A new occurrence of destinezite (diadochite), ideally Fe2(PO4)(SO4)(OH)·6H2O, is described from Alum Cave Bluff, Great Smoky Mountains National Park, Tennessee, where it occurs in soil and in a weathered Precambrian phyllite in unusually large crystals associated with other hydrated sulfates such as pickeringite-apjohnite. Destinezite is triclinic, P1̄, with a = 9.570(1), b = 9.716(1), c = 7.313(1) Å, α = 98.74(1)°, β = 107.90(1)°, γ = 63.86(1)° and Z = 2. Its crystal structure consists of infinite chains of Fe(O,OH,H2O)6 octahedra, sulfate tetrahedra and phosphate tetrahedra linked by a unique system of vertex sharing. The chains are weakly bonded into slabs by hydrogen bonding between OH and H2O of the Fe(III) octahedra and oxygen ions of the sulfate tetrahedra. Slabs of tetrahedral/octahedral chains alternate with sheets of H2O molecules. The structure thus somewhat resembles hydrated clay minerals, with H2O molecules that act as hydrogen bond donors and acceptors to oxygen atoms of adjacent slabs. Destinezite and diadochite occur at numerous localities worldwide and have been assumed to be identical, but this identity has never been proven. It is proposed that the name “destinezite” be applied to visibly crystalline, triclinic Fe2(PO4)(SO4)(OH)·6H2O and “diadochite” to massive to earthy, poorly ordered, X-ray amorphous materials that approximate destinezite in composition. Diadochite/destinezite may be an unrecognized component of soils where weathering of pyrite and apatite has occurred and pH is low. It may thus be a significant sink for phosphorus and sulfur in such soils.

This study examines the influence of minerals and amorphous phases associated with kaolin and kaolinitic rocks on kaolinite crystallinity indices (KCI) derived from X-ray diffraction (XRD) data in order to select the best index for systematic studies of commercial kaolins or geological sequences. For this purpose, 8 kaolins of differing structural order were chosen and used to prepare mixtures containing different weight fractions of quartz, feldspar, illite, smectite, chlorite, halloysite and iron hydroxide and silica gels. An additional 17 samples of kaolin were also studied to test the results and evaluate the restrictions. KCIs used included Hinckley (HI), Range and Weiss (QF), Liètard (R2), Stoch (IK), Hughes and Brown (H&B) and Amigó et al. (full width at half maximum, FWHM), and the “expert system” of Plançon and Zacharie.

Based on more than 15,000 KCI determinations, the HI and QF are influenced by quartz, feldspar, iron hydroxide gels, illite, smectite and halloysite. IK can be used in the presence of quartz, feldspar and iron hydroxide and silica gels. Also, R2 is the only KCI that could be measured in the presence of halloysite; FWHM indices should not be used in the presence of chlorite and/or halloysite; and H&B should only be used with pure kaolinite samples. The “expert system” of Plançon and Zacharie is strongly affected by the presence of other mineral phases, particularly with more than 25% of well-ordered kaolinite. Their system is less sensitive to other mineral phases when only disordered kaolinite is present, and it should not be used with kaolinite of medium order-disorder because the well-ordered phase is present in an inappreciable proportion (<10%). KCI is only measurable in kaolinitic rocks if kaolinite is >20 wt% and the precision increases with an increase in the quantity of kaolinite. In all cases, the reliability will depend on the other minerals present. When a KCI can be measured accurately, the others can be obtained by using the empirical relationships reported in this paper.

Dynamical and thermodynamic properties of water at room temperature in Ca- and hexade-cyltrimethylammonium- (HDTMA) exchanged bentonite were determined for 4 different water contents (~0.03–0.55 g water g-1 clay). Incoherent quasi-elastic neutron scattering (QENS) was used to measure the translational and rotational mobility of water in the clays, while chilled mirror dewpoint psychrometry measured water activity of the samples, differential scanning calorimetry (DSC) provided information about the temperature of dehydration and X-ray diffraction (XRD) quantified layer spacings for the clays. The neutron scattering data were fit to a jump diffusion model that yielded mean jump lengths, jump diffusion residence times and rotational relaxation times for water in the clays. Mean jump lengths were quite similar for the 2 different cation saturations at equivalent water contents, and decreased with increasing water content. The fitted jump lengths ranged from 0.27–0.5 nm and were 2–4 times larger than that found for bulk water (0.13 nm). Jump diffusion residence times were 3–30 times longer than that for bulk water (1.2 ps) and also decreased with increasing water content. The residence times were somewhat shorter for HDTMA-clay as compared with Ca-clay at equivalent water contents. Rotational motion was less strongly influenced than translational motion by the presence of the clay surface. The energy state of water in the 2 cation saturations were quite different; dehydration temperatures for the HDTMA-clay were approximately 30 °C lower than the Ca-clay at equal water contents, while water activities, as P/P0, were up to 0.6 units higher. A linear relationship was found between water activity and the translational diffusion coefficient, although at the highest water content, the diffusion coefficient of water for the HDTMA-clay was approximately 30% higher than that measured for bulk water.

Experimental data on structure formation in highly concentrated aqueous dispersions of kaolinite were analyzed using rheological models. The physicochemical properties of the clay mineral surface were studied during heating at a range of temperatures, and correlation of acid-base properties with physicomechanical characteristics of the spatial structures formed during heating was obtained. It was shown that interparticle interactions and plastic yield mechanisms under load are dependent upon interfacial phenomena. A method for estimating optimal structural parameters was developed for semidry dispersions, enabling regulation of physicochemical and mechanical properties of ceramic mixtures during processing.

Palygorskite and sepiolite show a high sorption capacity for organic molecules. Adsorption of 2 organic cations, methylene blue (MB) and crystal violet (CV), by palygorskite and sepiolite were examined. The maximum sorption of MB and CV far exceeded the cation exchange capacity (CEC) of these minerals. This shows that, besides the contribution of free negative sorption sites (P-), the sites satisfied with sorption of single cations (PXi0) and neutral sorption sites (N) on clay surfaces may contribute to the sorption of organic cations. The number of neutral sites was determined by examining the sorption of 2 neutral organic molecules, triton-X 100 (TX100) and 15 crown ether 5 (15C5), and by application of the Langmuir isotherm.

To determine the contribution of different sites, an adsorption model that applies the Gouy-Chapman equation and takes into account the formation of different clay-organic complexes in a closed system was employed. Application of this model to sorption data provided the calculation of binding coefficients for neutral sites, as well as the surface potential of the minerals at different sorbate concentrations.

At sorption maxima, for both palygorskite and sepiolite, the contribution of neutral sites for sorption of organic cations was the highest, followed by the PXi0 sites in case of CV sorption, while in sorption of MB the contribution of P- sites was the second highest. The Fourier transform infrared (FTIR) patterns of clay-organic cation complexes compared with pure clays confirm that the sorption of organic cations is by silanol groups located at the edge of fibrous crystals, which account for neutral sorption sites.

A new method is proposed for applying the chlorite geothermometer using X-ray diffraction (XRD) data. A linear correlation has been found between the (001) basal spacing of chlorite and its “crystallization” temperature. The basal spacing values were corrected for an increase of Al(IV) with Fe enrichment (Fe/Fe + Mg), when the Fe(II) value of chlorite is >2.6 in the formula unit. The regression coefficient of the best fit is r = 0.95. Only 2 Bragg lines need to be measured for application of the proposed technique: the (001) and (060) X-ray spacing. The proposed method is applied to 19 chlorite samples from 4 different geothermal fields. The temperatures of chlorite formation obtained with the present method and those calculated by the expressions formulated by Cathelineau (1988) and Kranidiotis and MacLean (1987) are presented. The method's validity was also tested on geothermal chlorites from the literature, and the results show good agreement with previous experimental trials.

Samples of Silica Springs allophane from Tongariro National Park, New Zealand, having Al/Si atomic ratios in the range 1.1-1.9, were studied by 27Al nuclear magnetic resonance (NMR) spectroscopy with high field strength (9.4 and 11.7 T) and fast magic-angle spinning (MAS) (9-13 kHz). Spectra for all samples show peaks for 6- and 4-coordinate Al and also for 5-coordinate Al. For 1 sample, the peak for 5-coordinate Al is dominant. Use of 2 instruments and 2 field strengths allowed the integrity of the spectra and the assignment of 5-coordinate Al to be verified. The “true” chemical shift (after a small correction for quadrupolar shift) observed for 5-coordinate Al in Silica Springs allophane is 36 ± 1 ppm, which is consistent with shifts reported for 5-coordination in well-characterized crystalline structures. We suggest that 5-coordination in Silica Springs allophane is associated with the edges of fragments of incomplete octahedral sheets that are bonded to disordered, though more complete, curved tetrahedral sheets in the primary particles of this allophane. Other allophanes with Al/Si < 2, and which are poor in octahedra relative to tetrahedra, may also have significant Al in 5-coordinate sites.

Otay-type waxy bentonites of San Diego County are illite-smectite (I-S) with 85% dioctahedral smectite mixed with dioctahedral illite showing a Reichweite of 0. Primary or secondary waxy bentonite exposures are found in all Eocene and Oligocene formations of southwest San Diego County and western Baja California north of Ensenada. Primary waxy bentonites formed when hot volcanic ash fell into quiet marine or brackish coastal water. The transformation from glass to bentonite occurred within hours or days but consolidation of the bentonite into its waxy consistency took longer. Primary waxy bentonite consists of 95 wt% I-S with the remainder consisting of volcanic glass shards, sanidine fourling twins, hexagonal biotite crystals and amorphous manganese oxides and hydroxides. Secondary waxy bentonite is primary waxy bentonite that was mixed with nonvolcanic detritus either before consolidation or after consolidation and subsequent erosion. The hydrophobic character of primary waxy bentonite allows it to reflect, accurately, the chemistry and petrology of the original volcanic material. Chemical analysis of primary waxy bentonites shows that the original lava was subduction-related and exhibited petrologic variations nearly identical to those of the modern Cascades of the northern Pacific coast of the lower United States. Primary and secondary waxy bentonites as well as smectites derived from the weathering of volcanic ash that fell outside the waxy bentonite-producing environments are the previously unrecognized products of extensive Eocene and Oligocene subduction-related volcanic activity. Baja California exposures of waxy bentonite demonstrate pre-Pliocene subduction tectonics that gave way to rifting tectonics.

The oxygen and hydrogen isotope compositions of volcanic ash layers from coastal outcrops of the Miocene Monterey Formation elucidate the progressive burial diagenesis of glass to bentonite and metabentonite. Volcanic glass that texturally appears unaltered is found to have δl8O and δD values that are significantly higher than fresh volcanic glasses. The positive shift in δ18O and δD values is proportional to the amount of hydration and chemical alteration of the glass samples. Initial hydration of the glass results in the exchange of Na for H; later hydration results in the loss of K and Fe in exchange for H and Na. The δ18O values of the most hydrated glass, and clay minerals from bentonite and metabentonite layers are approximately in equilibrium with slightly modified seawater. The δD values of the hydrated glass, and clay minerals from bentonite and metabentonite layers, are significantly depleted in D relative to seawater and suggest meteoric exchange associated with tectonic uplift and erosion in the Pliocene and Pleistocene. Smectite from bentonite layers has δ18O and δD values similar to the most hydrated glass samples, suggesting similar glass-water and smectite-water fractionation factors. Kaolinite and mixed-layered illite-smectite (I-S) altered from smectite have lower δ18O and higher δD values than their precursor. The δ18O and δD of nonvolcanic siliceous mudstones from the Pt. Arguello oil field show an unusual decrease in δD with increasing burial depth that probably reflects the presence of organic hydrogen in the analyzed samples as well as possible D-depleted formation waters from detrital illite-water and hydrocarbon-water exchange.

Two clay fractions of a Cambrian claystone from Estonia, consisting essentially of illite and 20% expandable illite-smectite, (I-S) were treated with C12 and C18 alkylammonium cations for K-exchange. Both the untreated and treated samples were dated by the K-Ar method. The treated clays lost several percent of their original K2O, with greater losses for longer-chain cations and for longer reaction time, in accordance with previously published studies. The dates of the treated clay fractions were 20–30 Ma lower than those of the untreated clays. The decrease in the dates suggests preferential opening of older, detrital clays. The K-Ar dates of the illite layers susceptible to K extraction by the various treatments were calculated by subtracting K2O and radiogenic 40Ar values of the consecutive step products, and they were plotted against the total % K2O removed, used as an indicator of the reaction progress. Extrapolation of the plot revealed a detrital (1550 Ma) and a diagenetic (380 Ma) age for the 2 illitic minerals present in the investigated shale sample. The inferred Devonian age of diagenesis of the Estonian clay corresponds to the period of massive dolomitization in the area. Both alteration processes can be related to a Devonian incursion of hot or alkaline fluids, which helps to explain the occurrence of 20% expandable I-S in claystones that have never been buried more than 1000 m.

Extrapolated K-Ar ages and K2O contents of the illitic minerals, estimated from the X-ray diffraction (XRD) data, were used to model the experimental data. A good agreement was reached when dilution effects (chlorite and expanded illite) were taken into account.

Fourier transform infrared (FTIR) spectroscopy investigations in the near infrared (N1R) region of synthetic and natural kaolinites with various octahedral substitutions have been carried out in order to elucidate the relationships between the substituted cations and specific features of the NIR spectra. The combination modes of the OH stretching and bending vibrations characterizing Fe(III), Ga(III) and Cr(III) octahedral substitutions are identified in the NIR region at 4466, 4498 and 4474 cm-1, respectively, and the first overtones of the OH stretching vibrations at 7018, 7018 and 6986 cm-1, respectively. As far as we know, the bands of kaolinites containing Ga(III) or Cr(III) have not been reported yet. For both Ga(III) and Cr(III), the NIR observations explain why the bending vibration bands of AlGaOH and AlCrOH groups are not observed in the middle infrared (MIR) region.