Rectorites containing various amounts of Ca were found at the Sano Mine, Nagano Prefecture, Japan. The Ca content in nonexchangeable form varied from 1.0 to 3.9% CaO. With more than 3.4%, they may be called Ca-rectorite. Chemical data of the most Ca-rich sample showed that Ca was the dominant interlayer cation, and gave a structural formula of (Mg0.16)EX(Ca0.59Na0.27K0.17)FIX[Al3.94Mg0.08 Fe0.07Ti0.01](Si5.85Al2.15)O20(OH)4. This sample is apparently the most Ca-rich rectorite reported to date. The Greene-Kelly test and an intercalation examination by octadecylammonium indicated that the expandable component layers were beidellitic. Assuming the tetrahedral composition of the expandable component layers are similar to the average tetrahedral composition of beidellite of (Si3.6Al0.4), the tetrahedral composition of the mica-like component layers was calculated to be (Si2.25Al1.75). This was closer to a brittle mica (margarite) than to a true mica. Examination of chemical data for several Ca-rectorite samples from different localities, including those from the Sano Mine, showed a trend of increasing Ca content as Al increased and Si decreased. Ca-rectorite exhibited characteristic infrared absorption bands at 480, 670–700 and 900–930 cm−1, which became more intense as Ca content increased. These bands also corresponded to major absorption bands of margarite.

The effects of reaction time (2 to 72 h) and NH4+/A13+ molar ratio (1.6, 2.4 and 3.2) on the hydrothermal synthesis of ammonium-saponites are investigated. The gels are obtained by mixing powders, resulting in a stoichiometric composition, Mg3Si34Al0.6O10(OH)2, with aqueous ammonium solutions, with and without F, to result in initial NH4+/Al3+ molar ratios of 1.6, 2.4 and 3.2. The solid bulk products are characterized by X-raydiffraction (XRD), X-ray fluorescence (XRF) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis. The cation exchange capacity (CEC) is determined with an ammonia selective electrode and the pH of the water from the first washing is measured. Ammonium-saponite is formed rapidly within 16 h. A higher NH4+/A13+ molar ratio and the presence of F facilitate the crystallization of saponite. Small metastable amounts of bayerite, Al(OH)3, are present at low NH4+/A13+ molar ratios; after short reaction times, they disappear. During the first 4 h, the pH decreases rapidly, then drops slowly to a constant level of approximately 4.6 after 60 h. With increasing reaction time, saponite crystallites grow in the ab directions of the individual sheets with almost no stacking to thicker flakes. The NH4+ CEC of the solid products increases strongly within the first 24 h. A maximum of 53.3 meq/100 g is observed. The saponite yield increases from approximately 25% after 2 h to almost 100% after 72 h.

The thermodynamic cationic exchange process involving divalent (Cu, Zn, Cd, Hg, Pb and Ca) and monovalent (Na) cations in Brazilian red Latosol soil was studied. Using a batchwise method, the exchange was monitored as a function of the added cation concentration and the aqueous suspension of the soil at different temperatures. The isotherm series obtained were adjusted to a modified Langmuir equation, whose results were compared with the proposed Rawat method. The cationic exchange equilibria constants (ln K) vary from 1.97 to 9.80 for the Langmuir equation and 7.06 to 13.50 for the Rawat method. The variation in enthalpies obtained by applying the van't Hoff equation gave, for Langmuir and Rawat procedures, exothermic values for Cu (65.5 and 97.3), Cd (36.9 and 45.6) and Pb (43.0 and 50.7) kJ mol−1, and endothermic values for Zn (40.8 and 30.5), Hg (15.0 and 11.3), Ca (30.4 and 40.0) and Na (32.7 and 42.3) kJ moL−1. The exchanges proceed spontaneously, as indicated by the free energy values: Cu (14.2 and 27.2), Zn (21.6 and 32.0), Cd (16.1 and 23.2), Hg (13.8 and 22.9), Pb (22.6 and 28.3), Ca (17.0 and 25.9) and Na (9.9 and 19.3) kJ mol−1 at 323 K. These results suggest that the interaction occurs by complex formation between the organic matter of the soil matrix and the cations dispersed in aqueous solution.

Testing shows that many of the present commercially available bentonite products used for clay liner/soil sealant applications may be susceptible to chemical degradation by certain contaminants. Testing also confirms that a recently developed contaminant resistant clay (CRC) is resistant to various contaminants that would otherwise attack and degrade the present commercially available products. The tests that were used to determine its effectiveness were American Petroleum Institute (API) fluid loss, rigid wall hydraulic conductivity, flexible wall hydraulic conductivity and a newly developed top loading filter press (TLFP) test (LSK method).

Oil recovery is strongly related to the wettability of reservoir rocks that are formed of quartz grains attached by mineral hydroxides and clay minerals. Illites and kaolinites are the most active due to their high specific surface areas and electrical charge densities. Therefore, these minerals’ relative affinities for oil or water when in contact with a water-oil mix are of great importance. In order to model such a complex system, we used a mix of organic model molecules of the oil constituents and water vapor. Their interactions were estimated by inverse gas chromatography (IGC). IGC experiments were performed using a carrier gas with controlled humidity. By means of IGC at infinite dilution conditions, the dispersive component of the surface energy, γsd, was determined. A strong decrease of γsd, due to water molecules shielding the highest-energy sites, was observed. The energetic surface heterogeneity of the clays was examined using IGC at finite concentration conditions, allowing the determination of organic probe adsorption isotherms in the presence of water. From these isotherms, adsorption energy distribution functions were computed for propanol-2 and pyridine probes. Water mainly modifies the illite distribution functions, whereas practically no change was observed in the case of kaolinite. This observation is related to the higher hydrophilicity of illite as compared with kaolinite, and explains the different behaviors of the 2 clay families in oil reservoirs.

The crystal structure of amesite-2H1 from the Postmasburg Mn ores of South Africa has been refined to R = 4.7% using Siemens P4 rotating-anode MoKα X-ray data and SHELXL-93 software. Partial ordering of tetrahedral Si,Al and especially of octahedral Mg,Al has reduced the ideal P63cm symmetry to triclinic P1 (refined as C1). Tetrahedral rotation of 15° moves the basal oxygens toward the octahedral cations in the same layer but away from the OH H-donors of the next layers. The ordering pattern of AlIV and AlVI is unique in that the locus of Al-rich sites consists of 2 intersecting sets of zigzag lines parallel to X2 and X3, plus 2 Al-rich octahedra in layer 2 instead of the usual 1 site.

The Mg-vermiculite from Santa Olalla has been treated with aliphatic amides—formamide (FM), acetamide (AM) and propionamide (PM)—in aqueous solution. These treatments produce the transformation towards NH4-vermiculite and interstratified NH4-vermiculite-Mg-vermiculite phases. The NH4-vermiculite, Mg-vermiculite and interstratified (mixed-layer) phases have been identified from basal X-ray diffraction (XRD) interval peaks between 10.3 Å and 14.4 Å, and confirmed by direct Fourier transform method, as well as by atomic absorption spectrometry (AAS), infrared (IR) spectroscopy and thermal analysis.

According to their NH4-vermiculite/Mg-vermiculite probability coefficients ratio (PA/PB), and PAA, these interstratified phases can be divided into 3 categories: 1) If the PA/PB ratio is ≥ 7/3 and PAA ≥ 0.7, there are interstratified phases with a strong tendency toward segregation (case of FM, AM and PM). 2) If the PA/PB ratio is between 5/5 and 6/4, with PAA in the range 0.45–0.6, there are nearly regular alternating and random interstratified phases (case of AM and PM). 3) If the PA/PB ratio is ≤ 5/5 and PAA ≤ 0.45, there are interstratified phases with a strong tendency toward alternation (case of PM).

Experimental evidence reported in the present work indicates that the mechanism of interaction of Mg-vermiculite with FM, AM and PM in an aqueous medium takes place by ion exchange of NH4 between the layers. The hydrolysis of these aliphatic amides leads to the liberation of NH4+ into the medium. It has been found that the NH4+ sorption depends on the physico-chemical characteristics of the particular aliphatic amide, and the transformation of Mg-vermiculite to interstratified and/or NH4-vermiculite phases depends on the amide concentration. These treatments allow one to control the formation of interstratified and NH4-vermiculite phases.

The crystal structure of synthetic deuterated kaolinite was refined by Rietveld analysis using time-of-flight (TOF) neutron powder diffraction data. For non-hydrogen atoms, Cl symmetry was assumed. Starting models were tested in which only the direction of O-D vectors was varied. The constraints were introduced to all Al-O, Si-O and O-D bonds. The refinement adopting the former gives Pl(C1), a = 5.169(1) Å, b = 8.960(2) Å, c = 7.410(2) Å, α = 91.26(2)°, ß = 104.99(2)°, γ = 89.93(1)°, Rwp = 3.17%, R1 = 5.78% and S = 1.34 with constraints of l(Al-O)= 1.93 ± 0.05 Å, l(Si-O)= 1.62 ± 0.03 Å and l(D-O) = 0.95 ± 0.15 Å. The inner O-D vector points toward the tetrahedral sheet. All inner-surface O-D groups form H bonding with basal O atoms in the next kaolinite layers. The results agreed with those obtained from natural kaolinite.

Burial diagenesis of shales of the Frio Formation resulted in an increase in the abundance of mixed-layer illite-smectite (I-S), albite and chlorite, and a decrease in the abundance of K-feldspar, illite and kaolinite. Some of the mineralogic trends determined in this study contrast with the results of Hower et al. (1976) and other studies of Frio shales. The differences are due to improvements in laboratory and clay quantification techniques since the time of the earlier research. I-S composition changed from ~20% to ≥80% illite, and mineralogic and chemical reaction of I-S continued throughout burial. Shale diagenesis was an open-system process that required addition of K2O and A12O3, and resulted in loss of SiO2. The amount of SiO2 made available by shale diagenesis is sufficient to be the source of the quartz-overgrowth cements in the associated Frio sandstones. The relationships between I-S diagenesis and fluid flow from shales into sandstones, generation of abnormal formation-water fluid pressure, onset of sandstone diagenesis and distribution of authigenic phases in sandstones indicate that reaction of the I-S in shales is one of the most important components of the sandstone/shale/formation water diagenetic system.

The Fe3+ substituted for Al3+ at the 2 octahedral positions is one of the most common impurities in the kaolinite structure detected by electron paramagnetic resonance (EPR). Evidence has been provided for a relationship between the shape of EPR spectra for structural Fe and the structural disorder in kaolinite. It is proposed that the structural Fe be used as a sensitive probe for the degree of disorder of natural kaolinites. With this aim in view, an EPR disorder index (E) is defined from the width of selected EPR lines. Using reference kaolinites, it is shown that this index can account as well for long-range disorder detected by means of X-ray diffraction (XRD) as for local perturbations such as radiation-induced defects (RID). It is shown that the disorder observed through EPR has some points in common with the XRD-measured one. The influence on E of the presence of RID is shown by the study of artificially and naturally irradiated kaolinites.

The swelling of some well-defined Mg-, Ca-, Sr- and Ba- homoionic montmorillonites was studied in the domain of water relative pressures lower than 0.95. This involves the expansion of the crystal lattice itself, commonly known as the “interlamellar expansion” or “inner crystalline swelling”. The initial freeze-dried clays were characterized by nitrogen adsorption-desorption volumetry and controlled transformation rate thermal analysis. The evolution of the structural and textural properties of these different clays at different stages of hydration and dehydration was investigated using water adsorption gravimetry, immersion microcalorimetry at different precoverage water vapor relative pressures and X-raydiffraction (XRD) under controlled humidity conditions. Large textural variations are observed in the dry state depending on the exchangeable cations. The 2-layer hydrate exhibits the most ordered layer stacking. Water is mainly adsorbed in the interlamellar space. With increasing water pressure, each homoionic species leads to a 1-layer hydrate and, with the exception of Ba-montmorillonite, to a predominant 2-layer hydrate. The relative pressure corresponding to the formation of the 2-layer hydrate decreases with increasing hydration energy of the interlayer cation. For Ca-, Sr- or Mg-montmoriHonites, simulation of XRD patterns leads to the definition of successive homogeneous states corresponding to the 2-layer hydrate. Furthermore, it yields the water filling ratio corresponding to the different hydration states during adsorption and desorption of water vapor.

This paper thoroughly describes the decomposition procedure, using the example of DECOMPXR (Lanson 1990). The steps of the decomposition procedure are: 1) preliminary data processing; 2) decomposition; 3) validation of results; and 4) use of the results. The use of decomposition is restricted to the separation of contributions from various phases. The effect of preliminary data processing steps (data smoothing, background stripping) on profile shape is shown to be limited and their implementation is detailed. Potential experimental limitations such as peak symmetry, experimental reproducibility or discrimination are equally minor. A logical decomposition process starts from the definition of the angular range to be fitted, proceeds with the determination of the number of elementary peaks to be fitted and ends with the check for results consistency.

Numerical data processing is a powerful tool for the accurate identification of monophases, because of the additional parameters available to constrain XRD profile simulation. Ultimately, however, the match over the whole angular range of both the experimental and the simulated patterns remains the only valid way to characterize the phases present in the sample. Additionally, the decomposition procedure permits both the identification of complex clay mineral assemblages and the characterization of their evolution. This step constrains, and may help to determine, the reaction mechanisms of a transformation; and, as a consequence, to characterize and to model the kinetics of this transformation.

Illite crystallinity and fluid inclusion techniques are used to understand the thermal histories of rocks on either side of the disconformity between the Lower and Upper Paleozoic strata in South Korea. Illite crystallinity studies show that the metamorphic grade of the upper strata of the Lower Paleozoic Joseon Supergroup, platform carbonates with subordinate siliciclastics, belongs to the epizone and that of the lowermost strata of the Upper Paleozoic Pyeongan Supergroup, paralic to nonmarine clastics, belongs to the anchizone. The maximum mode of homogenization temperature for fluid inclusion of the uppermost strata of the Joseon Supergroup is 260 to 270 °C and that of the lowermost strata of the Pyeongan Supergroup is 240 to 250 °C. These data reveal a difference in thermal histories of strata below and above the unconformity, suggesting that, in contrast to the previous supposition of a period of non-deposition, at least a 1-km thick section of sediment was removed by erosion during development of the unconformity. Burial and heat flux from a proposed hot spot are suggested as the dominant factors causing differences in a metamorphic grade for the Joseon Supergroup before the deposition of the Upper Paleozoic strata.

Vesicular and groundmass phyllosilicates in a hydrothermally altered basalt from the Point Sal ophiolite, California, have been studied using transmission electron microscopy (TEM). Pore-filling phyllosilicates are texturally characterized as having coherent, relatively thick and defect-free crystals of chlorite (14 Å) with occasional 24-Å periodicities. Groundmass phyllosilicates are texturally characterized as 1) randomly oriented crystals up to 200 Å in width and 2) larger, more coherent crystals up to 1000 Å in width. Small crystallites contain predominantly 14-Å layers with some 24-Å units. Large crystals show randomly interlayered chlorite/smectite (C/S), with approximately 50% chlorite on average. Adjacent smectite-like layers are not uncommon in the groundmass phyllosilicates. Electron microprobe analyses show that Fe/Mg ratios of both groundmass and vesicular phyllosilicates are fairly constant.

Termination of brucite-like interlayers has been identified in some of the TEM images. The transformation mechanisms represented by these layer terminations are 1) growth of a brucite-like interlayer within smectite interlayer regions and 2) the dissolution and reprecipitation of elements to form chlorite layers. Both mechanisms require an increase in volume as smectite transforms to chlorite.

The data, combined with that from previously published reports, suggest that randomly interlayered C/S is a metastable phase formed in microenvironments with low water/rock ratios. Chlorite forms in microenvironments in the same sample dominated by higher water/rock ratios. The relatively constant number of Mg's in the structure (Mg#) of both structures indicates that in both microenvironments the bulk rock composition has influence over the composition of phyllosilicates.

The adsorption of the sulfonylurea herbicide rimsulfuron, [N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-(ethylsulfonyl)-2-pyridinesulfonamide], on clay minerals with different saturating cations was studied. Three smectites with different lattice charge distribution (hectorite, montmorillonite and nontronite) were selected and made homoionic to Ca2+, Cu2+ and Al3+. Because of the instability of rimsulfuron in water, the experiments were carried out in chloroform solution. The interaction mechanism depends on the nature of the saturating cation and the tetrahedral layer charge of the silicate. Among the exchangeable ions studied, only Al3+ is able to produce degradation of the herbicide to N-(4,6-dimethoxypyrimidin-2-yl)-N-[(3-(ethylsulfonyl)-2-pyridinyl]urea. In this case, the lower the tetrahedral charge, the more active the degradation. The Ca2+-saturated clays are ineffective in the degradation. In contrast, the formation of a stable chelate complex with the saturating ion permits rimsulfuron to be adsorbed to a rather high extent into Cu(II)-clays and to be stable against degradation.

Two clay minerals, a dioctahedral, Na-montmorillonite from Wyoming and a trioctahedral, synthetic Na-laponite, were exchanged by cupric (Cu(II)) ions and subsequently heated at 100 °C intervals up to 500 °C. The resulting materials were analyzed by chemical analysis, X-ray diffraction (XRD), cation exchange capacity (CEC) measurements, combined thermogravimetric and differential thermal analysis (TGA-DTA), infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). Montmorillonite exhibits a well-known Hoffmann-Klemen effect in that, when heated, cupric (Cu) ions migrate into the lacunae of the octahedral sheet, where they compensate the negative charge deficit of the clay layer. In the case of laponite, CEC measurements and spectroscopic measurements reveal that Cu ions migrate into the octahedral sheet where they replace Li and Mg ions. After heating at 200 °C, approximately half the interlayer Cu ions are exchanged. The exchange appears to be 1 Cu for 1 Li, resulting in a slight decrease of the negative charge of the layer. After heating at 300 °C, the remaining Cu ions are exchanged by either 1 Mg or 2 Li, which does not result in any further charge reduction. At 400 °C, some of the extracted Mg remigrates into the structure and exchanges some Li (1 Mg for 2 Li). The final product at 400 or 500 °C is then a Li-laponite with Cu(II) in the octahedral sheet.

The mineralogy and geochemistry of shales reflect the composition of the initially deposited precursor mud, subsequently modified by diagenetic processes. To see if significant geochemical differences exist between shales that mainly owe their present-day composition to either deposition or diagenesis, we compare the published mineralogical, bulk and clay-fraction geochemical, and clay-fraction O-isotopic compositions of 2 shales. One shale is from the Western Canada Sedimentary Basin (WCSB), and its composition mainly reflects primary (depositional) chemical and mineralogical variations (smectitic to illitic illite/smectite) within this unit. The other shale is from the United States Gulf Coast (USGC), and its composition mainly reflects mixed-layer illite/smectite (I/S) diagenesis of deposited smectitic clay material. The chemical and mineralogical trends of WCSB and USGC shales, including one of increasing illite content in I/S with depth or maturity, are essentially indistinguishable, in both bulk shale and clay fraction, despite the contrasting genetic interpretations for the origin of the contained I/S. Thus, similar mineralogical and chemical trends with depth or temperature can result either from inherited depositional compositional heterogeneity of the sediment, from burial metamorphism of shale or a combination of both. Interestingly, the O-isotopic compositions of the clay fractions from the WCSB and USGC are significantly different, a fact that reflects original clay formation from source material and water of quite different isotopic compositions. The discrimination between depositional and diagenetic contributions to shale composition continues to pose challenges, but a combination of bentonite, illite polytype, clay isotopic and trace and rare earth elemental analyses together with illite age analysis holds promise for future work.

The vitric component of the silicic pyroclastic flows and surge deposits (Prassa ignimbrite unit), from the northwestern exposures of the pyroclastics formation of Polyegos Island, South Aegean Sea Volcanic Arc in Greece, is replaced by authigenic zeolite and clay minerals. Mordenite dominates, and clinoptilolite (heulandite type 3), illite and illite-smectite (I-S) are subordinate. Opal-CT, quartz, feldspar, biotite and halite complete the mineralogical suite. In the southwestern part of the pyroclastics formation (Myrsini pyroclastics unit), kaolinite, halloysite, alunite and amorphous silica are the major mineralogical constituents as a result of a strong hydrothermal alteration by solutions enriched in SO42-. Scanning electron microscope (SEM) examination proved that the 1st type of zeolites formed within the area were heulandite minerals, following the formation of smectite, as a result of the activity of pore fluids within the volcaniclastic pile. There was no substantial evidence to support a hypothesis that mordenite was formed with the heulandite minerals after the initial stages of glass dissolution, other than some very minor mordenite that was formed from a gel-like type of material. The majority of mordenite present is most often draped over and formed from the crystals of heulandite minerals. Heulandite minerals often show advanced dissolution effects. The mineral dissolution was due to the emplacement of rhyolite lava domes and flows and the associated temperature rise and circulation of hydrothermal fluids, which had also mixed with seawater. The volcanic activity raised the temperature and changed the pore fluid chemistry, and the more unstable members of the heulandite minerals group were transformed to mordenite. Clinoptilolite (heulandite type 3), which was found within a few samples, was thermally more stable than any heulandite type 1 or 2 phases initially present. Therefore, clinoptilolite was either transformed more slowly or within a very few cases, it has not been affected at all. A heulandite-minerals-derived material acted as the major precursor for the formation of mordenite. The temperature increase within the area and the later hydrothermal alteration effect are also indicated by the illitization of the smectite. Mordenite is also found to have formed from I-S clays. Overall, mordenite formed as a result of elevated temperature and high Na+ concentration.

The clay fraction of a Spodosol and its parent rock in the Apennine mountains of central Italy were studied by powder X-raydiffraction (XRD) and infrared (IR) spectroscopy, to evaluate the possibility of transformation of chlorite into low-charge expandable minerals. Results indicated that the main phyllosilicate in the rock was a slightly weathered trioctahedral chlorite, rich in both Mg and Fe, together with dioctahedral mica and minor amounts of kaolinite. In the BC horizon, chlorite has undergone partial transformation into 2 vermiculitic components, in 1 of which the interlayer could be removed by hot Na-citrate treatment; the presence of a regular interstratified mineral (high-charge corrensite) was also observed. Further changes in the structure of chlorite were detected in the Bsl horizon, becoming more evident towards the soil surface. The first stage of weathering of chlorite involved Fe oxidation and partial expulsion of Mg from the hydroxide sheet, followed by deposition of Al in the interlayer space. Iron is also removed from the interlayer sheet, possibly remaining, in the oxidized state, in the 2:1 octahedral sheet, and so contributing to the lowering of layer charge and transformation to a dioctahedral structure. When approaching the surface, Al removal from the interlayers is enhanced by complexing agents, and further charge reduction leads to the formation of 2:1 minerals with a smectite nature. Illite, because of its low content in the soil clay fraction, contributes marginally to this weathering sequence, forming the high charged expandable component observed in the Bhs horizon. At the soil surface, arandomly interstratified vermiculite/illite was detected, which probably originated from K fixation by the higher-charged expandable minerals. This study of weathering in a natural soil strongly supports the hypothesis, previously ascertained by laboratory experiments, that chlorite can transform into a low-charge expandable mineral.

The structure of Li- and Cs-montmorillonites was studied using infrared (IR) reflectance spectroscopy. The spectra of heat-treated clays between 80 and 220 °C were analyzed by Kramers-Krönig inversion in order to obtain the optical and dielectric properties of the clays. The analysis revealed the transverse-optic (TO) and longitudinal-optic (LO) components of the asymmetric stretching vibration of Si-O-Si bridges. Major differences, in particular the systematic development of new bands, were found in the Li-montmorillonite LO and TO spectra with increasing temperature. These changes were attributed to the migration of the Li-cations into the layer structure.