Two orientations of white micas with subordinate chlorite have been observed in a fine-grained (50 Å to 2 μm) matrix of a Silurian lower anchizonal mudrock from central Wales: one parallel to bedding and one parallel to cleavage that is approximately 30°-50° to bedding. Bedding-parallel micas consist of small (50-200 Å thick) deformed packets (1Md polytype) and larger (100 Å-2 μm) strain-free grains (2M1 polytype). All strained micas and some strain-free grains have compositions varying from Mu86Pg14 to Mu58Pg42, intermediate to muscovite and paragonite, and falling within the Mu-Pg solvus. Individual packets of layers are chemically homogeneous and some of them give only one set of 00l reflections (d ≈ 19.6 Å). Micas with such intermediate compositions are metastable. Some packets of coarse, strain-free micas have compositions of approximately Mu93Pg7 or Mu11Pg89. Split pairs of 00l reflections with d-values of 20 Å and 19.6 Å, and 20 Å and 19.2 Å, respectively, were observed in some SAED patterns, suggesting coexistence of muscovite and intermediate Na/K mica (∼Mu60Pg40), and of discrete muscovite and paragonite, consistent with the splitting of the basal reflections of micas as observed in bulk-rock XRD patterns. Cleavage-parallel micas (2M1 and 3T polytypes) occur as strain-free large grains (200 Å to 2 μm) of discrete muscovite (Mu100Pg0) and paragonite (Mu6Pg94), often with subhedral to euhedral cross-sections.

The data suggest that bedding-parallel metastable micas with disordered interlayer K and Na were initially derived from alteration of smectite during burial diagenesis. They subsequently underwent dissolution, with crystallization of more evolved bedding-parallel micas during deep burial. Discrete grains of stable muscovite and paragonite then crystallized in the cleavage orientation through tectonic stress-induced dissolution of bedding-parallel matrix micas. Combined XRD and TEM/AEM data further show that the so-called 6:4 ordered mixed-layer paragonite/muscovite actually corresponds to cation-disordered, homogeneous mica of intermediate composition.

A very simple technique is proposed for a quantitative or semiquantitative interpretation of X-ray diffraction (XRD) patterns for two-component mixed-layer structures. It is suitable for a determination of the Reichweite (R) values and proportions of component layers from graphical simulations of basal peak positions for mixed-layer structures with definite layer types. This technique can be successfully used for illite-smectites, but the accuracy of the results obtained for other mixed-layer structures is somewhat lower. In addition to the graphical technique, simple linear relationships are proposed for the calculation of layer proportions. Such relationships can be easily obtained for any mixed-layer structure with any R and any thicknesses of interstratified layers.

Structural parameters reported in the literature for mixed-layer illite-smectites, kaolinite-smectites, etc., were used to check the reliability of the method presented. It is concluded that the technique works well and produces parameters that are in agreement with those published.

The composition and origin of vanadium-bearing clay minerals in the Jurassic (Morrison and Entrada Formations) sandstones of the Colorado Plateau are reassessed using microanalyses (microprobe and scanning electron microscope). The main V-clays are authigenic illite and chlorite of various petrologic habits: clay casts and matrix, pore lining, replacement of detrital grains. The chemical composition of the V-clays is similar in three different localities in the Morrison Formation separated by about 50 km, suggesting that the V-clays are the result of a large regional event. In both illite and chlorite, Al and V are inversely correlated, showing that V replaces Al in the octahedral position. The chlorite contains a complex mixture of divalent and trivalent cations that cannot fit within a sudoite structure. A classification of V-micas is proposed that employs V3+/sum of the octahedral cations vs. the sum of the interlayer charges. V-illite and roscoelite from the Colorado Plateau are characteristic of diagenetic/hydrothermal environments. For a given locality the composition of the V-clays does not vary with habit, showing that these minerals formed at thermodynamic equilibrium.

The red snow algae species found in snow at Resolute, Canadian Arctic, is a unicellular Chlamydomonas nivalis. Investigations by SEM-EDX, TEM, FT-IR, GC and GC-MS suggest that clay aerosols may provide nutrients for these unique systems. The clays provide P, S, K, Si, Ca, and Mg. Soot is also present and halite is very common. This salt probably plays a significant role in lowering the freezing temperature. The red snow algae is coated by a sticky thin film composed of both organic membrane material and inorganics consisting of mica and smectite. Green algae rich in Ca are involved in active photosynthesis while red algae are in a resting stage. Protamine, stearic acid, and decanoic acid were found at Ca-rich green cells while carminic acid and nopalcol BR-13 were found at Ca-poor red cells. The cell wall of red algae is composed of protein with cellulose. The major fatty acides in cells are all of even-carbon species with maximum concentrations of palmitic acid, stearic acid, and behenic acid, suggesting normal chemistry of algae species without C22. High concentration of n-alkanes with n-C24 is a characteristic component in this red snow algae, suggesting the presence of hydrocarbons that could be derived from the Arctic cold desert and/or organic debris of wind-transported bacteria. It is likely that such organic and inorganic matter provide the nutrient sources for the red snow algae in ice.

Infrared (IR) spectroscopy, in combination with magnetic methods, was used to study the thermally induced transformation of synthetic lepidocrocite (γ-FeOOH) to maghemite (γ-Fe2O3). Magnetic analyses showed that the thermal conversion began at about 175°C with the formation of superparamagnetic maghemite clusters. The overall structural transformation to ferrimagnetic γ-Fe2O3 occurred at 200°C and was complete around 300°C. At higher temperatures, the maghemite converted into hematite (α-Fe2O3). Observation of the transformation from γ-FeOOH to γ-Fe2O3 using variable-temperature IR spectroscopy indicated that dehydroxilation on a molecular level was initiated between 145°C and 155°C. The lag time between the onset of the breaking of OH bonds and the release of H2O from lepidocrocite around 175°C can be explained by diffusive processes. Overall dehydroxilation and the subsequent breakdown of the lepidocrocite structure was complete below 219°C. The comparison of the magnetic and IR data provides evidence that the dehydroxilation may precede the structural conversion to maghemite.

Ammonium-saponite is hydrothermally grown at temperatures below 300°C from a gel with an overall composition corresponding to (NH4)0.6Mg3Al0.6Si3.4O10(OH)2. Using 27Al and 29Si solid-state Magic Angle Spinning NMR techniques it is demonstrated that synthetic ammonium-saponites have a rather constant Si/AlIV ratio (≈ 5.5) and an AlIV/AlVI ratio that varies between 1.5 and 3.8. The above ratios are independent of the synthesis temperature, although an increasing amount of Si, N, and, to a lesser extent, Al are incorporated in an amorphous phase with increasing temperature. 27Al MAS-NMR is unable to differentiate between Al at octahedral and Al3+ at interlayer sites. CEC, XRD, and the inability to swell prove the AlVI to be mainly on the interlayer sites. Based on the NH4- exchange capacity, X-ray fluorescence, 27Al and 29Si MAS-NMR, it is possible to calculate a relatively accurate structural formula.

Two samples, obtained by pillaring a Wyoming montmorillonite with hydroxy aluminium and oligosilsesquioxane cations, were studied by stepwise thermal desorption of ammonia and by highly sensitive diffuse reflectance IR-spectroscopy. For both clays, the adsorption of ammonia shows a total number of acid sites equal to 0.35 meq/g, with acid strengths comparable to that of HY zeolites. By IR reflectance spectroscopy, Brönsted acid sites with an acid strength comparable to that of bridging hydroxyls in zeolites were found in Al samples but not on Si-montmorillonites. These sites were characterized by an overtone band at 7100 cm-1 and an activity for ethylene oligomerization at 300 K.

Samples of ash layers and associated background sediments from Site 808 of ODP Leg 131 in the Nankai Trough accretionary prism were analyzed for changes in mineralogy, porosity and micro-fabric associated with alteration of volcanic ash. Ash layers range from incipient stages of alteration and dissolution to complete alteration to clay minerals and clinoptilolite. Ash layers contain greater abundances of total clay minerals and lower percentages of quartz than do surrounding background hemipelagic sediments. The clay-sized fraction of ash layers is dominated by pure dioctahedral smectite, whereas the background sediments contain primarily illite and chlorite with minor amounts of smectite. Analysis of microfabric revealed dramatic changes in the distributions and abundances of grains and pores during ash alteration. The relative abundances of large pores, grains, and matrix material were quantified on digital back-scattered electron images (BSEI) of ash layer and background sediment samples. During burial, the abundant glass shards of shallow ash layers are initially altered, presumably to smectite. Subsequent dissolution of the glass leaves open, shard-shaped pores, resulting in increased porosities. With greater burial, these pores are filled with clinoptilolite. Although the presence of ash and its alteration products clearly influences sediment physical properties, there is no apparent correlation of the abundance of ash or its alteration products with the formation of thrust faults or other structures within the Nankai Trough accretionary prism.

The quantification of the relative mineralogical composition of clay mixtures by powder X-ray diffraction or chemical mass balance methods has been severely hampered by a lack of representative standards. The recent development of elemental mass balance models that do not require standards for all minerals in the mixture may help circumvent this problem. These methods, which are based on the numerical optimization of systems of non-linear equations using the Marquardt algorithm, show promise for mineral quantification. The objective of this study is to make a preliminary assessment of the accuracy of these methods and to compare them to linear models that require standards for all mineral phases. Methods 1 and 2 are based on weighted average solutions to simultaneous linear equations solved for single samples with known standards. Solutions were achieved by a matrix decomposition algorithm and the Marquardt algorithm, respectively. Methods 3 and 4 are based on a set of simultaneous non-linear equations with reduced non-linearity solved by least squares optimization based on the Marquardt algorithm for multiple samples. Illite and halloysite compositions were fixed in Method 3, only the halloysite composition was fixed in Method 4. All models yielded relative weight fractions of the three mineral components; additionally, Methods 3 and 4 yielded compositions of smectite, and smectite and illite, respectively. Ten clay mixtures with varying proportions of the <0.2 μm size fraction of three different reference clays (Wyoming bentonite, Fithian illite, and New Bedford halloysite) were prepared gravi-metrically and analyzed by inductively coupled plasma-atomic emission spectroscopy. Accuracy of the four methods was evaluated by comparing the known mineralogical compositions of the mixtures with those predicted by the models. Relative errors of 5 and 10% (randomly +/-) were imposed on the elemental composition of the smectite standard to simulate errors due to lack of good standards. Not surprisingly, the accuracy of Methods 1 and 2 decreased rapidly with increasing error. Because Methods 3 and 4 optimized for the smectite composition and only used it for an initial guess, they were unaffected by the level of introduced error. They accurately quantified the mineralogical compositions of the mixtures and the elemental compositions of smectite, and smectite and illite, respectively.

The effect of interlayering montmorillonite with different amounts of hydroxy aluminum cation on the cation exchange capacity (CEC) and the point of zero charge (PZC) of the clay was studied. The CEC decreased as the Al content of the clay increased. Both the CEC and the loss in the CEC were linearly dependent on the Al content, thus indicating the predominance of a single polynuclear interlayered species. Its composition is [Al6(OH)16.5]1.5+. Acid base titration of the interlayered montmorillonites produced values for the PZC in the range 4.5-5.9, increasing with the Al content of the materials. The values, however, did not represent real conditions of zero charge and some samples were still negatively charged at the determined PZC. The PZC values obtained by acid-base titration are thought to be adversely affected by secondary reactions involving the interlayered material with a concomitant release of soluble Al in amounts dependent on the pH and ionic strength.

Greigites from a gley and a Tertiary sediment were investigated by X-ray diffraction and Mössbauer spectroscopy. The cell-edge length a of 9.8639 Å ± 0.0003 Å for the soil greigite was significantly smaller than that of the sedimentary greigite (9.8737 Å ± 0.0004 Å), but both cell-edge lengths were smaller than the value given on JCPDS card #16-713 (9.876 Å). Both greigites had 440 as strongest peak rather than 311 (as indicated on JCPDS card #16-713), but the other relative intensities did not deviate from the values given on this card within experimental error. Mean X-ray diffraction coherence lengths of 23 ± 2 nm for the soil greigite and of 60 ± 5 nm for the sedimentary greigite suggest superparamagnetic behavior. Mössbauer spectra nevertheless comprised two sextets with hyperfine fields of about 31.2 T (tetrahedral sites) and 30.7 T (octahedral sites), which resemble published values. It is postulated that aggregation may play an important role in determining the magnetic properties of the described samples.

Electron spin resonance (ESR) spectroscopy was used to measure the rotational mobility of an uncharged nitroxide spin probe (4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy) in hectorite gels of variable water content. Physical adsorption segregated the probe molecules into two populations: probes in the solution or a solution-like phase, and motionally restricted probes in the adsorbed phase. Although the spectra of these two populations were discrete, indicating that exchange between them was slow on the time scale relevant to ESR, their overlap prevented a straightforward determination of mobility of the adsorbed probes. Even though adsorption was weak, effects of the adsorbed population on the spectral lineshape were detectable for suspensions containing as little as 20 grams clay per liter of water. Orientation of the adsorbed probes on the fully hydrated hectorite surfaces was similar to that of a positively charged nitroxide probe, suggesting that steric factors rather than electrostatic forces control short-range organic molecule interaction with the silicate. The possibility of reaching false conclusions about probe mobility and interlamellar water viscosity when using a weakly adsorbing probe is discussed.

NEXAFS is shown to be an excellent technique, of potentially widespread application, for the determination of the orientation of organic molecules intercalated in preferentially oriented thin films of polycrystalline, layered minerals. A NEXAFS study of [Mg2Al(OH)6]+C7H5O2 · nH2O, a layered anionic clay, is described. This material shows a transition from a layer spacing of 15.4 Å to only 9 Å at a remarkably low temperature (below 100°C). This is shown to be accompanied by a change in the angle of the plane of the benzoate molecule to the 00ℓ planes from 35° ± 10° to 0° ± 10°. The tilt of the benzoate anion in the room temperature structure demonstrates the presence of an interaction between the phenyl ring and the positively charged, brucite-like layers. Furthermore it is suggestive of the importance of hydrogen bonding in determining the interlayer spacing and stability.

A stable 8.4 Å hydrate of kaolinite was prepared by exchanging ethylene glycol for water in the 10.8 Å intercalate of ethylene glycol in kaolinite. The hydrate of kaolinite was characterized by XRD, FTIR and TGA/DSC. From the TGA data, one can estimate that there is 0.60 water molecule per Al2Si2O5(OH)4 units. The IR data suggest a similarity of the local environment of the intercalated water in this 8.4 Å hydrate of kaolinite and the 8.4 Å hydrate of nacrite previously described by Wada (1965).

A series of organo-montmorillonites and organo-hectorites was prepared by complete ion-exchange from the pure sodium form of the parent smectites. The organic cations were tetramethylammonium, trimethylated quaternary ammonium derivatives of the lysine and of the ornithine methyl esters, quaternarized polyammonium cations, or tetraphenylphosphonium (TPP). These organo-smectites were used as packing material for gas chromatography columns. Mixtures of light hydrocarbons (methane to n-butane; “C1” to “C4”) could be separated. The degree of separation depends on the presence of micropores or of organophilic mesopores. The BET surface area, the micropore and mesopore volumes, as well as the size distribution of micropores and mesopores were measured for several systems. As a general trend, the retention times of the light hydrocarbons decrease with an increase of the micropore volume. In the case of TPP-montmorillonite, characterized by a large mesopore volume but for which no microporosity could be detected, separation of longer linear hydrocarbons (n-pentane to n-octane) could also be achieved.

Ba-bearing clinoptilolite (with >2 wt. % BaO) occurs in Neogene marine siliceous sediments from ODP Leg 127 Site 795 in the Japan Sea. Ba-bearing clinoptilolite is formed by reaction of volcanic glass and Ba-rich pore water during burial diagenesis.