Showing papers in "Clay Minerals in 2005"
TL;DR: Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states as discussed by the authors and diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity.
Abstract: Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states. Diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity. This review summarizes the extensive but scattered literature on halloysite, from its natural occurrence, through its crystal structure, chemical and morphological diversity, to its reactivity toward organic compounds, ions and salts, involving the various methods of differentiating halloysite from kaolinite. No unique test seems to be ideal to distinguish these 1:1 clay minerals, especially in soils. The occurrence of 2:1 phyllosilicate contaminants appears, so far, to provide the best explanation for the high charge and potassium selectivity of halloysite. Yet, hydration properties of the mineral probably play a major role in ion sorption. Clear trends seem to relate particle morphology and structural Fe. However, future work is required to understand the possible mechanisms linking chemical, morphological, hydration and charge properties of halloysite.
1,156 citations
TL;DR: In this article, the determination of the cation exchange capacity (CEC) of clays by exchange with cationic copper complexes [Cu(en)2]2+ and [cu(trien)]2+ is revisited.
Abstract: The determination of the cation exchange capacity (CEC) of clays by exchange with the cationic copper complexes [Cu(en)2]2+ and [Cu(trien)]2+ is revisited. The procedures reported by Bergaya & Vayer (1997) and Meier & Kahr (1999) are modified slightly. The concentration of the copper complexes in the equilibrium solutions is measured by spectral photometry. Correct CEC values of the [Cu(en)2]2+ exchange are only obtained when a buffer (‘tris’, tris (hydroxymethyl) aminomethane, pH = 8) is added to the equilibrium solution after separation of the clay, because the molar extinction coefficient of this complex depends on the pH of the solution. A standard procedure is recommended as a reference method. In most cases, tris addition is not needed for the determination with [Cu(trien)]2+ cations. Nevertheless, tris addition is recommended in the standard procedure. Determination of CEC for 40 samples (kaolins, ‘common clays’, bentonites, montmorillonites and beidellite) shows a good agreement between measurements using [Cu(en)2]2+ and [Cu(trien)]2+ cations and with results by the ammonium acetate method.
167 citations
TL;DR: In this article, grafted derivatives of kaolinite were directly intercalated with n-hexyl- and n-octadecylamine, using methanol-kaolinite as the precursor.
Abstract: Kaolinite was intercalated with n-hexylamine, n-octadecylamine and n-docosanamine, using methanol-kaolinite as the precursor. The intercalation compound with n-docosanamine presented the largest basal spacing for a kaolinite derivative thus far reported (64.2 A). Five grafted derivatives of kaolinite were directly intercalated with n-hexyl- and n-octadecylamine. During intercalation, the grafted molecules rearrange from parallel to perpendicular orientation to the kaolinite surface, in order to maximize the interaction with the amine and minimize the interlayer expansion needed. The octadecylamine intercalation compounds were delaminated in toluene, accompanied by the deintercalation of the amine molecules. Thin kaolinite particles rolled into a halloysite-like morphology, but forming much smaller tubes, some of which possibly consist of single kaolinite layers. The delamination was more efficient with the grafted kaolinites than with raw kaolinite.
165 citations
TL;DR: In this paper, synthetic schwertmannite, a common iron compound in acid mine drainage, completely converted in water to a sulphate-containing goethite within ~100 days.
Abstract: At 25°C, synthetic schwertmannite, a common iron compound in acid mine drainage, completely converted in water to a sulphate-containing goethite within ~100 days. The rate of transformation doubled as the pH increased from 4.0 to 7.2. In deviation from its normal acicular habit, the goethite appeared as spherical aggregates.
125 citations
TL;DR: In this article, interlayer-grafted derivatives of kaolinite were synthesized by esterification of inner surface hydroxyl groups with alkanols, diols and glycol mono-ethers starting with the dimethyl sulphoxide intercalate.
Abstract: Several new interlayer-grafted derivatives of kaolinite were synthesized by esterification of inner-surface hydroxyl groups with alkanols, diols and glycol mono-ethers starting with the dimethyl sulphoxide intercalate. The derivatives were characterized by X-ray powder diffractometry, thermal analysis, Fourier transform infrared spectroscopy and transmission electron microscopy. The grafted molecules are arranged in monolayers between the kaolinite layers, with typical basal spacings of ~11.3 A. Rheological studies of aqueous dispersions of the modified kaolinites revealed an exponential increase of the yield value and apparent viscosity with increasing alkyl chain length of the grafted molecules.
103 citations
TL;DR: In this article, the presence of clay minerals (montmorillonite and kaolinite) in marine or coastal environments contaminated with high concentrations of heavy-oil spills were able to support the growth of hydrocarbon degraders to enable bioremediation.
Abstract: This study focused on whether the presence of clay minerals (montmorillonite and kaolinite) in marine or coastal environments contaminated with high concentrations of heavy-oil spills were able to support the growth of hydrocarbon degraders to enable bioremediation. The bacterial growth experiment utilizing ~150 g/l of heavy oil (from the Nakhodka oil spill) was conducted with 1500 mg/l of montmorillonite or kaolinite. Bacterial strain Pseudomonas aeruginosa (isolated from Atake seashore, Ishikawa Prefecture, Japan), capable of degrading heavy oil, was employed in combination with other hydrocarbon degraders inhabiting the heavy oil and seawater (collected from the Sea of Japan). The interactions among microbial cells, clay minerals and heavy oil were studied. Both clays were capable of promoting microbial growth and allowed microorganisms to proliferate (to a greater degree than in a control sample which contained no clay) in an extremely high concentration of heavy oil. Observation by transmission electron microscopy of the clay-oil-cell complexes showed that microbial cells tended to be bound primarily on the edges of the clays. X-ray diffraction analysis showed that the clay-oil and clay-oil-cell complexes involved the adsorption of microbial cells and/or heavy oil on the external surfaces of the clays. How do the interactions among clay minerals, microbial cells and heavy oil contribute to environmental factors influencing the bioremediation process? To our knowledge, there are no previous reports on the use of clay minerals in the bioremediation of the Nakhodka oil spill in combination with biofilm formation.
65 citations
TL;DR: In this article, the authors used X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) techniques to study prograde sequences in Portugal, Spain and Hungary.
Abstract: Pelitic and basic rocks occurring within prograde sequences in Portugal, Spain and Hungary have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The minerals formed in typical prograde reactions define the general sequences, but smectite, chlorite-smectite (corrensite) and/or berthierine were found to have replaced chlorite, whereas kaolinite and mixed-layer illite-smectite replaced illite-muscovite. Alteration occurred under conditions normally associated with diagenesis, subsequent to regional metamorphism, and we therefore refer to such processes with the term “retrograde diagenesis”. In the cases studied and in other cited examples, reactions occurred on a regional basis via pervasive fluids under open-system conditions inferred to be related to tectonic stress. The observed alterations could generally not be inferred from XRD data, although the presence of pure smectite in sediments other than bentonite is suggestive of retrograde relations, especially where other minerals are consistent with a higher grade of diagenesis. Retrograde diagenesis is readily observed through imaging of textures by TEM, however. Textural features show that retrograde reactions are more common than generally assumed, and that care should be used in interpreting geological events where appropriate textural relations are not seen.
64 citations
TL;DR: In this article, the fluorine route was thoroughly investigated for the hydrothermal synthesis of montmorillonite in the Na2O-MgO-Al2O3-SiO2-H2O system.
Abstract: The fluorine route is thoroughly investigated for the hydrothermal synthesis of montmorillonite in the Na2O-MgO-Al2O3-SiO2-H2O system. Using the optimal conditions suggested by Reinholdt et al . (2001) for the crystallization of pure montmorillonites with the formula Na2 x (Al2(1− x )Mg2 x □)Si4O10(OH)2, several parameters ( x , Mg content, duration of crystallization, F/Si atomic ratio, pH, nature of counterbalance cation) are varied independently from their ideal values. The products are analysed by various techniques (X-ray diffraction, thermogravimetric analysis-differential thermal analysis, 29Si, 27Al and 19F magic angle spinning-nuclear magnetic resonance). It appears that a pure montmorillonite can only be obtained within a narrow x range (0.10 ≤ x ≤ 0.20). The presence of F in the starting hydrogel and the crystallization time also have significant effects on the purity of the final products. It is shown that a small amount of fluorine is needed for the crystallization of pure montmorillonite phyllosilicates.
62 citations
TL;DR: In this paper, mine-drainage waters and associated precipitates from several active and abandoned lignite mines and mine dumps in the Sokolov Basin, northwestern Czech Republic, were sampled and analyzed.
Abstract: Mine-drainage waters and associated precipitates from several active and abandoned lignite mines and mine dumps in the Sokolov Basin, northwestern Czech Republic, were sampled and analysed. The data showed considerable variations of effluent composition and pH that can generally be related to differences in the local microenvironments. Temporal changes such as seasonal fluctuations of precipitation, leading to variations of water infiltration through and runoff over mines and mine dumps, were also observed to noticeably affect effluent composition. These variations have led to a wide range of precipitates, the principal constituents of which are generally one or several of the ferric minerals jarosite, schwertmannite, goethite, ferrihydrite and lepidocrocite.
The present paper consists of two parts: a short review of the genesis and properties of the named minerals, and a study of mine-drainage precipitates formed under different local conditions in various lignite mines and mine dumps of the Sokolov mining district. We show that variations in mine-drainage precipitate mineralogy, such as the presence or absence of specific ‘key’ minerals, can serve as indicators for factors such as the pH and sulphate concentration, and thus – with certain limitations – for the genetic environment during precipitate formation. Such variations in composition are reflected, among other properties, in the precipitate colour, which can therefore be used for a rapid identification and classification – both in the field and by remote sensing – of regions that are potentially prone to acid mine drainage.
60 citations
TL;DR: In this paper, the authors describe the geological background, the general characteristics of the bentonites and major aspects of their formation, e.g. type of low-temperature hydrothermal solutions, mass balance, chemical evolutions of the smectites and geochemistry of trace elements.
Abstract: The Neogene volcanic region of Cabo de Gata, Almeria, SE Spain, is dotted with many outcrops of bentonite, some of them of significant economic interest. The bentonites have their origin in the hydrothermal alteration of pyroclastic rocks (15-7 Ma). The deposits are usually associated with fractures. The major mineral is a dioctahedral Fe- and Mg-smectite (89-75%) and this is accompanied by minor amounts of feldspars, quartz, amphiboles, pyroxenes, biotite, zeolites, disordered tridymite, calcite, etc. This paper describes the geological background, the general characteristics of the bentonites and major aspects of their formation, e.g. type of low-temperature hydrothermal solutions, mass balance, chemical evolutions of the smectites and geochemistry of trace elements. Finally, the characteristics of three of the most important deposits are described.
51 citations
TL;DR: Chaerun et al. as discussed by the authors investigated the bioavailability of kaolinite and the role it plays in remediating oil-polluted seawater, since Kaolinite is known to enable hydrocarbon-degrading bacteria to grow well.
Abstract: An investigation was carried out on the bioavailability of kaolinite and the role it plays in remediating oil-polluted seawater, since kaolinite is known to enable hydrocarbon-degrading bacteria to grow well. Experimental results revealed that significant amounts of Al and Si dissolved from kaolinite were not observed ((P > 0.05) in comparison with a control sample which contained no kaolinite) in the aqueous phase during the ~24 day experimental period. Transmission electron microscope observations and energy-dispersive spectroscope data revealed that some altered kaolinite particles appeared, connected to intact kaolinite and bacterial cells. Bacterial cells were associated and encrusted with intact and/or altered kaolinite clay particles, where mixed (C, O, Na and Si)-precipitates of kaolinite clays were formed on the surface of hydrocarbon-degrading bacterial cells. However, the uptake of Si (from kaolinite) by bacterial cells appeared to be more prevalent than Al, and there were no significant changes in basal spacings of kaolinite due to these altered kaolinite particles. Separate studies showed that hydrocarbon-degrading bacteria have a high resistance to Si. Thus, the present data suggest that Si from kaolinite may facilitate hydrocarbon-degrading bacterial growth as shown in our previous study (Chaerun et al., 2005), and the C-O-Na-Si complexes on the surfaces of bacterial cell walls may be the stimulator for hydrocarbon-degrading bacterial growth in seawater contaminated with oil spill.
TL;DR: In this article, SWy-1 and SAz-1 smectites and an Italian bentonite from Sardinia were mechanically deformed via high-energy ball milling for 20 h, in a controlled thermodynamic environment at constant temperature (25°C) under vacuum.
Abstract: SWy-1 and SAz-1 smectites and an Italian bentonite from Sardinia were mechanically deformed via high-energy ball milling for 20 h, in a controlled thermodynamic environment at constant temperature (25°C) under vacuum. The deformed smectites have a lower cation exchange capacity (CEC) and form thicker particles than the original ones, due to agglomeration of smectite crystallites. The 001 diffraction maximum shifted to lower d spacings, the intensity of the 060 reflection decreased and the background at 20-30°2θ increased, suggesting partial amorphization of the smectite. Moreover, the layer charge of the smectites decreased. The intensity of the complex stretching band at 3625 cm-1, and the AlAlOH, and AlFe3+OH bending bands at 916 cm-1 and 886 cm-1, respectively, decreased, while the band at AlMgOH bending at 849 cm-1, disappeared. Deformation mainly disrupted the octahedral sheet and preferentially destroyed those sites occupied by Mg cations, thus explaining the observed decrease in layer charge. Octahedral sites occupied by Fe were least affected. The disruption of the octahedral sheet is substantiated further by the almost total disappearance of the dehydroxylation peak, which is more pronounced in the Mg-rich SAz-1 smectite.
TL;DR: The Lias Group rocks have been estimated to have been buried to 4 km in the Cleveland Basin but to < 2 km in Worcester and Wessex basins as mentioned in this paper, which is deeper than previously estimated and does not need local heating events.
Abstract: The clay mineral assemblages and microtextures of a suite of mudrocks from the Lias Group of England and Wales indicate important regional differences in burial history. Samples from the northern Cleveland Basin are characterized by illite-smectite (I–S, 90% illite) and little carbonate whilst samples from the southern Worcester and Wessex basins contain less mature discrete smectite and are often calcite- and dolomite-rich. Lias Group rocks have been buried to 4 km in the Cleveland Basin but to <2 km in the Worcester and Wessex basins. Burial in the Cleveland Basin is deeper than previously estimated and does not need a local heating event. Illite- smectite (80% illite) detected in samples from the East Midlands Shelf suggests burial to 3 km, again deeper than previous estimates for this region.
TL;DR: In this article, K-Ar ages of Eocene glauconite pellets from the Isle of Wight are related to quantified amounts of older glauconsite pellets and to occurrences of detrital mica/illite particles that might have been added to synsedimentary pellets during reworking processes.
Abstract: K-Ar ages of Eocene glauconite pellets from the Isle of Wight are related to quantified amounts of older glauconite pellets and to occurrences of detrital mica/illite particles that might have been added to synsedimentary pellets during reworking processes. Addition of older glauconite did not significantly bias the K-Ar dates, as the results most often provide the expected stratigraphic reference ages or even significantly lower ages. Alternatively, K-Ar dates significantly greater than those suggested by the stratigraphy appear to result from non-glauconized detrital mica in the pellets which is not always removable, even by high-gradient magnetic separation. Unexpected ‘old’ K-Ar glauconite ages do not result from misapplication of the method, but from inability to systematically identify and remove the ‘contaminant’ particles from glauconite splits. Analysis of highly evolved glauconite separates is definitely appropriate for reliable isotopic age determinations, but it might not be enough for the final selection, as long-lasting diagenesis might have taken over the synsedimentary process. Much if not all depends on the separation and characterization of the separates, but also on the completion of the glauconitization process which effects cannot always be anticipated.
TL;DR: In this article, the intercalation of the cationic surfactant cetyltrimethylammonium (C16TMA) into the interlayer of an acid-activated clay in the presence of different anions has been studied in detail.
Abstract: The intercalation of the cationic surfactant cetyltrimethylammonium (C16TMA) into the interlayer of an acid-activated clay in the presence of different anions has been studied in detail. When Br or OH anions were used, the basal spacing increased significantly, the increase being related to the loading concentration of the surfactant solution. For intercalated compounds prepared from the hydroxide form, the basal spacing at room temperature varied from 1.6 to 3.8 nm. However, for organoclays prepared from the surfactant bromide, the basal spacing is almost loading-independent (1.9 nm). The use of hydroxide and bromide at higher pH is crucial to intercalating larger amounts of C16TMA cations and, hence, to improving the exfoliation of the silicate sheets. Magic-angle spinning 13 C nuclear magnetic resonance spectroscopy indicates that the intercalated surfactants exhibit a significant degree of gauche conformation. According to in situ powder X-ray diffraction, an increase of the basal spacing to 4.08 nm is observed at intermediate temperatures of 50 to 150°C for organoclay with an initial basal spacing of 3.7 nm. At higher temperatures, decomposition of the surfactant occurs and the basal spacing decreases to ~1.4 nm.
TL;DR: In this article, chemical analysis, X-ray diffraction, transmission electron microscopy, scanning electron microscope, and thin-section studies were performed on 16 major sedimentary rocks of the Fars and Kuhgiluyeh Boyerahmad Provinces.
Abstract: Clay minerals of calcareous sedimentary rocks of southern Iran, part of the old Tethys area, were investigated in order to determine their origin and distribution, and to reconstruct the palaeoclimate of the area. Chemical analysis, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and thin-section studies were performed on the 16 major sedimentary rocks of the Fars and Kuhgiluyeh Boyerahmad Provinces.
Kaolinite, smectite, chlorite, illite, palygorskite and illite-smectite interstratified minerals were detected in the rocks studied. The results revealed that detrital input is possibly the main source of kaolinite, smectite, chlorite and illite, while in situ neoformation during the Tertiary shallow saline and alkaline environment could be the dominant cause of palygorskite occurrences in the sedimentary rocks.
The presence of a large amount of kaolinite in the Lower Cretaceous sediments and the absence or rare occurrence of chlorite, smectite, palygorskite and illite are in accordance with the warm and humid climate of that period. Smaller amounts of kaolinite and the occurrence of smectite in Upper Cretaceous sediments indicate the gradual shift from warm and humid to more seasonal climate. The occurrence of palygorskite and smectite and the disappearance of kaolinite in the late Palaeocene sediments indicate the increase in aridity which has probably continued to the present time.
TL;DR: In this paper, a stable isotope study of the Blanquita and Equivocada mines of the Province of Rio Negro (Argentina) has been carried out.
Abstract: Kaolinite deposits, hosted by rhyolitic tuffs, are found in the SE of the ‘Los Menucos’ area (Province of Rio Negro, Argentina). The most representative examples are from the Blanquita and Equivocada mines. To discover the origin of these deposits, a mineralogical, geochemical (major and trace element) and stable isotope study (O and H) of kaolinite was carried out. Mineralogically, Blanquita mine is characterized by the presence of dickite, kaolinite, alunite and pyrophyllite, whereas in Equivocada mine, kaolinite is accompanied by dickite and traces of alunite (without pyrophyllite). The trace element contents and ratios of kaolin samples (P vs. S, Zr vs. Ti, (Cr + Nb) vs. (Ti + Fe), and (Ce + Y + La) vs. (Ba + Sr)) suggest that they formed from the hydrothermal alteration of the enclosing rhyolites although a possible contribution of kaolinite from residual processes cannot be discounted. δ18O values of kaolinite range from +4.8 to +10.3‰, and δD varies from −88 to −116‰. The presence of pyrophyllite in Blanquita mine suggests temperatures of formation >350°C. The calculated isotopic composition of the fluid in equilibrium with kaolinite at 350°C varies from +3.6 to +9.2‰ for O and from −74 to −103‰ for H. These values are compatible with fluids of magmatic origin or with fluids of surficial origin isotopically equilibrated with a rhyolitic magma at high temperatures. The isotope composition of kaolinite from the Blanquita and Equivocada mines is clearly different from kaolinite of residual origin from deposits in the Chubut and Santa Cruz provinces. The isotopic signature has proved to be a useful tool in discriminating between different genetic processes in the formation of kaolin deposits.
TL;DR: In this paper, the authors presented a synthesis of Na-magadiite under hydrothermal conditions in a water/alcohol medium with a theoretical ion exchange rate of 25-75% and showed that both thin and thick platelets are present.
Abstract: Syntheses of Na-magadiite were performed under hydrothermal conditions in a water/alcohol medium. It is only possible to obtain a pure and well crystallized magadiite sample using a water/ethanol medium at a water/ethanol molar ratio of ~0.12. As shown by thermal analysis and 1 H liquid nuclear magnetic resonance spectroscopy, ethanol is not incorporated into the magadiite. Intercalation of dodecyl- and hexadecyltrimethylammonium cations in the interlayer space of Na-magadiite at different theoretical ion-exchange rates shows that the experimental ion- exchange rates are in good agreement with the theoretical ones. However, scanning electron micrographs of the sample having a theoretical ion exchange rate of 25–75% shows that the exchanges are not homogeneous (both thin and thick platelets are present). Attempts to obtain a Si- pillared compound starting from C16TMA-magadiite as the host material leads to a microporous compound having a BET surface area of 778 m 2 g −1 .
TL;DR: In this paper, a Mg-Al-Cl-layered double hydroxide was synthesized and its ability to adsorb iodine was evaluated, and the results indicated that the adsorption isotherm for I− retention could be fitted to Freundlich and Dubinin-Radushkevich equations.
Abstract: From leaching experiments with metallic uranium-aluminium material test reactor fuel elements in repository-relevant MgCl2-rich salt brines, a Mg-Al-layered double hydroxide with chloride as interlayer anion was identified as a crystalline secondary phase component. In the present study, this Mg-Al-Cl-layered double hydroxide (Mg-Al-Cl-LDH) was synthesized and its ability to adsorb iodine was evaluated. The adsorption of I− was rapid, and equilibrium for an initial concentration of 4.25 × 10−5 mole/l was obtained within 48 h. Further results indicated that the adsorption isotherm for I− retention could be fitted to Freundlich and Dubinin-Radushkevich equations. The values obtained indicate that iodine is adsorbed on Mg-Al-Cl-LDH by an anion-exchange process. The adsorption of I− was also studied as a function of pH. In the pH range between 3.5 and 8.5, the adsorption was independent of the pH. The effects of competiting anions were investigated using an MgCl2-solution instead of water, and indicate that chloride anions have a greater affinity towards the Mg-Al-Cl-layered double hydroxide than iodine.
TL;DR: In this paper, the convergent-beam electron diffraction mode (CBED) of a transmission electron microscope (TEM) with a beam spot of ~800 A was used to examine undisturbed areas of montmorillonite crystallites.
Abstract: The small particle size and the random stacking of layers has previously hindered systematic structure investigations of montmorillonite. By applying the convergent-beam electron diffraction mode (CBED) of a transmission electron microscope (TEM) with a beam spot of ~800 A we were able to examine undisturbed areas of montmorillonite crystallites.
Because montmorillonite crystallites are mostly thin particles, kinematic theory can be applied and the CBED patterns can be interpreted directly, provided that the particle thickness remains below the critical value of 350 A. An average thickness of ~90 A was calculated here for montmorillonite of bulk samples from X-ray diffraction analysis and lattice-fringe images. However, satisfactory diffraction intensity patterns for quantitative evaluation were obtained only from crystallites with a thickness above the average, which yielded a sufficient scattering volume. These patterns could be described in terms of the kinematic theory and therefore these crystallites were <350 A thick. Yet, crystallites of adequate thickness were extremely rare in the three samples investigated (Clay Spur, Rock River and Upton, all in Wyoming, USA).
The diffraction intensities from the ab plane of single montmorillonite crystallites of the various origins fit the three structural models for a trans -vacancy distribution, a cis -vacancy distribution or a random-cation distribution within the octahedral sheets. The configuration of the diffraction patterns also shows a 1 M symmetry of the layer. Due to the limited data set of CBED patterns, a refinement of the structure could not be achieved. However, energy dispersive X-ray spectroscopy data and computation of the cation–anion distances and valences using the ‘distance valence least square’ program permitted a refinement of the models.
TL;DR: In this article, a number of bentonitic clay deposits from the Ordu area (NE Turkey) have been investigated by optical and electron microscopy, X-ray diffraction and chemical analysis.
Abstract: A number of bentonitic clay deposits from the Ordu area (NE Turkey) have been investigated by optical and electron microscopy, X-ray diffraction and chemical analysis. The clays are the alteration products of Late Cretaceous trachytic and trachyandesitic pyroclastic rocks. They contain volcanogenic sanidine, plagioclase, biotite and pumice, along with the diagenetic minerals opal-CT, cristobalite and rare calcite and zeolite (clinoptilolite). Ca-smectite (montmorillonite) is the dominant clay mineral. The rare earth element patterns of all the bentonitic clays are generally similar, although there are variations in the Eu anomaly indicating formation from different types of pyroclastic rocks. Oxygen and hydrogen stable isotope values suggest that the smectite was formed at 20–40°C in pore water of mixed meteoric and marine origin during argillization. These features, together with mass-balance calculations, indicate the enhanced MgO and Sr content of the smectite resulted from formation at shallow burial depths within a dominantly marine environment.
TL;DR: In this article, the colloidal state (sol, flocs, gels) of Na-montmorillonite dispersions was adjusted by the addition of poly(ethylene oxides) with terminal trimethylammonium groups.
Abstract: The colloidal state (sol, flocs, gels) of Na-montmorillonite dispersions (from bentonite from Bavaria, Germany) was adjusted by the addition of poly(ethylene oxides) with terminal trimethylammonium groups. The colloidal state of the dispersions changed with the molar mass of these end-capped poly(ethylene oxides). The sol-gel diagrams (up to 4.5% (w/w) montmorillonite) in the presence of TMA-PEO 1500 and TMA-PEO 4000 (up to 40 g/l) were characterized by large fields of gel whereas TMA-PEO 20000 and TMA-PEO 35000 caused peptization by steric stabilization. Even dispersions with the highest montmorillonite content (4.5%) were peptized by >0.2 g/l TMA-PEO 35000. The critical coagulation concentration of NaCl was increased by the polymer addition, but the increase was modest (from 8-12 mmol/l to 50 mmol/l). The changes of the colloidal state, the flow behaviour and the salt coagulation reveal the sensitive interplay between stabilization mechanisms (electrostatic, steric) and destabilization effects (bridging, charge compensation, depletion flocculation).
TL;DR: The Kawasaki and Dobuyama bentonite deposits in northeastern Japan show contrasting properties even though they are only 5 km apart in a sequence of Neogene sedimentary and pyroclastic rocks.
Abstract: The Kawasaki and Dobuyama bentonite deposits in northeastern Japan show contrasting properties even though they are only 5 km apart in a sequence of Neogene sedimentary and pyroclastic rocks. The Kawasaki deposit consists of stratiform bentonite layers up to >50 m thick, and its wall rocks are unaltered shallow marine sedimentary rocks. In contrast, the Dobuyama deposit consists of a funnel-shaped ore body 200 m across, and its wall rocks are hydrothermally altered terrestrial rhyolitic pyroclastic rocks. The Kawasaki and Dobuyama bentonites mainly consist of Na-Ca smectite and Ca smectite, respectively, with subordinate opal-CT, quartz and zeolite. The geological occurrences of the deposits and wall-rock properties suggest that the Kawasaki and Dobuyama deposits were probably formed by diagenesis and low-temperature hydrothermal alteration, respectively. The difference in exchangeable cation ratios of the smectite between the two deposits is attributable to the difference in their sedimentary environments and/or burial depth.
TL;DR: In this article, the role of minerals in controlling the trace element composition of a set of clay-sized fractions from Albian siliciclastic rocks in NE Spain is investigated.
Abstract: Mineralogical and geochemical techniques have been used to determine the role of minerals in controlling the trace element composition of a set of clay-sized fractions from Albian siliciclastic rocks in NE Spain. These clay-sized fractions are composed of kaolinite and illite, minor quantities of quartz, and accessory heavy minerals. Kaolinite has a smaller crystal size than illite, accounting for its relative concentration in these fractions. The μm-sized heavy minerals are rutile, Fe-Ti- and Fe-oxides, zircon, pyrite, cassiterite, monazite and xenotime. Geochemical data indicate that most of the trace elements are relatively concentrated in clay-sized fractions, except for Zr, Hf, Y and HREE. Statistical treatment shows three different associations in the clay-sized fractions: (1) Rb, Cs and Ba with clay phyllosilicates, especially illite; (2) REE with Th, Y and P phases; and (3) Sc, Cr and V with Ti- and Nb oxides. Therefore, these data do not support the dominant REE control by clay mineralogy that other authors have reported.
TL;DR: The adsorption of the large cationic alkaloid berberine by montmorillonite in aqueous suspensions was investigated in this paper, where the authors showed that the reaction process takes place in two different types of reaction mechanisms: (1) cation exchange and (2) a secondary organophyllic adaption.
Abstract: The adsorption of the large cationic alkaloid berberine by montmorillonite in aqueous suspensions was investigated. An adsorption isotherm of berberine and desorption isotherms of exchangeable Na + , K + , Mg 2+ and Ca 2+ were determined by chemical analysis of the non-adsorbed berberine and the released cations in the supernatants. The isotherms suggest that the adsorption of berberine takes place in two different types of reaction mechanism: (1) cation exchange, and (2) a secondary organophyllic adsorption. The cation exchange occurring first is followed by the secondary adsorption which is accompanied by Cl − adsorption. Monovalent cations are exchanged before the divalent cations. Samples loaded with increasing amounts of berberine were examined by X-ray diffraction at room temperature, and after gradual heating up to 420°C. The basal spacing of the loaded samples after the thermal treatment became 1.28 nm, indicating the formation of carbon in the interlayer, thus proving that the adsorbed berberine was located in the interlayer space. At room temperature the basal spacing of samples loaded with 8 and 15 mmol of berberine per 100 g of clay was 1.28–1.30 nm indicating that in the interlayer space berberine cations were lying parallel to the alumino-silicate layers. The basal spacing of a sample with 36 mmol of berberine per 100 g of clay was 1.48 nm. This spacing does not give conclusive information on the arrangement of berberine in the interlayer. The spacing of samples with 57–147 mmol of berberine per 100 g of clay was 1.59 nm, suggesting the presence of bilayers of berberine in the interlayers. During thermal dehydration, the spacing of samples with 36–73 mmol of berberine per 100 g of clay decreased, but that of samples with 105–147 mmol of berberine per 100 g of clay increased to 1.66 nm. These samples contain organophilic adsorbed berberine and it is suggested that due to the thermal treatment berberine was tilted relative to the TOT lamellae, with anhydrous Cl − between the berberine cations.
TL;DR: In this article, α-amylase was characterized by X-ray diffraction (XRD), surface area measurements, 27 Al nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM).
Abstract: α-amylase was immobilized on acid-activated montmorillonite K-10 via adsorption and covalent linkage. The immobilized enzymes were characterized by X-ray diffraction (XRD), surface area measurements, 27 Al nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). Surface area measurements indicate pore blockage due to linking of the enzyme in the vicinity of the pore mouth. The XRD demonstrates intercalation of enzyme upon immobilization. The NMR studies indicate that, during adsorption, tetrahedral Al sites are involved, while covalent binding occurs exclusively on the octahedral Al sites. The SEM images depict the changed morphology of the clay surface due to immobilization. The efficiency of immobilized enzymes for starch hydrolysis was tested in a batch and a fixed-bed reactor and the performances were compared. The immobilized α-amylase showed a broad pH profile and improved stability characteristics in both reactor types when compared to the free enzyme. The effectiveness factor increased in the fixed-bed reactor, implying that diffusional restrictions to mass transfer operate in the heterogeneous reaction and the use of a fixed-bed reactor leads to a reduction in these diffusional resistances. In the continuous run, 100% initial activity was maintained for 72 h, and after 96 h, >80% activity was retained.
TL;DR: In this paper, a study of wall-rock alteration in the 1.4 km long Wurmtal adit at the Kafersteige hydrothermal vein deposit (northern Black Forest, Germany) illite was found to be the only clay mineral within the Bunter sandstone and intercalated claystone.
Abstract: In a study of wall-rock alteration in the 1.4 km long Wurmtal adit at the Kafersteige hydrothermal vein deposit (northern Black Forest, Germany) illite was found to be the only clay mineral within the Bunter sandstone and intercalated claystone. Illite occurs mainly as a detrital mineral in the claystone, whereas it is hydrothermally neoformed in the sandstone, either in the pores or as an alteration product of K-feldspar. The extensive occurrence of authigenic illite along the entire 1.4 km long profile confirms that the fluids migrated far into the sandstone. The authigenic illite formed during a first pulse of high-temperature fluids ( T h of ~220°C) with a low salinity (~1 wt.% NaCl eq ). These fluids also dissolved Sr and Rb from detrital illite of the claystones at the vein. A later hydrothermal pulse with a lower temperature (~70–150°C) and higher salinity (21–28 wt.% NaCl eq ) silicified the sandstone adjacent to the vein and caused partial substitution of OH − by F − in the structure of the detrital and neoformed illite along the profile. Within analytical error, the K-Ar dates for the neoformed illite of the The hydrothermal fluids are attributed to recycled meteoric water and brines that ascended from the basement into the cover rocks during the opening of the North Atlantic and/or the nearby Tethys area.
TL;DR: In this paper, the homogeneity of the chemical compositions of these phyllosilicates, in different alteration environments, probably means that they are controlled by the composition of the hydrothermal fluid.
Abstract: Clay minerals occur as replacements of olivine, pyroxenes, plagioclase and interstitial materials, and as vesicle fillings, in altered basalts from the Middle Atlas (Morocco). Phyllosilicates are the main components of this alteration process. They have been characterized here by optical microscopy, X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy as saponite, talc, corrensite and chlorite. The homogeneity of the chemical compositions of these phyllosilicates, in different alteration environments, probably means that they are controlled by the composition of the hydrothermal fluid. Talc-saponite-corrensite (with dominant saponite) is the clay mineral association most frequently observed (corrensite being more abundant in the vesicular levels of the basalts). Such an association, with no evidence of albite and zeolite, suggests that these basalts have suffered minimal alteration at relatively low temperatures. Another association, chlorite-corrensite, was detected in a deeper (vesicular) sample, probably resulting from a slightly higher temperature. Lastly, only discrete phyllosilicates (i.e. no random mixed-layer minerals) were observed. This suggests that near-equilibrium conditions prevailed during this alteration stage and that a dissolution-crystallization process was the main mechanism of transformation.
TL;DR: In this article, the authors performed experimentally on four smectitic clays to evaluate the extent of clay alteration induced by this process and the associated "auto-transformation" of H+ clays.
Abstract: Hydrolytic exchange was performed experimentally on four smectitic clays to evaluate the extent of clay alteration induced by this process and the associated ‘auto-transformation’ of H+ clays. Clay samples were Na-saturated and submitted to 10, 50 and 100 wetting-drying (WD) cycles and characterized after treatment using X-ray diffraction (XRD), infrared spectroscopy (FTIR) and cation exchange capacity analysis. Evidence for hydrolytic exchange was given by increasing amounts of exchangeable Mg2+ and precipitation of Na soluble salts for samples subjected to 100 WD cycles. Results indicated a decrease in the interlayer charge after 10 WD cycles but no further decrease was observed after 50 and 100 WD cycles. For one sample, XRD data indicated a decrease in the proportion of the smectite phase and a relative increase in the concentration of illite-smectite mixed layers also present in the sample. The results suggested that the reaction induces first a decrease in the layer charge and then a partial dissolution of some smectite layers.
TL;DR: In this article, the authors investigated the effects of the mineralogical composition on their ion-exchange capacities, which vary in the range 0.19-2.00 mEq/g.
Abstract: Diagenetic alteration in two tuff horizons (the lower and upper tuff units) in the Gordes region of Turkey led to the formation of mainly heulandite-clinoptilolite-type zeolites and also clay and silica minerals and K-feldspar. Possible variations in the climate and geological environment followed by variations in the hydrological system and the composition of the Miocene lake water and groundwater at that time resulted in the mineralogical facies. The lower tuffs are unaltered or slightly altered in the northern part and are more altered, particularly to zeolite (clinoptilolite) in the southern part of the study area. Heulandite and K-feldspar are mainly authigenic minerals in the upper tuff unit. The ammonium-exchange capacities of the 16 samples were investigated to understand the effects of the mineralogical composition on their ion-exchange capacities, which vary in the range 0.19–2.00 mEq/g. It is observed that the ion-exchange capacities are strongly dependent on the zeolite contents of the rocks. The correlation coefficient of this linear relation is 0.86. The most significant increase in ammonium-exchange capacity (from 0.2 to ~1.0 mEq/g) was observed when the zeolite contents increased from 0 to 30 wt.%. The second increase in exchange capacity was observed for samples containing >80 wt.% zeolite. Although there is no significant effect from the other authigenic minerals, smectite has a positive effect, and K-feldspar and opal-CT have almost no effect on the ion exchange capacities.