Showing papers in "Clays and Clay Minerals in 2008"

Quantitative phase analysis of bentonites by the rietveld method

Abstract: Thirty six bentonite samples from 16 different locations were examined in order to demonstrate the applicability of a new Rietveld description approach for quantitative phase analysis. X-ray diffraction patterns of the bulk material were obtained and analyzed by the Rietveld method. The samples contain up to ten different minerals, with dioctahedral smectite as the major component. A model for turbostratic disorder of smectites was formulated inside a structure-description file of the Rietveld program BGMN. The quality of the refinements was checked using an internal standard mineral (10.0 or 20.0 wt.% corundum) and by cross-checking results with X-ray fluorescence (XRF) data. The corundum content was reproduced with only small deviations from the nominal values. A comparison of the chemical composition obtained by XRF and the composition as re-calculated from quantitative Rietveld results shows a satisfactory agreement, although X-ray amorphous components such as volcanic glasses were not considered. As a result of this study, the Rietveld method combined with the new structure model for turbostratic disorder has proven to be a suitable method for routine quantitative analysis of bentonites with smectites as the dominant clay minerals.

Preferred orientations and anisotropy in shales: callovo-oxfordian shale (france) and opalinus clay (switzerland)

Abstract: Anisotropy in clay-rich sedimentary rocks is receiving increasing attention. Seismic anisotropy is essential in the prospecting for petroleum deposits. Anisotropy of diffusion has become relevant for environmental contaminants, including nuclear waste. In both cases, the orientation of component minerals is a critical ingredient and, largely because of small grain size and poor crystallinity, the orientation distribution of clay minerals has been difficult to quantify. A method is demonstrated that relies on hard synchrotron X-rays to obtain diffraction images of shales and applies the crystallographic Rietveld method to deconvolute the images and extract quantitative information about phase fractions and preferred orientation that can then be used to model macroscopic physical properties. The method is applied to shales from European studies which investigate the suitability of shales as potential nuclear waste repositories (Meuse/Haute-Marne Underground Research Laboratory near Bure, France, and Benken borehole and Mont Terri Rock Laboratory, Switzerland). A Callovo-Oxfordian shale from Meuse/Haute-Marne shows a relatively weak alignment of clay minerals and a random distribution for calcite. Opalinus shales from Benken and Mont Terri show strong alignment of illite-smectite, kaolinite, chlorite, and calcite. This intrinsic contribution to anisotropy is consistent with macroscopic physical properties where anisotropy is caused both by the orientation distribution of crystallites and high-aspect-ratio pores. Polycrystal elastic properties are obtained by averaging single crystal properties over the orientation distribution and polyphase properties by averaging over all phases. From elastic properties we obtain anisotropies for p waves ranging from 7 to 22%.

Surface area and layer charge of smectite from cec and egme/h2o-retention measurements

Abstract: The total specific surface area (TSSA) and smectitic layer charge (Qs) calculated from the structural formulae and unit-cell dimensions of 12 pure smectite samples were used as a reference in the design and evaluation of TSSA and Qs measurement techniques based on cation exchange capacity (CEC), H2O retention at 47% RH, and ethylene glycol monoethyl ether (EGME) retention. A thermogravimetric analysis-mass spectrometry (TGA-MS) technique was used to study the release of H2O from smectite on heating, and to introduce a correction for H2O remaining in the smectite after heating to 110°C, because the sample weight at this temperature has been used routinely as a reference in CEC and EGME sorption measurements. A temperature of 200°C was found to be the optimum reference for such measurements. A good agreement between Qs from the structural formula and from CEC was obtained when this correction was applied. The TSSA of smectite was measured with similar accuracy (mean error of ±5–7%) by three techniques: (1) using mean H2O coverage; (2) using mean EGME coverage; and (3) using a combination of H2O coverage and CEC. A reduction of the mean error from 5–7% to 4% can be obtained by averaging these measurements, and a further reduction to 3% by introducing corrections for the dependence of H2O and EGME coverage on layer charge. The study demonstrates that Ca2+-smectite samples at 47% RH have H2O contents corresponding to 88–107% of the theoretical mass of a monolayer and offers an explanation of this variation.

Smectite-illite-muscovite transformations, quartz dissolution, and silica release in shales

Abstract: Quantitative analysis of the smectite-to-illite and illite-to-muscovite transformations indicates that 17–28 wt.% SiO2 and 17–23 wt.% SiO2, respectively, are liberated during these reactions, assuming that Al is conserved. Dissolution of quartz silt in shales yields up to 6–9% SiO2 in the range up to 200°C and a further 10–15% SiO2 in the 200–500°C range. For muds altered to shales at 200°C, 14–20 wt.% silica is evolved. From 200 to 500°C, a further 18–28 wt.% silica is evolved. Additional small amounts of silica may be released in the alteration of feldspar to clay and by stylolitization of quartz silt. Thus, in the burial and temperature range of diagenesis into the epizone, major quantities of silica are released from clays and by quartz dissolution in shales. Within this range of alteration, concomitant decline of whole-rock Si/Al (SiO2/Al2O3) in the transformation of smectite to illite to muscovite suggests the liberated silica migrates from the source shale. As a result, the metamorphosed shales are more micaceous and less quartzose than their progenitor muds. In the diagenetic zone and anchizone, the evolved silica is probably a major source of quartz cement in sandstones. In the epizone, evolved silica is commonly present in quartz veins in the parent rocks. Fluid-inclusion temperatures in quartz overgrowths and fracture fillings in some sandstones suggest that some cements may have been derived from downdip basinal shales and pressure solution in sandstones.

Chemical and mineralogical characteristics of french green clays used for healing.

Abstract: The worldwide emergence of infectious diseases, together with the increasing incidence of antibiotic-resistant bacteria, elevate the need to properly detect, prevent, and effectively treat these infections. The overuse and misuse of common antibiotics in recent decades stimulates the need to identify new inhibitory agents. Therefore, natural products like clays, that display antibacterial properties, are of particular interest.The absorptive properties of clay minerals are well documented for healing skin and gastrointestinal ailments. However, the antibacterial properties of clays have received less scientific attention. French green clays have recently been shown to heal Buruli ulcer, a necrotic or 'flesh-eating' infection caused by Mycobacterium ulcerans. Assessing the antibacterial properties of these clays could provide an inexpensive treatment for Buruli ulcer and other skin infections.Antimicrobial testing of the two clays on a broad-spectrum of bacterial pathogens showed that one clay promotes bacterial growth (possibly provoking a response from the natural immune system), while another kills bacteria or significantly inhibits bacterial growth. This paper compares the mineralogy and chemical composition of the two French green clays used in the treatment of Buruli ulcer.Mineralogically, the two clays are dominated by 1Md illite and Fe-smectite. Comparing the chemistry of the clay minerals and exchangeable ions, we conclude that the chemistry of the clay, and the surface properties that affect pH and oxidation state, control the chemistry of the water used to moisten the clay poultices and contribute the critical antibacterial agent(s) that ultimately debilitate the bacteria.

Xrd, ftir, and thermal analysis of bauxite ore-processing waste (red mud) exchanged with heavy metals

Abstract: The present work shows the results of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermal analysis of untreated (RMnt) and acid-treated red mud (RMa), a bauxite ore-processing waste, exchanged with Pb2+, Cd2+, and Zn2+ cations. These studies were performed in order to investigate the changes in the sorbent structure caused by the exchange with metals of different ionic radii. The XRD pattern of RMnt, analyzed according to the Rietveld method, showed a mixture of eight different phases. However, just three phases made up 78 wt.% of the RMnt: cancrinite (33 wt.%), hematite (29 wt.%), and sodalite (16 wt.%). X-ray diffraction patterns of RMnt exchanged with Pb2+ and Cd2+ cations revealed two additional phases, namely hydrocerussite [Pb3(CO3)2(OH)2 (10 wt.%))] and octavite [CdCO3 (8 wt.%)]. These two phases probably originated from the carbonate precipitation processes which were due to the decarbonation of cancrinite. Hydrocerussite and octavite were not found in the case of acid-treated red mud samples. In the FTIR spectra, the introduction of cations caused a distinct shift to higher wavenumbers in the peak at ∼1100 cm−1, which is attributed to the asymmetric stretch of Si-O-Al. This effect may be associated with the Pb2+, Cd2+, and Zn2+ adsorbed by the red muds which caused a deformation of the initial structure. Thermal analysis data of the red mud samples were obtained by thermogravimetric/differential thermogravimetric analysis, and these methods were employed to evaluate the desorption behavior of water and to clarify the thermal stability of the chemical phases of the different red mud samples. The loss of metal-bound water in the red mud samples was found to depend on the size of non-framework cations and water loss consistently followed the order: Zn2+>Cd2+>Pb2+.

Diffusion of Na and Cs in montmorillonite

Abstract: The state and dynamics of water and cations in pure and mixed Na-Cs-montmorillonite as a function of the interlayer water content were investigated in the present study, using Monte Carlo and classical, molecular-dynamics methods. While highly idealized, the simulations showed that the swelling behavior of hetero-ionic Na-Cs-montmorillonite is comparable to the swelling of a homo-ionic Na- or Cs-montmorillonite. The mixed Na-Cs-montmorillonite is characterized by intermediate interlayer distances compared to homo-ionic Na- and Cs-montmorillonites. Dry, hetero-ionic Na-Cs-montmorillonite is characterized by a symmetric sheet configuration, as is homo-ionic Cs-montmorillonite. We found that at low degrees of hydration the absolute diffusion coefficient of Cs+ is less than for Na+, whereas at greater hydration states the diffusion coefficient of Cs+ is greaterthan for Na+. An analysis of the relative diffusion coefficients (the ratio between the diffusion coefficient of an ion in the interlayer and its diffusion coefficient in bulk water) revealed that water and Na+ are always less retarded than Cs+. With large interlayer water contents, tetralayer or more, Na+ ions preferentially form outer-sphere complexes. The mobility perpendicular to the clay surface is limited and the diffusion is equivalent to two-dimensional diffusion in bulk water. In contrast, Cs+ ions preferentially form ‘inner-sphere complexes’ at all hydration states and their two-dimensional diffusion coefficient is less than in bulk water. The question remains unanswered as to why experimentally derived relative diffusion coefficients of Cs+ in the interlayer of clays are about 20 times less than those we obtained by classical molecular dynamics studies.

Diagenetic reorientation of phyllosilicate minerals in Paleogene mudstones of the Podhale Basin, southern Poland

Abstract: We used high-resolution X-ray texture goniometry to quantify changes in the mm-scale orientation of phyllosilicate minerals in a suite of Paleogene mudstones from the Podhale Basin in southern Poland. The sample set covers an estimated range of burial depths between 2.4 and 7.0 km, corresponding to a temperature range of 60–160°C. Although mechanical compaction has reduced porosities to ∼10% in the shallowest samples, the phyllosilicate fabric is only modestly aligned. Coarser-grained (>10 µm) detrital chlorite and mica appear to be more strongly aligned with (001) parallel to bedding, suggesting their deposition as single grains rather than as isotropic flocs or aggregates. From 2.4 to 4.6 km, R0 illite-smectite with 40–50% illite layers changes to R1 illite-smectite with 70–80%) illite layers. At the same time kaolinite is lost and diagenetic chlorite is formed. The mineralogical changes are accompanied by a strong increase in the alignment of illite-smectite, chlorite, and detrital illite, parallel to bedding and normal to the presumed principal effective stress. We propose that the development of a more aligned I-S fabric results from the dissolution of smectite and the growth of illite with (001) normal to the maximum effective stress. Water released by illitization may act as a lubricant for the rotation of all platy minerals into nanoporosity transiently formed by the illitization reaction. At greater depths and temperatures, further illitization is inhibited through the exhaustion of K-feldspar. After the cessation of illitization, a further 2.4 km of burial only results in a small increase in phyllosilicate alignment. At such small values for porosity and pore size, increasing stress does not substantially reorient phyllosilicates in the absence of mineralogical change.

The pH of Aqueous Bentonite Suspensions

Abstract: The pH of aqueous bentonite suspensions is known to be influenced by carbonates present even in minor amounts. On the other hand, at high solid:liquid ratios (at standard pH measurement conditions: 2% w/w suspension), the type of exchangeable cation in the smectite is also known to determine pH (particularly Na+ or Ca2+). By cation-exchange tests we proved that exchanging the Ca2+ for Na+ results in an increase in the pH. However, this increase in pH was only found if excess salts were removed from the system (by washing or dialysis, respectively). The effect of the type of exchangeable cation can, at least partially, be explained by hydrolysis of Ca2+. On the other hand, a pronounced alkalinity of Na bentonites is observed which can, at least partially, be attributed to the hydrolysis of montmorillonite (Na+ is exchanged for H+ of water). The increase in the volume of the Stern layer, caused by increasing the degree of delamination, is also suggested to play a role. H+ and Na+ are concentrated in the Stern layer. Hence, increasing the Stern layer volume decreases the amount of H+ and Na+ in solution and thus increases pH. Unfortunately, both processes, montmorillonite hydrolysis and delamination, depend on the ionic strength. Distinguishing the processes quantitatively, therefore, is an analytical challenge, and impossible based on the data presented here. To model the pore-water chemistry of clays and clay stones, all of the above-mentioned processes have to be considered. It is possible that other reactions, not identified in the present work, contribute toward the pH values of aqueous bentonite suspensions.

Low-temperature ftir study of kaolin-group minerals

Abstract: Low-temperature FTIR spectroscopy was used to characterize the v(OH) region of kaolin-group minerals including well ordered to poorly ordered kaolins from Georgia, Brazil, and England, along with samples of discrete dickite and nacrite. Low-temperature FTIR spectra were useful in resolving dickite- and nacrite-like features present in the spectra of kaolins when cooled to <30 K. These features were not resolved at room temperature and only partially resolved at liquid N2 temperature (77 K). The room-temperature and low-temperature positions of the ν(OH) bands of kaolinite, dickite, and nacrite were linearly correlated with the interatomic OH⋯O distances and this relationship served as the basis for polytype/disorder identification. Dickite or dickite-like disorder was found in high Hinckley-Index kaolinite from Keokuk, Iowa, and from Cornwall, England. Dickite- and nacrite-like features were observed in both high- and low-Hinckley-index kaolinite and the amounts of these stacking sequences generally increased with decreasing Hinckley Index.

Partitioning of Fe(II) in reduced nontronite (NAu-2) to reactive sites: Reactivity in terms of Tc(VII) reduction

Abstract: Clay minerals impart important chemical properties to soils, in part, by virtue of changes in the redox state of Fe in their crystal structures. Therefore, measurement of Fe(III)/Fe(II) and partitioning of Fe(II) in different reactive sites in clay minerals (during biological and chemical Fe(III) reduction) is essential to understand their role and their relative reactivity in terms of reduction and immobilization of heavy metal contaminants such as technetium. This study had three objectives: (1) to understand the degree of dissolution of nontronite (Fe-rich smectite) as a result of chemical and biological reduction of Fe(III) in the structure; (2) to quantify partitioning of chemically and biologically produced Fe(II) into different reactive sites in reduced nontronite, including aqueous Fe2+, ammonium chloride-extractable Fe(II) (mainly from the ion-exchangeable sites, denoted as ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ ), sodium acetate-extractable Fe(II) (mainly from the surface complexation sites, denoted as Fe(II)acetate), and structural Fe(II) (denoted as Fe(II)str); and (3) to evaluate the reactivity of these Fe(II) species in terms of Tc(VII) reduction. Chemical and biological reduction of Fe(III) in nontronite (NAu-2) was performed, and reduced nontronite samples with different extents of Fe(III) reduction (1.2–71%) were prepared. The extent of reductive dissolution was measured as a function of the extent of Fe(III) reduction. Our results demonstrated that chemically and biologically produced Fe(II) in NAu-2 may be accommodated in the NAu-2 structure if the extent of Fe(III) reduction is small ( ∼30%, dissolution of nontronite occurred with a corresponding decrease in crystallinity of residual nontronite. The Fe(II) produced was available for partitioning into four species: ${\rm{Fe}}_{\left( {{\rm{ab}}} \right)}^{2 + }$ , Fe(II)acetate, ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ , and Fe(II)str. The increase in Fe(II)acetate during the early stages of Fe(III) reduction indicated that the Fe(II) released had the greatest affinity for the surface-complexation sites, but this site had a limited capacity (∼60 µmol of Fe(II)/g of NAu-2). The subsequent increase in ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ indicated that the released Fe(II) partitioned into the exchangeable sites once the amount of Fe at the surface-complexation sites reached half of its maximum site capacity. The fraction of Fe(II)str decreased concomitantly, as a result of Fe(II) release from the NAu-2 structure, from 100% when the extent of Fe(III) reduction was <30% to nearly 65% when the extent of Fe(III) reduction reached 71%. The Fe(II)acetate and Fe(II)str exhibited greater reactivity in terms of Tc(VII) reduction than the ${\rm{Fe}}{\left( {{\rm{II}}} \right)_{{\rm{N}}{{\rm{H}}_4}{\rm{Cl}}}}$ . Clearly, the surface-complexed and structural Fe(II) are the desirable species when reduced clay minerals are used to reduce and immobilize soluble heavy metals in contaminated groundwater and soils. These results have important implications for understanding microbe—clay mineral interactions and heavy metal immobilization in clay-rich natural environments.

Mineralogy and genesis of smectites in an alkaline-saline environment of pantanal wetland, brazil

Abstract: Smectite formation in alkaline-saline environments has been attributed to direct precipitation from solution and/or transformation from precursor minerals, but these mechanisms are not universally agreed upon in the literature. The objective of this work was to investigate the mineralogy of smectites in the soils surrounding a representative alkaline-saline lake of Nhecolândia, a sub-region of the Pantanal wetland, Brazil, and then to identify the mechanisms of their formation. Soils were sampled along a toposequence and analyzed by X-ray diffraction, transmission electron microscopy-energy dispersive X-ray analysis, and inductively coupled plasma-mass spectrometry. Water was collected along a transect involving the studied toposequence and equilibrium diagrams were calculated using the databases PHREEQC and AQUA. The fine-clay fraction is dominated by smectite, mica, and kaolinite. Smectites are concentrated at two places in the toposequence: an upper zone, which includes the soil horizons rarely reached by the lake-level variation; and a lower zone, which includes the surface horizon within the area of seasonal lake-level variation. Within the upper zone, the smectite is dioctahedral, rich in Al and Fe, and is classified as ferribeidellite. This phase is interstratified with mica and vermiculite and has an Fe content similar to that of the mica identified. These characteristics suggest that the ferribeidellite originates from transformation of micas and that vermiculite is an intermediate phase in this transformation. Within the lower zone, smectites are dominantly trioctahedral, Mg-rich, and are saponitic and stevensitic minerals. In addition, samples enriched in these minerals have much smaller rare-earth element (REE) contents than other soil samples. The water chemistry shows a geochemical control of Mg and saturation with respect to Mg-smectites in the more saline waters. The REE contents, water chemistry, and the presence of Mg-smectite where maximum evaporation is expected, suggest that saponitic and stevensitic minerals originate by chemical precipitation from the water column of the alkaline-saline lake.

Hydrothermal synthesis, between 75 and 150°c, of high-charge, ferric nontronites

Abstract: High-charge nontronites were synthesized at 75, 90, 100, 110, 125, and 150°C from a silicoferrous starting gel with Si2FeNa2O6.nH2O composition. This gel was oxidized in contact with air and then hydrothermally treated, for a period of 4 weeks, under equilibrium water pressure. The synthesized nontronites were similar to each other, regardless of the synthesis temperature. Their structural formula, obtained from chemical analysis, X-ray diffraction (XRD), and Fourier transform infrared (FTIR), Mossbauer, and X-ray absorption fine structure spectroscopies is: $\left( {{\rm{S}}{{\rm{i}}_{3.25}}{\rm{Fe}}_{0.75}^{3 + }} \right){\rm{Fe}}_2^{3 + }{{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}{\rm{N}}{{\rm{a}}_{0.75}}$ . A strictly ferric end-member of the nontronite series was therefore synthesized for the first time. The uncommon chemistry of the synthesized nontronites, notably the high level of Fe-for-Si substitution, induced particular XRD, FTIR, and differential thermal analysis-thermogravimetric analysis data. The ethylene glycol expandability of the synthetic nontronites was linked to their crystallinity and depended on the nature of the interlayer cation, moving from smectite to vermiculite-like behavior. As the synthesis temperature increased, the crystallinity of the synthesized clays increased. The nontronite obtained at 150°C had the ‘best crystallinity’, which cannot be improved by increasing synthesis time or temperature.

Medicinal clay and spiritual healing

Abstract: The varied mineralogical composition of earthy materials and the quantity of elements extracted by simulated stomach acid substantiate the diversity of materials consumed by humans practicing geophagy. Direct consumption of ‘edible earths’ for medicinal and spiritual purposes occurs worldwide and is deeply rooted in ‘folk medicine’ and religion. The legends associated with the healing powers of the clay from Chimayo, New Mexico, provide an excellent example of the roots of geophagy. The clay mineral assemblages revealed by X-ray diffraction analysis of 22 samples from New Mexico, North America, and other parts of the world are highly variable. One might be monominerallic kaolinite or smectite, and another, a complex mixture of illite, kaolinite, smectite, and chlorite or vermiculite. The quantities of elements (Al, Si, K, Na, Ca, Mg, Fe, Mn, Ti, P, S, Ba, Sr, Pb, Zn, Cd, Co, Cu, Cr, Ni, V, Zr, Se, Mo, Be, Sb, and As) extracted by 0.12 M HCl varied from ~1.0 mg/g to the limit of detectability, 0.0001 mg/g. Potential long-term human health effects were evaluated with the Reference Dose Ratio (RDR). It divides the quantity of the element extracted from 50 g of the total sample by the recommended reference dose (RfD) reported in the Environmental Protection Agency’s (EPA, USA) IRIS (Integrated Risk Information System) database. Median RDR values for Na, Cr, Sb, and As exceeded 1.0 indicating an abnormally high potential intake. Materials consumed by humans are so varied that caution should be used in comparing the results of one clay study with those of another without mineralogical and chemical data.

Early clay diagenesis in Gulf Coast sediments: New insights from XRD profile modeling

Abstract: Samples from different depths in the Oligocene Frio formation (offshore Gulf of Mexico) were studied by X-ray diffraction (XRD), thermal analyses, and scanning electron microscopy. The experimental XRD patterns recorded from oriented and ethylene glycol (EG) solvated clay fractions of the samples were similar to those typical of random, mixed-layered illite-smectite (R0 I-S). The experimental XRD patterns recorded in air-dried (AD) and EG states were simulated using three different models. One of them corresponds to R0 I-S for which thickness and content of the interstratified layers were determined by the Środon technique. The second model is represented by a single homogeneous I-S in which illite and smectite layers are interstratified with a tendency to segregation. The expandability of the segregated I-S model varies from 48% to 75% without any rational relationship between the smectite layer content and depth. The third model assumes that the clay fraction is a physical mixture of smectite and an R0 I-S. In this model the I-S contains 65% illite and 35% smectite layers independent of depth, whereas the smectite content varies from 28% to 63%. This model has consistently smaller profile factors, Rp, for both EG and AD XRD scans compared with the Rp values determined for the other two models. The mineralogical association, volcanic origin, narrow stratigraphic interval (427 m), and low maximum temperature (42°C) of the studied Frio Formation are considered. These features are completely consistent with the two-phase model and so the segregation model must be rejected. An authigenic origin of the pure smectite and an alternative detrital or authigenic origin of the R0 I-S are discussed.

Preferred orientation of mineral grains in sample mounts for quantitative XRD measurements: How random are powder samples?

Abstract: The degree of preferred orientation of mineral grains in powder X-ray diffraction (XRD) samples prepared by standard techniques has been evaluated by means of a correction model implemented in the Rietveld program, BGMN. It is demonstrated that neither front- nor side-loading of mineral powders obtained by wet grinding in a McCrone micronizing mill yield powder mounts with randomly oriented particles. Despite fine grinding, the primary sizes and shapes of mineral grains contained in multi-phase samples influence the degree of preferred orientation in XRD powder mounts. Two minerals, both of platy habit, were found to show different degrees of preferred orientation in front- and side-loaded samples. In contrast to these methods of sample preparation, the spray-drying technique yielded perfect randomness of the particles. The experiments on artificial mineral mixtures demonstrate that the model applied can effectively correct for preferred orientation allowing reliable Rietveld quantitative phase analysis of moderately textured samples prepared by standard techniques.

INFLUENCE OF Mn(III) AVAILABILITY ON THE PHASE TRANSFORMATION FROM LAYERED BUSERITE TO TUNNEL-STRUCTURED TODOROKITE

Abstract: Todorokite is a common Mn oxide mineral in terrestrial and ocean-floor environments, and it is commonly synthesized from layered Na-buserite. Pyrophosphate, which is known to form strong complexes with Mn(III) at a pH range of 1–8, was added to a suspension of Na-buserite in order to sequester the available Mn(III) in Na-buserite. No Mn(III)-pyrophosphate complex was formed in solution at pH 10, and the treated Na-buserites were converted completely to todorokite. Significant transformation reductions were observed when Na-buserite was treated with pyrophosphate solution at pH 7. The presence of Mn(III) within the MnO6 octahedral sheets of Na-buserite is critical for the transformation from layered buserite to tunnel-structured todorokite at atmospheric pressure. At lower pH, two effects are combined to reduce the amount of Mn(III) in the layers: (1) the complexing power of pyrophosphate is increased; and (2) the transformation from Na-buserite to H-birnessite, which is concomitant with the migration of Mn(III) from layers to the interlayer, and the partial disproportionation of Mn(III). The results showed that Mn(III) played a key role in the transformation of layered Na-buserite to tunnel-structured todorokite at atmospheric pressure.

Cation mass-valence sum (cm-vs) approach to assigning oh-bending bands in dioctahedral smectites

Abstract: The assignments of OH-bending bands in the infrared (IR) spectra of dioctahedral smectites (montmorillonites, ferruginous smectites, and nontronites) have been revisited using a cation mass-valence sum (CM-VS) approach to quantify octahedral cation occupancy. The CM-VS approach enabled prediction of OH-bending band positions (in wavenumbers) related to OH-sharing octahedral cation pairs that had valence sums of 4 and 5, and cation masses associated with Fe(II) and Mg. Application of rules for the relationship enabled determination of the location of OH-sharing octahedral cation pairs containing Mg and Fe(II) for which previous assignments have been considered controversial, e.g. Fe(III)Mg-OH and MgMg-OH, or for which assignments have been missing due to lack of spectroscopic evidence, e.g. AlFe(II)-OH, Fe(III)Fe(II)-OH, Fe(II)Mg-OH, and Fe(II)Fe(II)-OH. Examples of these bands from several natural ferruginous smectites and nontronites are discussed. Quantification of IR spectra was used to develop a better understanding of the octahedral cation occupancy of this important class of Fe(III)-enriched smectites. While Fe(II) contents may be somewhat overestimated by the IR technique, those for four of the six ferruginous smectites studied here agree well with data from Mossbauer spectroscopy.

Microstructure of organo-bentonites in water and the effect of steric hindrance on the uptake of organic compounds

Abstract: To further elucidate adsorption-to-partition transitional mechanisms which have been proposed previously for organo-bentonites with different surfactant loadings, the structural characteristics of interlayer surfactant aggregates on organo-bentonite with different surfactant cetyltrimethylammonium bromide loading levels (0.20–2.56 times cation exchange capacity, CEC) have been investigated by in situ X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. The sorption properties and the structure of the clay interlayers changed according to the type of surfactant, the surfactant loading level, and the state of hydration in the clays. Based on the sorption of nitrobenzene, phenol, and aniline to organo-bentonites, the contaminant sorption coefficients ( K sf), normalized with the organic carbon content, show a remarkable dependence on surfactant loading levels. The K sf values first increased with surfactant loading until reaching a maximum at 1.0 to 1.2 times the CEC, and then decreased. According to the theoretical calculation of the volume fractions relating to the interlamellar space, the interlamellar microenvironment became a more hydrophobic medium, contributing to the dissolution of organic contaminants, as the surfactant loading increased from 0.20 to 2.56 times the CEC. However, the increase in packing density (ρ) for the intercalates, and induced steric hindrances both affect the result in terms of a reduction in the accessible free space where the organic contaminants can be located, which might be a negative factor in the sorption capacity.

SMECTITE CLAY ADSORPTION OF AFLATOXIN vs. OCTAHEDRAL COMPOSITION AS INDICATED BY FTIR

Abstract: The fungus Aspergillus flavus Link ex Fries can infect grains and oil seeds and develop Aflatoxin B1 (AfB1) in the fieldor in storage. Aflatoxin contamination is a serious health hazard — it is extremely toxic and hepatocarcinogenic for animals and humans. A practical approach to solve this problem is to use smectite clay as an amendment to animal feed. The objective of this research is to investigate smectite clay—AfB1 interactions by employing Fourier transform infrared (FTIR) spectroscopy to determine how clay composition influences AfB1 adsorption by smectites. When AfB1 was present in the clay, the spectral region from 1800 to 1300 cm−1 was altered, and the regions between 4000 and 1800 and 1300 and 400 cm−1 were unchanged except for the intensity in the broad region near 3400 cm−1 related to the abundance of water. The 1300–400 cm−1 region is attributed only to smectite clay properties, and it relates to the relative adsorption potential of the different smectites. Bonding between AfB1 and smectite clay appears to be in the furan rings. Other possible bonding is with the two oxygens in the coumarin ring of AfB1 and interlayer cations or their associated water molecules. The FTIR evidence of octahedral Fe in smectite and amorphous silica in the clays both indicate greater AfB1 adsorption potential. Other smectites with spectral absorption indicating predominantly Al in the octahedral positions adsorbed less AfB1.

The occurrence and genesis of clay minerals associated with quaternary caliches in the mersin area, southern turkey

Abstract: Caliche in various forms, namely powdery, nodule, tube, fracture-infill, laminar crust, hard laminated crust (hardpan), and pisolitic crust, is widespread in the Mersin area in southern Turkey. It generally occurs within and/or over the reddish-brown mudstone of the Kuzgun Formation (Tortonian, Miocene) and alluvial red soils of the Quaternary. The mineralogical distribution along representative caliche profiles was examined by X-ray diffraction, scanning electron microscopy, differential thermal analysis-thermal gravimetry, and chemical techniques. Calcite is the most abundant mineral associated with minor amounts of palygorskite in caliche samples, whereas smectite is prevalent mainly in the reddish-brown mudstone and alluvial red soils of the caliche parent materials and is associated with appreciable amounts of palygorskite. These minerals are also accompanied by trace amount of illite, quartz, feldspar, and a poorly crystalline phase. Palygorskite fibers and fiber bundles were developed authigenically on euhedral or subhedral calcite crystals of the caliche units and at the edges of smectite flakes in the caliche host-rocks or sediments. Intense, continuous evaporation of subsurface soil-water resulted in an increase in pH and the dissolution of detrital smectite within the red mudstones and alluvial red soils that enclose the isolated caliche forms, and caused an increase in the Al+Fe and Mg/Ca ratio, favoring the formation of palygorskite under alkaline conditions. The calcium required for caliche formation may have originated from eolian dust, detrital carbonate minerals, and/or other caliche materials, which are dissolved by carbonic acid.

Tracer diffusion in sintered stainless steel filters: measurement of effective diffusion coefficients and implications for diffusion studies with compacted clays

Abstract: The use of porous filters is indispensable in laboratory- and field-scale diffusion studies, where sample confinement is needed for mechanical reasons. Examples are diffusion studies with compacted swelling clays or brittle clay stones. Knowledge of the diffusion properties of these filters is important in cases where they contribute significantly to the overall diffusive resistance in the experimental setup. In the present study, measurements of effective diffusion coefficients ( D b ) in porous, stainless steel filter discs are reported for tritiated H 2 O (HTO), 22 Na + , Cs + , and Sr 2+ before and after use of the filters in diffusion experiments with different clay minerals. The D b values for used filters were found to be less than those of the as-received filters by ~30–50%. The D b values measured for the diffusion of HTO, 22 Na + , Cs + , and Sr 2+ in unused and used stainless steel filter discs correlated fairly well with the respective molecular diffusion coefficients in bulk water. Although such correlations are inherently associated with some uncertainties, they allow reasonable estimates to be made for diffusants for which no D b values are available. For the first time, a procedure is outlined that allows an integrative assessment to be made for the impact of the uncertainties in the filter diffusion properties on the combined standard uncertainties of the diffusion parameters obtained from through-diffusion experiments. This procedure can be used in the design and optimization of through-diffusion experiments in which the diffusive resistance of the porous filters must not be ignored. Shown here, as a general rule of thumb, is that, if the effective diffusion coefficient in the porous filter is at least three times larger than that in the clay, the choice of geometrical boundary conditions is rather uncritical, as long as the thickness of the clay sample is greater than that of the porous filters.

Adsorption of protamine and papain proteins on saponite

Abstract: Due to the increased importance of bionanocomposites, protamine and papain proteins were adsorbed on Na+- and on Cs+-exchanged saponite from aqueous solution. Protein analysis of equilibrium solutions and thermogravimetric analyses of biocomposites were used to prepare adsorption isotherms. Based on the isotherm shape, and on the amounts of protein adsorbed and the amounts of Na+ and Cs+ released, the initial protein sorption apparently was due to ion exchange. Additional sorbed protein was weakly retained and could be removed by washing with water. From ion exchange, the average charge of the protamine adsorbed was estimated to be +13.1 to +13.5. Similar papain measurements could not be made due to partial decomposition. Quantitatively, protamine was adsorbed at levels up to 400 mg/g on Na+-saponite and 200 mg/g on Cs+-saponite. The maximum protamine adsorption was 650 to 700 mg/g for Na+-saponite and 350–400 mg/g for Cs+-saponite. Protamine was sorbed to edge surfaces and the basal spacing of the interlamellar region of saponite was 1.75 nm. Protamine displaced only 36% of the Cs+ in Cs+-saponite and expanded the interlamellar region by 36% for a basal spacing of 1.6 nm. Papain sorption to Na+-saponite occurred by a two-step process: (1) adsorption to saponite particle external surfaces followed, (2) by partial intercalation. Quantitatively, Papain was adsorbed up to 100 mg/g for Na+-and Cs+-saponite. Greater initial papain concentrations resulted in a 450 mg/g maximum for Na+-saponite, but no increase above 100 mg/g for Cs+-saponite. Papain apparently only sorbed to external Cs+-saponite surfaces that were estimated to be 33–40 m2/g. Step-wise thermal decomposition of the saponite-protein composites occurred between 300 and 800°C.

ADSORPTION OF Cr(VI) AND As(V) ON CHITOSAN-MONTMORILLONITE: SELECTIVITY AND pH DEPENDENCE

Abstract: Montmorillonite modified with the cationic biopolymer, chitosan, has, in weak acidic solutions, protonated amine groups which act as anion-adsorption sites. Due to the specific surroundings of the adsorption sites and diffusion paths in the interlayer of chitosan-montmorillonite, preferential adsorption of certain anions is likely. In the present study, the adsorption properties for the inorganic anions Cr(VI) and As(V) were determined, taking into account solution pH and competitive adsorption in the presence of Cl− and ${\rm{SO}}_4^{2 - }$ . Chitosan-montmorillonite was prepared by adding an amount of chitosan equivalent to 500% of the cation exchange capacity (CEC) at pH 5 and 75°C. The resulting anion exchange capacity was ∼0.34 molc/kg. The adsorption properties for As(V) and Cr(VI) were determined with the batch technique at pH 3 to 9. Adsorption isotherms were fitted to the Langmuir and Dubinin-Radushkevich equations and judged quantitatively by the correlation coefficient. To describe the competitive adsorption, the selectivity (S) was determined by the ratio of amounts of anions A and B adsorbed (qA/qB) in a binary system. The ionic species adsorbed, i.e. either Cr(VI) or As(V), depended on the pH, as did the degree of protonation of the amine groups, and this played a decisive role in the amount of anions adsorbed. The maximum amount of Cr(VI) adsorbed was 180 mmol/kg at pH 3.5, whereas for As(V) it was 120 mmol/kg at pH 4.0 to 5.0. The adsorption process of Cr(VI) and As(V) fit well to the Langmuir isotherm. By increasing the concentration of the competitive anion, Cl−, in solution, the amount of Cr(VI) and As(V) adsorbed remained almostconstant, whereas ${\rm{SO}}_4^{2 - }$ had a more pronounced competitive effect. At concentration ratios of 0.5 and 1 for ${\rm{SO}}_4^{2 - }$ to Cr(VI) and As(V), respectively, the sorption capacity decreased by 10 and 25%, respectively. The sequence of the selectivity was: ${\rm{Cr}}\left( {{\rm{VI}}} \right) > {\rm{SO}}_4^{2 - } > {\rm{As}}\left( {\rm{V}} \right) > {\rm{C}}{{\rm{l}}^ - }$ . Chitosan-montmorillonite showed a high selectivity for Cr(VI), which adsorbed chemically. Despite the lower affinity for As(V) and physical adsorption, the adsorption capacity was relatively high.

Mixtures of fine-grained minerals - kaolinite and carbonate grains

Abstract: The behavior of mineral mixtures can be significantly different from the behavior of the individual components of the mixture due to differences between the mechanical and chemical properties of the individual minerals, and their ensuing effects on interparticle interactions and fabric formation. This study examines mixtures of kaolinite and calcium carbonate at different mass fractions using sedimentation, viscosity, and liquid-limit tests. These macroscale tests represent a wide range of solid-volume fractions and strain levels, with emphasis on high water-content conditions to magnify the effects of electrical forces. The results demonstrate that interparticle interactions depend on mineral surface-fluid effects, particle geometry, relative particle size, and solids content. With small solids contents, the kaolinite/calcium carbonate mixture behavior is a function of electrostatic interactions between oppositely charged mineral particles that promote flocculation; however, with large solids contents, the specific surface area of the minerals is the controlling factor. These results are relevant to many natural soil environments and to the possible development of engineered mineral mixtures for industrial applications.

Pyroxene weathering to smectite: conventional and cryo-field emission scanning electron microscopy, koua bocca ultramafic complex, ivory coast

Abstract: Air-dried and high-pressure frozen/freeze-etched samples of clinopyroxene and smectite in a saprolitized clinopyroxenite from Koua Bocca, Ivory Coast, West Africa, were compared to characterize textures developed during natural weathering of chain silicates. Comparison with air-dried material allowed evaluation of high-pressure cryofixation as a technique for preserving textures of hydrated clay minerals. Air-dried pyroxene surfaces appear very smooth. Small, flat lamellae, oriented parallel to the c axis, lend a distinct splintery appearance to pyroxene surfaces in fully hydrated samples. These lamellae often display a combination of straight (110) pyroxene edges and a crinkled border, suggestive of smectite. Narrow lenticular (110) open cleavages occur in both preparations and are not a pressurization artifact. Most often these openings contain no secondary minerals. Spaces between pyroxene denticles, lined with collapsed smectite in air-dried samples, are filled with thin packets of anhedral smectite crystallites oriented face to face when hydrated. Smectite microboxwork preserves original topotactic textures developed during isovolumetric pyroxene transformation, and smaller nanoporosity appears in hydrated cryofixed examples. Occasional regions of edge-to-face ‘house of cards’ texture also occur. Elimination of sample preparation artifacts induced by surface tension during air drying demonstrates that pores actually present during a hydration reaction-driven weathering episode are smaller and more numerous than would be inferred from examining air-dried materials.

Ionic liquids-kaolinite nanostructured materials. intercalation of pyrrolidinium salts

Abstract: Ionic liquids intercalated in kaolinite constitute a novel class of nanostructured material Kaolinite-pyrrolidinium halide intercalates have been prepared successfully by reacting the pyrrolidinium salts with kaolinite which was preintercalated with dimethyl sulfoxide (DMSO) using the melt condition under N2 X-ray diffraction, 13C magic angle spinning nuclear magnetic resonance, differential thermal analysis (DTA)-thermal gravimetric analysis, and Fourier transform infrared spectroscopy confirm the displacement of DMSO during the intercalation process Based on results from the various characterization techniques, a structural model is proposed in which one mole of the pyrrolidinium salt covers two or three structural units of kaolinite, depending on the structure and size of the salt The thermal stability was improved remarkably after intercalation of the pyrrolidinium salts, compared to the pre-intercalate The DTA-TGA data show that the largest number of organic units released and decomposed, occurs under N2 flow, at temperatures ranging from 260 to 340°C, depending on the nature of the intercalated organic salts

TRANSFORMATION OF SYNTHETIC Zn-STEVENSITE TO Zn-TALC INDUCED BY THE HOFMANN-KLEMEN EFFECT

Abstract: Stevensite-like sauconite, with the general composition: ${\rm{S}}{{\rm{i}}_4}\left( {{\rm{Z}}{{\rm{n}}_{3 - x}}{\square _x}} \right){{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}R_{2x}^ + $ , where □ is a vacant site, was synthesized. The objective was to study the possible migration of some cations (Li+ and Zn2+) within such trioctahedral smectites, under heating, following the so-called ‘Hofmann-Klemen’ (HK) effect. The initial gel was divided into five aliquots and placed in teflon-coated hydrothermal reactors with distilled water, and these were hydrothermally treated at 80, 100, 120, 150, and 200°C, respectively, over 30 days. X-ray diffraction (XRD) analysis confirmed that the samples synthesized were smectites. The number of vacant sites (x) per half unit cell (O10(OH)2) ranged from nearly 0 to 0.23 but no simple relationship was established between x and the temperature of synthesis. The samples were Li+- and Zn2+-saturated, and heated overnight at 300°C (HK treatment). Cation exchange capacity measurements were made by Fourier transform infrared spectroscopy (FTIR) on ${\rm{NH}}_4^ + $ -saturated samples. After LiHK treatment, the structural formula of samples could be expressed as: ${\rm{S}}{{\rm{i}}_4}{\rm{Z}}{{\rm{n}}_{\left( {3 - x} \right)}}{\rm{L}}{{\rm{i}}_x}{{\rm{O}}_{10}}{\left( {{\rm{OH}}} \right)_2}{\rm{NH}}_{4x}^{\; + }$ , while after ZnHK treatment, it could be expressed as: Si4Zn3O10(OH)2. Analysis by XRD and FTIR showed that the samples moved from a Zn-stevensite-like structure to Zn-talc-like structure after treatment with ZnHK. These results are interpreted asevidence that Zn2+ (and Li+) migrated into the previously vacant sites under HK treatment.

Nitrate removal by calcined hydrotalcite-type compounds

Abstract: The sorption of nitrate ions on calcined hydrotalcite-type compounds at 550°C (HT550), 650°C (HT650), and 850°C (HT850) from pure water solution at 25°C has been studied. The influence of the temperature was also investigated for the sample calcined at 850°C by studying the sorption process at 10 and 40°C. The experimental sorption data points were fitted to the Langmuir equation in order to calculate the sorption capacities (Xm) of the samples; Xm values range from 61.7 g kg−1 (HT550 at 25°C) to 147.0 g kg−1 (HT850 at 40°C). The values for the removal efficiency (R) obtained ranged from 70.5% for HT550 at 25°C to 99.5% for HT850 at 40°C. The sorption experiments showed that the greater the calcination temperature (850°C), the more effective the removal of nitrate. The increase in the temperature from 10 to 40°C for sample HT850 also tends to increase the sorption of nitrate from 63.3 g kg−1 to 147 g kg−1 and the corresponding removal efficiency from 71.5 to 99.5%.

Kaolinite formation from palygorskite and sepiolite in rhizosphere soils

Abstract: Palygorskite and sepiolite are fibrous clays that occur mostly in agricultural soils of arid regions. Although many investigations have examined the environmental conditions for the formation and stability of these clays, information on the transformation of these clays in the root zone (or rhizosphere) of agricultural crops is limited. In this study, changes in palygorskite and sepiolite within the rhizosphere of selected agricultural crops were determined and the ability of plants to extract Mg from these minerals compared. Alfalfa, barley, and canola were cultivated in pots under controlled conditions in a growth chamber using growth media that consisted of a mixture of Ottawa sand and clay-sized Florida palygorskite (PFl-1) or Spanish sepiolite (SepSp-1). After 100 days of cultivation, the biomass of plant roots and shoots were determined and Mg uptake measured by inductively coupled plasma analysis of the plant biomass after microwave oven digestion. The clay fraction in each pot was separated from the sand and analyzed using X-ray diffraction (XRD) and examined using transmission electron microscopy (TEM). The XRD reflection at 0.718 nm clearly indicated kaolinite in the rhizosphere after growth of the three crops. Furthermore, hexagonal kaolinite particles were observed, using TEM, and the amount of Mg extracted by the three crops was significantly greater for sepiolite than for palygorskite. Palygorskite and sepiolite kaolinization in the rhizosphere was apparently due: (1) to high acidity in the rhizosphere caused by root activity and organic matter decomposition; and (2) to fibrous clay destabilization caused by Mg uptake by plants. This study shows that kaolinite in agricultural soils of arid and semi-arid regions might be partly due to neoformation after fibrous clay dissolution and not entirely inherited from parent materials, as has been suggested in earlier literature.