Caustic nuclear wastes have leaked from tanks at the US Department of Energy’s Hanford site in Washington State (USA) causing hundreds of thousands of gallons of waste fluids to migrate into the underlying sediments. In this study, four simulant tank waste (STW) solutions, which are high in NaOH (1.4 and 2.8 mol/kg), NaNO3 (3.7 mol/kg) and NaAlO2 (0.125 and 0.25 mol/kg), were prepared and reacted with reference kaolinite KGa-1 and KGa-2 at 50 and 80°C for up to 2 months. The structure and morphology of the resulting products were characterized using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. The products were also examined for cation exchange and Cs+ sorption as a function of ionic strength and types of cations in the background solutions. Cancrinite and sodalite were the only new minerals observed in all of the conditions tested in this experiment. Two major chemical processes were involved in the reactions: dissolution of kaolinite and precipitation of cancrinite and sodalite. Increasing NaOH concentration and temperature, and decreasing NaAlO2 concentration increased the transformation rate. Both cancrinite and sodalite appeared stable thermodynamically under the experimental conditions. The newly formed feldspathoids were vulnerable to acid attack and pronounced dissolution occurred at pH below 5.5. Cancrinite and sodalite can incorporate NaNO3 ion pairs in their cages or channels. Sodium in cancrinite and sodalite was readily exchangeable by K+, but less easily by Cs+ or Ca2+. The feldspathoid products sorb nearly an order of magnitude more Cs+ than the unaltered kaolinite. The Cs adsorption is reduced by competing cations in the background solutions. At low ionic strength (0.01 M NaNO3 or 0.005 M Ca(NO3)2), Ca2+ was more competitive than Na+. When the concentration of the background solution was increased 10 times, Na+ was more competitive than Ca2+.

Two industrial bentonites, IBECO SEAL-80 and TIXOTON TE, have been proposed as potential backfill material in the German Asse salt dome, a test field for the disposal of low- to medium-grade active nuclear waste. Considering the unlikely but possible case of a barrier breakdown with infiltration of a highly concentrated salt brine, the physicochemical stability and material behavior of these bentonites in a saturated salt brine (predominantly MgCl2) at 25°C were studied over the time period of 150 days. The results show that no mineral transformations occurred throughout the duration of the experiments and minor dissolution was only active during the first days. Some chemical properties, namely sorption capability and swelling, were reduced during contact with the salt brine, but could be reversed by removing the salt after treatment. Despite restriction of the CEC in the presence of salt solution, interlayer cation exchange reactions are still active in this environment. The long-term chemical stability of smectite in salt brine is predicted under these low-temperature conditions, but the increased permeability during aggregate formation could lead to physical breakdown of the backfill component.

Waterproofing treatment is important for the preservation of smectite-rich rocks because of their shrinking and swelling properties. The effects of water repellents on the smectite structure and the water sorption of untreated and treated smectites were studied using X-ray diffraction. The hydrophobic Wacker BS 290 (around 100% silane/siloxane) does not prevent water from sorbing on the interlayer surface of smectite because the hydrophobic silane/siloxane is not intercalated into the interlayer space, but adsorbed onto the external surface of smectite. However, the hydrophilic Wacker BS 1001 (water-soluble emulsified silane/siloxane) prevents water from sorbing onto the interlayer surface beyond 33.3 wt.% because the hydrophobic part of the intercalated surfactant has a poor affinity for water. These results imply that water repellent containing a surfactant is suitable for smectite-rich rocks, but the expansion of smectite by intercalation of the surfactant is likely to influence volume change in smectite-rich rocks. This study notes that smectite within a rock can be one of the most important factors influencing the effectiveness of waterproof treatment. This study proposes that an intensive preliminary examination should be performed before applying water repellents to rocks, and furthermore, encourages development of new chemical reagents suitable for protecting smectite-rich rocks from moisture.

The adsorption of [M(bpy)3]2+ ions (M = Ru or Os) by clay films immersed in pure water and in electrolyte solutions was investigated by electrochemical quartz crystal microbalance (EQCM), UV-visible spectroscopy and powder X-ray diffraction. In water, the adsorption of the cations resulted in a decrease in the mass of the films. This decrease in mass is attributed to the expulsion of some 50 water molecules from the clay interlayer spaces for each cation adsorbed. Water is lost to make room for the large metal complex cations in the interlayer spaces, and because of decreases in the volume of the interlayer spaces during adsorption of the cations. In 0.05 M NaCl or 0.05 M Na2SO4, UV-visible measurements show a rapid initial adsorption of the cations by ion exchange, followed by a slower additional adsorption of the cations above the clay’s CEC, presumably as ion pairs with the electrolyte counter ions. The EQCM show initial reductions in the mass of the films that were two to three times larger in pure water. These initial mass decreases were followed by smaller mass ‘re-increases’ at longer times that were not observed in water. The larger initial mass losses are attributed to the loss of more water from the clay interlayer spaces. In 0.5 M Na2SO4 or 1.0 M NaCl, adsorption of the cations never exceeded the clay’s CEC. The initial decreases in mass upon addition of the cations all but disappeared, leaving only the smaller positive mass changes at longer times.

L-aspartic acid was intercalated into layered double hydroxides by coprecipitation. Two types of well crystallized material were obtained and were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry, differential thermal analysis and polarimetry. Schematic models of two intercalation structures with different basal spacings are given. It is proved that the optical activity of L-aspartic acid is retained during and after the intercalation process.

The Markovian model of mixed-layering that has been used until now for the modeling of X-ray diffraction (XRD) patterns of 2:1 phyllosilicates describes the mixed-layer crystals as stacks of ‘layer units’ (LUs) that associate a 2:1 layer with an interlayer content. This model is not consistent when it is applied to a mixed-layer mineral (MLM) involving electrically charged layers, i.e. most of the mixed-layer phyllosilicates with 2:1 layers. Two consistent models can be proposed for these MLMs, which, instead of LUs, stack ‘interlayer units’ (IUs), composed of an interlayer content sandwiched between two half-layers. The IU-NPL model (interlayer units, non-polar layers) imposes non-polarity on the 2:1 layers resulting from the stack of these IUs, which implies restrictions on the succession of the IUs. In the other consistent model, the IU-PL one (interlayer units, polar layers), these restrictions are not imposed. These two models reproduce the Non-Polar 2:1 Layer Model and the Polar 2:1 Layer Model described by Altaner and Ylagan for illite-smectite mixed layering, and the second model corresponds to the stacks of O0.5 T I′ T O0.5 units described by Olives et al.

The present work points out the similarities and discrepancies of the calculated XRD patterns by using computer programs designed for the three models of mixed-layering (LU, IU-NPL and IU-PL) and for two-and three-component MLMs. Illustrations are provided for some I-S and I-S-V MLMs.

The IU-PL model leads to XRD patterns similar to those of the LU model. It is in agreement with lattice-energy calculations, expandability measurement, HRTEM imaging and NMR spectroscopy.

Interstratified serpentine-smectite was found in the fine-grained fraction of altered metasomatic contact biotite-schists developed between serpentinite and granite-type rocks (Lower Silesia ophiolite sequence, Poland). Ni-rich serpentine-smectite is R0-interstratified lizardite (0.80)-stevensite (0.15)-vermiculite-like (0.05), with a coherent scattering domain (csd) of 5 layers (mean value). The Mg-rich variety of serpentine-smectite is R1 lizardite (0.80)-stevensite (0.20) with a csd size of 7 layers (mean value). A transmission electron microscope study revealed complex layer relationships, with zones composed of various serpentine-smectite packets having lizardite/smectite ratios of 3:1, 2:1, 1:1, 4:1 and scarce serpentine segregations. In both cases, the serpentine-smectites appear to be late products of alteration of the parent biotite-schist.

Experimental and calculated positions and intensities of reflections of the ethylene glycol-saturated, heated (250°C, thermal stage), and air-dried samples are in good agreement. Calculated X-ray diffraction patterns for interstratified glycolated and anhydrous serpentine-smectite are included in the Appendix.

Crystallization processes of the illite-smectite (I-S) mixed-layer mineral series during alteration of felsic vitric materials in volcaniclastic sediments through two drill holes (IT-2 and IT-8) near the Kakkonda active geothermal system, Japan, were examined by optical microscopy, scanning and transmission electron microscopy (SEM and TEM), electron microprobe analysis, X-ray diffraction (XRD), and oxygen isotope analysis. Temperatures measured through the drill holes increased nearly linearly with depth up to 317°C at the bottom (1700 m) of IT-8. Homogenization temperature measurements of fluid inclusions indicated that the alteration occurred at temperatures similar to the present temperatures. In selected volcaniclastic rocks, excluding andesitic rocks and black shales, clay minerals occurred as glass replacements and pore fillings as seen under SEM and optical microscopy, and exhibited predominantly euhedral hexagonal and elongated forms under TEM, implying that they precipitated in situ through hydrolytic reactions of glass and fluid. Based on XRD examination, I-S minerals showed a sigmoidal variation in illite layer percentage (%I) in the range of ∼150 to 220°C and R0 I-S minerals with intermediate %I between 20 and 40% rarely occurred (where R is the Reichweite parameter). The chemical composition also showed a specific variation with depth. Intermediate clays including smectite and I-S minerals are enriched in Al compared to those reported previously from hydrothermal alteration of almost equivalent parent rocks. The oxygen isotope data indicated that the reacting solution was percolating groundwater in the shallow levels and with fossil seawater in the deeper levels. Furthermore, calculating the fluid/rock (W/R) ratio from the isotope variations revealed that the alteration occurred at a nearly constant W/R ratio condition irrespective of %I. Consequently, the observed specific variations in structure and chemical composition of I-S minerals reflect the compositional variations of fluid participating in the crystallization at given temperatures under the conditions of a given original rock and constant W/R ratio. High pH and Na-rich solutions generated by progressive hydrolytic reactions between felsic glass and groundwater favored the precipitation of Al-rich smectite up to ∼150°C and was followed by precipitation of an aluminous R1 I-S mineral with few intermediate R0 I-S minerals at higher temperatures. The crystallization obeys Ostwald’s step rule behavior of smectite illitization processes under a high geothermal gradient.

A set of 99 samples covering the whole range of low- and very low-grade metamorphic conditions has been used to compare Kübler index (KI) values measured on the illite 10 Å reflection (KI10 Å) with those obtained from the 5 Å reflection (KI5 Å). Evaluation of peak widths have been carried out both graphically on the recorded peak profiles from chart-strip X-ray diffraction (XRD) patterns and with the WINFIT computer program (Krumm, 1996) on fitted and decomposed profiles. All the measurements were performed both on air-dried and glycolated preparations. The data collected show that in the rock samples where illite is associated with significant amounts of I-S interstratified minerals, and/or K/Na intermediate micas, paragonite and other interfering phases, full width at half-maximum (FWHM) measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts give more reliable KI values than those obtained from the 10 Å peak. This is because of the easier and more complete de-summation of the illite second reflection from the contributions of all the interfering phases. In each sample population in which the rocks have the same metamorphic grade, KI5 Å values from fitted and decomposed profiles show much lower scattering in comparison with KI10 Å values and appear consistent with the values measured in lithologies without interfering phases.

The relationship between KI10 Å and KI5 Å appears very close to a 1:1 linear relationship; nevertheless, the conversion from KI5 Å to KI10 Å through the appropriate equation (KI10 Å = KI5 Å × 0.965 + 0.023°2θ) is recommended in order to avoid a small, but systematic, error.

In the range from late diagenesis to middle anchizone, where several phases may give diffraction effects interfering with illite peaks, the proposed procedure (i.e. FWHM measurements on the 5 Å peak in fitted and decomposed XRD profiles from glycolated mounts) seems to allow better estimates of the metamorphic grade than those obtained through traditional KI measurements.

This paper describes a rare occurrence of nontronite associated with sulfide-bearing felsic metavolcanics, providing evidence of colloidal deposition in open spaces as result of a low-temperature water-rock interaction. Microbotryoidal masses of green nontronite with impurities of kaolinite, illite, barite, amorphous silica and iron oxyhydroxides are found as vein and cavity fillings in deeply kaolinized rhyolites and rhyolitic tuffs of Precambrian age, at Oliva de Merida in SW Spain. Clay mineral characterization has been carried out by X-ray diffraction, infrared spectroscopy, thermal analysis, analytical electron microscopy and stable isotope (oxygen and hydrogen) analysis. Nontronite was formed under low-temperature alteration conditions, from a continuous sequence of reactions and aqueous solution compositions, involving two basic processes that acted in concert: oxidative dissolution of pyrite and hydrolysis of K-feldspar. After acidity neutralization, dissolved silica released by incongruent dissolution of K-feldspar reacted with ferric sulfate derived from pyrite oxidation to form nontronite under oxidizing conditions, in the presence of relatively warm meteoric water.

The properties of Si-associated goethite from sediments in the Atlantis II and Thetis Deeps in the Red Sea have been investigated in order to determine the effect of Si on the mineral. Two types of morphologies dominate in most samples: multi-domain crystallites, probably due to elevated Na concentration in the initial brine from which the mineral had crystallized, and mono-domain, acicular crystals. Goethite crystals with elevated Si/Fe elemental ratios are usually smaller and poorly crystalline, exhibiting numerous crystal defects, whereas larger crystals with higher crystallinity have lower Si/Fe elemental ratios. The higher Si/Fe ratios in Atlantis II Deep goethites and the lower ratio in Thetis Deep goethites probably reflect the levels of Si concentration in the hydrothermal fluids from which goethite precipitated. At relatively low Si/Fe ratios, the major effect of Si is to retard growth of the crystallites, but only a small number of defects are formed. At high Si/Fe ratios the defect concentration affects the properties of the crystals, as observed with Mössbauer spectroscopy. The Si association with goethite affects crystallinity and crystal size as indicated by X-ray diffraction, infrared spectroscopy and high-resolution transmission electron microscopy.

Chinmen Island is located in the west of the Taiwan Strait, 15 km from the coast of mainland China. Mesozoic granitic gneiss forms the basement rocks of the island. High-defect kaolin deposits, both major sedimentary and minor residual types of clays, have been mined for ceramic uses for many years. The objectives of this study were to characterize the kaolin deposits and to discuss the genesis of kaolin minerals on the island. The kaolin samples were characterized by X-ray diffraction and transmission and scanning electron microscopy. In general, the particle-size distribution of the sedimentary kaolin was 0.5–5.0% sand, 15–55% silt and 30–85% clay. In the clay fraction, the ratio of kaolinite to illite ranged from 9:1 to 3:1. The sedimentary kaolin materials were originally transported by river from mainland China. Kaolinite occurred generally as pseudo-hexagonal platelets of ∼1 µm in diameter. The residual kaolin minerals resulted from the argillization of granitoid rocks by in situ weathering which possibly occurred during the Pleistocene. The residual kaolin contained more tubular halloysite.