The modification of the external surface area and the two types of microporosity of palygorskite (structural and interfiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: controlled-transformation-rate thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, conventional and continuous gas-adsorption volumetry (for N2 and Ar) at 77 K and CO2 at 273 and 293 K, water vapor adsorption gravimetry, and immersion microcalorimetry in water. At temperatures < 100°C only 18% of the structural microporosity was available to N2, 13% to Ar, and 100% to CO2 at 273 K. In both experiments the channels filled at very low relative pressures. At temperatures between 70° and 130°C the structure folded, and the mineral transformed to anhydrous palygorskite, which showed no structural microporosity. The interfiber microporosity was found to be independent of the temperature treatment, and the external surface area decreased slightly from 65 to 54 m2/g. The water adsorption isotherms showed that the folding of the structure was reversible up to final outgassing temperatures >225°C.

Dry ground phlogopite was placed in deionized water saturated with CO2 at room temperature and pressure. The bulk solution was buffered between a pH of 5 and 6 which is close to the pH of natural weathering systems. The conditions simulated a closed system. After 1010 hr, 2.0% of the total K, 0.95% of the Mg, 0.54% of the Si, and 0.74% of the F had been released, indicating that the dissolution was incongruent. Most of the K was released within 3 min, apparently by a rapid surface exchange with hydrogen ion. One-third of the cation-exchange capacity of this phlogopite arises from cations released from the outer surfaces, while two-thirds arises from the release of more deeply seated cations. All cations exhibited decreasing release with time, the slowest being Si. The rate-controlling “factor” in the later stages is related to the release of Si. It is difficult to distinguish linear from parabolic kinetics in the later stages because of the slow rate of dissolution; however, linear kinetics is most likely. If linear kinetics is applicable, the dissolution rate of Si was 3.8 × 10−17 mole/cm2/sec. Conclusions may be affected by the length of the experimental run.

Illite-smectite (I-S) minerals isolated from Upper Jurassic oil-source rock shales from Denmark and the North Sea have been investigated by X-ray diffraction, thermal analysis, infrared, Mössbauer, and solid-state nuclear magnetic resonance spectroscopies and chemical analysis. Detailed structures have been determined in order to reveal the diagenetic transformation mechanism in these shales. Generally, in oil-source rocks of sedimentary basins, oil generation takes place simultaneously with the diagenetic transformation of I-S. We demonstrate a link between the two reactions: NH3 released from kerogen during maximum oil generation is fixed as NH4+ in the NH4-bearing mica or tobelite layers formed from smectite or vermiculite layers in I-S, in a diagenetic interval which we name the ‘tobelitization window’. Due to this solid-state transformation, mixed-layer structures have been formed consisting of interstratified illite, tobelite, smectite and vermiculite layers (I-T-S-V) and having maximum ordering of illite + tobelite and smectite layers for R = 1. The tobelitization of smectite in I-S is probably typical for all oil-source rock shales.

At low levels of hydration, exchangeable D+ in montmorillonite interacts with lattice OH groups and quantitatively converts AlMgOH groups to AlMgOD. Hydroxyl groups coordinated to two Al ions undergo a slower exchange, the extent of which is restricted by octahedral Fe3+ ions. The OH stretching vibration of AlMgOH groups in montmorillonite is assigned an unusually high frequency (3687 cm−1) compared with that of the same group in phengites (3602 cm−1).

This study deals with the analysis of dielectric measurements made on montmorillonites saturated by bivalent cations. These measurements are performed between — 150°C and +30°C at frequencies ranging from 300 to 10,000 Hz. Their interpretation is based on a numerical analysis allowing determination of the dielectric losses due to free charge carriers conductivity phenomena and losses due to relaxation phenomena. The free charge carriers conductivity is due to the movement of protons. It depends very much on the nature of compensating cations and on the water content and seems to be closely related to the characteristics of the swelling.

Two types of relaxation phenomenon are described: a Debye relaxation due to electric dipole rotations and a Maxwell-Wagner relaxation due to heterogeneity effects. The analysis of the first phenomenon leads to the examination of the values of the relaxation time. It appears that the rotations of water molecules are difficult with bivalent cations. This essentially is shown by the high activation energy of the phenomenon. The discussion of these parameters shows that the state of adsorbed water molecules are certainly different as compared to the state of water molecules in ice or in liquid water. The characteristics of the second relaxation phenomenon are closely dependent on the free carriers charge conductivity.

Absorptions of purine and pyrimidine derivatives by Co- and Ni- montmorillonite at pH < 6 and by Cu-montmorillonite at pH < 3 are similar to their absorption by Ca-montmorillonite and take place primarily by a cation exchange process. In the weakly acidic to weakly alkaline range, absorption is due to complex formation with the inorganic cations, and decrease in the order Cu ≫ Ni > Co ≫ Ca. Adenine, 7-methyladenine, hypoxanthine, and purine are strongly absorbed, 9-methyladenine, 6-chloropurine, and cytosine are weakly absorbed, and thymine and uracil are not absorbed. At pH < 5, the nucleosides are absorbed by Co-, Ni-, and Cu-montmorillonite in approximately the same manner as by Ca-montmorillonite, but at pH > 6 their absorptions decrease in the order Cu ≫ Ni > Co > Ca. Fe(III)-montmorillonite behaves quite differently from the other mont-morillonites studied. With purines and pyrimidines, there is strong absorption from pH 3 to pH 7–8; with the nucleosides, the absorption varies considerably with the compounds considered decreasing in the order adenosine > cytidine ≫ guanosine ≫ inosine.

This paper describes structural models of four pyrophyllite edge faces: {010}, {110}, {100}, and {130}. Water molecules chemisorbed to Lewis acid sites stabilize edge faces both crystallochemically and electrostatically. The detailed assignment of protons to surface oxygens and the orientation of OH bond-vectors both influence the surface Coulomb energy.

The geometry chosen for the electrostatic calculations was infinite pyrophyllite ribbon the thickness of a single phyllosilicate layer and the width of 50 to 70 unit cells. Such a phyllosilicate ribbon has only two edges, a top and bottom, which were simulated using the edge-face models mentioned above. About 94% of the surface Coulomb energy is confined to the edge-face repeat unit. The surface Coulomb energies of the four edge faces are on the order of 2–3 nJ/m, varying ± 1 nJ/m with proton assignment. The Coulomb potential, measured either within the layer or parallel to the layer, has a distinct negative trend near the edge face that can be traced to chemisorbed water molecules. Finally, the correlation between proton Coulomb potentials at the edge face and the coordination environment of the protons is poor, obscured by long-range interactions.

Temperature-dependent clay mineral assemblages and vitrinite reflectance data have been used to investigate levels of diagenesis from the Messinian Laga Basin in the Central Apennines developed at the footwall of the Sibillini Mts. and the Gran Sasso Massif. Data are from stratigraphic units forming the main siliciclastic basin fill up to Middle Messinian gypsum-arenites and its pre-orogenic substratum. Specifically, the largest Rom% values and percentages of illite layers in illite-smectie (I-S) are found in the basin depocenter and at the footwall of the main carbonate thrust sheets. Smaller Rom% values, and percentage of illite layers in I-S characterize less subsided sectors surrounding the depocenter.

The X-ray diffraction data were treated using decomposition methods and the peaks identified were rationalized in terms of discrete and/or mixed-layer phases. Complex clay mineral assemblages were found in the Laga Fm. including three sub-populations of illitic material corresponding to authigenic and detrital components. I-S mixed layers record the maximum paleotemperature the Laga Fm. experienced, which is directly related to its burial history. Kübler index (KI) data, however, suggest higher temperatures related to detrital K-micas inherited from the uplift of the Alpine-Apennines chain.

A tentative calculation of paleotemperatures from selected data of organic and inorganic parameters is also proposed and compared with recent sedimentological, stratigraphic and structural data. We conclude that the Laga Basin fill never experienced temperatures of >100–110°C, generally due to variable sedimentary loading, whereas localized anomalous heating is due to the effect of the tectonic emplacement and subsequent local erosion of the Sibillini and Gran Sasso thrust sheets.

The present study compares the water-vapor adsorption capacity of bentonites (natural cation population) with the Enslin-Neff method. Water-vapor adsorption at 50% r.h. (relative humidity) or 70% r.h. is known to depend heavily on the amount of permanent charge and on the type of exchangeable cation. At ~80% r.h. Na+- and Ca2+/Mg2+-dominated bentonites take up equal amounts of water. Comparing the water-uptake capacity at 80% r.h. with the cation exchange capacity (CEC) revealed a close correlation between these two variables. Appreciable scatter apparent from this plot, however, suggests that additional factors influence the water-uptake capacity.Water adsorption at external surfaces was considered to be one of these factors and was, in fact, implicated by N2-adsorption data. The ratio of external/internal water ranged from 0 to 1, which suggests that water-adsorption values cannot be applied in the calculation of the internal surface area without correction for external water.

The Enslin-Neff water-uptake capacity, on the other hand, is unaffected by microstructural features (e.g. specific surface area and porosity). The amount of exchangeable Na+ is themost important factor. However, the relationship between the Na+ content and the Enslin value is not linear but may be explained by percolation theory.

The effect of anions on clay dispersion and the hydraulic conductivity (HC) of clay-sand mixtures has received little attention. This study investigates the effect that adding small amounts of anions has on the dispersivity and HC of reference clays. Mixtures of 3 and 6 g 100 g−1 kaolinite, smectite, and illite with quartz sand were packed in columns. The columns were saturated with Ca and then leached with 1 molc m−3 of one of the following organic and inorganic Na salts: chloride, hydroxide, EDTA, silicate, citrate, formate, oxalate, hexametaphosphate, orthophosphate, tartrate, or humate. Changes in HC and clay concentration in the effluent were measured and clay dispersion was evaluated as a function of the various anions added. In the kaolinite clay-sand mixtures, a significant amount of clay was observed in the effluent for all anions tested, and the HC increased above its original value. The HC of smectite clay-sand mixtures decreased following the addition of the various anions. Dispersed clay appeared in the effluent only upon addition of citrate or hexametaphosphate. In the latter two cases, the HC started to increase once maximum clay concentration appeared in the effluent. Clay concentration in the effluent of smectite was one order of magnitude lower than that of kaolinite. Illite clay-sand mixtures showed dispersion behavior intermediate between smectite and kaolinite but behaved in the same way as kaolinite with respect to HC changes.

Statistical analyses of chemical data from the literature of corrensite minerals suggest a large compositional variability, more evident in octahedral than in tetrahedral coordination. Mg occupies 40–80% of the octahedral sites, with Al and Fe2+ making up the remainder. Approximately 15–30% of the tetrahedral sites are filled by Al. Despite this compositional variability, distinct fields for the several types of mixed-layer trioctahedral chlorite/trioctahedral swelling layer are not apparent. Statistical analyses of the composition of corrensite compared with saponite, vermiculite, and chlorite suggest that corrensite is an intermediate between trioctahedral chlorite and trioctahedral smectite. If Fe/(Fe + Mg) > 50%, chlorite alone is favored, but with increasing Mg, chlorite appears to transform into corrensite and then, by iron oxidation, into trioctahedral smectite. Despite the chemical variability between corrensite, chlorite, and saponite, corrensite appears chemically to be a well-defined species. On the other hand, corrensite cannot be characterized chemically on the basis of its swelling component. Thus, the current definition of corrensite as a regular 1:1 interstratification of trioctahedral chlorite and either trioctahedral smectite or vermiculite is appropriate.

During electrochemical remediation of radionuclide, 235U, 238U, and 99Tc-contaminated aqueous solutions, pyroaurite-like phases, ideally [M(II)M(III)(OH)16CO3·4H2O] where M = Fe, were synthesized following coprecipitation with iron from metal iron electrodes. The effect of radionuclides on the transformation of amorphous precipitates to crystalline pyroaurite-like phases was investigated using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray analysis, Fourier-transform infrared (FTIR) spectroscopy, and fluorescence spectroscopy. The synthetic iron carbonate hydroxide phases showed primary XRD peaks at 0.7 and 0.35 nm and FTIR spectra that indicated the presence of a brucite-like sheet structure with carbonate anions occupying the interlayer. Divalent and trivalent iron, eroded from the electrode, occupies the octahedral sites of the brucite-like sheets. The carbonate anions in the interlayer balance the excess positive charge from isomorphous substitution of the Fe2+ or Fe3+ by reduced uranium (U4+) and technetium (Tc4+). Because of the lower solubility associated with crystalline phases than amorphous phases, incorporation of radioactive contaminants into pyroaurite-like phases by electrochemical syntheses represents a more effective approach for removing U and Tc from contaminated aqueous solutions than traditional technologies.

Six kaolin samples from the Lower Tertiary Huber Formation near Wrens, Georgia were analyzed using transmission electron microscopy (TEM), electron diffraction (ED), powder X-ray diffraction (XRD), chemical analysis, and magnetic susceptibility to characterize the Ti-bearing phases. Selected samples were treated with 5 M NaOH to remove kaolinite and concentrate the Ti-bearing phases for additional analysis. TiO2 content in the bulk fraction ranges from 1.2 to 5.4 wt. %. There are at least three Ti-bearing phases, including anatase, rutile, and a poorly defined nanocrystalline form. Anatase is most abundant and is commonly found with {010} faces in association with kaolinite edge and basal faces. The nanocrystalline form occurs at 0–1 wt. %, and rutile occurs in trace amounts. Bulk XRD analysis correlates well with the bulk TiO2 chemical measurements. Average anatase unit-cell parameters are a = 0.37908 ± 0.0002 nm and c = 0.951 ± 0.001 nm. These parameters indicate an approximate chemical formula of Fe3+0.05Ti4+0.95O1.95(OH)0.05.

The distribution of TiO2 content as a function of depth may be useful to obtain original grain-size variations associated with relative sea-level changes responsible for the deposition of the Huber Formation. Evidence for original depositional sediment properties can be seen in the occurrence of pseudomorphic replacement of micas and fecal pellets by kaolinite. Additional evidence for post-depositional changes includes the sub-micrometer euhedral character and low Fe content of the anatase (relative to soil-derived anatase). These observations for the Huber Formation are consistent with a previously published theory for kaolin genesis that includes biomineralization of originally coarser-grained aluminosilicates into a kaolinite-rich ore body.

An Fe-berthierine occurs in a buried laterite from the Late Cretaceous (Cenomanian) in southwestern Minnesota. It formed beneath a lignitic horizon in which reducing solutions percolated through a laterite comprising gibbsite, kaolinite and goethite. Morphologic differences suggest 2 separate conditions of Fe-berthierine formation. Early forms of Fe-berthierine include radial bladed or radial blocky crystallites coating pisoids, along with alteration of kaolinite at crystal boundaries. These morphologies formed in the vadose zone. Later forms precipitated under subaqueous conditions as macroscopic, pore-filling cement. The large size of the later-formed Fe-berthierines enabled microprobe characterization. This 1st reported occurrence of Mg-free berthierine has a structural formula close to an idealized Fe-berthierine: Fe2Al2SiO5(OH)4. Apart from their chemistry, the unique feature of the Minnesota Fe-berthierines is their formation in an exclusive nonmarine depositional environment. They formed in situ as part of a lateritic weathering profile developed on a broad, low relief peneplain. Physical evidence of formation under nonmarine conditions includes the presence of 1) scattered lignitic fragments; 2) concretions forming casts and molds of woody material; and 3) a nonmarine fossil (Unio sp. undet). Chemical evidence includes siderites collected from the berthierine-bearing horizon having stable isotope values indicating freshwater formation.

Formation of authigenic trioctahedral Mg-rich smectite is common in evaporative lake sediments, but was not described previously in modern marine evaporative environments. This study documents formation of authigenic K-rich, Mg-smectite during very early diagenesis in the dominantly siliciclastic Salina Ometepec (Baja California), a large supratidal evaporative sabkha complex near the mouth of the Colorado River. Here, sediment pore waters are exceptionally Mg2+-rich relative to other marine evaporative environments due to suppressed sulfate reduction which limits production of carbonate alkalinity and, hence, carbonate (particularly dolomite) precipitation. Sediment cores were obtained along a five km transect seaward across the hypersaline mud flat to evaluate how these atypical geochemical conditions would affect the clay mineral compositions.

Scanning transmission electron microscopy (STEM) observations show that the smectite from the marine Inlet, near the sediment source, consists of grains of irregular shape that give selected area diffraction (SAED) patterns reflecting dominant turbostratic stacking. Analytical electron microscopy (AEM) analyses indicate that K+ is the dominant interlayer cation; the mean composition is approximately K0.7(Al3.3Fe(III)0.3Mg0.5)(Al0.5Si7.5)O20(OH)4. Such smectite is implied to be detrital in part because it is similar to smectite known to be deposited by the Colorado River.

Smectite from the hypersaline mud flat occurs as aggregates of small subhedral pseudohexagonal plate or lath-shaped crystals ≤250 nm in diameter, with thicknesses varying between three and ten layers. The SAED patterns reflect substantial turbostratic stacking, but with a greater frequency of interlayer coherency as compared with detrital smectite. Crystals from greater sediment depths are larger and more nearly euhedral. This smectite is dominantly trioctahedral, with mean composition approximately K0.7(Al0.7Fe(III)0.5Mg4.45)(Al1.2Si6.8)O20(OH)4 (saponitic). This smectite is inferred to be dominantly authigenic in origin.

The X-ray diffraction (XRD) and STEM/AEM data collectively imply that detrital aluminous dioctahedral smectite reacts to form authigenic Mg-rich trioctahedral smectite, driven in part by the high Mg2+/ Ca2+ ratio of pore waters. Such early-formed Mg-rich smectite may be the precursor for the trioctahedral mixed-layer smectite, corrensite, and chlorite assemblages found in ancient marine evaporative sequences. These results also add to the accumulating evidence that interlayer K+ in marine smectite is fixed during the earliest stages of marine diagenesis near the sediment water interface.

Mixtures of synthetic Al-substituted goethite (α-Fe0.814Al0.186OOH) and hematite (α-Fe1.658Al0.342O3) (75, 50, 25, 3% hematite by weight) were studied by Mössbauer spectroscopy to evaluate the use of that technique for quantitative analysis. Mössbauer spectra for these mixtures, obtained in the temperature range 12–130 K, were better fitted by a distribution of magnetic fields than by two magnetic sextets. Spectra at 80 K were equally as good as those from lower temperature to determine the hematitegoethite ratio. The recoil-free fractions of the individual components were about equal at any fixed temperature, but thickness effects caused as much as 30% error in the determination of the ratio of components in mixtures.

Nontronite and biotite were analyzed by Electron Spectroscopy for Chemical Analysis (ESCA). Both minerals yielded ESCA spectra with well-defined peaks and the elements identified by the ESCA spectra were in good agreement with the molecular formulas. High resolution scans were made of the iron (2p3/2) and oxygen (1s) electron binding energies for oxidized and reduced forms of nontronite and biotite. Binding energies for Fe3+ were observed at 711.8 eV in dithionite-reduced nontronite and in oxidized biotite. Peaks for Fe2+ occurred at 710.0 eV for unaltered biotite, at 709 eV for oxidized biotite and at 708.6 eV for hydrazine-reduced and dithionite-reduced nontronite. The oxygen (1s) peak for unaltered nontronite was skewed to the high energy side of the 530.6 eV maximum, but became more symmetrical as the Fe2+ content increased.

Two octyl-ammonium vermiculite complexes with different 001 periodicities have been studied by i.r. spectroscopy. In each case i.r. spectroscopy affords information on the orientation of the — NH3+ groups and the strength of the hydrogen bond between these groups and the silicate oxygen surfaces. Also a perturbation of the vibration of the OH groups of the silicate has been observed that seems to be related to the distance from the center of the layer at which the — NH3+ groups are situated.

The i.r. results are discussed in relation to the structural models deduced from X-ray analysis.

57Fe Mössbauer spectra of a cleaned Weipa, Australia, kaolin showed that a considerable fraction of the structural iron exhibits paramagnetic relaxation between 4°K and 300°K, the first time that this has been observed for ferric ions in a mineral. The sample also contained a very fine particle ferric oxide/oxyhydroxide phase, probably of secondary origin.

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