Brachiopoda and Lamellibranchiata of the Raritan clays and greensand marls of New Jersey /

Mode of access: Internet.

Gasteropoda and Cephalopoda of the Raritan clays and Greensand Marls of New Jersey /

Includes index.

The Mineralogy and Strength Characteristics of Selected Glaciolacustrine Clays in the Puget Sound Region

The combination of rainy climate, glaciolacustrine clays, and steep topography of the Puget Lowland creates slope stability issues for the regional population. Several glaciolacustrine deposits of laminated silt and clay of different ages contribute to the likelihood of slope failure. The glaciolacustrine deposits are generally wet, range in thickness from absent to >30m, and consist of laminated silt and clay with sand interbeds at the tops and bottoms, sandy laminae throughout the deposits, occasional dropstones and shear zones. The glaciolacustrine deposits destabilize slopes by 1) impeding groundwater flow percolating through overlying glacial outwash sediments, 2) having sandy laminae that lower strength by increasing pore pressure during wet seasons, and 3) increasing the potential for block-style failure because of secondary groundwater pathways such as laminae and vertical fractures. Eight clay samples from six known landslide deposits were analyzed in this study for their mineralogy, clay fraction and strength characteristics. The mineralogy was determined using X-ray Diffractometry (XRD) which revealed an identical mineralogic suite among all eight samples consisting of chlorite, illite and smectite. Nonclay minerals appearing in the X-ray diffractogram include amphibole and plagioclase after removal of abundant quartz grains. Hydrometer tests yielded clay-size fraction percentages of the samples ranging from 10% to 90%, and ring shear tests showed that the angle of residual shear resistance (phi_r) ranged from 11° to 31°. Atterberg limits of the samples were found to have liquid limits ranging from 33 to 83, with plastic limits ranging from 25 to 35 and plasticity indices ranging from 6 to 48. The results of the hydrometer and residual shear strength tests suggest that phi_r varies inversely with the clay-size fraction, but that this relationship was not consistent among all eight samples. The nature of the XRD analysis only revealed the identity of the clay minerals present in the samples, and provided no quantitative information. Thus, the extent to which the mineralogy influenced the strength variability among the samples cannot be determined given that the mineral assemblages are identical. Additional samples from different locations within each deposit along with quantitative compositional analyses would be necessary to properly account for the observed strength variability.

A straightforward wet-chemical route to the nanocomposites of general layered clays and metal sulfides

The nanocomposites of general layered clays and metal sulfides could be produced from reactions of the layered clay aqueous suspensions and water-soluble metal-thiourea complexes. The clay could be saponite, montmorillonite, hectorite and laponite, while the metal sulfide could be cobalt sulfide, nickel sulfide, zinc sulfide, cadmium sulfide, and lead sulfide. In the nanocomposites, the clay could be incorporated with the metal sulfide pillars and metal sulfide nanoparticles. (c) 2006 Elsevier B.V. All rights reserved.

The adsorption of phenolic and organotin compounds by clays and cation exchanged clays

Quaternary ammonium exchanged laponites (Quat-laponites) show selectivity in the adsorption of phenols and chlorinated phenols. Strong adsorbate-adsorbent interactions are indicated by adsorption isotherms. Adsorption of phenols and chlorinated phenols by Quat-smectites is greater than that by the Bi Quat-Smectites prepared in this study. It is thought that the quaternary ammonium exchanged smectite components of the Bi Quat-smectites interact with each other (adsorbent-adsorbent interactions) reducing the number of sites available for adsorbate-adsorbent interactions. Solidification/stabilisation studies of 2-chlorophenol show that a blend of ground granulated blast furnace slag and ordinary Portland cement attenuates 2-chlorophenol more effectively than ordinary Portland cement alone. Tetramethyl ammonium- (TMA-) and tetramethyl phosphonium- (TMP-) montmorillonites were exposed to solutions of phenol or chlorinated phenols. TMP- montmorillonite was the better adsorbent and preferentially adsorbed 4-chlorophenol over phenol. Hydration of the interlayer cations occurs to a greater extent in the TMA-montmorillonite than the TMP-montmorillonite restricting interlayer adsorption. Contrary to that observed for phenols and chlorinated phenols, the Quat-smectites were ineffective as adsorbents for triphenyltin hydroxide and bis(tributyltin) oxide at room temperature. Under microwave conditions, only bis(tributyltin) oxide was adsorbed by the quaternary ammonium exchanged smectites. Bis(tributyltin) oxide was adsorbed from ethanol on the surface of the smectite clays at room temperature and under microwave conditions. The adsorbate-adsorbent interactions were weak. Adsorption is accompanied by conversion of bis(tributyltin) oxide to a different tin(IV) species and the release of sodium cations from the montmorillonite interlayer region. Attempts to introduce conditions suitable for charge transfer interactions between synthesised quaternary ammonium compounds and 2,4,6-trichlorophenol are documented. Transition metal complex exchanged clays adsorb 2,4,6-trichlorophenol and phenol. Strong adsorbate-adsorbent interactions (Type I isotherms) occur when the adsorbate is 2,4,6-trichlorophenol and when the adsorbent is [Fe(bipy)3]2+ exchanged montmorillonite or [Co(bipy)3]3+ exchanged montmorillonite. The 2,2'-bipyridyl ligands of the adsorbents are electron rich and the 2,4,6-trichlorophenol is electron deficient. This may have enhanced adsorbate-adsorbent interactions.

Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

Petrology of weathered lower lias clays

In weak argillaceous rocks the unweathered strength may be barely sufficient to meet civil engineering reguirements and any reductjon due to weathering will be critical. This study investigates the weathering of the Lower Lias clays with particular reference to their petrography and engineering properties. Investigations revealed the Midland Basin of deposition to contain reasonable thicknesses of clay, relatively uniform in nature with a well developed weathered zone, From the available exposures, the weathering zone of the Blockley Clay pit was selected and sampled for laboratory investigations of; Structure, Mineralogy and Chemistry and Engineering Properties. The nature and orientation of the fissures in the unweathered clay were analysed. A close relationship was found to exist between the major joint set and the ground surface, with stress release due to excavation being almost negligible. Thin sections of the clay, examined for structural data, suggested that there exist layers or areas that have been disturbed as a result of density differences. Shear planes were found in both the unweathered and weathered clay, in the latter case often associated with remoulding of the material. A direct measure of remoulding was obtained from the birefringence ratio. The fabric was examined in closer detail using the scanning electron microscope. Mineralogy, as revealed by X-ray and optical techniques indicated illite as the dominant clay mineral, with kaolinite subsidiary; quartz, calcite, pyrite, chlorite/vermiculite are present as accessory minerals. Weathering changes this relationship, calcite and pyrite being removed early in the process, with illite being degraded. The cementing action of calcite and iron oxides was investigated however, this was shown to be negligible. Quantitative measurements of both fixed (with minerals) and free (oxide coatings) iron were obtained by atomic absorption, with the Fe 3+/ Fe2+ ratio obtained by Mossbauer spectroscopy, Evidence indicates that free iron oxide coatings only become important as a result of weathering with the maximum concentration in the very highly weathered material. Engineering index properties and shear strength values were taken throughout the profile, Relationships between moisture content and strength, liquid limit and iron (Fe) were obtained and a correlation between the weathering zomes and the shear strength/depth curve has been established.

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH 3OD and (CH2OD)2 in deuterated clay allows us to measure the diffusion of the CH3- and CH2-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.

Nondestructive measurement of water content and moisture migration of unsaturated red clays in South China

To reveal the moisture migration mechanism of the unsaturated red clays, which are sensitive to water content change and widely distributed in South China, and then rationally use them as a filling material for highway embankments, a method to measure the water content of red clay cylinders using X-ray computed tomography (CT) was proposed and verified. Then, studies on the moisture migrations in the red clays under the rainfall and ground water level were performed at different degrees of compaction. The results show that the relationship between dry density, water content, and CT value determined from X-ray CT tests can be used to nondestructively measure the water content of red clay cylinders at different migration time, which avoids the error reduced by the sample-to-sample variation. The rainfall, ground water level, and degree of compaction are factors that can significantly affect the moisture migration distance and migration rate. Some techniques, such as lowering groundwater table and increasing degree of compaction of the red clays, can be used to prevent or delay the moisture migration in highway embankments filled with red clays.

(Table 2) Relative contents of clay minerals in aeolian pelagic clays from the Pacific Ocean

For determining importance, composition, and history of aerosol material accumulation in formation of pelagic clays a study with use of light microscopy and scanning electron microscopy, X-ray diffractometry, and chemical methods has been carried out.

Grain size and mineral compositions of Pacific red clays

Hypotheses of origin of ocean deep red clays are under discussion. On an example of the Pacific Ocean grain size, mineralogy and chemical composition of clays are considered. It is shown that they formed from atmospheric dust and andesite pyroclastics. Accumulation of the clays occurred through deposition particle-by-particle and by pellet transport.

Growing spherulitic calcite grains in saline, hyperalkaline lakes : Experimental evaluation of the effects of Mg-clays and organic acids

Acknowledgements BP Exploration Co. is thanked for funding, and particularly the Carbonate Team (Anna Matthews, Teresa Sabato Ceraldi, and Darryl G. Green) for supporting this research and for fruitful discussions. Mark Anderson, Kim Rosewell, and Tony Sinclair (University of Hull) are thanked for laboratory assistance, and for SEM sample preparation and set-up respectively. The technical and human support from Prof. Jörg Hardege and Maggy A. Harley (University of Hull) was key to perform these experiments. We would like to acknowledge an anonymous reviewer for the detailed and constructive comments, and Brian Jones's editorial handling of the manuscript which is greatly appreciated.