Showing papers in "Clays and Clay Minerals in 2017"

Outcomes of 12 years of the reynolds cup quantitative mineral analysis round robin

Abstract: In 2000, The Clay Minerals Society established a biennial quantitative mineralogy round robin. The so-called Reynolds Cup competition is named after Bob Reynolds for his pioneering work in quantitative clay mineralogy and exceptional contributions to clay science. The first contest was run in 2002 with 40 sets of three samples, which were prepared from mixtures of purified, natural, and synthetic minerals that are commonly found in clay-bearing rocks and soils and represent realistic mineral assemblages. The rules of the competition allow any method or combination of methods to be used in the quantitative analysis of the mineral assemblages. Throughout the competition, X-ray diffraction has been the method of choice for quantifying the mineralogy of the sample mixtures with a multitude of other techniques used to assist with phase identification and quantification. In the first twelve years of the Reynolds Cup competition (2002 to 2014), around 14,000 analyses from 448 participants have been carried out on a total of 21 samples. The data provided by these analyses constitute an extensive database on the accuracy of quantitative mineral analyses and also has given enough time for the progression of improvements in such analyses. In the Reynolds Cup competition, the accuracy of a particular quantification is judged by calculating a “bias” for each phase in an assemblage. Determining exactly the true amount of a phase in the assemblage would give a bias of zero. Generally, the higher placed participants correctly identified all or most of the mineral phases present. Conversely, the worst performers failed to identify or misidentified phases. Several contestants reported a long list of minor exotic phases, which were likely reported by automated search/match programs and were mineralogically implausible. Not surprisingly, clay minerals were among the greatest sources of error reported. This article reports on the first 12 years of the Reynolds Cup competition results and analyzes the competition data to determine the overall accuracy of the mineral assemblage quantities reported by the participants. The data from the competition were also used to ascertain trends in quantification accuracy over a 12 year period and to highlight sources of error in quantitative analyses.

Baseline studies of the clay minerals society source clay montmorillonite stx-1b

Abstract: For more than forty years, The Clay Minerals Society has dispensed a set of source clays which have enabled a large number of researchers to work on similar materials. Many of these source clays remained unchanged over the years but, conversely, other clays have gone out of stock and thus were replaced. This was the fate of montmorillonite STx-1a, which was replaced by STx-1b. Although STx-1a and STx-1b share many basic chemical and mineralogical features, some minor differences exist that can affect behavior. A baseline characterization of the source clay STx-1b, which was the objective of this study, was, therefore, necessary to provide researchers a tool useful not only for new investigation but also to compare new results obtained on STx-1b with literature data on STx-1a. This characterization was gained using traditional and advanced methods that included: 1) chemical composition (major and trace elements); 2) cation exchange capacity determination; 3) thermal analyses coupled with evolved gas mass spectrometry; 4) quantitative mineralogical characterization using powder X-ray diffraction and Rietveld-RIR (Reference Intensity Ratio) refinement; 5) X-ray absorption spectroscopy at the Fe K -edge; 6) diffuse reflectance ultraviolet-visible and infrared spectroscopies; and 7) 29 Si, 27 Al, and 1 H magic-angle spinning nuclear magnetic resonance measurements. According to this multi-analytical approach, the chemical formula for STx-1b is [4] (Si 7.753 Al 0.247 ) [6] (Al 3.281 Mg 0.558 Fe 0.136 Ti 0.024 Mn 0.002 ) [12] (Ca 0.341 Na 0.039 K 0.061 )O 20 (OH) 4 .

REMOVAL OF Co2+, Ni2+, AND Pb2+ BY MANGANESE OXIDE-COATED ZEOLITE: EQUILIBRIUM, THERMODYNAMICS, AND KINETICS STUDIES

Abstract: The removal of Co2+, Ni2+, and Pb2+ from aqueous solutions using a modified zeolite was investigated because of the need to eliminate toxic contaminants from wastewaters. In the present study the ways in which equilibrium, thermodynamics, and kinetics parameters affected the removal of heavy metals were evaluated and compared. An Iranian clinoptilolite with a Si/Al ratio of 6.5 was used as an adsorbent. In order to increase the adsorption capacity of the adsorbent, it was converted to a manganese oxide-coated zeolite (MOCZeo) using various Mn solutions. The initial concentration of metals, pH, contact time, and temperature were the variables studied and optimal conditions were established. The maximum amount of Co2+, Ni2+, and Pb2+ adsorption on MOCZeo was ascertained. A thermodynamics study, using Δ G , Δ H , and Δ S state functions showed that adsorption of Pb2+ was more spontaneous than that of Co2+ and Ni2+ ions. The adsorption of these ions on MOCZeo was an endothermic reaction. Investigation of the adsorption models revealed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed both the Langmuir and Freundlich models. Kinetics studies showed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed the pseudo-second order kinetics model with a high correlation coefficient.

Mapping soil particle-size fractions using additive log-ratio (alr) and isometric log-ratio (ilr) transformations and proximally sensed ancillary data

Abstract: Together, the three particle size fractions (PSFs) of clay, silt, and sand are the most fundamental soil properties because the relative abundance influences the physical, chemical, and biological activities in soil. Unfortunately, determining PSFs requires a laboratory method which is time-consuming. One way to add value is to use digital soil mapping, which relies on empirical models, such as multiple linear regression (MLR), to couple ancillary data to PSFs. This approach does not account for the special requirements of compositional data. Here, ancillary data were coupled, via MLR modelling, to additive log-ratio (ALR) or isometric log-ratio (ILR) transformations of the PSFs to meet these requirements. These three approaches (MLR vs. ALR-MLR and ILR-MLR) were evaluated along with the use of different ancillary data that included proximally sensed gamma-ray spectrometry, electromagnetic induction, and elevation data. In addition, how the prediction might be improved was examined using ancillary data that was measured on transects and was compared to data interpolated from transects spaced far apart. Although the ALR-MLR approach did not produce significantly better results, it predicted soil PSFs that summed to 100 and had the advantage of interpreting the ancillary data relative to the original coordinates (i.e. clay, silt, and sand). For the prediction of PSFs at various depths, all ancillary data were useful. Elevation and gamma-ray data were slightly better for topsoil and elevation and electromagnetic (EM) data were better for subsoil prediction. In addition, a smaller transect spacing (26 m) and number of samples (9–16) might be adopted for mapping soil PSFs and soil texture across the study field. The ALR-MLR approach can be applied elsewhere to map the spatial distribution of clay minerals.

PROPERTIES OF THERMALLY TREATED GRANULAR MONTMORILLONITE-PALYGORSKITE ADSORBENT (GMPA) AND USE TO REMOVE Pb2+ AND Cu2+ FROM AQUEOUS SOLUTIONS

Abstract: The adsorption properties of clay minerals (e.g. montmorillonite and palygorskite) have been improved through chemical treatment methods. However, the addition of extra chemicals is often not friendly to the environment and powdered clay-mineral adsorbents are inconvenient for some applications. To overcome these drawbacks in the present study, granular montmorillonite-palygorskite adsorbents (GMPA) were successfully prepared using Na-alginate and thermal treatments to improve heavy metal removal from water. The properties of GMPA samples under different calcination temperatures were examined using thermogravimetric (TG) analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), and specific surface area (BET). The results indicated that loss of mass by GMPA relative to the untreated montmorillonite-palygorskite was due to the loss of water, adsorbed Na-alginate, and mineral decomposition during thermal treatment. Changes in the morphology and crystallinity were significant at calcination temperatures from 500°C to 1000°C. The layered morphology totally disappeared after calcination at 1000°C, while transformation of the montmorillonite and palygorskite to a non-crystalline material was almost complete at 800°C and new crystalline phases appeared. Calcination temperature had a significant influence on the specific surface areas and pore volumes of GMPA. Both the changes in texture and chemical structure affected Pb2+ and Cu2+ removal. The GMPA sample produced at a 600°C calcination temperature was the most promising adsorbent for heavy metal removal from water.

Insights into Diagenesis and Pore Structure of Opalinus Shale Through Comparative Studies of Natural and Reconstituted Materials

Abstract: Shales have undergone a complex burial diagenesis that involved a severe modification of the pore structure. Reconstituted shales can provide new insights into the nature of the pore structure in natural materials. The effects of diagenesis on the microfabric, pore size distribution, and porosity of Opalinus shale were measured by comparing the behavior of natural and reconstituted specimens. The parent material (Opalinus shale) was reconstituted through multiple grinding operations, sedimentation from a dispersed slurry, and one-dimensional isothermal consolidation. This process produced uniform specimens that were not cemented and had replicable microfabric and engineering properties. The microfabric and mineralogy of the materials were examined using high-resolution scanning/backscattered electron microscopy (SEM/BSEM) and energy-dispersive X-ray spectroscopy (EDS) for specimens with broken and milled surfaces. Mercury intrusion porosimetry (MIP) and N 2 adsorption were used to assess the pore size distributions and specific surface areas of the materials. The microstructure of natural shale was characterized to be highly heterogeneous with significant concentrations of calcareous microfossils, calcite, and quartz particles embedded within the clay matrix. The microfossils were observed to be locally infilled and rimmed by a calcite cement that showed evidence of dissolution. The reconstituted specimens showed a double-structure microfabric that evolved with the level of consolidation stress and converged into a single-structure material (comparable to the natural shale) at a consolidation stress of more than twice the estimated maximum in situ effective stress. The natural shale had a lower specific surface area in comparison to the reconstituted material, which was consolidated at large effective stresses. These differences can be attributed to cementation at a submicron pore scale and highlight chemical diagenesis effects that were not replicated in the reconstituted specimens.

Influence of montmorillonite nanoclay content on the optical, thermal, mechanical, and barrier properties of low-density polyethylene

Abstract: Although low density polyethylene (LDPE) has long been widely used in packaging applications, some limitations in its use still exist and are due to its relatively poor gas barrier properties and low mechanical strength which can restrict its extensive use for more advanced applications, such as electronic and pharmaceutical packaging. The purpose of this study was to investigate the possibility of using montmorillonite (MMT) nanoclay as a means to enhance the thermal, mechanical, and barrier properties of LDPE prepared via melt extrusion. The level of exfoliated dispersion of the MMT nanoclay in the prepared LDPE-MMT composite was confirmed using transmission electron microscopy (TEM). The relationship between the resulting morphology and the thermal, mechanical, and barrier properties as a function of the MMT content was evaluated. The results showed that incorporating >3 wt.% of MMT nanoclay produced significant changes in the morphology of the LDPE-MMT nanoclay composite in that the segregated matrix adopted an oriented arrangement of exfoliated clay platelets. Thermogravimetric analysis (TGA) showed that the thermal stability of LDPE improved significantly as a result of MMT nanoclay incorporation. Furthermore, differential scanning calorimetry (DSC) analysis indicated that increasing clay content above 3 wt.% effectively reduces the crystallinity of LDPE-MMT composites through the suppression effect. The tensile strength of LDPE increased gradually with an increased content of MMT nanoclay and the maximum value of 16.89 N/mm2 was obtained at 10 wt.% MMT content. This value represents a 40.87% increase relative to the tensile strength of the pristine LDPE. Barrier properties of LDPE and LDPE-MMT nanoclay composites were assessed by examining the permeability with respect to oxygen and water vapor. As the content of MMT nanoclay was increased to 10 wt.%, the permeability of the nanocomposite films to oxygen and water vapor notably decreased to 42.8% and 26.2%, respectively.

Kaolinite Aggregation in Book-Like Structures from Non-Aqueous Media

Abstract: To control a vast spectrum of applications and processes, an understanding of the morphologies of clay mineral assemblies dispersed in aqueous or non-aqueous media is important. As such, the objective of this study was to verify the relationship between dispersion medium type and the size and morphology of the clay aggregates that are formed, which can increase knowledge on the assembly formation process. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy were used in an attempt to describe kaolinite platelet organization in non-aqueous media and to compare it to the organization in aqueous media or in media with or without a selection of dissolved organic polymers. The SEM images indicated that the kaolinite platelet assembly process occurs during slow evaporation of the solvent. Because the experimental procedure was rigorously identical for all cases in this study, the SEM images compared how the effects of various media and environments on kaolinite platelet interactions can lead to different morphologies. Quite spectacular morphological differences were indeed observed between samples dispersed in aqueous and non-aqueous media, particularly when the kaolinite platelets were dispersed in an organic solvent with dissolved organic polymers. For kaolinite dispersed in water, only small aggregates were observed after slow evaporation. In contrast, large kaolinite booklets or vermiform aggregates were formed by slow solvent evaporation when kaolinite was first dispersed into some organic solvents. The aggregates were particularly large when an organic polymer was dissolved in the organic solvent. For example, kaolinite aggregates dispersed in a binary cyclohexane/toluene mixture with dissolved ethyl cellulose (EC) had top apparent surface areas (i.e. stacking length × width) of more than 3,000 µm2. Other dissolved polymers, such as polystyrene or the polysaccharide, guar gum, gave similar results. Kaolinite platelet aggregation resulted from face-to-face interactions as well as edge-to-face and edge-to-edge interactions. The XRD results showed that ethyl cellulose led to the formation of smaller kaolinite platelets with an increased tendency to form larger aggregates, which is due to the ability of EC to chemically interact with silanol and/or the aluminol groups of kaolinite.

Crystal-Chemical Regularities and Identification Criteria in Fe-Bearing, K-Dioctahedral 1M Micas from X-ray Diffraction and Infrared Spectroscopy Data

Abstract: Iron-bearing K-dioctahedral 1 M and 1 M d micas are abundant in diverse geological environments and vary in composition from illite to celadonite through Fe-illite, Al-glauconite, and glauconite. The chemistry and structural features of these micas are complex and heterogeneous, reliable diagnostic criteria are lacking, and the conventional mineralogical nomenclature is ambiguous, which complicate the identification of these mica varieties. The objectives of the present study were to reveal the structural and crystal-chemical variability in Fe-bearing, K-dioctahedral 1 M micas and to define composition ranges and identification criteria for the mica varieties in the series. A collection of samples of various compositions was studied using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. Analysis of the relationships between unit-cell parameters and cation composition showed that the series included four groups, namely, Fe-bearing illites, Al-glauconites, glauconites, and celadonites and each group was characterized by a specific combination of unit-cell parameters and variation ranges. The illite group contained two distinct subgroups; Fe-bearing, Mg-rich illites and Fe-illites; which differ in the range of cation compositions and in FTIR characteristics. The boundary between Fe-illites and Al-glauconites occurs at a unit cell b value of ~9.05 A and at ratios of octahedral Al to total trivalent octahedral cations that range between 0.60 and 0.65. The partially overlapping cation composition and cell parameter ranges may complicate the distinction between Al-glauconites and glauconites, which can still be unambiguously differentiated using FTIR data. The dramatically different XRD and FTIR characteristics confirmed that glauconite and celadonite should be treated as separate mineral species. The distinctive features of celadonite are relatively low c sinβ values and reduced | c cosβ /a | values combined with b parameters lower than glauconites, but similar to Fe-illites. Celadonites also have distinct and sharp FTIR absorption bands at specific positions in the Si-O and OH stretching regions.

The Properties of Clay Minerals in Soil Particles from Two Ultisols, China

Abstract: Soil aggregates consist of sand, silt, and clay size particles Many of the clay size particles in soils are clay minerals, which actively influence soil behavior The properties of clay minerals may change significantly as soil particle size decreases to the nanoscale; however, little information is available about these properties for the Ultisols in China In the present study, the clay mineral components and structural characteristics of four particle-size fractions (ie, <2000, 450–2000, 100–450, and 25–100 nm) of two Ultisol samples (Ult-1 and Ult-2) were investigated using elemental analysis, X-ray diffraction, Fouriertransform infrared spectroscopy, and thermal analysis The molar SiO2 to Al2O3 ratios were lower in the nanoscale particle-size fraction (25–100 nm) than in the 450–2000 and <2000 nm fractions This indicates greater desilicification and allitization of the smaller Ultisol particles Furthermore, the Fe oxide and Al oxide contents increased and reached a maximum level in the 25–100 nm fraction of the two Ultisols Goethite was mainly found in the 100–450 nm and 25–100 nm fractions The dominant clay minerals in the Ultisol 25–100 nm fraction were kaolinite and illite with a small amount of a hydroxy-interlayered mineral in Ult-1 and gibbsite in Ult-2 The kaolinite crystallinity decreased as particle size decreased The low crystallinity of the kaolinite in the A horizon 25–100 nm fraction was attributed to a reduction in the thickness of coherent scattering domains, as well as to decreases in OH groups and the dimensions of octahedral AlO6 sheets A determination of the chemical and mineralogic properties of the different size fractions of the Ultisols is important to understand the desilicification and Al and Fe oxide enrichment mechanisms during soil formation The significance of these results can help to reveal the nanoscale transformations of clay minerals Analysis of clay mineral compositions in nanoparticles can provide the additional data needed to understand the adsorption and mobility of nutrients and pollutants

Mineralogy, geochemistry, and genesis of bentonites in miocene volcanic-sedimentary units of the ankara-çankiri basin, central anatolia, turkey

Abstract: Widespread alteration in the Miocene lacustrine volcanic/sedimentary rocks of the Ankara-Cankiri basin of central Anatolia has resulted in the formation of sizeable (economic) quantities of bentonite deposits. No detailed characterization of the geological, mineralogical, and geochemical properties or the depositional environments of these primary and secondary bentonite deposits has been carried out to date. The present study was undertaken to close this knowledge gap. Two possible hypothetical processes were examined to explain the genesis of the bentonites: 1) The bentonites were formed by the devitrification of volcanic glass in a lacustrine setting; and 2) The bentonites were formed by the chemical weathering of previously deposited volcanic-clastic sediments and ophiolitic materials. The characteristics of the bentonites were examined using X-ray diffractometry, scanning and transmission electron microscopy, energy dispersive spectroscopy, and chemical analyses of major and trace elements. The Ankara-Cankiri bentonites are found gradationally interbedded with parent Miocene volcanic and volcaniclastic rocks. These bentonites were deposited in a shallow lacustrine setting based on observed desiccation cracks, locally enclosed coal seams, plant rootlets, gypsum lenses, yellow sulfate-like fracture infillings, and ferric iron oxide stains. Smectite resulted from the chemical weathering of feldspar and possibly also the weathering of biotite and hornblende. This smectite was precipitated in situ on partially dissolved glass and feldspar. The average major-element composition of the smectite-rich clay fractions yielded the following montmorillonitic smectite structural formula: (Na 0.33 Ca 0.31 K 0.18 )(Al 2.35 Fe 0.80 Mg 0.78 )(Si 7.79 Al 0.21 )O 20 (OH) 4 . The interlayer cation occupancy in the smectite-rich clay fractions was based on the use of Na + /(Na ++ Ca 2+ ) ratios and showed a composition between a Ca-smectite and a Na-smectite. The relative increases in several groups of elements according to the LREE /( MREE + HREE ) ratio, Al 2 O 3 , the sum of Ni+Co+Cr, the sum of Fe 2 O 3 +MgO+TiO 2 , the positive correlation between Rb+Ba and Na 2 O+K 2 O, Sr and Rb, Rb/Sr and Zr, Zr/Sm and SiO 2 , the negative Eu anomaly, and the field and petrographic observations further showed that the Si, Al, Fe, and Mg required to form smectite were mainly supplied from the decomposition of feldspars, amphiboles, and volcanic glass from volcanic materials and were partially supplied from the chemical weathering of ophiolitic basement units.

Preparation of organo-montmorillonites and the relationship between microstructure and swellability

Abstract: Hydrophobicity, swellability, and dispersion are important properties for organo-montmorillonites (OMnt) and have yet to be fully characterized for all OMnt configurations. The purpose of the present work was to examine the preparation of OMnt from the reaction of Ca2+-montmorillonite (Ca2+-Mnt) with a high concentration of surfactant and to reveal the relevant properties of hydrophobicity and dispersion of the resultant OMnt. A series of OMnt samples were prepared using a small amount of water and cetyltrimethylammonium bromide (CTAB) with a concentration more than the CTAB critical micelle concentration (CMC). The relationship between OMnt microstructure and the hydrophobicity and swellability properties was investigated in detail. The resulting OMnt samples were characterized using powder X-ray diffraction patterns (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric and differential thermogravimetry (TG-DTG), water contact angle tests, swelling indices, and transmission electron microscopy (TEM). The addition of CTAB and water in the OMnt preparation affected the OMnt microstructure and properties. An increase in CTAB concentration led to a more ordered arrangement of cetyltrimethylammonium (CTA+) cations in the interlayer space of the OMnt and a large amount of CTA+ cations on the outer surfaces of the OMnt. The swelling indices and the water contact angles of OMnt samples depended on the distribution of the CTAB surfactant on OMnt and the orientation of the surfactant hydrophilic groups on the inner and on the outer surfaces of OMnt. A maximum swelling index of 39 mL/g in xylene was achieved with an average water contact angle of 62.0° ± 2.0° when the amount of CTAB added was 2 times the cation exchange capacity (CEC) of Mnt and the lowest water to dry Mnt mass ratio was 3 during the preparation of OMnt samples. The platelets of OMnt aggregated together in xylene by electrostatic attraction and by hydrophobic interactions.

The Solid-State Conversion of Kaolin to KAlSiO4 Minerals: The Effects of Time and Temperature

Abstract: In recent years KAlSiO4 polymorphs have become minerals of interest from an industrial point of view; they have various applications in technological and medical fields. The costs of synthesis processes are often significant and so, in the present study, an attempt was made to develop a new synthesis protocol using a widely available and inexpensive, natural starting material. The KAlSiO4 polymorphs synthesized here were kalsilite and KAlSiO4-01 — 01 refers to the high-temperature polymorph of KAlSiO4 (Cook et al., 1997; Gregorkiewitz et al., 2008; Kremenovic et al., 2013). KAlSiO4 polymorphs were synthesized using kaolin; the effects of time and temperature on the synthesis process were investigated. A solid-state synthesis protocol was developed which required the mixing of the calcined kaolin with K2CO3 in stoichiometric proportions at temperatures of 700 and 800°C at atmospheric pressure. Crystallization of kalsilite at 700°C was demonstrated while that of KAlSiO4-01 was revealed at 800°C. Synthetic kaliophilite H2 was found in both of the experiments as a metastable phase. The products of synthesis were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR), and 29Si magic-angle spinning solid-state nuclear magnetic resonance spectroscopy (29Si MAS NMR). Calculation of cell parameters (through Rietveld refinement) and the density and specific surface area of the phases synthesized was also achieved. The amount of amorphous phase in the synthesis powders was estimated by means of quantitative phase analysis using the combined Rietveld and reference intensity ratio methods. In particular, the results of the spectroscopic, chemical, and morphological characterizations are in agreement with the data available for these minerals in the literature, thus confirming the effectiveness of the experimental protocol. The quantitative phase analysis (QPA) also indicated the high purity of the powders synthesized, thus allowing for industrial applications.

Adsorption of pyrene from aqueous solutions onto sepiolite

Abstract: Polycyclic aromatic hydrocarbons (PAHs) are commonly referred to a large class of organic compounds, which have been shown to be highly carcinogenic, and to have a significant persistence in an environment for many years. In this study, the adsorption of pyrene, which was chosen as a model PAH due to its specific volatility, miscibility, and relatively soluble properties, onto sepiolite (Turkish origin) was investigated in detail. Pyrene used as a model PAH due to its specific volatility and miscibility characteristics, relatively soluble yet hydrophobic to explore the potential of sepiolite (Turkish origin) to sorb hydrophobic organic compounds from aqueous solution. The microstructure and morphology of sepiolite were characterized by using Elemental analysis, X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscope (FE-SEM), and surface property evaluation by the BET method from nitrogen adsorption isotherms. The results for the adsorption isotherms were closely fitted with the Langmuir model, and the coefficient of determination (R2) was higher than 0.999. The results indicated that the high affinity of pyrene on sepiolite surfaces was dominated by structural channels and large number of Si-OH groups located at the basal surfaces. However, its intracrystalline interactions with pyrene were more favorable than the surface Si-OH groups which could react directly with pyrene to form compounds with true covalent bonds (chemical interactions) between sepiolite and pyrene. Finally, the FE-SEM images initially revealed that after loading with pyrene, fairly straight and rigid fiber arrangement (aggregation of laths to form rods) occurred due to increasing sorption of pyrene onto sepiolite.

Density functional theory computation of organic compound penetration into sepiolite tunnels

Abstract: Sepiolite is a fibrous clay mineral and consists of 2:1 silicate blocks connected at the corners and separated by tunnels (channels on external surfaces) that extend in the direction of fiber length. The tunnels, 3.7 A × 610.6 A in cross-section, are responsible for the incorporation of organic and inorganic compounds. The present study aimed to examine the capacity of twelve different organic molecules, such as pyridine, indigo, methylene blue, and quaternary amines, to gain access to the tunnels of sepiolite using quantum chemistry techniques. The interaction energy computations performed at the B97-D/TZVP level showed that all of the considered organic molecules tend to access the tunnels of sepiolite if external water molecules are absent. This finding is in agreement with experimental studies that included pyridine, indigo, 2,2-bipyridyl, and methylene blue. Interestingly, 2,6-dimethyl pyridine preferred to remain in a tunnel rather than an external channel of the sepiolite.

An Approach to Genesis of Sepiolite and Palygorskite in Lacustrine Sediments of the Lower Pliocene Sakarya and Porsuk Formations in the Sivrihisar and Yunusemre-Biçer Regions (Eskişehir), Turkey

Abstract: The Lower Pliocene lacustrine sediments of the Sakarya and Porsuk Formations in the Sivrihisar and Yunusemre-Bicer regions consist of claystone, argillaceous carbonate, carbonate, and evaporites No detailed studies of paleoclimatic conditions have been performed previously The present study aimed to determine the depositional environment and paleoclimatic conditions for the formation of these economically important sepiolite/palygorskite/carbonate/evaporite deposits based on detailed mineralogical, geochemical, and isotopic studies Samples from various lacustrine sediments were examined using polarized-light microscopy, X-ray diffraction, canning electron microscopy, and chemical and isotopic analysis methods Dolomites are predominantly of micrite, which is partly recrystallized to dolomicrosparite/dolosparite close to desiccation fractures The presence of ostracods and dacycladecean algae in the carbonates reflects a restricted depositional environment The formation of sepiolite and palygorskite fibers, either as cement between/enclosing dolomite and/or as calcite crystals, reflects occasional changes in physicochemical conditions provided by fluctuations in the lake-water level and influx of groundwater in relation to climatic changes during and after dolomite precipitation The positive correlations of ΣREE with Al2O3, Nb, high-field-strength elements, and transition elements are due to alteration of feldspar and hornblende in the volcanic units The high values of Ba and Sr relative to Cr, Co, Ni, and V also indicate that felsic rather than ophiolitic rocks were the parent material The crossplot of whole-rock SiO2vs Al2O3+K2O+Na2O and V/Cr ratio suggests deposition of carbonate-dolomitic sepiolite-sepiolitic dolomite under arid climate and oxic conditions, whereas the Ni/Co and V/(V+Ni) ratios of the sediments indicate deposition of organic-bearing sepiolite/palygorskite under anoxic-dysoxic conditions An enrichment in δ13C and δ18O values of dolomite with respect to calcite is probably due to differences in mineral fractionations The δ34S and δ18O values and 87Sr/86Sr isotope ratios for gypsum suggest an intensely evaporitic lacustrine environment fed by an older marine evaporitic source The Si, Al, Mg, Ca, and enhanced TOT/C required for periodic precipitation of organic-rich brown sepiolite/palygorskite characterize deposition in a swampy environment, while dolomitic sepiolite and sepiolitic dolomite formed in ponds by partial drying of the main alkaline lake

Characterization of the Second Parcel of the Alternative Buffer Material (ABM) Experiment — I Mineralogical Reactions

Abstract: The performance of bentonite barriers for high level radioactive waste (HLRW) disposal is currently being tested in various real-and up-scale disposal tests. One of the disposal tests, the ABM test (ABM = alternative buffer material), was conducted by SKB (Svensk Karnbranslehantering) as a mediumscale experiment at the Aspo hard rock laboratory in Sweden. The present study deals with the second parcel (ABM-II), which was retrieved after 6.5 years with 2.5 years of water saturation and 3–4 years of heating up to 141°C. Nine different bentonites and two marine clays were tested to investigate the performance. The aim of the study was to provide a detailed characterization of the mineralogical and chemical changes that took place in ABM-II, compare the findings with ABM-I (the first of the six test parcels), and try to draw some general conclusions concerning the use of bentonites in such geotechnical barriers. The ABM-II test parcel revealed a set of reactions that a HLRW bentonite might undergo. The most prominent reaction was the rather complete exchange of cations, which was discussed in a second part to this publication (II — cation exchange; Dohrmann and Kaufhold, 2017). The corrosion of the Fe in metal canisters was observed, but no discrete corrosion product was identified. At the interface of bentonite and the metal canister, the formation of smectite-type trioctahedral clay minerals was observed. In contrast to the ABM-I test, anhydrite was present in many of the bentonite blocks of the ABM-II test. In most concepts used for HLRW disposal in crystalline rocks, a temperature below 100°C at the canister surface was applied to avoid boiling. In the ABM-II test, boiling of water was possibly observed. Throughout the experiment, a pressure/water loss was recorded in the upper part of the geotechnical barrier and water was added to maintain pressure in the bentonite. As a result of evaporation, NaCl crusts might have formed and the barrier was partly disintegrated. These results demonstrated that a reasonable assumption is that no boiling of water occurs in disposal concepts in which a pressure loss can occur.

Solid-State 1H and 27Al NMR Studies of DMSO-Kaolinite Intercalates

Abstract: Nuclear magnetic resonance (NMR) provides a powerful tool to describe local nuclear environments. In this work, unique structural information on kaolinite and on kaolinite dimethylsulfoxide (DMSO) intercalate were provided by solid-state 1H and 27Al magic-angle spinning (MAS) NMR. The interlayer chemistry of kaolinite (K) was examined by intercalating a select group of highly polar organic molecules or salts into kaolinite as a first step. Once the interlayer space is expanded, the intercalated compounds can be replaced in a second step. Intercalating DMSO into kaolinite to form the DMSO-K intercalate is, thus, a particularly useful first step toward the intercalation of a large variety of molecules, including polymers and ionic liquids. Well developed characterization methods are essential to define the structural modifications of kaolinite, and MAS NMR is a useful complement to other techniques. The use of 1H and 27Al MAS NMR for this purpose has been relatively rare. 1H NMR, nevertheless, can give unique information about kaolinite hydroxyls. Because quadrupolar interactions are sensitive to the local octahedral Al(III) geometry, solid-state 27Al NMR can follow subtle structural modifications in the octahedral sheet. In the present work, the 1H MAS NMR chemical shifts of KGa-1b were unambiguously attributed to the internal surface hydroxyls at 2.7 ppm and to the internal hydroxyls at 1.7 ppm. The 1H MAS NMR chemical shifts of the two methyl groups in DMSO-K are not equivalent and can be attributed to the 2.9 and 4.2 ppm peaks. The 27Al MAS NMR spectra of KGa-1b obtained under different magnetic fields revealed that most of the quadrupolar effects were highly reduced at 21.1 T, whereas the spectra at lower field, 4.7 T, were dominated by quadrupolar effects. The two octahedral Al(III) sites are not equivalent and can be distinguished in the low-field spectral simulation. Increased quadrupolar constants were observed and showed the major perturbations of the local Al symmetry that resulted from DMSO intercalation. Both the 1H and 27Al MAS NMR studies at different magnetic fields afforded important information about the local environments of the kaolinite hydroxyl groups and structural Al(III).

Preferred Orientation Patterns of Phyllosilicates In Surface Clays

Abstract: The alignment of phyllosilicates in clays has received a lot of attention because it is a major cause of seismic anisotropy in the Earth’s crust. Thus far, all attention has been on shales where the orientation pattern has been attributed to compaction and observed to increase with burial depth and diagenetic processes. Here, for the first time, the same methods that were developed to quantify shale preferred orientation were applied to clays forming in surface environments, a seasonal streambed in Death Valley, California; a mudpool from mud volcanoes in Imperial Valley, California, close to the Salton Sea; and a glacial lake from Val Albigna in the Swiss Alps. Preferred orientation was analyzed quantitatively with high-energy synchrotron X-ray diffraction. All three samples showed strong alignment of phyllosilicates with (001) pole figure maxima 2–4 multiples of a random distribution, comparable to shales, and indicating that significant preferred orientation can be produced at surface conditions. The original alignment during sedimentation may be an important factor for the final microstructure in many shales.

Molecular Dynamics Simulation of Alkylammonium-intercalated Vermiculites

Abstract: In order to understand the microscopic properties of alkylammonium-intercalated vermiculites, molecular dynamics simulations employing the clayff-CVFF force field were performed to obtain the interlayer structures and dynamics. The layering behavior of alkyl chains was uncovered. With the model used in the present study (1.2 e per unit cell), the alkyl chains formed monolayers with carbon-chain lengths of C6, bilayers from C7 to C10, and pseudo-trimolecular layers from C15 to C18. Intermediate states also existed between bilayer and pseudo-trimolecular layer states from C11 to C14. The ammonium groups had two locations: most ammonium groups were located over the six-member rings (~90%), and the rest above the substitution sites (~10%). The ammonium groups interacted with the vermiculite surface through H bonds between ammonium H atoms and surface O atoms. The ammonium groups were fixed firmly on surfaces and, therefore, had very low mobility. The alkyl chains were slightly more mobile. The similarities and differences between alkylammonium-intercalated vermiculites and smectites were revealed. The layering behaviors of alkyl chains were similar in alkylammonium-intercalated vermiculites and smectites: the alkyl chain behavior was controlled by both the amount of layer charge and the carbon chain length. The distributions of ammonium groups, however, were different, caused by the layer-charge distribution in vermiculites being different from that in smectites. The atomic-level results derived in the present study will be useful for future research into and the applications of organo-vermiculites.

Controllable Preparation of Zeolite P1 From Metakaolin-Based Geopolymers via a Hydrothermal Method

Abstract: A more controllable method to synthesize particular zeolites from geopolymers is needed in order to effectively use these materials in industrial applications. In the present study, a well-crystallized zeolite P1 was synthesized from a metakaolin-based geopolymer (SiO2/Al2O3=3.2) using a hydrothermal method. The products obtained by hydrothermal treatment were identified using X-ray diffraction (XRD), scanning electron microscopy (SEM), and specific surface areas. The XRD patterns and SEM micrographs indicated that the structure and morphology of zeolite P1 could be controlled by the NaOH solution concentration, hydrothermal temperature, and the hydrothermal treatment time. The crystalline structure of the prepared zeolite P1 was refined using the Rietveld method and the crystal structure parameters were as follows: a = 10.01 A, b = 10.01 A and c = 10.03 A. The optimal hydrothermal conditions to form zeolite P1 were 24 h at a hydrothermal temperature of 100°C and 2.0 M NaOH solution. Moreover, the synthesized zeolite P1 had a specific surface area of 36.56 m2/g.

Characterization of the Second Package of the Alternative Buffer Material (ABM) Experiment — II Exchangeable Cation Population Rearrangement

Abstract: Bentonites are candidate materials for encapsulating radioactive waste within barrier systems in crystalline rocks In the ‘Alternative Buffer Material’ (ABM) test in the hard rock laboratory in Aspo, Sweden, six packages of eleven different buffer materials (mainly bentonites) with various exchangeable cation populations were packed vertically with an iron tube used as a heater in the center After installation, the second ‘ABM package’ (ABM-II) was first allowed to saturate with water for approximately 25 years The blocks were then exposed to a temperature of up to 141°C for approximately 3–4 years The hypotheses for the present study were: (1) no horizontal gradient of the cation exchange population was present in the individual blocks of ABM-II because ABM-II had a longer reaction time in comparison to the ABM-I package, which did not have horizontal gradients; (2) the exchangeable cation Ca2+:Na+:Mg2+ ratio was equal in all blocks of ABM-II and was independent of block position in the package As expected from ABM-I, all blocks in the ABM-II experiment showed large differences between the measured values of the reference materials and the reacted samples The exchangeable Na+ and Mg2+ values in ABM-II were reduced by up to 55% to 59% in comparison to the reference material Contrary to the first hypothesis, horizontal gradients were observed in ABM-II; and, contrary to the second hypothesis, the exchangeable cation ratios differed markedly in the different reacted buffer materials The largest total Na+ loss was observed in the middle part (-67%), whereas Mg2+ values decreased by 79% in the upper part The exchangeable Ca2+ values increased strongly in ABM-II, particularly in the upper part The most useful parameter to distinguish between ion exchange equilibria of ABM-I and ABM-II was the Na+/Mg2+ ratio This ratio was constant in ABM-I (30) and had a similar ratio (35) in the lower part of ABM-II; however, the ratio strongly increased (5–10) in the upper part of the ABM-II package The large Na+/Mg2+ ratios in the upper part of ABM-II could possibly be explained by water loss into the rock (caused by a pressure drop and boiling) and subsequent water uptake

Effect of Temperature on Halloysite Acid Treatment for Efficient Chloroaniline Removal from Aqueous Solutions

Abstract: Monochloroanilines and dichloroanilines are important reagents or chemical intermediates in the production of dyes, pharmaceuticals, and agricultural chemicals. These toxic compounds have a large tendency to accumulate in the environment and a low natural biodegradability, so improved methods to remove or sequester them are needed. Halloysite is used as an efficient adsorbent to remove toxic compounds, such as aniline, from aqueous solutions. The purpose of this study was to evaluate whether acid-activated halloysites from the “Dunino” (Poland) strip mine could be effective in the removal of not just aniline but also of its chloro-substituted forms from aqueous solutions. The composition, structure, and morphology of activated halloysites were characterized using the following methods: wavelength dispersive X-ray fluorescence analysis (WDXRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), and N2 adsorption-desorption analysis. The acidactivated halloysites had an increased ability to remove aniline and chloroanilines from aqueous solutions as the acid activation temperature was increased. This suggests that the acid activation temperature is an important factor that influences the ability of acid activated halloysites to adsorb aromatic amines (anilines) from water. The efficiency of aniline and chloroaniline removal by halloysite activated at 80°C reached maximum levels, especially for the removal of aniline and 4-chloroaniline. The adsorption isotherm data were best described by the Langmuir adsorption model. The values of the Langmuir adsorption constants were calculated using the inverse liquid chromatography method.

Application of the Rietveld method in the Reynolds Cup contest.

Abstract: The Reynolds Cup (RC) is a unique round-robin competition that was established by The Clay Minerals Society in 2000 to assess the level of precision and accuracy that is attainable for the mineralogical analysis of a wide range of complex clay-rich materials. Although the Reynolds Cup roundrobin allows any possible analysis methods, X-ray diffraction (XRD) is by far the most frequently used technique. It is not only used to identify components, but also for quantitative phase analysis (QPA). QPA means determination of the relative concentrations of the coexisting phases in a mixture, commonly as a weight percent (wt.%) or mass fraction. Several approaches allow a quantitative determination of mineral contents, such as the Rietveld method (Rietveld, 1967). The successful application of the Rietveld method for QPA requires that all components are correctly identified and that the component diffraction patterns are appropriately described, which is preferably based on structure. In addition, the quality of a Rietveld quantification also depends on suitable sample preparation and measurement conditions, as well as a correct description of instrument configurations. Results from all previous Reynolds Cup contests show that a successful quantification depends strongly on the skill of users. Although the refinement procedure itself is automatic and, therefore, user independent, the results are strongly influenced by the structural models and refinable parameters that are selected and on the limitations of those parameters. Selected examples for the successful application of Rietveld refinement as well as the limitations of the method will be discussed in this article. The goal of the present work was to demonstrate that the Rietveld method is in principle capable of quantifying all Reynolds Cup samples with a high degree of accuracy, but sample specific difficulties and analysts’ inexperience may impede successful application. Incorrect results are often not indicated simply by low residuals or good fits. All refinement results should be validated and corrected using supplementary techniques, even if the results appear acceptable.

An experimental study on transforming montmorillonite to glauconite: implications for the process of glauconitization

Abstract: The objective of this study was to explore the geological origin of glauconite, which is believed to precipitate and mature very slowly (~1 Myr) in neritic environments (shallow water, oceanic coastal zones, at water depths of 100–200 m) with very low sedimentation rates. A series of simulation experiments was designed and carried out in sealed tubes placed in an oven and heated to a constant temperature of 50°C (±2°C) for 60 or 150 d. The parent materials used for these experiments were two low-Fe montmorillonites with different crystallinities. The montmorillonites were introduced to solutions with concentrations of 0.02–0.1 mol/L Fe3+ and 0.05–0.2 mol/L K+ with various values of pH and Eh. The products were analyzed using X-ray powder diffraction (XRD), Fourier-transform infrared (FTIR) spectrometry, electron spin resonance (ESR) spectrometry, scanning electron microscopy (SEM), and Mossbauer spectroscopy. The morphological changes from parent material to product were observed under SEM, which revealed the formation of a flaky mineral (e.g. a product formed in the interstitial spaces between montmorillonite crystals). The formation of a flaky mineral indicates that the product is a layer silicate. Qualitative analysis of XRD patterns revealed that the main product phase was a mica group mineral and the d060 value was consistent with the presence of glauconite (0.152 nm) and/or Fe-illite (0.150 nm). A glauconite and Fe-illite mineral assemblage formed in a weakly acidic solution, while Fe-illite, mixed-layer Fe-illite, and montmorillonite formed in neutral and alkaline solutions. Stretching vibrations of Fe(III)Fe(III)OH-AlFe(II)OH and/or MgFe(III)OH were observed in FTIR spectra (3550–3562 cm−1) of the products formed in acidic solutions, which along with the g = 1.978 ESR signal indicated that Fe(III) entered octahedral positions in the tetrahedral/octahedral/tetrahedral layer (TOT) platelets. The AlFe(II)OH-MgFe(III)OH (3550–3562 cm−1) and AlFe(III)OH (870 cm−1) vibrations were only observed in products formed in neutral and alkaline solutions. Analysis of the Mossbauer spectra showed that Fe(III) substituted for Al and Mg in the cis octahedral sites of montmorillonite. The simulation experiments demonstrated that the pH and redox conditions (Eh) of the environment controlled the nature of the product mineral species. Results of the present study revealed that glauconitization and illitization occurred under different conditions, where glauconitization preferentially occurred in an acidic environment and illitization preferentially occurred in a nearly neutral to alkaline environment.

Thermal Conductivity and the Unfrozen Water Contents of Volcanic Ash Deposits in Cold Climate Conditions: A Review

Abstract: Layers of volcanic ash and Andosol soils derived from the ash may play an important role in preserving snow and ice as well as in the development of permafrost conditions in (a) the immediate vicinity of volcanoes at high elevations or at high latitudes and (b) land areas that are often distant from volcanic activity and are either prone to permafrost or covered by snow and ice, but have been affected by subaerial ash deposition. The special properties of volcanic ash are critically reviewed, particularly in relation to recent research in Kamchatka in the Far East of Russia. Of special importance are the thermal properties, the unfrozen water contents of ash layers, and the rate of volcanic glass weathering.Weathering of volcanic glass results in the development of amorphous clay minerals (e.g. allophane, opal, palagonite), but occurs at a much slower rate under cold compared to warm climate conditions. Existing data reveal (1) a strong correlation between the thermal conductivity, the water/ice content, and the mineralogy of the weathered part of the volcanic ash, (2) that an increase in the amounts of amorphous clay minerals (allophane, palagonite) increases the proportion of unfrozen water and decreases the thermal conductivity, and (3) that amorphous silica does not alter to halloysite or other clay minerals, even in the Early Pleistocene age (Kamchatka) volcanic ashes or in the Miocene and Pliocene deposits of Antarctica due to the cold temperatures. The significance of these findings are discussed in relation to past climate reconstruction and the influence of volcanic ash on permafrost aggradation and degradation, snow and ice ablation, and the development of glaciers.

Oxidation and catalytic oxidation of dissolved sulfide by manganite in aqueous systems

Abstract: As one of the strongest inorganic oxidizers in natural environments, manganese oxides participate in the oxidation processes of dissolved sulfides, affecting their migration, transformation, and toxicity The amount of and sites for Mn(III) influence significantly the oxidation activity of Mn(IV) oxides As an easily formed Mn oxide in supergene environments, manganite consists of Mn(III)O6 octahedra; further study is needed of the interaction processes of manganite and dissolved sulfide In the present study, the interaction mechanisms of dissolved sulfide and manganite were studied systematically The influences of pH, temperature, and oxygen atmosphere were also investigated in detail X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the crystal structures, compositions, and micromorphologies of manganite and the intermediate products The sulfide species were identified by visible spectroscopy, high-performance liquid chromatography, UV-visible (UV-Vis) spectroscopy, and ion chromatography during the reaction process The results indicated that in a nitrogen atmosphere, elemental sulfur was formed as the main oxidation product of dissolved sulfide by manganite at the initial stage, and polysulfide ions were observed as the intermediates Elemental sulfur was further oxidized slowly to S2O 3 2− The initial oxidation rate of dissolved sulfide by manganite increased with temperature from 20 to 40°C The reaction rate increased at first and then decreased as the pH changed from 40 to 120, and the greatest oxidation rate was achieved at pH 80 In the presence of oxygen, S2O 3 2− was the main product The oxidation rate of dissolved sulfide decreased, and manganite exhibited significant catalytic activity and stability with respect to the oxidation of dissolved sulfide in the oxygenated aqueous systems These findings are of fundamental significance in understanding the interaction and transformation of dissolved sulfide and manganese oxides in nature

Formation of NH4-Illite-Like Phase at the Expense of Dioctahedral Vermiculite in Soil and Diagenetic Environments — An Experimental Approach

Abstract: Selective sorption and/or fixation of cations with low hydration energies (e.g. K+, NH 4 + , Rb+, Cs+) by vermiculites is a well known phenomenon in soil science and it has been described by many investigators since the 1950s. Because most of the available studies deal with trioctahedral vermiculites, cation fixation in dioctahedral vermiculites is not as well understood as fixation by trioctahedral structures. The objective of the present study was to investigate the influence of NH 4 + saturation on the structure of a natural dioctahedral vermiculite. Because no dioctahedral vermiculite standard reference material was available, two natural dioctahedral vermiculite-rich soil clay samples were used in the study. The clays were saturated with NH 4 + using different protocols to simulate natural processes that likely take place in soils. The degree of NH 4 + fixation by the dioctahedral vermiculite was evaluated using X-ray diffraction, elemental N analysis, and infrared spectroscopy. All the treatments that involved NH 4 + saturation caused NH 4 + fixation and irreversible collapse (i.e. contraction to ~10 A) of at least a portion of the previously hydrated (vermiculitic) interlayers. Air drying of the NH 4 + -saturated samples greatly enhanced the degree of the collapse. The results indicated that the collapse of dioctahedral vermiculite leads to the formation of a NH4-illite-like phase that is likely to occur in some soils and sediments that are rich in organic matter. The formation of a NH4-illite-like phase by NHNH 4 + fixation in vermiculitic interlayers needs to be taken into consideration in studies that deal with the clay mineralogy of sedimentary basins.

Measurement of swelling of individual smectite tactoids in situ using atomic force microscopy

Abstract: Atomic force microscopy (AFM) is a novel method for measuring changes in clay swelling in situ at the tactoid level in an aqueous environment While the swelling process has been directly observed at the mesoscale level for multi-tactoid aggregates and the associated pores, no method to date has allowed the direct observation of swelling dynamics at the nanoscale In initial proof-of-concept studies, individual tactoids of a Na-exchanged nontronite (NAu-1) were imaged in a solution of 5 mM NaCl When multiple line profiles were examined on the same tactoid, the changes in height varied and depended on which layers of the profile were transected, and demonstrated that AFM analyses can be used to directly probe intratactoid heterogeneity in the swelling process To better visualize this heterogeneity, a method was developed to restrict AFM images to include only the portions of a tactoid above a threshold height A comparison of the changes in these images for multiple threshold values revealed that swelling in one part of a tactoid may occur simultaneously with compression in another portion, which suggests that the encroachment of layers into intra-tactoid micropores can partially compensate for the overall volume change Finally, to demonstrate the ability of this technique to monitor in situ swelling changes as the surrounding aqueous environment is modified, a tactoid of K-montmorillonite (SWy-2) was monitored during cation exchange as a KCl solution was replaced with NaCl After exchange, a transition from the crystalline swelling regime to the osmotic regime was observed Subsequent height profiles were unchanged for a period of several hours and indicated that the AFM measurements were stable in the absence of changes to the aqueous phase composition Because this technique is the first method that allows the swelling of a single tactoid to be monitored in an aqueous solution, it complements the ensemble-averaged data obtained from diffraction and scattering techniques

Testing high-voltage electrical discharges in disintegrating claystone for isotopic and mineralogical studies: an example using Opalinus claystone.

Abstract: The radiogenic isotope systematics of clay minerals are complex because of the intimate mixture of minerals from different origins such as detrital and authigenic sources. An important aspect of dating clays is the primary sample preparation and disintegration method. In the present study, a sample of weakly deformed Opalinus claystone from the Mont Terri underground site (Switzerland) was investigated after disintegration by three different methods. The Opalinus Clay was sedimented in the late Toarcian and early Aalenian and reached maximum temperatures of ~85°C during burial in the Cretaceous. The present study reports data from a comprehensive investigation comparing the effects of disintegration by: (1) disc milling; (2) repeated freezing and thawing; and (3) high-voltage discharges. K-Ar age values of the finest clay (<0.1 µm) released by the different disintegration methods are indistinguishable, indicating that the high-voltage liberation method does not influence grains as small as 100 nm. The K-Ar age values of particle-size separates decreased with decreasing particle size. The age values of the 2–6 µm separates correspond to the Carboniferous Period, which reflects the dominance of Paleozoic detritus in that size range. The age values of the smallest separates (<0.1 µm), on average 213 ± 4 Ma, exceed the numerical age of the formation (~177−172 Ma), which show predominance of detrital grains over authigenic grains even in the finest illite. In summary, isotope geochronology data suggest that the high-voltage method can be applied reliably for disintegrating claystones.