Kaolinite was hydrothermally synthesized from two kinds of silica-alumina gels to examine the effect of the structure of the starting material. Two kinds of gels were prepared by precipitation at different pH conditions (pH = 9.6 and 4.2) from solutions containing water glass and aluminum sulfate. Na ions in the gels were removed with a resin before the hydrothermal treatment, but a slight amount of sulfate ions was still present in the gels. The nuclear magnetic resonance spectra of the starting gels suggested that the gel prepared at pH 9.6 consists of networks with alternating SiO4- and A1O4-tetrahedra (partially AlO6-octahedra), whereas the gel prepared at pH 4.2 consists of a sheet structure related to allophane. After the hydrothermal treatment at 220°C for 9 days, kaolinite particles with spherical shape were obtained from the former gel, and platy kaolinite was crystallized from the latter one. The difference in morphology of synthetic kaolinite was attributable to the structures of the starting gels, and the pH values in the hydrothermal reactions were not very significant to the morphology.

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.

Vermicular glaucony grains observed by transmission electron microscopy (TEM) show three irregularly alternating zones. Zone A has a high degree of linear orientation, no void space, and relatively defect-free lattice-fringe images. Zone B has an amalgamated bundle texture with a sub-parallel, linear orientation of bundles to each other and to zone A. Zone B has little or no void space, and lattice images appear to be a combination of those typical of zone C with minor amounts of modified zone A forms. Zone C has a randomly oriented, curved, and circular or semicircular bundle texture. In addition, zone C has much void space and curvilinear and linear lattice-fringe images with numerous defects, including edge dislocations. Such morphologic and crystallographic characteristics indicate that zones B and C probably comprise the glauconitic minerals of the vermicular glaucony grains, and that zone A comprises non-glauconitic micaceous minerals of higher structural order. Zone B is sharply demarcated from zone A, but B zone bundle textures merge gradationally to those of zone C. These spatial relationships suggest that zone B forms first on the surface of zone A. Sub-parallel orientation in the B zone could be produced by initial confinement between adjacent A zones. Once constraints change or are removed, the randomly oriented, curved, and semicircular or circular bundles of zone C develop.

In studies on the fate of aluminium in the environment, nontronite and saponite have been obtained by synthesis in reducing alkaline conditions close to those prevailing in poorly drained soils developed from limestones. The two minerals obtained have different structures and organizations corresponding to two different growth and/or maturation mechanisms. High-resolution transmission electron microscopy of ultrathin sections of a synthetic aluminous nontronite embedded in resin showed the presence of crystallites consisting of two to ten co-terminating parallel layers, indicating synchronous growth. Electron diffraction showed that the individual crystallites had hk-ordering, i.e., orientation of layers with respect to the six-fold pseudosymmetry of the unit cell. Deposits of a synthetic saponite included hk-ordered crystallites and crinkled films with turbostratic stacking. The two saponite phases had slightly different b dimensions. Lattice fringe images of sections of saponite embedded in resin showed a high angular disorientation of the layers in the stacking direction, suggesting multiple nucleation and growth of individual layers, subsequently aggregated with imperfect parallelism.

Exploration of the synthetic conditions of the aluminous nontronite indicated that calcium was essential for an hk-ordered product. Syntheses using potassium or sodium hydroxides and carbonates for pH control gave poorly organized nontronites. Hydrazine was not essential for nontronite formation, but better crystallized products—judging by their IR spectra—were obtained in its presence by maintaining reducing conditions in the early stages of synthesis. Attempts to prepare ferruginous beidellites under similar conditions to those in which aluminous nontronites formed were unsuccessful.

Magnetic fractionation, chemical, and structural analyses prove that alteration of ilmenite from Manavalakurichi deposit extends only up to the formation of pseudorutile with traces of rutile. The data indicate that ferrous to ferric iron transformation, ferric iron oxide formation, and iron removal contribute to the alteration sequence. The first two highly magnetic fractions are not unaltered ilmenite. A reduction in ilmenite unit cell volume indicates the ferrous-ferric conversion occurred during alteration.

A ferrous saponite (griffithite) from Griffith Park (California, USA) was treated with solutions of HCl (0.62, 1.25 and 2.5% by weight) at 25°C for 2, 6, 24 and 48 hours. The resulting solids were characterized by XRD, FT-IR spectroscopy, thermal analyses, SEM, TEM and nitrogen adsorption isotherms at 77 K, showing the destruction of silicate structure by the treatments. The free silica generated by these treatments was digested and determined in all samples. Several samples had specific surface areas up to 250 m2/g, with maximum values which are 10 times higher than the surface area of natural saponite (35 m2/g). A sudden decrease in specific surface areas was observed when free silica was digested, which indicates that free silica makes a very important contribution to the surface area of leached samples.

An improved regression method for the evaluation of standard free energies of formation (ΔG°f) of clay minerals is here proposed in an attempt to remove some of the limitations of the earlier method (Chen, 1975). Particularly, this method suggests a procedure for the assignment of rankings for Σ ΔG°f, i values. Moreover, an iterative least-squares fitting technique is applied to solve the exponential equation to obtain the estimated ΔG°f. The estimated ΔG°f data for the various standard clay minerals are derived and compared with data available in the literature; in general, there is good agreement between the values. It is also shown how the regression method can be extended to clay minerals of variable composition. The ΔG°f's for several such minerals have been evaluated; a large number of combination equations required for such computations have been listed, so that for other similar minerals the process of evaluation of ΔG°f is greatly simplified.

Monolayer to bilayer (MTB) and bilayer to pseudotrimolecular (BTP) transitions were observed for smectites exchanged with symmetrical tetraalkylammonium cations of increasing sizes: +NR4, where R = (CH2)nCH3, with 0 ≤ n ≤ 7. In the case of SWy-1, SHCa-1 and SWa-1, the variation in layer spacing observed from intercalation of tetramethylammonium up to tetraoctylammonium cations showed a behavior characteristic of smectites with homogeneously distributed interlayer cations. In the case of STx-1, the change in interlayer spacing with the increase of the alkyl chain length was characteristic of a very high charge heterogeneity. Higher charge smectites (SAz-1 and SCa-3, CEC > 1.20 mmol/g) were found to have decreasing cation exchange with increasing cation size, resulting in a "leveling off’ of the interlayer spacing toward larger cations. The MTB and BTP transitions were used to determine the internal surface area of various smectites. The proposed method was found to be a quicker and simpler alternative to the polar liquid sorption method for this measurement, but was ineffective for high-charge smectites (CEC > 1.20 mmol/g).

A synergistic mechanism for the retention of organic and inorganic pollutants in clays is discussed in this paper. The mechanism of adsorption of cis- or trans- 1,2-dichloroethylene vapor (CDE or TDE, respectively) by hydrated smectite clay (hectorite) exchanged with Pb2+, Hg2+, Cd2+, Ca2+, Ag+, or Na+ has been investigated by simultaneously measuring chlorohydrocarbon uptake and water desorption isotherm and by recording the infrared (IR) spectrum of the adsorbed phase. Hydrated hectorite saturated with divalent cations adsorbs about 55% more CDE or 35% more TDE than those saturated with monovalent cations. The quantity of chlorohydrocarbon adsorbed is also a function of the hydration of the clay interlayer space. When dehydrated, hectorite does not adsorb CDE or TDE. Upon long outgassing at room temperature or even at 100°C, the characteristic IR bands of clays with adsorbed chlorohydrocarbon, although much weakened, are still observable. The ratio of the amount of water desorbed to the amount of chlorohydrocarbon adsorbed varied from about 0.22 to 0.34. A shift of the center of gravity of the hydration water OH stretching frequency towards a higher wavenumber and of the asymmetric CC1 stretching vibration toward a lower frequency suggest that the formation of hydrogen bonds between CDE or TDE and water is the driving force for adsorption and that the cation-dipole interaction does not play a major role.

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.

Oxygen isotope composition of three types of unique nodules which consist of amorphous silica-apatite, cristobalite-apatite and tridymite-apatite associations interspersed amidst basaltic pyroclastics from the Har Peres volcano, Golan Heights, Israel is reported. Unusual isotopic temperature (75°C estimated from oxygen isotope fractionation between cristobalite (δ18O = +25.5‰)-apatite (δ18O = +12.9‰) pair suggests that the nodule was not formed by present-day pedogenesis as has been previously proposed, but was a xenolith incorporated probably from the underlying siliceous phosphorites at a higher temperature. An observed negative oxygen isotopic fractionation (δ18O = −5.1‰) between tridymite (δ18O = +9.9‰) and associated apatite (δ18O = +15.0‰) is indicative of the nodular formation under disequilibrium conditions. A plausible mechanism of formation of the apatite (and calcite) associated with tridymite is an epitaxial overgrowth on template tridymite of magmatic origin under the current weathering regime. Oxygen isotopic evidence indicates a complicated origin for the nodules.

Sorption parameters are important components of models used to predict mass transport through dense or compacted earthen materials. These parameters are, however, generally determined in batch tests with loose, unconsolidated materials. Here we directly measure, using a specially designed cell, the extent of Cs+ sorption on bentonite compacted to a series of densities ranging from 0.50 to 1.50 Mg/m3, and compare the results with those obtained from batch tests with loose bentonite. The clay was saturated with a Na-Ca-Cl-dominated solution with an effective ionic strength of 220 mol/m3. The sorption data were expressed as distribution coefficients, Kd. Over the clay density range examined, Kd values for Cs+ with compacted clay are about one-half to one-third the value of those with loose clay. The lower sorption on compacted clay is attributed to small and occluded pores that Cs+ cannot enter; thus it cannot access the entire volume, or all the sorption sites, of compacted clay. The data suggest that reasonable estimates of Kd with compacted clay can be obtained by scaling down the Kd values measured on loose clay by a factor na/n, where na is the accessible porosity and n the total porosity of compacted clay.

The substitution of Fe3+ in the kaolinite structure is studied by EPR spectrometry and by FTIR spectrometry on a large set of kaolins from different origins (sedimentary and primary ores, soil kaolins). The IR bands at 3598 and 875 cm−1, observed in the literature only in the case of disordered kaolins or in Fe-rich environments (synthetic, lateritic), are revealed by high-resolution IR analysis, whatever the origin and the total Fe content of the samples. The EPR bands corresponding to Fe3+ substituted in sites II of the octahedral sheet increase when the IR absorbance near 3600 cm−1 increases. Two IR absorption bands near 4465 cm−1 and 7025 cm−1 are observed for the first time, both in transmission and diffuse reflectance on all samples. These bands are assigned to the combination of the 3598 and 875 cm−1 bands and to the first harmonic of the band at 3598 cm−1, respectively. The area of the band at 4465 cm−1 in diffuse reflectance is quantitatively correlated to the abundance of Fe3+ located in centers II as measured by ESR. This directly confirms the assignment of the two IR bands at 3598 and 875 cm−1 to OH stretching and deformation vibration bands in octahedral FE3+ environment in the kaolinite structure, respectively. Effects due to the size of particles and to the main kaolins impurities on the near infrared spectra, are also discussed.

X-ray absorption fine structure (XAFS) spectra were collected on a series of ferrihydrite samples prepared over a range of precipitation and drying conditions. Analysis of the XAFS pre-edge structures shows clear evidence of the presence of lower coordination sites in the material. These sites, which are most likely tetrahedral, are believed to be at the surface and become coordination unsaturated (CUS) after dehydroxylation. With chemisorbed water molecules, the CUS sites become the crystal growth sites responsible for the phase transformation of ferrihydrite to hematite at low temperatures. On the other hand, when impurity anions such as SiO4−4 are present in the precipitation solution, the CUS sites may instead absorb the impurity anions, thereby blocking the crystal growth sites and inhibiting the formation of hematite.

A kaolin clay occurring in Carboniferous mudstone near the Jiangshan-Shaoxing deep fault in Zhejiang Province, eastern China was characterized by XRD and IR. Although the dominant mineral appeared to be kaolinite, IR also suggested the possible occurrence of nacrite. This was confirmed by forming intercalation complexes with potassium acetate and with hydrazine hydrate, both water complexes having the same characteristic spacing at 8.35 Â. Different particle size fractions of the kaolin clay were studied and the results indicated that nacrite content increased with increasing particle size. This occurrence of nacrite is consistent with previous findings of the polytype in high temperature and pressure environments.

The amount of Mn2+ adsorbed or removed from solution by birnessite is several times greater than its reported cation exchange capacity. Extractability of the sorbed Mn2+ decreases with aging. It is uncertain whether the sorbed Mn2+ is oxidized on the surface or incorporated into the structure of birnessite. Using X-ray powder diffractometry and transmission electron microscopy, a study was conducted to examine the mineralogical alteration of birnessite after treatment with various concentrations of MnSO4 and solution pH.

The sorbed Mn2+ was not directly oxidized and remained on the birnessite surface. The sorption of Mn2+ was followed by alteration of birnessite with the formation of new Mn minerals. The specific Mn minerals formed were governed by the pH of the reaction, and the rate of the transformation was determined by Mn2+ concentration and pH. Nsutite and ramsdellite were identified at pH 2.4, crypto-melane at pH 4, groutite at pH 6, and manganite at pH 8. Other Mn minerals formed at these and other pH levels could not be identified. As the concentration of Mn in the solution decreased, the time required to form new minerals from the birnessite increased. The newly formed phases were the result of structural conversion since dissolution of birnessite and reprecipitation of new phases were not observed.

Commercial spreadsheet programs allow calculation of reasonable reaction paths for weathering of silicate minerals in a dilute acidic aqueous solution. These calculations use reaction coefficients of simplified weathering reactions and ignore speciation in the aqueous solution. The method is illustrated using the example of dissolution of microcline. When plotted on a log-log activity diagram, the obtained reaction paths are clearly curved, unlike the straight lines shown in most recent geochemistry textbooks. The calculated reaction paths are strongly dependent on the initial pH of the solution. At higher pH the speciation in the solution must be included in the calculations. The most important speciation reactions (the dissociation of H2O and H4SiO4) can be easily included using commercial mathematical programs. p ]The presented examples include closed systems with different initial pH values and an open system case describing the evolution of a soil profile. All reaction paths calculated using the simplified methods agree well with those obtained using sophisticated modeling codes.

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.

Hydration behavior of Na-smectite crystals synthesized at a pressure of 5.5 GPa and temperatures of 1400°–1500°C was examined by X-ray powder diffraction at various relative humidities (RH) in the range of 0–100%. The basal spacing of the Na-smectite crystal increased stepwise with increase in RH. The reflections observed were only normal reflections of a single or dual hydration states of smectite. No irrational, intermediate, or asymmetrical reflections were observed. The simple hydration behavior, not known for natural smectite with fine particle sizes and low crystallinity, indicates that the Na-smectite crystals are as perfect as common inorganic crystals with an ordered structure.