bluuebunny/crossref_metadata_2025 huggingface dataset:
The Kinetics of the Smectite to Illite Transformation in Cretaceous Bentonites, Cerro Negro, New Mexico
Authors: Elliott W. Crawford , Edenfield Andrea M. , Wampler J. Marion , Matisoff Gerald , Long Philip E.
Published: August 2006

The thermal effects, as well as the survivability and origins of microorganisms in Cretaceous rocks, are evaluated from the timing and extent of the smectite to illite transformation in Cretaceous bentonites collected from cores outside the thermal aureole of the Pliocene Cerro Negro volcanic neck. Overall, randomly ordered mixed-layered illite-smectite (I-S) is the predominant clay mineral in these bentonites, and the K-Ar ages of I-S range from 36 to 48 Ma (21 analyses, two additional analyses were outside this range). Increased temperature from burial is thought to be the primary factor forming I-S in these bentonites. Kinetic model calculations of the smectite to illite transformation are also consistent with I-S formed by burial without any appreciable thermal effects due to the emplacement of Cerro Negro. In a core angled toward Cerro Negro, the percentages of illite layers in I-S from the bentonite closest to Cerro Negro are slightly higher (32-37%) than in most other bentonites in this study. The K-Ar ages of the closest I-S are slightly younger as a group (38-43 Ma; Average = 41 Ma; N = 4) than those of I-S further from Cerro Negro in the same core (41-48 Ma; Average = 44 Ma; N = 6). A small amount of illite in this I-S may have formed by heat from the emplacement of Cerro Negro, but most illite formed from burial. Vitrinite reflectance, however, appears to record the effects of heating from Cerro Negro better than I-S. Tentatively, the temperature of this heat pulse, based on vitrinite data alone, ranged from 100 to 125°C and this is most evident in the CNAR core. The upper temperature, 125°C, approximates the sterilization temperatures for most microorganisms, and these temperatures probably reduced a significant portion of the microbial population. Thermophiles may have survived the increased temperatures from the combined effects of burial and the intrusion of Cerro Negro.
New Techniques for Studying the Intercalation of Kaolinites from Georgia with Formamide
Authors: Frost Ray L. , Lack Daniel A. , Paroz Gina N. , Tran Thu Ha T.
Published: August 2006

A new technique utilizing Raman microscopy and Fourier transform infrared (FTIR) microsacopy is described. This technique uses thin films of oriented clay aggregates on glass slides suitable also for X-ray diffraction (XRD). Raman microscopy proved the most useful technique providing both better resolution of the OH-stretching bands and greater spectral resolution. Kaolinites from Washington County, Georgia, with varying defect structures involving layer stacking were intercalated with formamide and additional Raman bands were observed at 3610 and 3627 cm−1. A concomitant decrease in the inner-surface OH band intensities at 3695 and 3685 cm−1 occurred. These bands are attributed to the inner-surface OH hydrogen bonded to the formamide molecule through the C=O group. The 3627 cm−1 band is sharp with a half width of 7.5 cm−1 and comprises 11% of the total normalized band area. When two additional OH bands are observed at 3610 and 3627 cm−1 two C=O bands at 1674 and 1658 cm−1 are observed also. The two additional Raman inner-surface OH bands were not observed in the IR spectra. However, a band of low intensity was observed at 3590 cm−1. Models for the intercalation of formamide in kaolinites are proposed.
Interaction of Synthetic Sulphate “Green Rust” with Phosphate and the Crystallization of Vivianite
Authors: Hansen Hans Christian Bruun , Poulsen Inge Fiil
Published: August 2006

Because layered Fe(II)Fe(III)-hydroxides (Green rusts, GRs) are anion exchangers, they represent potential orthophosphate sorbents in anoxic soils and sediments. To evaluate this possibility, two types of experiments with synthetic sulphate-interlayered GRs (GRSO4 = Fe2+4Fe3+2(OH)12SO4 ×H2O) were studied. First, sorption of phosphate in GRSO4 was followed by reacting suspensions of pure GRSO4 synthesized by oxidation of Fe(II) with an excess of Na2HPO4 (pH 9.3). Second the possible incorporation of phosphate in GR during formation by Fe(II)-induced reductive dissolution of phosphate-containing ferrihydrites was examined in systems containing an excess of Fe(II) (pH 7). With excess phosphate in solution, GRSO4 initially sorbed phosphate in the interlayer producing a basal layer spacing of 1.04 nm, but only ~50% of the interlayer sulphate was exchanged with phosphate. This GR slowly transformed to vivianite within months. In the Fe(II)-rich systems, reaction with synthetic ferrihydrites produced GRSO4 similar to that produced by air oxidation. Reaction of Fe(II) with phosphate-containing ferrihydrites initially produced amorphous greenish phosphate containing precipitates which, after 3–4 h, crystallized to GRSO4 and vivianite. In these solutions, stable phosphate-free GRSO4 can form since precipitation of vivianite produced low phosphate activity. Consequently, in both systems GR or amorphous greenish precipitates act as reactive intermediates, but vivianite is the stable end-product limiting phosphate concentration in solution. It is also inferred that Fe(OH)2 is an unlikely phosphate sorbent in mixed Fe(II)-Fe(III) systems because GR phases are more stable (less soluble) than Fe(OH)2.
Occurrence of Clinoptilolite and Mordenite in Tertiary Calc-Alkaline Pyroclastites from Sardinia (Italy)
Authors: Ghiara Maria R. , Petti Carmela , Franco Enrico , Lonis Roberto , Luxoro Santina , Gnazzo Lucio
Published: August 2006

Clinoptilolite and mordenite occur as diagenetic products of medium-grained, moderately welded and poorly sorted pyroclastic flows belonging to the Tertiary calc-alkaline volcanism of Sardinia. Both clinoptilolite and mordenite occur within pyroclastic flows of the same stratigraphic unit. Mordenite frequently occurs in the late volcanic sequences from Anglona area (northern Sardinia). Textural features indicate that zeolites are products of glass alteration. Thin sections show either complete alteration of glassy shards by clinoptilolite and mordenite or unaltered shards with clinoptilolite or mordenite confined to the cineritic matrix. During the zeolitization process, interacting fluids were important in the mobilization and distribution of alkali elements. The compositional variations of clinoptilolite and mordenite within a single sample showed trends that suggest steps in a continuous process probably evolving towards equilibrium conditions.
Distinguishing Between Surface and Bulk Dehydration-Dehydroxylation Reactions in Synthetic Goethites by High-Resolution Thermogravimetric Analysis
Authors: Ford Robert G. , Bertsch Paul M.
Published: August 2006

Synthetic goethites studied by high-resolution thermogravimetry (HRTGA) show variability in surface characteristics and structural stability as a function of aging conditions. Goethites were synthesized at either pH 6 or 11, at temperatures of 40 or 70°C, and in the presence or absence of sorbed Mn or Pb. Data from HRTGA analysis revealed at least four distinct weight-loss events near goethite dehydroxylation that relate to 1) three events involving the evolution of water associated with surface Fe-O functional groups and 2) bulk dehydroxylation of goethite during transformation to hematite. The relative mass of evolved surface and bulk structural water was related to the predominant particle morphology as determined by transmission electron microscopy (TEM). Differentiation of surface and bulk decomposition reactions allowed the identification of bulk structural dehydroxylation. Goethite crystallin-ity, estimated by the bulk dehydroxylation temperature, appeared to depend on the kinetics of crystallization. This trend was most evident for systems aged at pH 11 and 40°C. Greater concentrations of coprecipitated Mn or Pb dramatically improved goethite crystallinity as indicated by higher dehydroxylation temperatures and smaller widths of the (110) Bragg reflection. Comparison of bulk dehydroxylation temperatures for these samples to other preparations suggests that structural defects predominated over the effects of particle size and Mn/Pb substitution in determining goethite thermal stability. A conceptual model is proposed to account for the disparate dehydroxylation profiles displayed by goethites of varying crystallinity.
A New Approach to Compositional Limits for Sepiolite and Palygorskite
Authors: Galan Emilio , Carretero Ma Isabel
Published: August 2006

Most bulk chemical analyses of sepiolite and palygorskite available in the literature are erroneous because samples analyzed are admixtures of minerals that are difficult to separate or identify by other techniques. Some chemical analyses performed on selected individual particles by energy dispersive X-ray analysis (EDX) are also influenced by the same problem. Chemical analyses are summarized for sepiolite and palygorskite reported in the literature (bulk and EDX analyses). The analyses are evaluated by comparison to three sepiolite and three palygorskite pure samples analyzed by EDX techniques. Results indicate that sepiolite is a true trioctahedral mineral, very pure (near end-member) with negligible structural substitution and with eight octahedral positions filled with magnesium, close to the theoretical formula Mg8Si12O30(OH)4(OH2)4(H2O)8. Palygorskite is intermediate between di- and trioctahedral phyllosilicates. The octahedral sheet contains mainly Mg, Al, and Fe with a R2/R3 ratio close to 1, and with four of the five structural positions occupied. The theoretical formula is close to (Mg2R23+?1)(Si8-xAlx)O20(OH)3(OH2)4·R2+x/2(H2O)4, where x = 0–0.5. Sepiolite and palygorskite are thus more compositionally limited than previously reported.
A Synthetic Na-Rich Mica: Synthesis and Characterization by 27Al and 29Si Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy
Authors: Komarneni Sridhar , Pidugu Rajyalakshmi , Hoffbauer W. , Schneider Hartmut
Published: August 2006

A swelling mica, Na2Mg3(Al2Si2)O10F2·xH2O, (hereafter “Na-4 mica”) was synthesized from metakaolinite + MgO and Mg aluminosilicate gels at different temperatures and durations using NaF flux. The various samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and 27A1 and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The results showed that phase-pure Na-4 mica was obtained from metakaolinite which serves as a cost-effective aluminosilicate source. 27Al MAS NMR spectra showed that all or nearly all Al is in tetrahedral coordination whereas 29Si MAS NMR spectra showed that the nearest neighbor environment of Si is mainly Si(3Al), as expected based on the Si:Al ratio.
The Effect of Dry Grinding on Antigorite from Mulhacen, Spain
Authors: Drief A. , Nieto F.
Published: August 2006

Alteration of the crystal structure of Mulhacén antigorite caused by dry, vibration grinding was investigated by X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analyses (TG), grain-size distribution, and transmission and analytical electron microscopy (TEM, AEM). Grinding for 1 min reduces particles to a size ideal for IR and TG. With prolonged grinding, XRD and electron diffraction patterns showed that the crystal structure was affected mainly along the c axis, causing a partial loss of crystallinity. TG analyses revealed that vibration grinding modified mineral dehydration, accelerating the dehydroxylation process and transforming the structural OH to adsorbed water in the resulting matrix. IR spectra and AEM showed that grinding affected the tetrahedral sheet to a lesser extent than the octahedral sheet. Partial release of Mg by preferential destruction of the octahedral sheet after 10 min grinding produced an increase in the Si/Mg ratio in semi-crystalline particles, whereas the amorphous material product after 120 min showed the same composition as the initial antigorite. TEM and grain-size distribution results revealed that grinding led to a general decrease in particle size at the beginning of the experiment followed by the agglomeration of ultrafine particles as grinding proceeded.
Ambient-Temperature Synthesis, Evolution, and Characterization of Cobalt-Aluminum Hydrotalcite-Like Solids
Authors: Thompson Hillary A. , Parks George A. , Brown Gordon E.
Published: August 2006

Double hydroxide solids precipitated homogeneously from three laboratory-synthesized aqueous solutions that simulated mildly contaminated surface or groundwater. Over a limited pH range, precipitates formed rapidly from dissolved ions, and more slowly by incorporating ions dissolving from other solids, including highly soluble aluminous solids. The precipitates were characterized by size and shape via transmission electron microscopy (TEM), by composition via inductively coupled plasma-mass spectrometry (ICP-MS) of mother solutions and analytical electron microscopy (AEM) of precipitates, and by structure via powder X-ray diffraction (XRD), TEM, and extended X-ray absorption fine structure (EXAFS) spectroscopy. They were identified as nanocrystalline cobalt hydrotalcite (CoHT) of the form [Co(II)1-xAl(III)x(OH)2]x+(An−x/n)·mH2O, with x = 0.17–0.25, A = CO32−, NO3−, or H3SiO4−n = anion charge and m undetermined. Complete solid solution may exist at the macroscopic level for the range of stoichiometrics reported, but clustering of Co atoms within hydroxide layers indicates a degree of immiscibility at the molecular scale. Composition evolved toward the Co-rich endmember with time for at least one precipitate. The small layer charge in the x = 0.17 precipitate caused anionic interlayers to be incomplete, producing interstratification of hydrotalcite and brucite-like layers. Solubility products estimated from solution measurements for the observed final CoHT stoichiometries suggest that CoHT is less soluble than the inactive forms of Co(OH)2 and CoCO3 near neutral pH. Low solubility and rapid formation suggest that CoHT solids may be important sinks for Co in contact with near neutral pH waters. Because hydrotalcite can incorporate a range of transition metals, precipitation of hydrotalcite may be similarly effective for removing other trace metals from natural waters.
Partial Stabilization of Fe(II) in Reduced Ferruginous Smectite by Li Fixation
Authors: Komadel Peter , Madejová Jana , Stucki Joseph W.
Published: August 2006

Partial stabilization of Fe(II) in chemically reduced smectite, which normally readily undergoes reoxidation in air, was achieved. The purpose of this study was to determine if Fe(II) can be stabilized in reduced smectites by Li fixation upon heating. More than 80% of total Fe in ferruginous smectite SWa-1 was reduced to Fe(II) using the citrate-bicarbonate-dithionite (CBD) method while purging the clay dispersion with N2. The reduced smectite was Li-saturated, washed free of excess ions, freeze-dried, and heated in N2 atmosphere at 260°C for 24 h to produce Li-fixation. This treatment caused partial stabilization of Fe(II) in the clay structure. Chemical analysis, Mössbauer spectroscopy, and Fourier transform infrared (FTIR) spectroscopy proved that <20% of total Fe was Fe(II) after reoxidation with oxygen in a water dispersion, a treatment which causes complete reoxidation of Fe(II) in reduced Na-smectites. Decomposition of the OH-stretching band evident in the IR spectra indicated migration of Li into the vacant octahedra. Some of the OH groups in the reoxidized smectite were found in local trioctahedral configurations, associated with the AlFe(II)Li or Fe(III)Fe(II)Li groupings of central atoms in the octahedral sheet.
Effect of Acid Activation on the De-Tert-Butylation Activity of Some Jordanian Clays
Authors: Mahmoud Sabri , Saleh Sadiq
Published: August 2006

Jordanian natural kaolin and bentonite show good catalytic activity towards debutylating 2-tert-butylphenol, and varying debutylation vs. isomerization selectivity after acid activation. The resulting catalytic activity of these samples is dependent on the acid employed for activation; the samples treated with acetic acid showed relatively low conversions, whereas those treated with hydrochloric or phosphoric acid were found to be very active. Treatments with strong acids such as HCl have various effects on the activity of the samples depending on the concentration of the acid. For example, treatment with 1 M HCl gives the highest activity, whereas a treatment using 12 M HCl produced the lowest activity. The debutylation selectivity of the acid-activated samples is affected by the acid type and/or concentration. This selectivity ranges from 20 to 60%, whereas that of water-treated samples is between 46–82%.
Preferred Orientation of Phyllosilicates in Gulf Coast Mudstones and Relation to the Smectite-Illite Transition
Authors: Ho Nei-Che , Peacor Donald R. , van der Pluijm Ben A.
Published: August 2006

Development of preferred orientations of illite-smectite (I-S) has been studied using X-ray diffraction (XRD) texture goniometry to produce pole figures for clay minerals of a suite of 16 mudstone samples from a core from the Gulf Coast. Samples represent a compaction-loading environment in which the smectite-to-illite (S-I) transition occurs. In five shallow, pre-transition samples, there is no significant preferred orientation for smectite-rich I-S. Development of preferred orientation of I-S, although weak, was first detected at depths slightly less than that of the S-I transition. The degree of preferred orientation, which is always bedding-parallel, increases rather abruptly, but continuously, over a narrow interval corresponding to the onset of the S-I transition, then continues to strengthen only slightly with increasing depth. The degree of post-transition preferred orientation is also dependent on lithology, where the preferred orientation is less well-defined for quartz-rich samples.

Previously obtained transmission electron microscope (TEM) data define textures consistent with the change in orientation over many crystallites. The smectite in pre-transition rocks consists largely of anastomosing, “wavy” layers with variable orientation and whose mean orientation is parallel to bedding, but which deviate continuously from that orientation. This results in broad, poorly defined peaks in pole figures. Post-transition illite, by contrast, consists of thin, straight packets, with most individual crystallites being parallel or nearly parallel to bedding. This results in pole figures with sharply defined maxima. By analogy with development of slaty cleavage in response to tectonic stress during metamorphism, the S-I transition is marked by dissolution of smectite and neocrystallization of illite or I-S locally within the continuous “megacrystals” of smectite. The transition is inferred to have some component of mechanical rotation of coherent illite crystals within a pliant matrix of smectite. The data suggest that change in orientation and coalescence of clay packets plays an important role in the formation of the hydraulic seal required for overpressure generation.
Pedogenic Formation of Kaolinite-Smectite Mixed Layers in a Soil Toposequence Developed from Basaltic Parent Material in Sardinia (Italy)
Authors: Righi Dominique , Terribile Fabio , Petit Sabine
Published: August 2006

Formation of kaolinite-smectite (K-S) mixed layers in a soil toposequence developed from basaltic parent material was examined. The soil formed in a temperate climate with alternating dry and wet seasons in Sardinia (Italy). Chemical composition and charge characteristics of the smectite component in the K-S mixed layers were analyzed to help determine a mechanism for formation. Soils were sampled at the top, intermediate, and base of a steep (35%) slope. As indicated by X-ray diffraction data, the fine clay fraction (>0.1 μm) in the soils is dominated by K-S with a decreasing proportion of kaolinite from the top (70%) to the base (30%). Rapid internal drainage induced by the slope is probably the major factor responsible for the formation of K-S. Chemical composition and charge characteristics of the smectite component in the K-S were analyzed by X-ray diffraction (intercalation with alkylammonium ions), cation exchanged capacity (CEC) and surface area measurements, and infrared spectroscopy. Results indicate that the smectite component is nearly identical over the soil toposequence. The smectite component is the same with respect to charge magnitude and chemical composition, independent of the proportion of kaolinite and smectite components. This suggests the pedogenic formation of K-S by transformation of smectite through dissolution of some smectite layers and subsequent crystallization of kaolinite between the layers of the remaining smectite crystallites.
Mineral-Content and Particle-Size Effects on the Colloidal Properties of Concentrated Lateritic Suspensions
Authors: Cerpa A. , García-González M. T. , Tartaj P. , Requena J. , Garcell L. , Serna C. J.
Published: August 2006

The rheological behavior of concentrated lateritic suspensions from Cuba is affected by mineral composition and particle size. Electrophoretic mobility and yield stress were considered. The lateritic samples were found to be mostly composed of mixtures of serepentine and goethite in varying proportions. The flow properties of the lateritic suspensions are strongly affected by the mineral composition and particle size. This result was determined by comparison of flow properties of the bulk sample and the colloidal fraction. The electrokinetic curves suggest that heterocoagulation is present in all samples, with a zeta potential minimum at the isoelectric point (IEP), which varies with the serpentine to goethite ratio. A relationship between yield stress (τ0) and the sample volume fraction (ϕ) and particle size (d) was obtained at the IEP from the expression τ0 = kϕ3/d0.5, with the constant k dependent on the sample serpentine to goethite ratio.
Synthesis of Smectite Clay Minerals: A Critical Review
Authors: Kloprogge J. Theo , Komarneni Sridhar , Amonette James E.
Published: August 2006

Smectites are one of the most important groups of phyllosilicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature (<100°C), (2) under moderate hydrothermal conditions (100–1000°C, pressures to several kbars), (3) under extreme hydrothermal conditions (>1000°C or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrothermal conditions are the most numerous and the most successful in terms of smectite yield and phase-purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The presence of Mg2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temperatures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under-and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody-namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.
Removal of Nickel and Cobalt from Aqueous Solutions by Na-Activated Bentonite
Authors: Triantafyllou Stella , Christodoulou Eirini , Neou-Syngouna Paraskevi
Published: August 2006

The ability of Na-activated bentonite to remove Ni2+ and Co2+ from aqueous solutions at room temperature (22 ± 1°C) was studied under various experimental conditions. The parameters studied were solid-to-liquid ratios and initial cation concentrations. Experiments involved the behavior of bentonite vs. Ni and Co separately and where Ni and Co were present in solution at different concentrations and ratios. Bentonite retained substantial amounts of both metals readily, but it showed a higher affinity for Ni. Over-exchange appears when initial metal concentration exceeds the concentration corresponding to the cation exchange capacity (CEC) of bentonite. The presence of both metals in solution may be either synergistic or antagonistic sorption, depending on the initial ion concentrations.
Methods for Performing Atomic Force Microscopy Imaging of Clay Minerals in Aqueous Solutions
Authors: Bickmore Barry R. , Hochella Michael F. , Bosbach Dirk , Charlet Laurent
Published: August 2006

Three methods were developed that allow for the imaging of any clay mineral in aqueous solutions with atomic force microscopy (AFM). The methods involve fixing the particles onto special substrates that do not complicate the imaging process, but hold the particles sufficiently so that they do not move laterally or float away during imaging. Two techniques depend on electrostatic attraction under circumneutral pH conditions, between the negatively charged clay particles and the high point of zero charge substrate (either aluminum oxide or polyethyleneimine-coated mica) whereas the third technique depends on adhesion to a thermoplastic film. The first electrostatic technique involves a polished single crystal α-Al2O3(sapphire) substrate. This was used successfully as a substrate for clay-sized minerals with high permanent layer charge localized on the basal planes (phlogopite and vermiculite) and when the AFM was operated in TappingMode to limit the lateral forces between the probe tip and the particles. However, electrostatic attraction between the sapphire surface and clay minerals such as smectite and kaolinite (low or no permanent layer charge) is not sufficiently strong to adequately fix the particles for imaging. The second electrostatic technique involves a polyethyleneimine-coated mica surface designed to immobilize a larger variety of clay minerals (phlogopite, vermiculite, montmorillonite, and kaolinite), and in this technique weak bonding between the clay and the organic film is also a factor. The third technique, which does not depend on electrostatic attraction, fixes clay particles into the surface of a thermoplastic adhesive called Tempfix. This has proven useful for fixing and imaging relatively large clay particles with well-defined morphology. The Tempfix mount also requires imaging in TappingMode because the Tempfix is relatively soft.
Crystal Chemistry of Layer Silicates of the Miocene Green Grain (Congo Basin) from Transmission Electron Microscopy (TEM) and Analytical Electron microscopy (AEM) Observations
Authors: Wiewióra A. , Giresse P. , Jaunet A. M. , Wilamowski A. , Elsass F.
Published: August 2006

Transmission electron microscopy (TEM) and analytical electron microscopy (AEM) methods were used to study the crystal chemistry of phyllosilicates occurring in green grains of Miocene sediments from the Congo continental shelf. Using diagrams based on wt. % K and the (Fe + Mg)/Al ratio, minerals were distinguished from mixed-layer phases. The most abundant detrital mineral is Fe-kaolinite. The morphology and composition identify this mineral as a component of ferralitic soils. This Fe-rich kaolinite has undergone a complex process of partial dissolution and recrystallization and further enrichment in Fe and, to a lesser extent, in Mg in the marine environment. The detrital mica observed with TEM retains the original morphology and chemistry of muscovite. Alteration processes resulted in the crystallization of 1:1 trioctahedral Fe2+ and Mg-rich minerals and interstratified phases with 1:1 and 2:1 layers in varying proportions observed with the aid of high-resolution transmission electron microscopy (HRTEM) imaging. Included among the newly formed 7-Å phases are those apparently containing excess Si. The smectites are apparently neoform, and chemical analyses showed that these marine K-smectites belong to the beidellite-nontronite series and have tetrahedral substitutions similar to muscovite. Their compositions are closer to beidellite than to nontronite, although the latter was observed in association with goethite. The TEM observations and crystallochemical data show that mineral alteration ceased after forming mixed-layer minerals, and alteration did not reach the glauconitization stage. Apparently, the Miocene assemblages experienced rapidly changing environmental conditions and high sedimentation rates that continue today.
Structural Fe3+ in Natural Kaolinites: New Insights from Electron Paramagnetic Resonance Spectra Fitting at X and Q-Band Frequencies
Authors: Balan Etienne , Allard Thierry , Boizot Bruno , Morin Guillaume , Muller Jean-Pierre
Published: August 2006

Structural Fe3+ in kaolinites and dickites covering a broad range of disorder was investigated using electron paramagnetic resonance (EPR) spectroscopy at both the X and Q-band frequencies. A procedure based on a numerical diagonalization of the spin Hamiltonian was used to accurately determine the second and fourth-order fine-structure parameters. A least-squares fitting method was also developed to model the EPR spectra of Fe3+ ions in disordered local environments, including multimodal site-to-site distributions. Satisfactory fits between calculated and observed X and Q-band spectra were obtained regardless of the stacking order of the samples.

In well-ordered kaolinite, Fe3+ ions are equally substituted in sites of axial symmetry (Fe(II)sites, namely Fe(II)a and Fe(II)b) which were determined to be the two non-equivalent Al1 and Al2 sites of the kaolinite structure. In dickite, Fe3+ ions were also found to be equally substituted for Al3+ in the two non-equivalent Al sites of the dickite structure. In poorly ordered kaolinites, the distribution of the fine-structure parameters indicates that Fe3+ ions are distributed between Fe(II) sites and other sites with the symmetry of the dickite sites.

Hence, when stacking disorder prevails over local perturbations of the structure, the near isotropic resonance owing to Fe3+ ions in rhombically distorted sites (Fe(I) sites) is a diagnostic feature for the occurrence of C-layers in the kaolinite structure, where C refers to a specific distribution of vacant octahedral sites in successive layers.
Sorption of Heavy-Metal Cations by Al and Zr-Hydroxy-Intercalated and Pillared Bentonite
Authors: Matthes Winnie , Madsen Fritz T. , Kahr Guenther
Published: August 2006

The sorption of Cd, Cu, Pb, and Zn ions by Na-rich bentonite, Al and Zr-pillared Na-rich bentonite (Al-MX80, Zr-MX80), the uncalcined hydroxy-intercalated precursors (HAl, HZr-MX80), and commercial Al-pillared bentonite EXM 534 was investigated. Experiments were conducted in ultrapure water and artificial leachate with varying pH. The experiments were performed over periods to 30 wk. Sorption characteristics were described with one and two-site Langmuir isotherms. The non-exchangeable quantities of heavy metals were determined by fusion of the sorbents after ion exchange with ammonium acetate.

The sorption of Cd, Cu, Pb, and Zn by bentonite was dominated by cation exchange. In artificial leachate, the sorption was reduced due to competition with alkali and alkaline-earth cations. The sorption of Cu, Zn, and Pb at pH 4.9 and Cd at pH 6.9 by Al and Zr-hydroxy-intercalated and pillared MX80 was governed also by cation exchange. In contrast, the sorbed quantities of Zn at pH 6.9 exceeded the cation exchange capacity (CEC) of HAl, HZr, Al, Zr-MX80, and EXM 534 and were partially non-exchangeable. The increase of the sorption of Zn with pH and its independence of the ionic strength of the solution at neutral pH suggest a complexation of Zn ions to surface hydroxyl groups of the intercalated Al and Zr-polyhydroxo cations and pillars. This complexation is the dominating sorption mechanism. Removal of dissolved Zn from solution with time is attributed to surface precipitation. Al-hydroxy and pillared bentonites are considered potential sorbents of Zn ions from neutral pH aqueous solutions, such as waste waters and leachates.
Transmission X-ray Diffraction of Undisturbed Soil Microfabrics Obtained by Microdrilling in Thin Sections
Authors: Denaix L. , van Oort F. , Pernes M. , Jongmans A. G.
Published: August 2006

Clay mineralogical studies by X-ray diffraction performed on extracted <2-µm fractions do not always represent all clay mineral constituents present in the soil. In this work, transmission X-ray diffraction (TXRD) was applied to undisturbed microsamples of optically homogeneous mineral soil fabrics and features. These microsamples were isolated by microdrilling their periphery in soil thin sections, then removing them, and transferring them to glass capillaries for TXRD analysis. The usefulness of this technique for supplying in situ mineralogical information on identification, structure, and natural orientation of soil constituents was tested on mineral microfabrics and features of primary and secondary phyllosilicates. The study demonstrated that TXRD allowed detailed, representative interpretations of undisturbed mineral features and fabrics. In particular, this technique allowed us (1) to compare mineralogical compositions at selected microlocalities, (2) to study natural preferred orientations, and (3) to detect small amounts of minor mineral interstratification phases. In addition, complementary information on crystallography and crystal chemistry may be obtained by performing analytical transmission electron microscopy on the same microsample.
Selective Gas Adsorption by Amorphous Clay-Mineral Derivatives
Authors: Volzone Cristina , Thompson John G. , Melnitchenko Alexandra , Ortiga José , Palethorpe Stephen R.
Published: August 2006

Amorphous derivates prepared by aqueous reaction of various aluminosilicate clay minerals with concentrated KF solution at 80–110°C were studied for their gas adsorption properties. The four clay minerals studied are halloysite, a well-crystallized kaolinite, a poorly crystallized kaolinite, and a montmorillonite. The gases tested are N2, O2, CH4, CO, CO2, and C2H2. The kaolin-group mineral derivatives are characterized by substantial reduction in particle size, high specific surface, and significant selectivity towards CO2 and C2H2 relative to the other gases. The montmorillonite derivative shows no increase in adsorption over the starting material, however, for all the materials high adsorption of CO2 and C2H2 was observed. Levels of gas adsorption and gas adsorption ratios are comparable to pillared clays.
Role of Tartaric Acid in the Inhibition of the Formation of Al13 Tridecamer using Sulfate Precipitation
Authors: Krishnamurti G. S. R. , Wang M. K. , Huang P. M.
Published: August 2006

Polynuclear Al13 tridecamer species are the major hydrolyzed species of aluminum, but their occurrence in terrestrial environments has not been established. X-ray diffraction (XRD), 27Al nuclear magnetic resonance (NMR), and scanning electron microscope (SEM) analyses show that the presence of tartaric acid (concentration range of 10−5–10−3 M), one of the commonly occurring low-molecular-weight organic acids, inhibits the formation of the Al13 tridecamer species.

In the absence of tartaric acid, the basic aluminum sulfate crystals were of tetrahedral morphology and conformed to isometric symmetry with a = 17.748 Å and space group of P4232. Increasing amounts of tartaric acid [tartaric acid/Al molar ratio (R) ranging from 0.01 to 0.05] modified the crystal morphology from the tetrahedral particles of isometric symmetry (R = 0) to rod-shaped particles of monoclinic symmetry (R = 0.01) to irregularly shaped X-ray noncrystalline microparticles (R = 0.05). Failure to detect the presence of Al13 tridecamer, the dominant hydrolyzed species of aluminum, in terrestrial environments may be partially attributed to the presence of low-molecular-weight organic acids, which inhibit the formation of Al13 tridecamer species.
Effects of Exchange Cations and Layer-Charge Location on Cysteine Retention by Smectites
Authors: Brigatti Maria Franca , Lugli Cristina , Montorsi Stefano , Poppi Luciano
Published: August 2006

This study investigates the complexes formed between amino acids, which are the natural degradation products of organic matter, and smectites. Thus, the adsorption and desorption behavior of cysteine and Na-, Ca-, Cu-homoionic smectites with different layer-charge location, a montmorillonite, and a beidellite, were studied. The clay samples were treated with Na, Ca, and Cu 1 N solutions and then with a 0.2 M cysteine solution. To test smectite-cysteine stability at acidic pH, the solids obtained were repeatedly treated with distilled water acidified to pH = 5. All treated samples were characterized by thermal, X-ray diffraction, chemical, and infrared analyses. The results showed that: 1) Na- and Ca-rich smectites adsorbed and retained small amounts of cysteine, and did not show interlayer cation-cysteine complexes, whereas the amino acid was strongly retained in the interlayer by Cu-rich smectites; 2)d(001)-values for Na- and Ca-rich smectites showed little or no expansion, whereas for the Cu-rich smectites the intercalation of the organic molecule produced a swelling of the structure; 3) the interaction mechanism of homoionic smectites with cysteine in an aqueous medium occurs by weak interactions, (e.g., van der Waals interactions, hydrogen bonding, dipole-dipole interactions, and other electrostatic forces such as entropy-driven hydrophobic bonding), and/or by complexes involving interlayer cations and organic ligands. The formation of a stable chelate complex with the saturating ion permits cysteine to be adsorbed by Cu(II)-rich smectites and to be resistant to migration in soils and groundwaters.
Complex Formation of Cation-Exchanged Montmorillonites with Propylene Carbonate: Osmotic Swelling in Aqueous Electrolyte Solutions
Authors: Onikata Masanobu , Kondo Mrrsuji , Hayashi Naoki , Yamanaka Shoji
Published: August 2006

Montmorillonites saturated with Li+, Na+, K+, NH4+, Mg2+, Ca2+, Ba2+, or Ni2+ ions can form complexes with propylene carbonate (PC) by intercalation; the d(001) of montmorillonite expands to 19 Å. In the infrared absorption spectra of these complexes, the C=0 stretching band of the intercalated PC molecules shifts to lower frequencies, and the amount of the shift increased with the increase of the polarizing power of the interlayer cations. Water molecules were strongly bound to the cations. The PC molecules interacted with the cations by way of H2O molecules. With the removal of H2O, the PC molecules directly coordinate to the cations and the PC molecules show a much larger red-shift in the C=O frequency. The PC-montmorillonite complexes exhibited osmotic swelling, even in aqueous electrolyte solutions. This finding is interpreted in terms of the formation of thick electric double-layers consisting of PC and H2O between the 2:1 layers.
Cation-Exchange Capacity (CEC) of Zeolitic Volcaniclastic Materials: Applicability of the Ammonium Acetate Saturation (AMAS) Method
Authors: Kitsopoulos Konstantinos P.
Published: August 2006

The ammonium acetate saturation (AMAS) method was used to study the cation-exchange capacity (CEC) of zeolitic volcaniclastic materials from Santorini and Polyegos Islands, Greece. The AMAS method was tested with respect to the time required to saturate the samples of zeolites with ammonium (NH4+) ions, the efficient liberation of NH4+ ions, and the suitability of two widely used techniques to measure ammonia (NH3) (Kjeldahl ammonia distillation technique and the ammonia electrode technique). By using the inductively coupled plasma-mass spectrometry (ICP-MS) technique and measuring the number of cations exchanged during ammonium acetate (NH4OAc) saturation, it was found that the saturation period for zeolitic materials must be increased to 12-day cycles to ensure effective saturation. Following NH4OAc saturation, the AMAS method produces NH4+ solutions, after the NH4+-saturated samples of zeolites are washed with 10% NaCl. The amount of the NH4+ ions in solution (i.e., exchangeable cations) is a measure of the CEC. The NH4+ ions can not be directly measured and must be converted to NH3. The Kjeldahl ammonia distillation technique and the ammonia electrode technique for measuring NH3 give identical CEC results. However, the ammonia electrode technique, when used directly with the NH4+ samples of zeolite without 10% NaCl treatment, generally gives higher CEC values. The amount of NH4+ treated (converted to NH3), when the NH4+-saturated zeolitized samples were used directly, was higher than the amount of the NH4+ treated when the NH4+ solutions were obtained after washing the NH4+-saturated zeolitized samples with 10% NaCl. Therefore, washing with 10% NaCl does not facilitate the release of all NH4+ initially within the zeolite structure. A modified AMAS technique is proposed for measuring the CEC of zeolitic material.
Impact of Different Asbestos Species and Other Mineral Particles on Pulmonary Pathogenesis
Authors: van Oss C. J. , Naim J. O. , Costanzo P. M. , Giese R. F. , Wu W. , Sorling A. F.
Published: August 2006

Factors that are potentially important in the pulmonary pathogenesis of asbestos and other mineral particles are: 1) morphology, 2) Fe-content, 3) solubility under intraphagosomal conditions, 4) value and sign of the surface potential of the particle, 5) hydrophobicity or hydrophilicity, 6) capacity to activate phagocytic leukocytes, and 7) duration of exposure to the particles. The order of importance of these factors in causing severe or fatal pulmonary pathogenicity is estimated to be: 1 > 3 > 7 > 6 ≫ 5 > 4 > 2. The order of pathogenicity of the minerals is estimated as: amphibole asbestos: crocidolite, tremolite, amosite > erionite > serpentine asbestos: chrysotile > talc > silica > simple metal oxides. Particle length, duration of exposure to the particles, and pre-treatment of the particles may however enhance the pathogenic potential of any of the lower-ranked particles.
Clay Minerals in Hydrothermally Altered Volcanic Rocks, Eastern Pontides, Turkey
Authors: Çelik Muazzez , Karakaya Necati , Temel Abidin
Published: August 2006

Extensive hydrothermal alteration is observed around volcanogenic massive sulfide deposits. These deposits are related to Late Cretaceous volcanism in various parts of the Eastern Pontide province. Mineral assemblages resulting from alteration consist of mostly clay minerals and silica polymorphs, some sulfate minerals, and scarce zeolite minerals. The clay minerals are kaolinite, illite, and smectite. These minerals were examined using X-ray diffraction (XRD), scanning electron microscopy (SEM)-energy dispersive spectrometry (EDS), X-ray fluorescence spectroscopy (XRF), and differential thermal analysis (DTA)-thermal gravimetry (TG) techniques. The illite and the toseki deposits are a result of hydrothermal alteration of dacitic-andesitic volcanites. Two groups of bentonite deposits occur; the first mainly formed by hydrothermal solution whereas the second group resulted from halmyrolysis.

The smectite in these alteration zones is generally montmorillonitic in composition and the interlayer cation is mostly Ca and lesser amounts of Na. The SiO2 and Fe2O3 contents of the hydrothermal bentonites are higher than those of the halmyrolysis smectites; however, the MgO content of both groups is similar. The Na2O and K2O contents of both groups are generally <0.5%. The hydrothermal bentonites are not plastic and have open honeycomb microtextures, although the halmyrolitic smectites are plastic with ultrafine and rod-shaped textures. Illite, which contains some smectite layers, is a 1M polymorph, and has an asymmetry to the low-angle side of the XRD peaks. The impure illite deposits contain various combinations of smectite, kaolinite and gypsum, galena, sphalerite, pyrite, goetite, and quartz. The illite has >35 wt. % Al2O3. The toseki raw material, which may be possibly useful as a porcelain raw material, is composed mainly of illite, kaolinite and quartz, or illite and quartz. The crystallinity of the kaolinite is poor.
Physico-Chemical Properties of Illite Suspensions after Cycles of Freezing and Thawing
Authors: Schwinka V. , Mörtel H.
Published: August 2006

The effect of freezing and thawing on the rheological behavior of illite suspensions was studied by examining viscosity and plasticity. Stability of suspensions was characterized by a hysteresis loop of thixotropy. Thermal gravimetric and differential scanning calorimetry analysis were also used. After initial freezing and thawing, the flow curves of the suspensions show an increased viscosity, an “irregular up line”, and a greater hysteresis loop of thixotropy. The ratios of mean viscosity of previously frozen (F) and control (O) samples (ηF/ηO) for non-expandable 2:1 phyllosilicates ranges from 1.3 to 2.1. Addition of monovalent (0.1% Na2SiO3) and divalent cations (0.3% CaCl2 or BaCl2) increase and decrease the shear-stress difference between F and O samples, respectively. Prior freezing of clay samples results in an increase of plasticity by ∼20–30%. The thermal analysis data of F samples show an increase in weight loss, and a decrease in enthalpy of dehydration. The changes of physico-chemical properties from cycles of freezing and thawing are long lasting. The freezing memory effect of illite-type clays is expected to play an important role in ceramic processing, i.e., casting processes, plastic formation, and sintering.
A Nickel Hydroxide-Vermiculite Complex: Preparation and Characterization
Authors: Uehara Motoki , Yamzaki Atsushi , Umezawa Taku , Takahashi Koichiro , Tsutsumi Sadao
Published: August 2006

A nickel hydroxide-vermiculite complex (NHVC) with csinβ = 1.41 nm and particle sizes from 0.075 to 0.15 mm was obtained hydrothermally by adding nickel nitrate solution to vermiculite from Transvaal, South Africa. The quantity of nickel hydroxide included in NHVC was controlled by adjusting the concentration of the nickel nitrate solution. The thermal behavior of NHVC at 450°C or above was independent of the Ni content. However, small differences exist in the dehydration behavior of NHVC below 450°C. One-dimensional Fourier electron density analysis of the NHVC structure containing 2.43 mol of Ni per half unit cell showed that Ni cations occupy the interlayer of NHVC, and 10% of the total Ni cations is in the ditrigonal cavity of the basal-oxygen plane of the tetrahedral sheet.