An X-ray diffraction study of vermiculitized micas in ultramafic and mafic intrusive rocks from Cheongyang, Korea, shows the following weathering sequence: mica → ordered mica/vermiculite interstratification → vermiculite. Electron microprobe analyses show the general trends of K leaching and Ca enrichment with increased weathering. The vermiculitization of phlogopite from ultramafic rocks proceeds by means of a continuous decrease in Al-for-Si tetrahedral substitutions and a progressive increase in Al-for-(Fe2+ + Mg) octahedral substitutions in the early stage of weathering. These substitutions occur to compensate for the excess of negative charge in the mica-like layer, in agreement with currently accepted vermiculitization mechanisms. They change to a slight increase of Al-for-Si tetrahedral substitutions in the late stage of the vermiculitization of phlogopite, owing to the oxidation of Fe despite its low content. However, the behavior of Fe in the late stage of the transformation of biotite into vermiculite is significantly different; that is, Fe increases substantially. The reason for this Fe increase in the late stage remains unresolved. Recalculations of the structural formulas on the basis of several assumptions indicate that the oxidation of Fe is necessary for the vermiculite derived from biotite to form the reasonable structural formulas.

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.

The “modified chlorite structure” forms by the dehydroxylation of the interlayer octahedral sheet of magnesian chlorite at around 500°C and results in a structure with a basal spacing near 27 Â (Brindley and Chang 1974). This process involves drastic textural modifications as indicated by gas adsorption experiments which reveal the formation of structural micropores. Infrared spectroscopy as well as thermogravimetry and mass spectrometric analysis show that these micropores are filled with molecular atmospheric water, carbon dioxide, nitrogen, argon and hydrocarbons which condense once the samples cool down. A high temperature treatment is needed in order to release the different phases. A heterogeneous dehydroxylation mechanism is proposed in which micropores are formed in donor regions and magnesium and oxygen are concentrated in acceptor regions. This leads to a 27 Å structure with micropore zones and enriched interlayer oxide zones alternating along the z-axis of the mineral.

Surface diffusion, or migration within the electrical double layer next to mineral surfaces, is often invoked as a significant contributor to the overall diffusion coefficient in compacted clays, particularly where model predictions underestimate measured diffusion coefficients. The potential for surface diffusion of Sr2+, Ca2+ and Na+ on three clays compacted to dry bulk densities of 1.25 and 1.60 Mg/m3 was examined. The clays were a bentonite, an illite/smectite, and a glacial lake clay (composed mainly of smectite, illite, kaolinite and quartz). The clays were saturated with a Na-Ca-Cl-dominated synthetic groundwater solution with an effective ionic strength of 220 mol/m3. Total intrinsic diffusion coefficients for the cations were determined from their steady-state flux through compacted clays, and apparent diffusion coefficients were obtained from the time-lag technique. Models of diffusive transport in compacted clays, based only on diffusion in the pore solution, adequately described the diffusion data for all clays and diffusants, and there was no need to invoke other transport mechanisms, like surface diffusion. The data indicate that surface diffusion is not a significant transport mechanism in compacted clays at least to a clay density of 1.60 Mg/m3.

The crystal structure of cronstedtite-3T from Kutná Hora (Bohemia, Czechoslovakia), space group P31, was refined to Rw(all) = 3.1% for 1336 independent diffractions. There are two and three independent tetrahedral and octahedral positions, respectively, in this structure. The tetrahedra are occupied by 0.75 Si and 0.25 Fe while the octahedra are uniformly occupied by Fe. The refinement process was hindered by two problems: a “strong” superposition structure (all atoms of the octahedral sheets, i.e., ÷ 70% of the total diffraction power contribute almost solely to the family diffractions with mod(h–k, 3) = 0), and a slight disorder of the investigated crystal. The first problem was resolved by a preliminary block-diagonal refinement procedure where the atoms coinciding in the superposition structure were separated into individual blocks. The second problem was resolved by including two scale factors into the final full-matrix refinement: one for family diffractions, the other for the remaining ones which are characteristic for this polytype.

The effects of three organic ligands on the adsorption of copper on Ca-montmorillonite were studied. The results indicate that these effects include three different processes:

1. 1) Enhanced uptake of positively charged copper-ligand complexes by ion-exchange.

2. 2) Formation of ternary surface complexes involving surface aluminol groups.

3. 3) Inhibited uptake due to competition between the surface ligands and the dissolved ligands for dissolved copper.

Ethylenediamine promotes copper uptake by ion-exchange at low pH but tends to suppress adsorption at aluminol groups by ligand competition at high pH. The same mechanisms are operative for β-alanine; however, the uptake of Cu(β-ala)+ by ion-exchange is not promoted by the attached ligand. The influence of malonate includes both ligand competition and formation of ternary complexes. A quantitative interpretation based on the surface complexation model using the least-squares programs FITEQL (Westall, 1982) and GRFIT (Ludwig, 1992) is presented. The obtained equilibrium constants are listed in Tables 2b and 3.

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.

Kaolinite from the Black Ridge, Clermont, has relatively low δ18O (12.3‰ to 14.8‰) and very low δD values with a large variation (−120‰ to −85‰). Comparison of these data with those from the nearby Denison Trough and elsewhere in eastern Australia, together with previous studies of the mineralogy of the sedimentary rocks, suggests that extensive kaolinization of the “White Section” resulted from weathering during the Late Triassic to Early Jurassic periods. The relatively large variation in δD values of kaolinite probably derives from post-formational isotopic exchange with other fluids.

The similarity between δ18O values of kaolinites from Black Ridge and from the Denison Trough suggests that the small Miclere-Black Ridge basin may have been part of the Denison Trough before the Late-Triassic inversion. The preservation of original δD values in kaolinite at Black Ridge indicates that unlike the Denison Trough, which was reburied at more than 1000 m, the Miclere-Black Ridge basin was not rebuffed at great depth during the Mesozoic period.

Clay samples of greenish colour were collected from submarine hydrothermal chimneys of the Galapagos Rift and Mariana Trough. Mineralogical and chemical investigations of the clay by scanning and transmission electron microscopy, X-ray diffraction, differential thermal analysis, infrared-spectros-copy, X-ray fluorescence, and determination of specific surface area, and oxygen isotope composition identify it as a well crystallized nontronite. This nontronite of hydrothermal origin has a nearly monomineralic character, a low Al-content, and a formation temperature of 21.5 to 67.3°C. The most remarkable characteristic, however, of the nontronite deposit is its microstructure, a network of microtubes composed of fine frequently folded clay sheets. These delicate filaments show close similarity in size and form to sheath forming bacteria. The correlation between clay mineral and chemical characteristics, as well as biological conditions at marine hydrothermal smoker chimneys, let us suggest that Fe oxidizing, sheath forming bacteria are playing a decisive role in nontronite formation at these sites.

Clay minerals from the MacAdams Sandstone, Kettleman North Dome, California, have been studied by electron microscopy. The clay minerals fill pore space associated with fractured and brecciated clasts of K-feldspar. Curved packets of muscovite and kaolinite are caused by deformation of detrital muscovite that resulted in opening of fissures subsequently filled with dominant kaolinite and minor intergrown mixed-layer illite/smectite (I/S). Regions of authigenic R1 I/S (rectorite) with characteristic ~20 Å periodicity are intergrown with kaolinite in microfissures within K-feldspar or detrital muscovite. Clusters of small grains of muscovite with nearly ideal composition occur as stacks and intergrown with kaolinite and are tentatively inferred to be authigenic. Contrary to previous reports, no illite was found in these samples.

Electron microprobe analyses previously obtained on Kettleman Dome “illite” and subsequently used as a prime example of analyses of illite rich in excess interlayer water (H2O) and hydronium ion (H3O+) are shown to have been obtained on mixtures, and are not representative of the actual clay mineral compositions. Previous conclusions regarding significant H3O+ and H2O contents of illite are invalid because of inaccuracies inherent in bulk and EMPA analyses of illite, and do not affect arguments regarding the metastability of illite. Hydronium substitution should be favored via the reaction H2O + H+ = H3O+ only in highly acidic fluids. Ordinary illite forming in sedimentary environments with carbonates and iron oxides is unlikely to have significant H3O+ substituted for K+.

The hydrolysis of 2-(2-trichlorosilylethyl)pyridine (TCSEP) or 3-aminopropyltrimethoxysilane (APTMS) yields a complex mixture of oligomers, the composition of which is a function of time. 29Si NMR measurements show that the same oligosilsesquioxanes can be obtained from both compounds after prolonged hydrolysis. Ion exchange by montmorillonite with the pillaring solution obtained from TCSEP results in partial intercalation, with a noticeable fraction of the clay exchange sites occupied by protons not by the Si cationic species. Calcination of this pillared clay results in a mixture of phases showing 1.86 or 1.56 nm basal spacings. Pillaring of the same montmorillonite by the solution obtained by partial hydrolysis of APTMS results in a homogeneous solid with a basal spacing of 2 nm, which reduces to 1.65 nm upon calcination above 773 K. The microporous volume (pores < 1 nm) of these Si-clays, determined after calcination at 773 K, 0.15 ml/g for the PILC obtained from TCSEP, and 0.186 ml/g for the PILC obtained from APTMS is comparable to that measured for Al or Zr pillared clays. A better thermal stability is observed for the clay pillared by APTMS, which retains a large microporosity (0.167 ml/g) up to 973 K in air. These Si-pillared clays show a small number of weakly acidic sites and some strongly acidic sites retaining ammonia up to 723 K, which are most likely localized on the clay layers.

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.

A new, well-ordered, thermally robust ethylene glycol intercalate of kaolinite was formed by refluxing the dimethyl sulfoxide intercalate of kaolinite (Kao-DMSO) with dry ethylene glycol (EG). This new phase (Kao-EG 9.4 Å) which is characterized by a d001 of 9.4 Å is distinct from a previously reported ethylene glycol intercalated phase of kaolinite (Kao-EG 10.8 Å) which has a d001 of 10.8 Å. The characterization of these two phases was studied by XRD, NMR, FTIR, and TGA/DSC. It was found that the concentration of water in the ethylene glycol reaction media played a crucial role in governing which of the phases predominated. Water favored Kao-EG 10.8 Å formation, while anhydrous conditions favored the formation of Kao-EG 9.4 Å. It is hypothesized that Kao-EG 9.4 Å is a grafted phase resulting from the product of the condensation reaction between an aluminol group on the interlamenar surface of kaolinite and the alcohol group of ethylene glycol. Ethylene glycol units would be attached to the interlamellar surface of kaolinite via Al-O-C bonds. The Kao-EG 9.4 Å phase was found to be resistant to both thermal decomposition up to 330°C and also, once formed, in the absence of interlamellar water molecules, to decomposition by hydrolysis in refluxing water.

This paper compares the results of 27Al nuclear magnetic resonance spectroscopy (NMR) and Al-K-edge X-ray Absorption Near Edge Structure (XANES) of natural imogolite and allophanes and some crystalline reference minerals. All soil allophanes studied contain 4-coordinated Al (AlIV). The highest relative proportion of AlIV, 21% of the total Al, was found in Si-rich allophane. This value is close to that found in spring allophanes, which were previously considered to be different from soil allophanes. For a quantitative determination of the AlIV/Altotal ratio, NMR is more reliable than XANES, because of the sensitivity of the chemical shift to low AlIV concentrations, but XANES may be used even if paramagnetic impurities (mostly Fe) are present. Al-K XANES also yields more information than NMR on the local environment of AlVI and especially site multiplicity. AlVI XANES of imogolite and allophanes are similar regardless of the Al/Si ratio. They yield two well-resolved resonances with maxima near 1568 and 1570 eV, which indicates the presence of a unique AlVI site by comparison with crystalline references. The presence of only one AlVI site indicates that imogolite and allophanes have an octahedral sheet with a structure similar to 2/1 dioctahedral phyllosilicates but different from gibbsite or kaolinite, previously considered as structural analogues. The 27AlIV MAS NMR peak maxima of allophanes are between 58.6 and 59.8 ppm, in the range observed for crystalline and amorphous framework alumino-silicates, and less positive than those of sheet silicates, which are typically in the range 65–75 ppm. 27Al-H1 CPMAS NMR spectra suggest that both AlIV and AlVI have Al-O-H linkages.

Nacrite crystals from a vug within a matrix of dickite at Red Mountain near Silverton, Colorado, have a = 8.906(2), b = 5.146(1), c = 15.664(3) Å, β = 113.58(3)°, V = 657.9(3) Å3, and space group Cc. The structure was solved by direct methods to determine phase angles, followed by electron density maps to locate all atoms. Refinement by least-squares ceased at R = 4.5%. Each 7 Å layer has structural detail very similar to those of dickite and kaolinite, although nacrite stacking is based on — a/3 interlayer shifts along the 8.9 Å axis (with octahedral cations alternating between the I and II sites in successive layers), whereas dickite and kaolinite are based on shifts of — a/3 along the 5.1 Å axis (with octahedral cations in the same set of sites in each layer). The angle of tetrahedral rotation is 7.8°, and the octahedral counterrotations are 7.6° and 8.1°. The H+ protons were located on DED maps. The inner 0..H1 vector points exactly toward the vacant octahedron and is depressed — 18.6° away from the level of the octahedral cations. All three surface OH groups have 0...H vectors at 50° to 66° to (001), although OH2 may not participate in interlayer hydrogen bonding. All three interlayer OH-H-O contacts are bent to angles between 132° and 141° and form contacts between 2.94 and 3.12 Å. The interlayer separation of 2.915 Å is slightly larger than in dickite, interpreted as due to a less favorable meshing of the oxygen and hydroxyl surfaces in nacrite—a direct consequence of layer shifts along the 8.9 Å axis.

Interlayer cations and moisture content greatly influence the molecular vibrations of H2O in montmorillonite as shown through reflectance spectroscopy in the infrared. The absorptions due to H2O have been studied in montmorillonites exchanged with H, Na, Ca, Mg and Fe3+ interlayer cations under variable moisture environments. Band assignments have been made for absorptions in the 3 µm region due to structural OH vibrations, symmetric and asymmetric H2O stretching vibrations and the H2O bending overtone. Changes in the energies of the absorptions due to H2O stretching vibrations were observed as the samples were dehydrated by reducing the atmospheric pressure. Absorptions near 3620 cm−1 and 3550 cm−1 have been assigned to water bound directly to cations (inner sphere) and surface-bonded H2O and absorptions near 3450 cm−1 and 3350 cm−1 have been assigned to additional adsorbed water molecules. Band assignments have been made for combination bands in the near-infrared as well. Absorptions near 1.41 μm and 1.91 μm are assigned to bound H2O combination bands, while the shoulders near 1.46μm and 1.97 μm are assigned to combinations of additional H2O molecules adsorbed in the interlayer regions and along grain surfaces.

Hydrotalcite (HT) interlayered with hexacyanoferrate(II) ions ([Mg4.62Al1.52(OH)12][(Fe(CN)6)0.30-(CO3)0.29]) has been synthesized from the carbonate-HT ([Mg4.52Al1.50(OH)12][(CO3)0.77]) through double ion exchange reactions, and the products have been studied by chemical and physical methods. Mössbauer spectroscopy shows that hexacyanoferrate(II) is held rigidly in the interlayer by electrostatic forces and is characterized by a singlet at 0.01 mm s−1 at 80 K. X-ray diffraction shows an increase of the basal spacing (d003 from 0.78 to 1.1 nm following exchange. Hexacyanoferrate(II) in the interlayer was oxidized to hexacyanoferrate(III) (up to 20%) by dioxygen on dehydrating the interlayer either by drying at 70°C or by washing with nonaqueous solvents like acetone or ethanol. The CN (ν6) band of hexacyanoferrate(II) and (III) is found at 2036 cm−1 and 2112 cm−1, respectively. The presence of an absorption band at 2080 cm−1, assigned to free cyanide anions in the interlayer, suggests that the hexacyanoferrate(II,III) complexes are not inert in the interlayer, cyanide ligands being substituted with either water or hydroxyls. Oxidation and ligand exchange of the hexacyanoferrate(II) are also indicated by Mössbauer spectroscopy.

The acid hydrolysis products of trioctahedral fluorohectorite and phlogopite have been investigated by XRD, MAS NMR spectroscopy and nitrogen BET surface area analysis in an effort to assess the relative importance of edge attack and gallery access mechanisms. A dramatic loss of X-ray crystallinity and the formation of Q3 and Q4 SiO4 sites accompanied the depletion of Mg2+ from the octahedral sheet of both 2:1 layered structures. Depending on the extent of hydrolysis, the products derived from fluorohectorite exhibited surface areas up to 208 m2/g, whereas phlogopite hydrolysis products gave values <20 m2/g. The dramatic differences in surface areas were not related to differences in hydrolysis mechanisms. 19F MAS NMR studies indicated that the hydrolysis of fluorohectorite occurred primarily by an edge attack mechanism equivalent to the hydrolysis pathway for phlogopite. A gallery access mechanism contributed to the hydrolysis of fluorohectorite only at the later stages of octahedral Mg2+ depletion. Solvation effects appeared to be important in determining the surface areas of the reaction products derived from the swelling (fluorohectorite) and non-swelling (phlogopite) precursors.

2H NMR spectra of synthetic deuterated kaolinite have been collected in the temperature range from 150 K to 350 K. Hydroxyl groups show a Pake doublet pattern with an asymmetry factor of 0. They are almost fixed spatially, and undergo a wobbling motion with increasing temperature. The quadrupole coupling constant is 273 ± 3 kHz at 150 K, which indicates that interlayer hydrogen bonding is relatively weak.

Submicron-sized (~3–60 nm) powders of Al-substituted magnetite were synthesized in the laboratory by precipitation methods by mixing appropriate molar volumes FeCl2, FeCl3 and AlCl3 solutions and precipitating with 20% NH4OH. Precipitates were dialyzed for 48 hr to remove excess salts and then freeze-dried. The nominal Al mole fractions [Als = Al/(Al + Fe)] in the initial precipitate ranged from 0.001 to 0.42. Portions of the resulting powders were heated sequentially in air at 400° and 500°C. Powders were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), and visible and near-IR reflectance spectroscopy. Solubilities were determined in ammonium oxalate (pH = 3) and dithionite-citrate-bicarbonate (DCB) solutions. As determined by XRD, the mineralogy of precipitated powder samples was predominantly magnetite. Powders having Als > 0.20 contained minor goethite and a poorly crystalline iron oxide phase (ferrihydrite?), and powders having Als > 0.25 also contained gibbsite. The color of the magnetites was black throughout the range of Al-substitution. Powders heated to 400°C were reddish brown; Munsell colors ranged from 5R 2/2 to 10R 3/4 for Als from 0.1–41.5%, respectively. By XRD, these powders were maghemite, but hematite was also detected by Mössbauer spectroscopy. XRD and Mössbauer data indicate powders heated to 500°C are hematite; their Munsell colors are not noticeably different from the corresponding 400°C samples. Mean crystallite dimensions (MCDs) of the magnetite powders increase with the Al mole fraction from ~10 nm for Als = 0.001% to a maximum value of 35 nm for Als = 0.15 and decrease slightly with further increasing Al substitution. Heating magnetite powders to 400°C did not change the MCDs significantly. Heating to 500°C resulted in hematites having MCDs larger than those for corresponding precursor magnetites for Als < 0.10. The opposite is true for hematites derived from magnetites having Als > 0.10. For hematite powders with Als > 0.05, MCD decreased with increasing Al-substitution. Solubilities of powders in oxalate solutions were independent of Al content and decreased in the order unheated samples (mostly magnetite) >400°C-heated samples (maghemite + hematite) >500°C-heated samples (hematite). All powders dissolved completely in DCB. The low crystallinity of the magnetite powders and the presence of ferrous iron are responsible for their relatively high solubility in oxalate solutions.