energy Ea = 16 kJ/mol) was found to be controlled by a mechanism of two-dimensional diffusion of water molecules through the interlayer space, whereas for mono-hydrated layers the variation of thickness (Ea = 18 kJ/mol) occurred as a mechanism of slight local layer collapse and collapse propagation, attributed to a rearrangement of the configuration of the interlayer cation hydration shell. For the transition between the bi- and mono-hydrated state (Ea = 84 kJ/mol), the mechanism of reaction was found to evolve gradually with increasing temperature from local layer collapse and collapse propagation to a two-dimensional diffusion mechanism, as the forced diffusion of water molecules produced by the layer collapse transfers the control of the process to diffusion mechanism. This phenomenon causes the coexistence of two hydration states in a given interlayer. Finally, the transition between mono-hydrated and dehydrated layers (Ea = 132 kJ/mol) indicated the concomitance of water diffusion and local layer collapse and propagation mechanisms, although the structures were found to be homogeneous during this transition. The determination of both mechanisms and the activation energy for these processes were used to establish a model of smectite dehydration at the crystal scale. This model can be used to calculate crystal shrinkage and interlayer water content upon dehydration, and to predict the evolution of the system.

INTERPRETATION OF REFLECTANCE SPECTRA OF CLAY MINERAL-SILICA MIXTURES: IMPLICATIONS FOR MARTIAN CLAY MINERALOGY AT MAWRTH VALLIS

The Al-clay-rich rock units at Mawrth Vallis, Mars, have been identified as mixtures of multiple components based on their spectral reflectance properties and the known spectral character of pure clay minerals. In particular, the spectral characteristics associated with the ~2.2 μm feature in Martian reflectance spectra indicate that mixtures of AlOH- and SiOH-bearing minerals are present. The present study investigated the spectral reflectance properties of the following binary mixtures to aid in the interpretation of remotely acquired reflectance spectra of rocks at Mawrth Vallis: kaolinite-opal-A, kaolinite-montmorillonite, montmorillonite-obsidian, montmorillonite-hydrated silica (opal), and glassillite-smectite (where glass was hydrothermally altered to mixed-layer illite-smectite). The best spectral matches with Martian data from the present study’s laboratory experiments are mixtures of montmorillonite and obsidian having ~50% montmorillonite or mixtures of kaolinite and montmorillonite with ~30% kaolinite. For both of these mixtures the maximum inflection point on the long wavelength side of the 2.21 μm absorption feature is shifted to longer wavelengths, and in the case of the kaolinite-montmorillonite mixtures the 2.17 μm absorption found in kaolinite is of similar relative magnitude to that feature as observed in CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) data. The reflectance spectra of clay mixed with opal and of hydrothermally altered glass-illite-smectite did not represent the Martian spectra observed in this region as well. A spectral comparison of linear vs. intimate mixtures of kaolinite and montmorillonite indicated that for these sieved samples, the intimate mixtures are very similar to the linear mixtures with the exception of the altered glass-illite-smectite samples. However, the 2.17 μm kaolinite absorption is stronger in the intimate mixtures than in the equivalent linear mixture. Modified Gaussian Modeling of absorption features observed in reflectance spectra of the kaolinite-montmorillonite mixtures indicated a strong correlation between percent kaolinite in the mixture and the ratio of the area of the 2.16 μm band found in kaolinite to the area of the 2.20 μm band found in montmorillonite.

ELECTRON MICROSCOPY STUDY OF VOLCANIC TUFF ALTERATION TO ILLITE-SMECTITE UNDER HYDROTHERMAL CONDITIONS

Experimental alteration of volcanic tuff from Almeria, southeastern Spain, was performed in solutions with different Na/K ratios (0.01, 1, 10, and 100), different total salt concentrations (0.01, 0.1, 0.2, 0.33, and 1 M), and in deionized water, at 60, 80, 120, and 160°C, for periods of 60, 90, 180, and 360 d. Two particle size fractions of volcanic tuff were used: 10–200 and 20–60 μm. Alteration products were examined by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), laser-particle size analysis, scanning electron microscopy equipped with an energy dispersive X-ray spectrometer (SEM-EDS), image computer analysis, and transmission electron microscopy with microanalysis (TEM-AEM). XRD detected neoformed phases only in the products from experiments of 180–360 d at high temperatures (120–160°C), and with Na/K ratios above unity and in deionized water. The synthesized phase is a random mixed-layer illite-smectite (I-S) with 75% smectite. The quantity of newly formed I-S, determined by FTIR, ranged between 3–30%. There was no apparent change in grain size and shape of the grains after the experiments as compared to before.SEM-EDS and TEM-AEM revealed the following alteration sequence: 1) intense etching on glass-grain surfaces; 2) formation of hemispherical morphologies on grain surfaces; 3) precipitation of very thin, individual flakes of illite-smectite on glass-grain surfaces; 4) development of I-S at the edges of glass grains; and 5) development of I-S honeycomb structures either covering large areas of the glass grains or resulting from the complete alteration of glass grains. A direct transformation of glass to I-S seems to be the major reaction mechanism, although there also is evidence of glass dissolution and subsequent I-S precipitation.

FTIR INVESTIGATION OF THE EVOLUTION OF THE OCTAHEDRAL SHEET OF KAOLINITE-SMECTITE WITH PROGRESSIVE KAOLINIZATION

Twenty two samples were studied to investigate the nature and evolution mechanism of mixed-layer kaolinite-smectite (K-S). We examined the <2 µm or <0.2 µm fraction of K-S formed by hydrothermal and hypergenic alteration of volcanic material. The samples are from three localities: 20 specimens from a Tortonian clay deposit in Almería, Spain; one specimen from weathered Eocene volcanic ash from the Yucatan Peninsula, Mexico; and one sample from a weathered Jurassic bentonite from Northamptonshire, England. The samples were studied using chemical analysis, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The XRD patterns of the oriented, glycolated mounts were modeled using NEWMOD and the proportion of smectite and kaolinite layers was determined, ranging between 0 and 80% kaolinite. The analysis of the OH-stretching region of the FTIR spectra at different temperatures (180–550°C) showed the progressive dehydroxylation of kaolinite domains and, perhaps, of smectite domains, but no detailed information could be obtained about the sequential OH loss in different cation environments. The abundance and short-range ordering of the octahedral cations were studied using the OH-bending bands. The chemical and FTIR-estimated octahedral cation abundances were broadly similar. Aluminum showed a tendency to mix with Fe and Mg rather than to form AlAl pairs. Al-for-Mg substitution accompanying kaolinization was evident from the increase in AlAl pairs and decrease in AlMg pairs. Iron is retained in the structure. No other octahedral cation rearrangement was observed. The intensity of the 750 cm−1 band, assigned to translational vibrations of external OH groups in a kaolinitic environment, was quantified and modeled in relation to kaolinite layer proportion. The chemical data show that there are residual interlayer cations in kaolinite domains, which, in accordance with the model mentioned above, disturb external OH-translation vibrations. These results indicate the persistence of certain chemical and structural smectite features in kaolinite domains and thus support a smectite kaolinization process via a solid-state transformation. This confirms previous XRD, thermal, chemical and NMR analyses of the same sample set.