Al-rich di, trioctahedral chlorite exists as the species cookeite and sudoite. Di,dioctahedral chlorite exists as the species donbassite. Cookeite has essential Li in its structure, sudoite has essential Mg, and donbassite has only small amounts of either element. To date, sudoite has been reported to have only IIb structural units and donbassite to have only Ia structural units. Cookeite is based primarily on Ia structural units, but IIb units are present in specimens from two localities. Most Al-rich chlorite species have regular-stacking “r” or “s” 2-layer stacking sequences, but 1-layer Ia-2 and Ia-6 polytypes also are known. The structural units (Ia or IIb) and the specific stacking sequences can be explained by a combination of local charge balance and minimization of cation-cation repulsion involving the interlayer and tetrahedral cations. X-ray powder diffraction data are adequate to differentiate Al-rich chlorite from trioctahedral chlorite and to identify the type of structural unit present, but single crystal study is necessary to identify the 2-layer and 1-layer sequences with certainty.

High-resolution transmission electron microscope images of dioctahedral mixed-layer clay structures (illite/smectite) having various substitutional and polytypic schemes were modeled using computer simulation methods. Both one- and two-dimensional calculations were performed using parameters characteristic of a typical range of imaging conditions. One-dimensional images formed by imaging only 00/ diffractions show three important results: (1) The 20-Å periodicity resulting from rigorously ordered R1 illite/smectite can be imaged, but unconventional focus conditions may be necessary. (2) For crystals oriented with the electron beam perfectly parallel to the layers, the brightest fringes in the image correspond to either the octahedral sheets or the interlayer sites, depending on focus conditions. Misorientation of the crystal, however, by only 1° or 2° shifts the positions of the fringes by 1 to 3 Å. Furthermore, in tilted specimens, some defocus values produce images suggesting that smectite layers have a 11–13-Å periodicity, despite the uniform 10-Å periodicity present in the model structure. Thus, direct correlations between image and structure generally should not be made. (3) Two-layer polytypes of pure illite or pure smectite can also produce images with a 20-Å periodicity.

Two-dimensional images additionally showed that the cross fringes produced by some hkl diffractions can be imaged. The simulations showed that these cross fringes ideally might permit the determination of both layer stacking and compositional periodicity, but the fringes are lost by misorientations of a few degrees. These image simulations demonstrated, therefore, that mixed layering of illite and smectite theoretically can be directly imaged by transmission electron microscopy of chemically untreated specimens, but ambiguities may exist in the detailed intepretation of the images.

The structure of kaolinite (non-hydrogen atoms only) from Keokuk, Iowa, was refined in space group C1 using CuKα X-ray powder diffraction data and Rietveld refinement techniques (Rwp = 12.3%). A distance least-squares (DLS) model for the initial atomic coordinates avoided a false minimum and unrealistic results characteristic of previous Rietveld refinements of kaolinite. All Keokuk samples examined contain small amounts of dickite. The profile of the mixture was calculated using a fixed set of dickite atomic parameters and by constraining the dickite profile parameters to those refined for kaolinite. Results indicate that the individual kaolinite layer is very similar to the dickite layer; bond distances, which are similar to dickite and nacrite, are: Si-O, 1.60-1.63 Å; Al-O, 1.87-1.97 Å. The tetrahedral rotation angle is 6.9°, compared with 7.3° for dickite and 7.4° for nacrite. Previous Rietveld refinements apparently suffered from poor preferred orientation models, failure to consider the presence of dickite as a second phase, and, most importantly, refinement to a false-minimum structure. The conclusions based on the earlier refinements must therefore be reevaluated, especially regarding the kaolinite space group and hydrogen positions. Existing X-ray and electron diffraction and spectroscopic data support the presence of C-centering in kaolinite.

Illite diagenesis in Tertiary and Mesozoic shales in the Bergen High area, northern North Sea, was studied using mineralogic, isotopic, and computerized thermal modeling techniques. The Tertiary shales are dominated by smectite, with lesser amounts of illite, kaolinite, and chlorite. At present burial temperatures of >70°C smectite is absent, and the shales contain abundant lath-shaped illite which yields a mixed-layer illite/smectite (I/S) X-ray powder diffraction (XRD) pattern. Transmission electron microscopy (TEM) indicates that the illite laths increase in abundance and thickness with increasing depth; XRD patterns indicate a progressive increase in the illite component of the I/S. The deepest samples were found to contain long-range ordered (R=3) I/S, which showed platy particle morphology with the TEM. K-Ar ages of most of the <0.1-μm-size illite separates imply that illitization was a relatively brief event affecting a thick sequence of sediments during late Cretaceous to early Paleocene time (65–87 Ma); however, measured ages were affected by trace levels of detrital Ar contamination and do not represent the true age of diagenesis.

Several methods of quantifying Ar contamination were used to correct measured ages to obtain a reasonable estimate of the true age of diagenesis. The corrected ages are imprecise due to uncertainties in quantifying the levels of sample contamination, but generally suggest a Paleogene (38–66 Ma) period of illitization. In contrast, simple kinetic models of smectite-illitization suggest much younger ages of diagenesis (0–40 Ma at the Veslefrikk field; 0–60 Ma at the Huldra field). The timing of the diagenesis and the morphologic aspects of the authigenic illite suggest that illite precipitated before late Tertiary compaction and resulted in a decrease in fluid permeability. Low trapping efficiency of early Tertiary sediments, vertical escape of warm fluid from the Brent sandstone, and high heat flow may have promoted illite diagenesis in the shales prior to deep late-Tertiary burial.

A review is presented of work carried out over the last 40 years on non-porous sorbents and on microporous shape-selective sorbents derived from palygorskite, smectite, and vermiculite. Among such materials four kinds of behavior were observed. In some systems uptake was restricted to external surfaces; in others, intercalation also occurred but only above threshold pressures. If the interlayer region was completely filled by long-chain organic cations, imbibition was possible, but in amounts which were very strongly dependent upon the cohesive energy density of the sorbate. Finally, in certain permanently expanded derivatives of layer silicates intercalation proceeded without any threshold pressure, just as in zeolites.

In this latter group, micropores existed which sometimes resulted in shape-selective sorption and molecule sieving. The micropores in clay minerals were modified by varying the size and shape of the interlayer cations, their charge, and the charge density of the siliceous layers. The interplay of these factors was investigated and the micropore sorbents were shown to be highly effective in the separation of mixtures.

The vitric matrix of pre-caldera acid tuff and tuff breccia of the Santorini volcano, Aegean Sea, Greece has been generally replaced by one or more of the following authigenic minerals: K-rich and (K,Ca)-rich clinoptilolite, mordenite, opal-CT, and clay minerals. Halite is also present in some samples. Initial compositional inhomogeneities between the dacitic blocks in tuff breccia and tuff seem to have controlled the type of K-rich heulandite-group zeolite that formed. Mordenite postdates the heulandite-group zeolites and opal-CT. Some mordenite has replaced the rims of glass shards. The alteration minerals are not related to vertical or lateral zonation, and the irregular distribution of their assemblages is attributed to variations in heat flow, ionic activity in interstitial waters, and permeability. The pyroclastic rocks were in a region of active heat flow during and after their emplacement. The formation of authigenic silicates may have led to the sealing of open spaces and fractures, imposing barriers to permeability and subdividing the original open system into smaller closed systems. As alteration progressed, some of the trapped water in each individual domain was consumed in hydration reactions. Salts could have been concentrated by such a process, and halite probably precipitated from solutions of appropriate composition in the individual closed systems.

During an electron microscope study of the weathering of granite from southern New South Wales, Australia, an assemblage of minerals including florencite and rhabdophane was discovered replacing apatite. Light rare earth elements released from allanite early in weathering apparently combined with P released by leaching of primary apatite to form secondary phases exhibiting a range of morphologies and compositions. Chondrite normalized fractionation patterns La > Nd > Sm > Ce; La > Ce > Nd ≥ Sm and La = Sm = Nd > Ce were identified. The rare earth elements were present in very small crystals and aggregates of secondary minerals (< 10 μm) and coexisted with clays and secondary Fe-Ti oxides. The weathered granite was enriched about 6 to 10 times in all rare earth elements except Ce relative to fresh granite if the abundances were corrected for apparent enrichment due to reduction in density. The rare earth elements were probably derived from higher in the weathering profile, possibly by destruction of florencite and rhabdophane in very intensively weathered rock. Ce remained relatively immobile during weathering, probably due to its oxidation to Ce4+.

Hydrotalcite-like compounds, described by the formula [Zn1-xAlx(OH)2][(CO3)x/2 · nH2O], were prepared by coprecipitation methods at 80°C and characterized by bulk chemical analysis, X-ray powder diffraction (XRD), nuclear magnetic resonance (NMR), and scanning-transmission electron microscopy (STEM). An x value of 0.33 was previously assumed to be an upper limit, but recently, Al-rich hydrotalcite-like compounds have been prepared with x as large as 0.44 by hydrothermal synthesis. In the Zn-Al system, Al-rich hydrotalcite was synthesized at normal pressure by coprecipitation. Zn-Al hydrotalcite-like compounds were obtained in the range of x = 0.3 to 0.4. An Al-rich hydrotalcite-like compound with x = 0.44 was formed in mixtures containing large amounts of a poorly crystalline Zn-Al phase. A continuous contraction of the hydrotalcite-like structure occurred as x increased, both the a and c lattice parameters decreasing for x values as large as 0.44. This study illustrates the advantages of using quantitative analytical electron microscopy with high spatial resolution to complement conventional (and bulk) characterization techniques for correlating structural and compositional characteristics of finely divided materials.

Potentiometric titration analysis was used to examine the hydrolysis behavior of Fe2+ Fe3+, and Al3+ in pure solution and in mixture, in order to evaluate the potential for coprecipitation and mixed solid-phase formation. Mixtures of Fe3+ and Al3+ did not interact during neutralization; base consumed in their respective buffer regions was equivalent to the total metal added. Fe2+-Al3+ solutions, however, showed excess base consumption in the Al3+ buffer region, indicating hydrolysis of Fe2+ at lower than normal pH. Ferric/ferrous iron analyses of systems at the Al endpoint (pH 5.5) showed amounts of oxidized Fe equivalent to the excess base consumption (∼10% of total Fe), with substantial amounts of Fe2+ sorbed to or occluded within Al polymers present. Increased electrolyte levels or the presence of SO42- inhibited oxidation and sorption of Fe2+ on Al surfaces, suggesting that Fe hydrolysis and oxidation was catalyzed at the surfaces. Increasing Al3+: Fe2+ ratios in the titrated solutions also increased the amount of Fe2+ coprecipitation, supporting a surface-mediated reaction mechanism. Ferrous iron oxidation was sensitive to O2 levels, which also affected the amount of coprecipitation. These findings suggest that surface-facilitated oxidation of Fe2+ may be important in the formation of mixed Fe-Al mineral phases in dilute soil solutions.

Previous studies of the defect structure of kaolinite have examined samples having a restricted level of defects. This study examined nine kaolinite samples having a large diversity of defect contents, as indicated by Hinckley indexes ranging from 1.44 to 0.18. The samples were chosen so as to cover this range in as regular a manner as possible. The types and abundances of the defects were determined by examining the X-ray powder diffraction profiles for the 02,11 and 20,13 bands. The diffraction intensities were measured by counting for a fixed time in steps of 0.01°2θ. Analysis of these diffraction profiles indicated that (1) the major defect is the existence of a translation between adjacent layers, which is not the usual (approximately a/3), but is related to that translation by the pseudo-mirror plane coincident with the long diagonal of the unit cell; (2) the existence of a few C layers among the B layer stacking is a minor defect; (3) many of the samples could be accurately modeled only by assuming the existence of two kaolinite phases; (4) the existence of only a few C layers in some samples does not support the idea of a continuous series from kaolinite to dickite through disordered intermediates; and (5) the Hinckley indexes of several samples depend on the relative proportions of the two types of kaolinite in the mixture.

The nine kaolinite samples fall into three groups: those having a low to moderate abundance of defects (Hinckley index > 0.43) are mixtures of two types of kaolinite (one almost free of defects, the other richer in defects); those having low Hinckley indexes (0.43 to 0.18) are single phases with different proportions of defects; and those which contain a single type of kaolinite, unlike the others in the nature of the interlayer translations and the greater abundance of C layers. The agreement between calculated and observed X-ray diffraction profiles is excellent for all specimens, except one sample (from Charentes) for which the fit is acceptable but not perfect.

A monoclinic IIb-2 clinochlore from the Achmatov mine, Ural Mountains, U.S.S.R., was investigated by neutron diffraction. The formula, based on electron microprobe and wet chemical analyses, is (Mg4.54Al0.97Fe2+ 0.28 Fe3+ 0.18Mn0.01)(Si2.85Al1.15)O10(OH)8. A refinement based on 512 unique reflections converged in space group C2/m to a final R =.066. Cation disorder was found in the two octahedral positions of the 2:1 layer, whereas partial Mg and Al ordering occurs in the interlayer sheet. The two hydroxyl dipoles are roughly perpendicular to the interlayer sheet, forming weak to medium hydrogen bonds with O…O distances of 2.859 and 2.881 Å. The OH-dipole of the 2:1 layer is perpendicular to the (001) plane.

A comparison of the structural characteristics of the kaolin-group minerals, mainly kaolinite and dickite, shows that they differ in both the two-dimensional periodicity in the 1:1 layers and the rotation angles of the polyhedra. Distortions in a real 1:1 layer, compared with an idealized layer, do not allow such stacking faults as ± 120° layer rotations and vacancy displacements, because the second layer is incommensurable with the first. The 1:1 layer structure and the fact that the unit cell is symmetrical with respect to the plane passing through the long diagonal of the unit cell suggest the possibility of defects resulting from the two stacking sequences for the same layers. For a regular alternation of translations, a halloysite-like structure should be the end-member of such a series of defect kaolinite types.

The formation of layers having vacant octahedral C-sites is another possible type of fault. Because of the minor dilference between γ and 90°, dickite-like layers should exist. A regular alternation of B and C layers yields dickite as the end-member structure. In materials containing few defects, stacking faults of both types lead to similar X-ray powder diffraction patterns. Thus, the nature of the stacking faults is difficult to determine experimentally. In materials containing many defects, however, the two models lead to different calculated diffraction patterns. Therefore, only a study of defect-rich types of kaolinite can determine which types of defects exist in natural kaolinite samples.

Illite/smectite (I/S) and illite samples that appear to be 1Md polytypes on the basis of the lack of diagnostic reflections can be resolved as partly either 1M or 2M1 or both by either vapor solvation in ethylene glycol for 40 to 80 hr at ambient temperatures or for 4 hr at 80°C, or by heating to 375°C for 2 hr. If samples are so treated, a distinct narrowing of the I/S 003/005 peak occurs and diagnostic hkl reflections are revealed. These treatments, however, do not seem to affect diagnostic polytypic peak intensities, but rather the adjacent background. We propose that the 1Md term be restricted to its original definition—the disordered polytype associated with only the 1M ordered polytype. For illites in which disorder exists with a mixture of polytypes, the generic term Ad (disordered group A micas) should be used. Correct polytype determination of illitic material is significant because it reveals thermal history of the sediments and allows greater understanding of the depositional and diagenetic history of sedimentary basins.

The weathering products of primary biotite, chlorite, magnetite, and almandine in mica gneiss and schist in the North Carolina Blue Ridge Front were determined. Sand-size grains of biotite, the most abundant, readily weathered mineral in the parent rock, have altered to interstratified biotite/vermiculite, vermiculite, kaolinite, and gibbsite in the saprolite and soil. Fe2+-chlorite in the parent rock was relatively resistant to chemical weathering, which appears to be confined to the external surfaces of particles. Magnetite grains in the saprolite are essentially unaltered, but those in the soil contain abundant crystallographically controlled etch pits and are coated with oxidation crusts. Almandine altered to goethite, hematite, and gibbsite as the rock weathered to saprolite. Extensively weathered almandine grains were found to contain etch pits and what appeared to be oxide coatings. Apparently, a rapid release of Fe during weathering produced hematite, whereas slower release of Fe favored the formation of goethite.

Triclinic IIb-4 and monoclinic IIb-2 clinochlore polytypes from Kenya are intergrown laterally in (001) platelets and are separated optically in some places by sharp lines of demarcation and in other places by embayed boundaries. Electron microprobe analyses show no compositional differences between the two polytypes. Structural refinements of each show that the 2:1 layer is identical in the two structures with no tetrahedral or 2:1 octahedral cation ordering in either ideal or subgroup symmetries. The two interlayer sheets dilfer only in the distribution of A1 and Mg over interlayer sites M3 and M4, but not in the distribution of Fe3+, Fe2+, or vacancies. The monoclinic IIb-2 polytype is less ordered than the triclinic IIb-4 polytype. The mean M-O,OH bond length of 1.990 Å indicates significantly less of the smaller A1 present in the M4 site of IIb-2 than for the mean M-O,OH value of 1.957 Å for the M4 site of IIb-4. The textural relations and the structural refinements suggest that the monoclinic IIb-2 structure is inherently less stable than the triclinic form. This is in accord with the observed lesser abundance in nature of the monoclinic form.

Hornblende of the Carrol Knob mafic complex (southern Blue Ridge Mountains, North Carolina) has weathered under humid, temperate conditions. Hornblende weathering appears to have been a dissolution-reprecipitation reaction, in which hornblende dissolved stoichiometrically, and the ferruginous and aluminous weathering products (goethite, gibbsite, and kaolinite) precipitated from solution (neoformation). During the earliest stage of alteration, ferruginous weathering products formed as linings of fractures within and around crystals and cleavage fragments of hornblende. Side-by-side coalescence of lenticular etch pits during more advanced weathering produced characteristic “denticulated” terminations on hornblende remnants in dissolution cavities bounded by ferruginous boxworks. Dissolution cavities are devoid of weathering products. Small “pendants” of ferruginous material project from the boxwork into void spaces. Because these products are separated from the hornblende remnants by void space, they must have been produced by dissolution-reprecipitation reactions. Complete removal of the parent hornblende left a ferruginous microboxwork or “negative pseudomorph.” Only Al and Fe were conserved over microscopic distances; alkali and alkaline-earth elements were stoichiometrically removed from the weathering microenvironment during the weathering process.

Observation of quadrupolar splittings for 2H and 17O nuclei from D2O solvent molecules in suspensions of the Ecca Gum BP bentonite points unambiguously to the ordering of water molecules with respect to a static magnetic field. The application of the magnetic field apparently orients the clay platelets as tactoids. Some water molecules adhere to the platelets and are oriented. The magnitude of the quadrupolar splitting depends strongly on the nature of the interstitial cations. The sign of the splitting changes as the ratio of divalent to monovalent cation increases, reflecting a switch in the microdynamics of water molecules next to the plates. With the entry of divalent cations, the clay becomes more cohesive due to the vertical electrostatic attraction of the counterions to the charged plates. More of these hydrated divalent ions compared with monovalent ions condense onto the charged sheet, thereby increasing metal coordination to those water molecules in contact with the clay surface. The dominant reorientation mode of the water molecules switches from rotation of water molecules around hydrogen bonds to the charged sheets to rotation around the electrostatic bond to the divalent metal cation. The effect is spectacular and important in understanding the chemical properties of cation-exchanged montmorillonites.

A new type of environmental chamber for X-ray diffraction was designed that could sustain elevated, internal pressures of nitrogen or any other gas under oxygen-free conditions and that allowed the positions of the specimen and edge aperture to be adjusted by remote control. It was used to determine the values of the interlayer spacing, λ, of nontronite from Garfield, Washington, in different stages of reduction at different values of Π, the swelling pressure of the nontronite. At equilibrium, Π was equal to the pressure under which water was expressed from the clay. Both partially and fully expanded layers were found to exist in the reduced nontronite, the fraction of partially expanded layers increasing with increasing Π and Fe2+/Fe3+, the ratio of Fe2+ to Fe3+ in octahedral sites. Also, λ for the partially expanded layers was found to depend on Fe2+/Fe3+ but not on Π, and λ for the fully expanded layers was found to depend on Π but not on Fe2+/Fe3+. These findings were interpreted to mean that the reduction of Fe affected the short-range interlayer forces, but not the long-range ones.

Aqueous Al passes from octahedral to tetrahedral coordination over a narrow pH interval, or threshold. This interval is 5.5–6.5 at 25°C and shifts to lower pH as temperature increases. The concentration of aqueous tetrahedrally coordinated Al is a quasi-step function of the solution pH, and, by the mass-action law, so should be the amount of tetrahedral Al incorporated by a silicate that crystallizes from the aqueous solution. Qualitative support for this prediction (which applies to quartz, opal-CT, kaolin-group minerals, pyrophyllite, micas, chlorites, and other low-temperature silicates) comes from the very topology of equilibrium activity diagrams and from several pairs of associated waters and authigenic silicates from weathering, hydrothermal, and diagenetic environments. The uptake of tetrahedral Al also depends on the aqueous concentrations of monovalent cations and silica, and on the mineral's structural constraints.

Solid solution of tetrahedral Al in halloysite in turn produces the characteristic bent or tubular crystals of this mineral. This genetic link between aqueous chemistry (mainly pH), tetrahedral-Al uptake by a low-temperature silicate, and the mineral's crystal morphology may operate also in other silicates.

Solid-state nuclear magnetic resonance (NMR) spectroscopy, thermal analysis, and X-ray powder diffraction data on the tubular, hydrous aluminosilicate imogolite were found to be fully consistent with a previously proposed crystal structure consisting of a rolled-up, 6-coordinate Al-O(OH) sheet, bonded to isolated orthosilicate groups. The calculated 29Si chemical shift of this structure agreed with the observed shift within 3 ppm. Thermal dehydroxylation of the Al-O(OH) sheet produced predominantly NMR-transparent 5-coordinate Al, but a few 4- and 6-coordinate sites and some residual hydroxyl groups may also have formed, as shown by NMR spectroscopy. Changes in the 29Si NMR spectrum on dehydroxylation suggest a condensation of the orthosilicate groups, but steric considerations rule out bonding between adjacent silicons. To account for these observations, an alternative mechanism to orthosilicate condensation has been proposed, involving the fracture and unrolling of the tubes, followed by the condensation of fragments to form a layer structure. The layer structure has a calculated 29Si chemical shift of -95.6 ppm, in good agreement with the observed value of -93 ppm.