Showing papers in "Clays and Clay Minerals in 2009"

Application of chemical geothermometry to low-temperature trioctahedral chlorites

Abstract: Low-temperature chlorites formed in diagenetic to low-grade metamorphic environments generally have greater Si contents and larger numbers of octahedral vacancies, and smaller Fe+Mg contents than higher-grade metamorphic chlorites. The compositional variations are characterized approximately by four end-member components: Al-free trioctahedral chlorite, chamosite, corundophilite, and sudoite. The solid solution is considered to be a random mix of cations and vacancies in the octahedral sites. Using the compositions of chlorites from Niger, Rouez, and Saint Martin diagenetic-hydrothermal series, a new, more convenient geothermometer, applicable to low-T chlorites is proposed and comparison made with geothermometers proposed previously. The chlorites studied contain appreciable amounts of Fe(III) (>14% of the total Fe), determined by Mossbauer spectroscopy. The calculations under which all Fe was regarded as ferrous gave considerable overestimates for the formation temperature, irrespective of the geothermometer used. This problem was reduced by taking into account the presence of Fe(III) in the octahedral sites. The geothermometer from this study gave more reasonable estimates than the geothermometers proposed by Walshe (1986) and Vidal et al. (2001), particularly in the case of the Niger chlorites which crystallized in the lowest-temperature conditions. The ordered-site substitution model of solid solution developed by Vidal et al. (2001) predicted satisfactorily the formation temperature of the Rouez chlorites and of some of the Saint Martin chlorites, suggesting that the chlorite compositions are controlled by the ${\rm{Si}}\square R_{ - 2}^{2 + }$ exchange at low-T conditions while they are controlled by Tschermak exchange at higher temperatures. The decreasing number of vacancies with temperature are poorer in Fe-rich than in Fe-poor chlorites. Furthermore, the ordered-site occupation of cations and vacancies in trioctahedral chlorite occurs concomitantly with the compositional changes ruled by increasing temperature conditions.

Clay profiling: the classification of montmorillonites

Abstract: Montmorillonites, with the general composition $M_{\rm{x}}^ + \left( {{\rm{S}}{{\rm{i}}_{4 - y}}{\rm{A}}{{\rm{l}}_y}} \right)\left[ {{{\left( {{\rm{Al}},{\rm{F}}{{\rm{e}}^{3 + }}} \right)}_{2 - z}}{{\left( {{\rm{Mg}},{\rm{F}}{{\rm{e}}^{2 + }}} \right)}_z}} \right]{{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}$ where x = ξ = 0.2–0.6, x = y+z, and y≪z, vary widely in composition and structure. The commonly used classification into five montmorillonite and two beidellite groups for the solid-solution sequence does not allow an unambiguous classification with respect to structural features and the resulting properties. The smectite structure reveals five features that allow an unambiguous description of a sample: (1) identification as either a dioctahedral or a trioctahedral smectite; (2) layer charge; (3) charge distribution between tetrahedral and octahedral sheets; (4) cation distribution within the octahedral sheet; and (5) Fe content. In addition, the nature of interlayer cations should be given as they influence certain properties of montmorillonites. Analytical methods are now available to measure and determine these structural features. Therefore, a precise classification for montmorillonites requires determination of layer charge and exchangeable cations, analysis of chemical composition, and thermal analysis (to determine the octahedral structure), in addition to X-ray diffraction analysis. A comprehensive classification of montmorillonites based on these parameters is proposed. Ninety-six structural variations (expressed by systematic names) theoretically exist within the montmorillonite-beidellite series. Descriptive names can be used to elucidate the macroscopic properties of the montmorillonite samples in question.

SWELLING BEHAVIOR OF Na- AND Ca-MONTMORILLONITE UP TO 150°C BY IN SITU X-RAY DIFFRACTION EXPERIMENTS

Abstract: The effects of temperature on the swelling properties of smectites are important for a variety of different geological conditions, but studies on this topic have been rather limited. The purpose of this study was to investigate the swelling behavior of Na- and Ca-montmorillonite at various temperatures greater than room temperature, up to 150°C, using in situ X-ray diffraction (XRD) analysis. A sample chamber was designed, the temperature and humidity of which were controlled precisely, for environmental in situ measurements. The XRD measurements were performed at small relative humidity (RH) intervals for precise observation of the swelling behavior.

Three new, quick CEC methods for determining the amounts of exchangeable calcium cations in calcareous clays

Abstract: The cation exchange capacity (CEC) is one of the most important properties of clays in terms of their performance in both natural and technical processes. For decades, common methods for determining exchangeable cations have failed when calcareous clays or soils were examined, because calcite is at least partly dissolved throughout the exchange experiment which in turn increases measureable Ca2+ concentrations. As a result, exchangeable Ca2+ and the sum of exchangeable cations by far exceed the amount of negative charges. In the past, the silver-thiourea method (AgTU) has been modified to overcome this problem (AgTUcalcite), but is unsatisfactory as the method is laborious. In the present study three new methods based on two alternative metal complexes, cobalt(III) hexamine (CoHex) and copper(II) triethylenetetramine (Cu-trien), are proposed. The optimum solid/liquid ratios of these methods and the optimum complex concentration of Cu-trien are reported, depending on the mineralogical composition of the samples. The key development is that the exchange solutions are saturated with respect to calcite prior to the experiment. Approximately 70–90% of the dissolution of calcite present as an admixture in a clay sample is suppressed in the subsequent cation exchange experiment, but not all. The Ca2+ exchange is not suppressed and there is no evidence for any precipitation of this Ca2+. Three possibilities for how to handle this problem are discussed, one of which is to perform no further correction. The resulting error arises from the remaining calcite solubility of the different solutions after pre-treatment with calcite. This corresponds to errors of 0.2–1.3 (CoHexcalcite)and 0.7–8.4 (Cu-triencalcite) meq/100 gCa2+ for samples with small and large CEC values, respectively. As a consequence of the poor performance of Cu-triencalcite for samples with large CEC, a more concentrated Cu-trien5 × calcite solution was developed which performed much better: 0.1–0.8 meq/100 g(Cu-trien5 × calcite). For Cu-trien5 × calcite and CoHexcalcite at least, the errors are in the range of the non-systematic scattering for exchangeable Ca2+ determination. Therefore, the methods suggested provide ‘operationally correct’ Ca2+ values without additional effort. Moreover, owing to the high selectivity of the index cations applied in the present study, only one exchange step is required, providing a significant advantage over the AgTUcalcite method.

A comprehensive characterization of dioctahedral smectites

Abstract: The term 'montmorillonite' encompasses a wide range of chemical compositions and structures. Comprehensive and reliable characterization is essential for unambiguous classification. Twenty eight purified, Na-exchanged smectites ( 0.3 mol/f.u. are trans-vacant, mostly with additional cis-vacancies. Tetrahedral substitution also appeared to be a function of the number of trans-vacancies. The parameters analyzed provide the basis for a new descriptive classification system.

The effect of structural order on nanotubes derived from kaolin-group minerals

Abstract: Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

The charge of component layers of illite-smectite in bentonites and the nature of end-member illite

Abstract: The nature of component layers of mixed-layer illite-smectite and their possible evolution in the course of illitization have been debated since the 1960s. The present study is a new attempt to solve these problems, using samples collected from diverse geological formations around the world. Twenty three purified illite-smectites from bentonites and hydrothermal rocks, covering the complete range of expandability, were analyzed chemically, including ${\rm{NH}}_4^ + $ determination, and their structural formulae were calculated. The exchangeable cations (EXCH) were plotted vs. the fixed cations (FIX) yielding the following experimental regression: $${\rm{EXCH}} = - 0.43 \times {\rm{FIX}} + 0.41\;\;\left( {{{\rm{R}}^2} = 0.98} \right)$$ FIX and EXCH depend on the charge of the illite (Qi) and smectite (Qs) interlayers, and the fractions of these interlayers in the bulk clay leading to: $${\rm{EXCH}} = - {Q_{\rm{s}}}{\rm{/}}{Q_{\rm{i}}} \times {\rm{FIX}} + {Q_{\rm{s}}}$$ Analysis of these relations and independent measurements of the total specific surface area (TSSA) indicate that the layer charges of both types do not change in the course of illitization. The smectite layer charge is equal to 0.41 and the illite layer charge is equal to 0.95 per O10(OH)2. End-member illite has a well defined composition that is close to intermediate between muscovite and phengite, with fixed cations content greater than that specified in the AIPEA classification of layer silicates: $${\rm{FI}}{{\rm{X}}_{0.95}}\left( {{\rm{S}}{{\rm{i}}_{3.25}}{\rm{A}}{{\rm{l}}_{0.75}}} \right)\left( {{\rm{A}}{{\rm{l}}_{1.81}}{\rm{F}}{{\rm{e}}_{0.01}}{\rm{M}}{{\rm{g}}_{0.19}}} \right){{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}$$ The established relationship allows the calculation of the mean number (N) of 2:1 layers in all fundamental particles and also the fraction of smectitic layers (fs) from FIX: $$N = {Q_{\rm{i}}}{\rm{/}}({Q_{\rm{i}}} - {\rm{FIX}})\;\;{f_{\rm{s}}} = ({Q_{\rm{i}}} - {\rm{FIX}}){\rm{/}}{Q_{\rm{i}}}$$ N and fs can be used to calculate TSSA, and all three parameters can also be calculated from cation exchange capacity and from X-ray diffraction peak positions, utilizing the regressions established here.

Relationship between Pb2+ adsorption and average Mn oxidation state in synthetic birnessites

Abstract: The relationship between vacant Mn structural sites in birnessites and heavy-metal adsorption is a current and important research topic. In this study, two series of birnessites with different average oxidation states (AOS) of Mn were synthesized. One birnessite series was prepared in acidic media (49.6–53.6 wt.% Mn) and theother in alkalinemedia (50.0–56.2 wt.% Mn). Correlations between the Pb2+ adsorption capacity and the d110 interlayer spacing, the AOS by titration, and the release of Mn2+, H+, and K+ during adsorption of Pb2+ were investigated. The maximum Pb2+ adsorption by the birnessites synthesized in acidic media ranged from 1320 to 2457 mmol/kg with AOS values that ranged from 3.67 to 3.92. For birnessites synthesized in alkaline media, the maximum Pb2+ adsorption ranged from 524 to 1814 mmol/kg, with AOS values between 3.49 and 3.89. Birnessite AOS values and Pb2+ adsorption increased as the Mn content decreased. The maximum Pb2+ adsorption to the synthetic birnessites calculated from a Langmuir fit of the Pb adsorption data was linearly related to AOS. Birnessite AOS was positively correlated to Pb2+ adsorption, but negatively correlated to the d110 spacing. Vacant Mn structural sites in birnessite increased with AOS and resulted in greater Pb2+ adsorption. Birnessite AOS values apparently reflect the quantity of vacant sites which largely account for Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is mostly determined by the Mn site vacancies, from which Mn2+, H+, and K+ released during adsorption were derived.

Simultaneous incorporation of Cr, Zn, Cd, and Pb in the goethite structure

Abstract: In order to improve our understanding of how the goethite crystal structure is affected by the incorporation of metals (and by variations in the amount of the incorporation), and to review any possible synergistic and antagonistic effects of co-metals, the present investigation focused on the incorporation of multiple (di-, tri-, and tetra-) metals, i.e. Cr, Zn, Cd, and Pb, in the goethite crystallographic structure. A series of single- and multi-metal M-Cr/Zn/Cd/Pb-substituted goethites with M/(M+Fe) molar ratios = 0.10 were prepared. The general sequence of metal entry in single-metal substituted goethites was Zn = Cr > Cd > Pb and in multi-metal-substituted goethites was Zn > Cr ⩾ Cd > Pb. Simultaneous incorporation of Cr, Zn, Cd, and Pb up to 10.5 mole % was achieved in goethite. Synchrotron X-ray diffraction and extended X-ray absorption fine structure (EXAFS) techniques were employed to assess the structural characteristics of the synthesis products. Rietveld refinement of XRD data showed small changes in unit-cell parameters and Fe/M-Fe/M distances due to M substitution(s). A typical goethite-like crystalline structure remained intact, however. The unit-cell parameters were mutually, linearly correlated, though Fe/M-Fe/M distances were not, indicating that complex changes occurred at the local scale. In single-metal substituted goethites, incorporation of Cr reduced the unit-cell volume by 0.13% while that of Zn, Cd, and Pb increased it by 1.09, 3.58, and 0.56%, respectively. The changes in multi-metal-substituted goethites appeared to be the complex combination of that of the individually incorporated metals. The X-ray absorption near edge structure study of Pb-substituted goethites showed that the majority of associated Pb was Pb2+, while Pb4+ was preferred over Pb2+ in the bulk structure. Measurements by EXAFS at the Fe K-edge indicated that the Fe polyhedra contracted in the presence of Cd2+ and Pb2+, providing room for the substitution of larger cations. Measurements by EXAFS at the Cr and Cd K-edges indicated symmetric Cr/Cd polyhedra with single Cr/Cd-O distances and, at Fe and Zn K-edges and the Pb LIII-edge, indicated asymmetric polyhedra with two sets of Fe/Zn/Pb-O distances. The Zn octahedra were possibly Zn(OH)4O2, which enlarged the metal-metal corner-sharing distance to 3.86 A. This configuration of ligands around the Zn2+ cation might occur to balance local charges. Symmetric polyhedra appeared to reduce steric strains in the structure, compared to the asymmetric polyhedra. The result was that Cr enhanced the incorporation of Zn, Cd, and Pb, while the converse was true for Zn.

Bacteria-clay interaction: structural changes in smectite induced during biofilm formation

Abstract: Bacteria play an important role in determining the properties and behavior of clay minerals in natural environments and such interactions have great potential for creating stable biofilms and carbon storage sites in soils, but our knowledge of these interactions are far from complete. The purpose of this study was to understand better the effects of bacteria-generated biofilms on clay interlayer expansion. Mixtures of a colloidal, 2-water hectorite clay and Pseudomonas syringae in a minimal media suspension evolve into a polysaccharide-rich biofilm aggregate in time-series experiments lasting up to 1 week. X-ray diffraction analysis reveals that upon aggregation, the clay undergoes an initial interlayer contraction. Short-duration experiments, up to 72 h, result in a decrease in the d001 value from 1.50 to 1.26 nm. The initial interlayer contraction is followed in long-duration (up to 1 week) experiments by an expansion of the d001 value of 1.84 nm. The expansion is probably a result of large, biofilm-produced, polymeric molecules being emplaced in the interlayer site. The resultant organo-clay could provide a possible storage medium for carbon in a microbial colony setting.

Trans-vacant and cis-vacant 2:1 layer silicates: Structural features, identification, and occurrence

Abstract: A comprehensive study of clay minerals should include determination of the vacancy pattern of the dioctahedral sheet. The purpose of this report is to consider the advantages and limitations in various diffraction and non-diffraction methods for the determination of the layer types in clay minerals. Identification of trans-vacant (tv) and cis-vacant (cv) clay minerals reported here is based on powder X-ray diffraction (XRD) patterns calculated for different polytypes consisting of either tv or cv layers, on the simulation of experimental XRD patterns corresponding to illite or illite fundamental particles in which tv and cv layers are interstratified, and on the semi-quantitative assessment of the relative content of the layer types in the interstratified structures by generalized Mering’s rules. A simple and effective method for identification of tv and cv layers in dioctahedral 2:1 layer silicates employs thermal analysis and is based on different dehydroxylation temperatures for tv and cv illite and smectite layers. Crystal chemical analysis of various dioctahedral 2:1 layer silicates consisting of tv and cv layers indicates that compositional control is present in the distribution of octahedral cations over trans- and cis-sites. In dioctahedral smectites the formation of tv and cv layers is related to the layer composition and local order-disorder in the distribution of isomorphous cations. Dioctahedral 1M micas with abundant Fe3+ and Mg occur only as tv varieties. In contrast, 1M-cv illite, as well as cv layers in illite fundamental particles of I-S, can form only as Fe- and Mg-poor varieties. In illites and illite fundamental particles of I-S consisting of tv and cv layers, cv layers prevail when the amounts of Al in octahedra and tetrahedra are >1.55 and >0.35 atoms per O10(OH)2, respectively. The main factors responsible for the stability of cv and tv illites have been established. Monomineral cv 1M illite, its association with tv 1M illite, and interstratified cv/tv illite occur around ore deposits, in bentonites, and in sandstones mostly as a result of different types of hydrothermal activity. The initial material for their formation should be Al-rich, and hydrothermal fluids should be Mg- and Fe-poor. Tv and cv smectites of volcanic origin differ in terms of octahedral cation composition and distribution of isomorphous octahedral cations. Mg-rich cv smectites have random distribution of isomorphous octahedral cations, whereas in Mg-bearing tv smectites octahedral Mg cations are dispersed so as to minimize the amount of Mg-OH-Mg arrangements.

Clayey cap-rock behavior in h2o-co2 media at low pressure and temperature conditions: an experimental approach

Abstract: The storage of CO2 in geological reservoirs requires an understanding of the impact of CO2 on clay-rich sealing cap-rocks to identify and explore critical parameters that modify petrophysical properties such as permeability and fracturing. The purpose of this study was to investigate the effect of heating, under different hydrated-CO2 partial pressures, on the chemical compositions and relative amounts of mineral phases in the Saint Martin de Bossenay (SMB, Paris Basin, France) cap-rock in order to identify possible mineral-phase transitions and to estimate reaction kinetics induced by the presence of excess dissolved CO2. X-ray diffraction, transmission electron microscopy, and electron microprobe analyses were employed to study mineral alteration, with particular attention given to visualization and quantification of the mineral evolution of clay minerals. In all the altered mixtures investigated, the illitization of clays was combined with the formation of anhydrite. These changes were accompanied by a dolomitization and a slight increase in the quartz content. The CO2-rich samples crystallized Fe2+-and K+-enriched illites, whereas the CO2-free experiments precipitated Al3+-deprived and Mg2+-enriched illites. Advanced characterizations of cap-rock material allowed reaction paths, induced by the increase in dissolved CO2 in the porous media, to be determined precisely. The results place strong constraints on numerical models aimed at evaluating the safety of an SMB site.

Functionalization of the interlayer surfaces of kaolinite by alkylammonium groups from ionic liquids

Abstract: The objective of this study was to design new, functional, nanostructured materials from the abundant claymineral kaolinite, in spite of development problems with the interlayer chemistry of kaolinite because of its non-swelling properties. A particular goal of this work was to graft, in a controlled way, alkylammonium groups onto the aluminol interlayer surfaces of kaolinite. This was successfully achieved by soft-chemical approaches, more specifically by the melting intercalation process of alkylammonium ionic liquids which were synthesized for this purpose. The resulting nanohybrid materials were characterized chemically and structurally by X-ray diffraction analysis, thermal analysis (TG/DTA), 13C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy, and Fourier-transform infrared spectroscopy. The amount of grafted organic material was quantified from TGA results. Alkylammonium salts with a short alkyl chain were grafted directly using a melting reaction at 180°C under N2 involving the in situ displacement of dimethylsulfoxide (DMSO) from a DMSO-kaolinite pre-intercalate; for longer alkyl chains, the grafting was done in two steps. In the first step, the corresponding amino-alcohol was grafted into the kaolinite by displacement of DMSO from the interlayer space. The second step consisted of quaternarization of the grafted material byreaction with iodomethane or iodoethane.

Birnessites with different average manganese oxidation states synthesized, characterized, and transformed to todorokite at atmospheric pressure.

Abstract: Todorokite is a common manganese oxide mineral, with a tunnel structure, found in Earth surface environments, and is easily synthesized from layered birnessite. The aim of the current study was to prepare birnessites with different average manganese oxidation states (AOS) by controlling the ${\rm{MnO}}_4^ - {\rm{/M}}{{\rm{n}}^{2 + }}$ ratio in concentrated NaOH or KOH. A series of (Na,K)-birnessites, Na-birnessites, and K-birnessites with different AOS was synthesized successfully in strongly alkaline media. The (Na,K)-birnessites and Na-birnessites prepared in NaOH clearly contained both large (500–1000 nm) and small (40–400 nm), plate-shaped crystallites. The K-birnessites prepared in KOH media consisted mostly of irregular (100–200 nm), plate-shaped crystallites. The degree of transformation of birnessite to todorokite at atmospheric pressure decreased as the AOS values of (Na,K)-birnessites and Na-birnessites increased from 3.51 to 3.80. No todorokite was present when a Na-birnessite with an AOS value of 3.87 was used as the precursor. Pyrophosphate, which is known to form strong complexes with Mn3+ at a pH range of 1–8, was added to a suspension of (Na,K)-birnessites in order to sequester the available Mn3+ in (Na,K)-birnessites. Removal of Mn3+ from birnessite MnO6 layers by pyrophosphate restricted transformation to todorokite — no (Na,K)-birnessite transformed to todorokite after pyrophosphate treatment. The interlayer K+ initially within (Na,K)-birnessites could not be completely ion-exchanged with Mg2+ to form todorokite at atmospheric pressure. No todorokite was forthcoming from K-birnessites even from those with small AOS values (3.50).

Rapid dehydroxylation of nickeliferous goethite in lateritic nickel ore: X-ray diffraction and TEM investigation

Abstract: A method for extracting Ni and other metals from lateritic ores by means of shock heating has been investigated. Shock heating releases some of the metal from its goethitic host. Even though the transformation of pure goethite to hematite is known to occur via intermediate hydroxylated phases, the effect of other metals such as Ni substituting for Fe in goethites on this thermal transformation to hematite is unknown. The purpose of this study was to fill this gap, with the hope that the results will lead to more energy-efficient extraction methods and/or a better understanding of Fe geochemistry in thermally activated soils. X-ray diffraction, transmission electron microscopy with EDS, and thermal analysis were used to investigate mineralogical changes in nickeliferous goethites from five oxide-type lateritic nickel ore deposits that had been subjected to shock heating at temperatures in the range 220–800°C. Acicular, nano-sized goethite was the main constituent of the samples with minor to trace amounts of quartz, talc, kaolinite, chromite, maghemite, and Mn oxides. Goethite was partially dehydroxylated to OH-hematite at 340–400°C and had completely altered to well ordered hematite at 800°C. The OH-hematite was characterized by broad XRD peaks for reflections associated with the Fe sublattice. The goethite unit-cell a and b lengths remained almost constant with increasing preheating temperature up to 300°C, while the size of the c axis dimension contracted. The neoformed hematite crystals were larger than the precursor goethite crystals due to development, by sintering and surface diffusion, of regularly ordered hematite domains. The increase (1.5–2.6 fold) in surface area with increasing heating temperature (up to 340–400°C) reflected the development of slit-shaped micropores (∼300°C), which further developed into elliptically shaped micropores (∼400°C) in OH-hematite. With increased heating temperature, well ordered hematite formed with only a few micropores remaining. Such results may contribute to the development of more efficient procedures for extracting Ni from lateritic nickel ores, as the rate of dissolution of goethite in acid in ‘heap and pressure’ leach facilities will be enhanced by the increases in surface area and microporosity. The results may also provide valuable information on the probable effects of natural heating on pedogenic Fe oxides.

A new massive deposit of allophane raw material in Ecuador

Abstract: In Ecuador, DINAGE (known today as the Servicio Geologico Nacional) and the German Federal Institute for Geosciences and Natural Resources have discovered a huge allophane deposit covering an area of >4000 km2 This study presents the results from an investigation of a 16-m thick vertical sequence from this deposit, supposedly the weathering product of two different volcanic ash deposits In particular, the distribution of alkali metals within the uppermost layer indicates that the weathering process is still ongoing According to the mineralogical composition, an allophane-rich layer (allophane facies) could be distinguished from the underlying halloysite-rich layer (halloysite facies) A 2-m thick transition zone is characterized by the presence of gibbsite and intermediate specific surface area values Only a few imogolite fibers could be identified (by scanning electron microscopy), indicating the dominance of allophane over imogolite in the allophane facies Single allophane particles were investigated by atomic force microscopy, though this method was less accurate than transmission electron microscopy with respect to the determination of the primary particle diameter Carbon isotope analysis (14C) suggested an age of ∼20,000 y for the allophane layer Within the allophane facies, a 4-m thick layer occurs containing 70–80 wt% allophane with an N2-BET specific surface area of >300 m2/g Based on infrared and energy-dispersive X-ray diffraction measurements, an Al/Si ratio of 13–14 was established for this allophane, which is between Al-rich and Si-rich allophane The allophane layer may be of economic value due to the large allophane content, the small amount of organic matter, and the significant thickness of the deposit

Variation of preferred orientation in oriented clay mounts as a result of sample preparation and composition

Abstract: In X-ray diffraction (XRD) analysis, preparation of oriented clay specimens enhances their 00l reflections by arranging basal surfaces parallel to the specimen surface. In one-dimensional modeling of XRD intensities, degree of preferred orientation is one of the variable parameters and a user may choose different σ* values for different minerals. The usual assumption is, however, that the layers of all clay minerals that are present exhibit a similar degree of preferred orientation to that of the clay mineral flakes parallel to the basal plane. If the orientation of individual clay minerals is significantly different, and if this is not taken into account, the relative proportions of the constituent minerals cannot be modeled accurately. The actual or so-called ‘preferred’ orientation is a potentially large source of error in any attempt at quantitative XRD analysis because it cannot be assumed to be constant among different minerals and may also vary as a result of pretreatment. In the present study the influence of sample composition and sample pretreatment on the degree of preferred orientation was determined using the parameter σ*. A statistical parameter was calculated to determine and ensure the reproducibility of σ* measurements. The most important result was that, when mixed together, clay minerals influence each other in terms of the degree of preferred orientation. Among individual samples, the degree of preferred orientation can be different for each clay mineral. The power of sonication used in sample pretreatment of a pure kaolinite and a pure illite had no significant influence on the degree of preferred orientation. The changes in intensities upon variation of the tilting angle (χ) allowed for calculation of σ* of smectites in pure samples, in admixtures, and in samples treated in two different ways (air-dried and glycerol-intercalated), which is reported here for the first time. Smectites are very fine grained with flexible morphology which is believed to be the reason for their tendency to exhibit poor orientation (σ* = 22°); further research is required to establish whether this is a general feature of smectites. After glycerol treatment a soil smectite showed a slightly better orientation compared to the air-dried pattern. The results of the study illustrate the difficulty of predicting changes in preferred orientation of clay mineral admixtures, even if non-platy minerals such as clay-sized quartz are added. In general, σ* decreased when non-platy minerals were added, which is explained by changes in geometry of the specimen. Not all clay minerals, however, showed simultaneous changes in their orientation behavior.

Near-infrared spectroscopic analysis of acid-treated organo-clays.

Abstract: The potential use of near-infrared (NIR) spectroscopy as a characterization tool for organo-clays would be a great asset but little work has been done in this regard because the application of NIR to clay mineral studies is a relatively new phenomenon. The purpose of this study was to use NIR spectroscopy to investigate the effect of alkylammonium cations on the acid dissolution of a high-charge montmorillonite (SAz-1). Detailed analysis of the spectra of Li+-, TMA+- (tetramethylammonium), and HDTMA+- (hexadecyltrimethylammonium) saturated SAz-1 montmorillonite in the NIR region was achieved by comparing the first overtone (2ν) and combination (ν+δ) bands of XH groups (X = O, C) with the fundamental stretching (ν) and bending (δ) vibrations observed in the mid-infrared (MIR) region. Comprehensive analysis of the vibrational modes of CH3-N, CH3-C, and -CH2-C groups of TMA+ and HDTMA+ cations detected in the MIR and NIR regions was also performed. Both MIR and NIR spectra demonstrated that exchange of Li+ by TMA+ only slightly improved the resistance of SAz-1 layers to dissolution in 6 M HCl at 80°C, while exchange by the larger HDTMA+ cations almost completely protected the montmorillonite layers from acid attack. Use of NIR spectra in reaching these conclusions was crucial. Only in the NIR region could the creation of SiOH groups be monitored, which is an important indicator of the acidification of the montmorillonite surface. The OH-overtone region in the spectra of Li-SAz-1 and TMA-SAz-1 revealed that the SiOH band near 7315 cm−1 increases in intensity with enhanced acid treatment. In contrast, no SiOH groups were identified in the NIR spectra of HDTMA-SAz-1 treated in HCl, indicating that HDTMA+ completely covers the inner and outer surfaces of the montmorillonite and hinders access ofprotons to the Si-O− bonds created upon acid treatment.

MINERALOGICAL AND PHYSICOCHEMICAL INVESTIGATION OF Mg-SMECTITE FROM JBEL GHASSOUL, MOROCCO

Abstract: ‘Ghassoul’ clay is a Mg-rich clay from Morocco which is of great industrial use and interest, but its characterization is still incomplete. The purpose of this study was to provide further details regarding the structure and characteristics of this important commercial clay mineral. Mineralogical and physicochemical characterizations of the raw form of ‘Ghassoul’ clay from Jbel Ghassoul in Morocco, and of its 800°C and that quartz was transformed to cristobalite when the temperature exceeded 1100°C. These transformations were irreversible. The specific surface area and cation exchange capacity (CEC) of the ‘Ghassoul’ clay are 133 m2/g and 75 meq/100 g, respectively. The main exchangeable cation is Mg2+ (53 meq/100 g).

PARTIAL DISSOLUTION OF GLAUCONITIC SAMPLES: IMPLICATIONS FOR THE METHODOLOGY OF K-Ar AND Rb-Sr DATING

Abstract: The K-Ar dating of glauconite has been used as an important stratigraphic tool for many decades. The application of this technique is limited to pure glauconites, free of detrital contamination by K-bearing phases, often not easy to detect. This study extends the application of isotope dating to the contaminated glauconites and offers a precise technique for detecting the detrital contamination of glauconites. The most common K-bearing detrital contaminants have smaller (K-feldspars, Al-rich dioctahedral micas) or greater (trioctahedral micas) dissolution rates than glauconite in extremely low pH solutions. The differences in the dissolution rates can be applied to evaluate the purity of the glauconite and its crystallization age. The interlaboratory GLO glauconite standard and grain-size fractions separated from glauconitic sandstones of the Paleogene (sample GL) and Jurassic (sample GW8) ages were treated with acid (3M HCl, at 99±2°C) for different reaction times (0.5–7 h) and measured for their apparent isotopic ages. Microporous amorphous silica with large specific surface area is the solid product of the reaction and its content increases with reaction time. The K-Ar dates (apparent ages) of the solid residues increase significantly with reaction time: from 44.6 to 107 Ma for the GL sample and from 125.7 to 394.7 Ma for GW8. The increase is negligible in the case of the GLO standard. The Rb-Sr data of the GL sample were modeled using initial 87Sr/Sr ratios of 0.707–0.709, which resulted in a 29.9–35.8 Ma date for the untreated portions of GL, and ∼42.6 Ma after 7 h of treatment. The increase of isotopic K-Ar date with increasing time of dissolution is interpreted to be a result of increasing concentration of detrital, acid-resistant, K-bearing minerals, observed also with the electron microscope and X-ray diffraction. Probabilistic modeling based on single (K-Ar) or double (K-Ar and Rb-Sr) isotopic systems evaluated the isotopic ages of the detrital and authigenic minerals, and their K2O and Rb concentrations. The crystallization ages computed using these two methods are: 24.0, 26.5, and 32.3 Ma for the GL material, and 117.3–121.8 Ma for the GW8 series. The proposed method based on partial dissolution is a potential tool for evaluating the reliability of glauconite dating.

Magnetic enhancement during the crystallization of ferrihydrite at 25 and 50°c

Abstract: Soil formation usually results in an increase in magnetic susceptibility. The magnetic properties of the products of transformation of ferrihydrite, a typical precursor of other soil Fe oxides, were examined in the present work. Synthetic 2-line ferrihydrite was aged at two temperatures (25 and 50°C) and two different relative humidities (80 and 100%) in the presence of silicate, phosphate, citrate, and tartrate as adsorbed ligands (molar anion/Fe ratio = 1–3%). The ligands delayed or prevented the transformation of ferrihydrite to hematite. The magnetic susceptibility of the ferrihydrite transformation products increased with aging, the rate of increase depending on the type of ligand added and its concentration. The largest increase in magnetic susceptibility, sixfold, was obtained with ferrihydrite in a citrate/Fe ratio of 1%, after 1500 days. The resulting magnetic products exihibited superparamagnetic behavior at room temperature and high coercivity at 5 K. The formation of an intermediate ferrimagnetic phase in the ferrihydrite-to-hematite transformation might explain the magnetic enhancement observed in many aerobic soils lacking other sources of magnetic minerals.

Terahertz Time-Domain Spectroscopy of Selected Layered Silicates

Abstract: Micaceous layer silicate clay minerals are attractive materials for applications involving non-linear optics because of their low cost and ability to form well ordered, platy aggregates, but such applications require precise knowledge of the dielectric behavior of the clay. The purpose of the present study was to use Terahertz time-domain spectroscopy (THz-TDS) to determine the dielectric properties of certain cleavable layered clay minerals, including muscovite, vermiculite, phlogopite, and biotite. The samples were characterized by X-ray diffraction and Fourier transform infrared spectroscopy as well as chemical analysis by Energy dispersive X-ray spectroscopy. The THz frequency window investigated was the far-infrared region of 3.3 to ∼40.0 cm−1 corresponding to 0.1 and 1.2 THz, respectively. The samples were selected so that the hydrated form of the interlayer cation, e.g. Mg2+ present in the interlayer gallery of vermiculite, could be compared to species such as phlogopite, biotite, and muscovite with the dehydrated form of interlayer cations such as K+ or Na+. The frequency-dependent complex index of refraction of these natural materials was determined to vary between 2.50 and 2.80. The presence of water in the interlayer space of vermiculite was reflected in the detection of increased values of the absorption index in comparison with the muscovite, phlogopite, and biotite.

ADSORPTION OF A C10E3 NON-IONIC SURFACTANT ON A Ca-SMECTITE

Abstract: The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C 10 E 3 ) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C 10 E 3 non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C 10 E 3 -clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C 10 E 3 adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca 2+ counterions. The adsorption of C 10 E 3 did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 A suggested a complete dissociation of the C 10 E 3 lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.

Kaolinite intercalation precursors

Abstract: The preparation and characterization of intercalated kaolinite is important for industries such as those using nanocomposites, but the number of compounds that can be intercalated into these clay minerals is rather limited. The purpose of this study was to expand the range of possible intercalants by developing intercalation precursors using both single and multiple (co-intercalation) precursor agents. Characterization of the resulting precursors was by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). The results show that the most successful single intercalation agent was DMSO and, among the co-intercalation agents, the DMSO/CH3OH system was the best. The preparation and characterization of kao-DMSO-KAc showed that the displacement reaction is the most efficient way to expand the interlayer spacing of kaolinite. At the same time, the lateral-bilayer arrangement of the Ac− in the interlayers was proven by study of de-intercalation of kao-KAc under high temperature.

The role of clay minerals in the preservation of organic matter in sediments of qinghai lake, nw china

Abstract: The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depth-related systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

Removal of a binary dye mixture of Congo red and malachite green from aqueous solutions using a bentonite adsorbent.

Abstract: An important application of clay is as a solid adsorbent for industrial dyes. The aim of the present work was to carry out an experimental-theoretical study of the adsorption of dye mixtures, namely malachite green (MG) and Congo red (CR), by bentonite. Adsorption studies were conducted after evaluation of the impact of several parameters, including pH, adsorbate dose, and contact time, on the removal of MG and CR. The pH of the dye solution is strongly affected by the chemistry of both the dye molecules and of the adsorbent in an aqueous solution. Where both dye molecules exist in solution, the optimum pH was found to be 8.2 in order to achieve the maximum adsorption of both MG and CR. Preliminary studies showed that 60 min of contact time is sufficient to reach adsorption equilibrium. The adsorption studies were carried out using 1.0 g samples of bentonite. The amount of dye adsorbed was found by application of classical least squares to the synthetic dye mixtures. Data from equilibrium adsorption on bentonite were analyzed by Freundlich, Langmuir, Redlich-Peterson, and Temkin isotherm equations using regression analysis for non-linear forms of those equations. For binary-mixture analysis, isotherm parameters were determined from single-component adsorption studies and the theoretical amount of dye adsorbed was calculated using an extended Langmuir isotherm. Non-linear error analysis showed that the Temkin and Redlich-Peterson isotherms gave the best fits to the equilibrium data for adsorptive removal of MG and CR by bentonite.

Crystal-chemical changes of mixed-layer kaolinite-smectite with progressive kaolinization, as investigated by tem-aem and hrtem

Abstract: The mechanism for the kaolinization of smectite is extremely complex. The purpose of this study was to explore this mechanism by providing more microscopic information about kaolinite-smectite (K-S) intermediate phases. Crystal-chemical changes were investigated and integrated in a model of the transformation mechanism. Eight K-S samples from three localities, derived from volcanic ash beds, were studied using transmission and analytical electron microscopy (TEM, AEM) and high-resolution TEM (HRTEM). The study completes a previous investigation, using several analytical techniques. The samples cover the range of K-S composition available from the previously studied sample set. Analysis by TEM indicated the preservation of particle morphology throughout the process. Most K-S particles had anhedral, smectite-like morphology, and only the most kaolinitic specimen revealed the coexistence of anhedral and euhedral, hexagonal particles. Analytical electron microscopy showed large chemical variations within samples, corresponding to various degrees of smectite kaolinization. Comparison of chemical results (Si/Al) and d060 values (proxy for octahedral composition) with the extent of kaolinization from thermogravimetry (TG) indicates that chemical changes in the octahedral sheet occur mainly when the proportion of kaolinite is 40–70%. The results above are consistent with kaolinization occurring via layer-by-layer transformation through the progressive loss of individual tetrahedral sheets in smectite layers and subsequent chemical changes in the octahedral sheet. Such a mechanism would produce the results observed in this study: (1) most particles preserve their original morphology; (2) significant variation in terms of the extent of transformation of particles within samples, and (3) formation of crystal structures intermediate between those of smectite and kaolinite, with parts of the tetrahedral sheets missing (kaolinite-like patches). Such structures become least stable at kaolinite ∼50%, when the perimeter of the kaolinite-like patches is largest and chemical changes in the octahedral sheet can occur more easily. Kaolinite layers could not be resolved by HRTEM in most cases and showed lattice fringes corresponding to superstructures. A model was established to quantify kaolinite and smectite layers in the HRTEM images with results which matched TG-derived values.

REMOVAL OF Fe FROM KAOLIN BY CHEMICAL LEACHING AND BIOLEACHING

Abstract: The use of microorganisms to remove Fe (oxyhydr)oxides from kaolins has the potential to be an effective method for upgrading the whiteness and brightness, and therefore the commercial value, of the kaolin. The purpose of the present study was to compare kaolin products obtained by currently used chemical leaching methods with a bioleaching treatment using Aspergillus niger in order to remove Fe from kaolin (from Canakkale, Turkey). The effects of pulp density, temperature, and oxalic acid concentration on the chemical leaching experiments were investigated using the ANOVA-Yates test. The greatest degree of removal of Fe from the kaolin sample (at 15% w/v pulp density, temperature of 80°C, oxalic acid concentration of 0.2 M, and a particle size of <63 µm) was found to be 94.89% in 120 min of leaching. The Fe content decreased from 1.723%) Fe2O3 to 0.088% Fe2O3. In a shake flask, bioleaching of kaolin by Aspergillus niger resulted in removal of 77.13% of the total Fe, suggesting that this strain is effective at removing Fe impurities from kaolin. The removal efficiency generally decreased with increased pulp density. The Fe content of the kaolin decreased from 1.723% Fe2O3 to 0.394% Fe2O3 (at 1% w/v pulp density, temperature of 25°C, Aspergillus niger 3 × 107 spores, and particle size of <63 µm) after 21 days of bioleaching.

Effect of silica polymerization on the oxalate-promoted dissolution of goethite

Abstract: Numerous studies have investigated the ligand-promoted dissolution of Fe (oxyhydr)oxides. In natural environments, inorganic ligands can compete with organic ligands for surface sites on (oxyhydr)oxides which may influence dissolution rates. Published research of this interaction and its effect on the dissolution of (oxyhydr)oxides is rare. The objective of the present study was to examine the extent to which silica, as a naturally occurring competitive ligand added in the form of silicic acid, impacts the oxalate-promoted dissolution of the common soil Fe (oxyhydr)oxide goethite. Sorbed silica reduced the oxalate-promoted dissolution rate of goethite at all surface coverages investigated. As initial silica solution concentrations increased from 0.50 mM to 5.0 mM, relatively little change in the dissolution rate was observed. Fourier-transform infrared (FTIR) spectra indicated that, as silica-surface coverages increased, the silica underwent polymerization on the goethite surface. Initially, silicate was associated with surface functional groups, but as polymerization occurred some of the silica appeared to desorb from the goethite surface without being released into the bulk solution, suggesting that silica polymers formed discrete islands or surface clusters that grew away from the goethite surface rather than expanding epitaxially across the surface. Minimal changes were observed in the quantity of reactive goethite surface, which is responsible for the observed dissolution rates, as silica-surface coverages increased.

APPLICATION OF 29Si AND 27Al MAS NMR SPECTROSCOPY TO THE STUDY OF THE REACTION MECHANISM OF KAOLINITE TO ILLITE/MUSCOVITE

Abstract: Understanding the mechanisms for illitization of clay minerals has important applications in reconstructing geologic histories and determining the origins of physical and chemical characteristics of buried sediments. While many studies have been carried out on this topic, few have focused on the mechanism of illite formation from kaolinite. The purpose of this study was to investigate more deeply the illitization of kaolinite in KOH solution at a high solid/liquid ratio (1000 mg/mL). X-ray diffraction (XRD) and infrared spectroscopy were used to follow the formation of new crystalline phases and the composition of the octahedral sheet, while the transformation of the Si and Al local environments was analyzed by 29 Si and 27 Al magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The results revealed that the first reaction stage consists of the diffusion of Al from the octahedral to the tetrahedral sheet of the kaolinite TO layers, giving rise to the precursors of the illite/muscovite nuclei. Combination of XRD with 27 Al MAS NMR measurements indicated that a minimum amount of tetrahedral Al is required in the original TO layer before condensation of a second tetrahedral sheet occurs to complete the formation of the illite/muscovite TOT layers.