Transmission X-ray diffraction (XRD) of C6–16 alkylammonium ion-exchanged montmorillonite SAz-1 with Ag-behenate as an internal standard provided accurate estimates of d(001) values of the alkylammonium ion-exchanged montmorillonite. Inspection of d(001) values were made to assess the possible formation of gauche conformers (alternate arrangements of the molecules) in the interlayer and to determine the critical carbon chain length, nC. Using conventional constraints for nC(I′) and nC(II) equal to 1.36 and 1.77 nm, respectively, provided ambiguous nC(I′) and nC(II) values. The dependence of full-width at half-maximum values on nC allowed better estimates of nC(I′) and nC(II) because “integral” and “non-integral” peak characteristics relating to interstratification could be included in the assessment.

The effect of inaccurate estimates of nC(I′) and nC(II) values on calculated interlayer cation exchange capacity (Ci) using two conventional concepts of calculation were compared. It was found that a procedure based on the summation of fractions of the layer charge gave relative errors of Ci <2%, even where the number of carbon atoms corresponding to both nC(I′) and nC(II) differed by ± 1 nC from the correct values. This method of calculation of Ci is recommended when reliable values of Ci are needed.

Siltstones from the Precambrian Freda Formation in Wisconsin have been studied by scanning, scanning-transmission and analytical electron microscopy (SEM, STEM and AEM), and X-ray diffraction (XRD). XRD data for drill core samples show a change from smectite-rich Illite-Smectite (I-S) in shallow samples to illite in deeper samples, implying a transition during burial diagenesis.

Transmission electron microscopy (TEM) observations of shallow samples reveal the presence of three clearly distinguishable kinds of dioctahedral clay minerals: (1) detrital grains of micrometer-sized, mature muscovite; (2) small packets in the matrix consisting of dominant (Reichweite) R1 I-S or (3) small packets of illite. The illite and I-S stacks occur separately and have similar textures, with packet thicknesses averaging ∼400 Å, within the range of anchizonal illite. Illite and detrital muscovite commonly display strain features typical of the effects of tectonic stress. Void space within I-S or illite packets is inferred to be a strain feature, and to have served as pathways for fluids. Detrital muscovite shows abundant alteration features including (001) boundaries which are continuous with parallel packets of I-S; individual layers commonly show along-layer transitions of muscovite to smectite or I-S. Trioctahedral clays consist primarily of detrital chlorite which commonly shows direct alteration to R1 I-S and smectite, as with detrital muscovite.

Deep samples contain only unaltered, coarse detrital muscovite, and thin packets of illite forming stacks and comprising most of the matrix. The texture of the illite appears to be identical to that of shallow samples, with characteristics such as packet size typical of anchizonal illite. Trioctahedral clays consist almost entirely of detrital grains of chlorite and corrensite. They occur as separate grains with rather constant composition, without signs of alteration.

The data imply that all of the studied rocks have been subjected to a uniform anchizonal grade of metamorphism in which detrital grains were largely unchanged but matrix clays were transformed to packets of illite. The unusually abrupt transition with depth from highly expandable I-S to illite is inferred to actually be the result of subsequent alteration of authigenic illite and detrital chlorite and muscovite to R1 I-S and smectite in shallow rocks. This late overprinting of the anchimetamorphic clay mineral assemblage is inferred to have been locally caused by fluids with temperatures less than those of peak metamorphism. This process, called “retrograde diagenesis”, gave rise to a sequence of dioctahedral I-S and illite which mimics classic prograde sequences. Interpretations of such sequences as being prograde, especially in cases of ancient rocks, should be interpreted with caution when high-resolution images of textures are not available.

The Late Westphalian to Artinskian Haushi Group in the Sultanate of Oman consists of the glaciogenic Al Khlata Formation and the Gharif Formation which contains marginal marine, coastal plain, and fluvial sediments. The sequence was deposited during a global-warming event following the Permo-Carboniferous glaciation of Gondwana. Because of a varied subsidence history, these sediments range from the surface in the SE to almost 5000 m in the NW of the basin.

Mixed-layer illite-smectite (I-S) is an important constituent of the <2 µm size fraction of sandstone and shale samples in both formations at all depths. Different starting compositions lead to three distinct trends of illite layers in I-S versus temperature for different sedimentary environments and paleoclimatic conditions. The starting compositions of I-S at the surface range from an ordered I-S in the Al Khlata Formation to smectite-rich in the Upper+Middle Gharif members.

Physical, chemical and environmental factors were investigated as causes for the different starting compositions of I-S. Both formations share an identical burial history, paragenesis, thermal evolution, and source of detrital material. They differ only in environmental conditions during sedimentation. Thus, the variation in starting composition of I-S appears to be best explained by distinct weathering conditions during sedimentation of the three units. In particular, the expected low intensity of chemical weathering during glaciogenic conditions is marked by the presence of higher amounts of unstable volcanic and sedimentary rock fragments in the Al Khlata Formation.

The Tazzeka Mountain, located approximately 20 km south of Taza, eastern Morocco, is composed of a Westphalian volcano-sedimentary complex. It contains rhyolitic ignimbrites with the following minerals: quartz, potassium feldspar, oligoclase-andesine, and biotite. The ignimbrites are extensively altered because of a dense network of fractures in the massif. Alteration has resulted in the formation of spheroidal rocks and saprolite, the thickness of which depends on local topography. The evolution of the biotites in the ignimbrites was investigated by microprobe analysis of the mica crystals. This technique provides data that are not accessible through classical analytical methods. Biotites are transformed into secondary clay minerals, mainly chlorites and illites; intermediate stages are related to the degree of alteration of biotite, the latter being expressed by the K2O content which decreases progressively from 7.3 to 1.3%. Next come protochlorites and chlorites sensu stricto, in which the K2O content is 0.3%. Several processes including retrodiagenesis, hydrothermal activity, fumarolic activity, and geochemical weathering contributed to the transformation of the biotites at Tazzeka.

Previous investigations of goethite revealed a substantial variation of color and diffuse reflectance spectra (DRS) in the extended visible range (350–2200 nm). To better understand the causes of this variability and to assess the potential of DRS as a mineralogical tool, we investigated the DRS of pure and Al-substituted goethite, α-Fe1−xAlxOOH with x from 0 to 0.33, and mean crystal lengths (MCL) from 170 to 1800 nm. The strongly overlapping ligand field bands were extracted by fitting the single-electron transitions 6A1 → 4T1, 6A1 → 4T2, 6A1 → (4E; 4A1), and 6A1 → 4E(4D) as functions of the ligand field splitting energy, 10 Dq, and the interelectronic repulsion parameters, Racah-B and -C. With x increasing from 0 to 0.33, 6A1 → 4T1 decreased from 10,590 to 10,150 cm−1 (944 to 958 nm), and 6A1 → 4T2 decreased from 15,310 to 14,880 cm−1 (653 to 672 nm), while 10 Dq increased from 15,770 to 16,220 cm−1. From the change of 10 Dq we calculated a decrease of the Fe-(O,OH) distances from 202.0 to 200.9 pm (−0.5%). This decrease is smaller than the average decrease of all (Al,Fe)-(O,OH) distances (−1.8%) calculated from the change of the unit-cell lengths (UCL). That is, there remains a substantial difference in size between the larger Fe- and the smaller Al-occupied octahedra in the solid solution which may indicate the existence of diaspore clusters within the goethite structure. The increasing strain in the crystal structure due to the size mismatch and limited contractibility of the oxygen cage around Fe may be the primary reason for Al substitution being restricted to x < 0.33. The bands 6A1 → (4E; 4A1) and 6A1 → 4E(4D) did not shift, indicating a constant covalency of the Fe-(O,OH) bonds with B = 628 cm−1 and C = 5.5B. Whereas variation of band energies could be explained in terms of the Fe-(O,OH) ligand field, the variation of color and band intensities was mainly determined by crystal size. Although our study confirmed the potential of DRS for mineralogical investigations, there is still a gap between the fundamental theory and the explanation of some spectral features.

The Ayvacık bentonites, products of Miocene calc-alkaline volcanic rocks, are composed of smectite of the montmorillonite-beidellite series. Fault-related hydrothermal solutions have altered andesitic rocks to dioctahedral smectites. Differences in the micro-morphology of the two end-members are distinguished by scanning electron microscopy (SEM) studies. The beidellite particles are of delicate ribbons and rosette habits, whereas montmorillonite particles are very thin, curled sheets and flakes. Clay size (<2 µm) fractions contain (in wt. %) 54.90–56.80 SiO2, 19.65–28.54 Al2O3, 0.45–6.28 Fe2O3, 0.10–1.72 CaO, 0.80–4.15 MgO, 0.55–1.88 K2O, and 0.08–1.15 Na2O, which confirm that the beidellites are Fe-rich (5.06–6.28 wt. %), except for one sample (0.45 wt. % Fe2O3). The Greene-Kelly test (Li-saturation and heating) gave very good results for the measurement of the d(001) of the two end-members. Nickel, Ti, and Cr enrichment in smectite is related to the chemical composition of hydrothermal solutions that passed through the ophiolite complex.

Experimental cation exchange capacities (CEC) of kaolinites were determined and compared to theoretical calculations of CEC. The comparison reveals that the exchangeable cations occur mostly on the edges and on the basal (OH) surfaces of the mineral. It also shows that permanent negative charge from isomorphous substitution of Al3+ for Si4+ is insignificant. The CEC of kaolinite strongly depends on the particle size (both thickness and diameter in the (00l plane) and pH value. Particle size is more important than crystallinity in affecting kaolinite CEC. This study shows that the hydroxyls on the exposed basal surfaces may be ionizable in aqueous solutions. The amount of negative charge on the edges and the exposed basal hydroxyls depends on pH and other ion concentrations. A higher pH value gives rise to more negative charges, which lead to a higher CEC value. This study indicates that charge from broken edges and exposed OH planes rather than charge from Al/Si substitution determines the kaolinite CEC, even at zero point charge. A high CEC in some kaolinites is found to be due to smectite layers on the surface of the kaolinite crystals.

High-resolution transmission electron microscopy (HRTEM) examinations have indicated that three types of surface layers may exist in natural kaolinite crystals. Type 1 has the expected 7-Å surface layer as terminations. Type 2 has one 10-Å pyrophyllite-like (or low-charge beidellite-like) layer as the surface layer on one side of a kaolinite particle (i.e., the layer sequence is TOTOTO … TOTOTOT, where T stands for tetrahedral sheet, O for octahedral sheet). Some industrial-grade highly-ordered kaolinites have such a 10-Å 2:1 surface layer on one side of the crystal. The spacing between the 10-Å layer and the adjacent 7-Å layer is not expandable. Type 3 kaolinite has one or several 10-Å collapsed smectite-like layers at one or both sides of a stack, i.e., (TOT)TOTO … TOTOTOT(TOT), forming a special kind of kaolinite-smectite interstratification. This type has only been recognized in some poorly-ordered kaolinites. The surface smectite layer(s) contribute to higher cation exchange capacity (CEC) values. These 10-Å surface layers were not detectable by X-ray diffraction (XRD). HRTEM and electron diffraction examination also revealed the structural features of individual kaolinite crystals. All kaolinites (from various origins and sources) studied show C-face-centering Of non-hydrogen atoms. Defects within the layer structure are common in both well-ordered kaolinite and poorly-ordered kaolinite.

Monte Carlo simulations based on tested water-water, cation-water, and water-clay potential functions were applied to calculate radial distribution functions for O-O, O-H and H-H spatial correlations in the interlayer region of the two-layer hydrates of Na- and K-montmorillonite. The simulated radial distribution functions then were used to compute the total radial distribution function for interlayer water, a physical quantity that can be determined experimentally by H/D isotopic-difference neutron diffraction. The simulated total radial distribution functions were compared with that for bulk liquid water, and with a total radial distribution function determined experimentally for the two-layer hydrate of Na-montmorillonite by Powell et al. (1997). This comparison suggested that water molecules in the two-layer hydrate of montmorillonite have nearest-neighbor configurations which differ significantly from the tetrahedral ordering of nearest neighbors that characterizes bulk liquid water.

The residual kaolin deposits near Lastarria, South-Central Chile, were formed by weathering of subvolcanic quartz porphyry stocks, which intruded the metamorphic basement of the Coastal Cordillera. The clay fractions (<2 µm) consist mainly of poorly-ordered, very fine-grained kaolinite and lath-shaped illite (17–38 wt. %) with minor amounts of quartz, sanidine, and goethite. A sample from the top of the deposit contains major quantities of gibbsite morphologically indistinguishable from kaolinite flakes. The gibbsite-free clays contain 35.5–36.6 wt. % Al2O3, 0.4–2.6 wt. % Fe2O3, 1.3–3.9 wt. % K2O, and have low TiO2 concentrations (<0.02 wt. %). The absence of quartz veining, the abundance of melt inclusions, and the scarcity of secondary fluid inclusions in quartz phenocrysts from altered rocks imply a lack of significant hydrothermal activity in the quartz porphyries. The δ 18O and δD values of the kaolins indicate formation in a weathering environment at significantly higher annual mean air temperatures (∼12°C) than present mean temperatures of ∼9.4°C. Uplift of the region alone probably cannot account for the change in climate. The stable isotope composition of gibbsite is consistent with an origin of desilication of kaolinite at superficial temperatures. Various criteria proposed to distinguish supergene from hypogene kaolins are discussed.

Hydrothermal synthesis experiments were conducted to study the transition from smectite to corrensite. A mixture of oxides with the bulk composition of corrensite—Na0.4(Si6.4Al1.6)(Mg7.8Al1.2)-O20(OH)10—was sealed in platinum capsules with 29–37 wt. % water. One set of samples was treated in cold-seal vessels at 500°C and 2 kbar for durations of 2, 3, 6, 12, and 24 h; the other set was treated at 350°C and 2 kbar for periods of 12 to 89 d. X-ray diffraction patterns (XRD) of oriented aggregates from treated products were obtained from ethylene glycol-solvated and air-dried preparations. Samples were also heated to 350°C either in a calibrated muffle furnace, removed and quickly placed in a nitrogen filled chamber on the diffractometer, or were heated at 350°C by using a calibrated heating stage mounted on the diffractometer.

Initial mineral assemblages at both temperatures contained only saponite and serpentine. In experiments at 500°C, saponite transformed to corrensite within 6 h; in experiments at 350°C, the transformation occurred as early as 22 d. Increased experiment times at both temperatures produced increasing amounts of well-crystallized corrensite, as indicated by several well-defined XRD peaks. No evidence of a randomly interstratified chlorite-smectite (C-S) precursor to corrensite was found. The identification of pure smectite, as opposed to highly-expanded randomly interstratified C-S, was possible only when clays were dehydrated on a heating stage on the diffractometer.

These results call for a new examination of hydrothermally-altered basalt that has been reported to contain randomly interstratified C-S as an intermediate step in the reaction of smectite to corrensite or chlorite. These results also strengthen the view held by increasing numbers of investigators that corrensite should be regarded as a single phase, not as a mixed-layered phyllosilicate.

Vermiculite from Santa Olalla, Spain, was intercalated with tetramethylphosphonium [P(CH3)4+ = TMP], using a TMP-bromide solution at 70°C for three weeks. The resulting TMP-exchanged vermiculite, which contained a small (<5% of a site) amount of residual interlayer Ca, showed near perfect three-dimensional stacking. Cell parameters are a = 5.3492(8) Å, b = 9.266(2) Å, c = 14.505(6) Å, β = 97.08(2)°, space group is C2/m, and polytype is lM. Single-crystal X-ray refinement (R = 0.052, wR = 0.061) located two crystallographically unique sites for the phosphorus atoms (TMP molecule). The phosphorus atoms are occupied partially [P1 = 0.146(6), P2 = 0.098(5)] and are offset from the central plane of the interlayer by 1.23 Å to form two P-rich planes in the interlayer. Electrostatic interactions between the P cations and basal oxygen atoms essentially balance the negative charge associated with Al for Si substitutions in the tetrahedral sites. In addition, the orientations of the TMP molecules are probably different owing to packing constraints. The H2O site is located in the center of the interlayer, at the center of the silicate ring, and ∼3.09 Å from the Ca, which is also located on the central plane of the interlayer. Other H2O molecules are present in the interlayer, but could not be located by the diffraction experiment because they are randomly positioned in the interlayer. The tetrahedral rotation angle, α, is affected by the intercalation of TMP relative to tetramethylammonium (TMA), thus indicating that 2:1 layers are not simply rigid substrates, and that dynamic interactions occur during reactions involving adsorption and exchange.

Competitive adsorption between phosphate, tartrate and oxalate was studied on two hydroxy aluminum montmorillonite complexes (AlMt1.6 and AlMt6), which were prepared by adding a base to pH 5.5 to samples containing 1.6 and 6.0 mol Al per kg clay. The quantities of phosphate, tartrate and oxalate adsorbed were more closely related to the amount of OH-Al species coatings on the montmorillonite than to the surface area of the complexes. The adsorption capacity of phosphate was much greater than that of tartrate or oxalate for both samples. Adding molar amounts of oxalate and tartrate resulted in an oxalate/tartrate adsorption ratio (Rf) of ∼1. However, in the presence of phosphate, Rf values were <1.0, and the Rf values decreased with increasing amounts of added phosphate, indicating that tartrate competed with phosphate more effectively than oxalate. The presence of tartrate also reduced phosphate adsorption by the complexes. The efficiency of tartrate in reducing phosphate adsorption increased by increasing the initial tartrate/phosphate molar ratio and by adding tartrate 2 h before phosphate addition. Tartrate and oxalate added as a mixture in equimolar quantities were much more effective in inhibiting phosphate sorption than tartrate alone under the same organic ligand concentrations, probably because more sites with high affinity for both the organic ligands were occupied by tartrate and oxalate than by tartrate alone. The efficiency of tartrate alone, or combined with oxalate, in preventing phosphate adsorption was greater for the complex containing a lesser amount of OH-Al species coating the montmorillonite surfaces. This result may be attributable to a greater proportion of sites specific for organic ligands present on AlMt1.6 compared to AlMt6 complex.