Special reports on the mineral resources of Great Britain.

v.31 Ball clays -- v.32 Granites of Scotland -- v.33 Synopsis of the mineral resources of Scotland -- v.34 Rock wool -- v. 35 Limestones of Scotland -- v.36 Cambro-Ordovician limestones and dolomites of the Ord and Torran areas, SKye and the Kishorn area, Ross-Shire -- v.37 Limestones of Scotland : chemical analyses and petrography

Using Terrestrial LiDAR to Monitor Erosion within the Gold Basin Landslide Complex, Verlot, WA

In 2014 the United States Forest Service closed the Gold Basin Campground of western Washington in an effort to protect the public from unstable hillslopes directly adjacent to the campground. The Gold Basin Landslide Complex (GBLC) is actively eroding via block fall, dry ravel, and debris flows, which contribute sediment into the South Fork of the Stillaguamish River. This sediment diminishes the salmonid population within the South Fork of the Stillaguamish River by reducing habitable spawning grounds, which is a big concern to the Stillaguamish Tribe of Indians. In this investigation, I quantified patterns of degradation and total volume of sediment erosion from the middle lobe of the GBLC over the period of July 2015 through January 2016 using terrestrial (ground-based) LiDAR (TLS). I characterized site specific stratigraphy and geomorphic processes, and laid the groundwork for future, long-term monitoring of this site. Results of this investigation determined that ~ 4,800m3 of sediment was eroded from the middle lobe of the GBLC during the 6 month study period (July 2015 – January 2016). This erosion likely occurred from debris flows, raveling of poorly sorted sand and gravel deposits and block failures of high plasticity silts and clays, and/or other mass wasting mechanisms. The generalized stratigraphic sequence in the GBLC consists of alternating massive beds of sand and gravel with silts and clays. The low permeability of these silts and clays provide a perfect venue for groundwater to percolate, as I observed during field investigations, which likely contributes to the active instability of the hillslopes. Continued monitoring and mapping of this complex will lead to viable information that could help both the United States Forest Service and the Stillaguamish Tribe.

The Ledgewood-Bonair Landslide toe and where did it go? A case study in littoral sediment budgets from a deep-seated landslide in Island County, Washington

On the morning of March 27th, 2013, a small portion of a much larger landslide complex failed on the western shoreline of central Whidbey Island, Island County, Washington. This landslide, known as the Ledgewood-Bonair Landslide (LB Landslide), mobilized as much as 150,000 cubic meters of unconsolidated glacial sediment onto the coastline of the Puget Sound (Slaughter et al., 2013, Geotechnical Engineering Services, 2013). This study aims to determine how sediment from the Ledgewood-Bonair Landslide has acted on the adjacent beaches 400 meters to the north and south, and specifically to evaluate the volume of sediment contributed by the slide to adjacent beaches, how persistent bluff-derived accretion has been on adjacent beaches, and how intertidal grain sizes changed as a result of the bluff-derived sediment, LiDAR imagery from 2013 and 2014 were differenced and compared to beach profile data and grain size photography. Volume change results indicate that of the 41,850 cubic meters of sediment eroded at the toe of the landslide, 8.9 percent was redeposited on adjacent beaches within 1 year of the landslide. Of this 8.9 percent, 6.3 percent ended up on the north beach and 2.6 percent ended up on the south beach. Because the landslide deposit was primarily sands, silts, and clays, it is reasonable to assume that the remaining 91.1 percent of the sediment eroded from the landslide toe was carried out into the waters of the Puget Sound. Over the course of the two-year study, measurable accretion is apparent up to 150 meters north and 100 meters south of the landslide complex. Profile data also suggests that the most significant elevation changes occurred within the first two and half months since the landslides occurrence. The dominant surficial grain size of the beach soon after the landslide was coarse-sand; in the years following the landslide, 150 meters north of the toe the beach sediment became finer while 100 meters south of the toe the beach sediment became coarser. Overall, the LB Landslide has affected beach profile and grain size only locally, within 150 meters of the landslide toe.

Geology and landslide geomorphology of the Burpee Hills, Skagit County, Washington, USA

Landforms within the Skagit Valley record a complex history of land evolution from Late Pleistocene to the present. Late Pleistocene glacial deposits and subsequent incision by the Skagit River formed the Burpee Hills terrace. The Burpee Hills comprises an approximately 205-m-thick sequence of sediments, including glacio-lacustrine silts and clays, overlain by sandy advance outwash and capped by coarse till, creating a sediment-mantled landscape where mass wasting occurs in the form of debris flows and deep-seated landslides (Heller, 1980; Skagit County, 2014). Landslide probability and location are necessary metrics for informing citizens and policy makers of the frequency of natural hazards. Remote geomorphometric analysis of the site area using airborne LiDAR combined with field investigation provide the information to determine relative ages of landslide deposits, to classify geologic units involved, and to interpret the recent hillslope evolution. Thirty-two percent of the 28-km2 Burpee Hills landform has been mapped as landslide deposits. Eighty-five percent of the south-facing slope is mapped as landslide deposits. The mapped landslides occur predominantly within the advance outwash deposits (Qgav), this glacial unit has a slope angle ranging from 27 to 36 degrees. Quantifying surface roughness as a function of standard deviation of slope provides a relative age of landslide deposits, laying the groundwork for frequency analysis of landslides on the slopes of the Burpee Hills. The south-facing slopes are predominately affected by deep-seated landslides as a result of Skagit River erosion patterns within the floodplain. The slopes eroded at the toe by the Skagit River have the highest roughness coefficients, suggesting that areas with more frequent disturbance at the toe are more prone to sliding or remobilization. Future work including radiocarbon dating and hydrologic-cycle investigations will provide a more accurate timeline of the Burpee Hills hillslope evolution, and better information for emergency management and planners in the future.

Zr-Laponite pillared clay-based nickel catalysts for methane reforming with carbon dioxide

Zr-Laponite pillared clays were prepared and used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of supports and catalysts were systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron spectroscopy (TEM) techniques. The catalytic performance and carbon deposition were investigated. It is found that Zr-Laponite pillared clays are promising catalyst supports for carbon dioxide reforming of methane. The pore structure and surface properties of such supports greatly affect the catalytic behaviors of catalysts derived. Carbon deposition on catalysts was also affected by the property and structure of supports. The sintering of nickel metal and zirconia was another factor responsible for catalyst deactivation. This new-type nickel supported catalyst Ni/Zr-Laponite(8), with well-developed porosity, gave a higher initial conversion and a relatively long-term stability, and is therefore a promising catalyst for potential application to carbon dioxide reforming of methane to synthesis gas. (C) 2002 Elsevier Science B.V All rights reserved.

Sorption and desorption behaviour of acetochlor in surface, subsurface and size-fractionated soil

Pesticides leaching through a soil profile will be exposed to changing environmental sorption and desorption conditions as different horizons with distinct physical and chemical properties are encountered. Soil cores were taken from a clay soil profile and samples taken from 0.0 to 0.3 m (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with the chloroacetanilide herbicide, acetochlor. Freundlich isotherms revealed that sorption and desorption behaviour varied with each depth sampled. As soil depth increased, the extent and strength of sorption decreased, indicating that the potential for leaching was increased in the subsoils compared with the surface soil. Hysteresis was evident at each of the three depths sampled, although no significant correlations between soil properties and the hysteresis coefficients were evident. Desorption studies using soil fractions with diameters of > 2000, 250-2000, 53-250, 20-53, 2-20, 0-2 and 0-1 mum separated from each of the three soil depths showed that differential desorption kinetics occurred and that the retention of acetochlor significantly correlated (R-2 = 0.998) with organic matter content. A greater understanding of the influence of soil components on the overall sorption and desorption potential of surface and subsurface soils is required to allow accurate prediction of acetochlor retention in the soil. In addition, it is likely that the proportion of each size fraction in a soil horizon would influence acetochlor bioavailability and movement to groundwater.

The decomposition of starch grains in soils: implications for archaeological residue analyses

Recent research involving starch grains recovered from archaeological contexts has highlighted the need for a review of the mechanisms and consequences of starch degradation specifically relevant to archaeology. This paper presents a review of the plant physiological and soil biochemical literature pertinent to the archaeological investigation of starch grains found as residues on artefacts and in archaeological sediments. Preservative and destructive factors affecting starch survival, including enzymes, clays, metals and soil properties, as well as differential degradation of starches of varying sizes and amylose content, were considered. The synthesis and character of chloroplast-formed 'transitory' starch grains, and the differentiation of these from 'storage' starches formed in tubers and seeds were also addressed. Findings of the review include the higher susceptibility of small starch grains to biotic degradation, and that protective mechanisms are provided to starch by both soil aggregates and artefact surfaces. These findings suggest that current reasoning which equates higher numbers of starch grains on an artefact than in associated sediments with the use of the artefact for processing starchy plants needs to be reconsidered. It is argued that an increased understanding of starch decomposition processes is necessary to accurately reconstruct both archaeological activities involving starchy plants and environmental change investigated through starch analysis. (C) 2004 Elsevier Ltd. All rights reserved.

Molecular dynamics simulation of the structural and dynamic properties of dioctadecyldimethyl ammoniums in organoclays

The structural and dynamic properties of dioctadecyldimethylammoniums (DODDMA) intercalated into 2:1 layered clays are investigated using isothermal-isobaric (NPT) molecular dynamics (MD) simulation. The simulated results are in reasonably good agreement with the available experimental measurements, such as X-ray diffraction (XRD), atom force microscopy (AFM), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR) spectroscopies. The nitrogen atoms are found to be located mainly within two layers close to the clay surface whereas methylene groups form a pseudoquadrilayer structure. The results of tilt angle and order parameter show that interior two-bond segments of alkyl chains prefer an arrangement parallel to the clay surface, whereas the segments toward end groups adopt a random orientation. In addition, the alkyl chains within the layer structure lie almost parallel to the clay surface whereas those out of the layer structure are essentially perpendicular to the surface. The trans conformations are predominant in all cases although extensive gauche conformations are observed, which is in agreement with previous simulations on n-butane. Moreover, an odd-even effect in conformation distributions is observed mainly along the chains close to the head and tail groups. The diffusion constants of both nitrogen atoms and methylene groups in these nanoconfined alkyl chains increase with the temperature and methelene position toward the tail groups.

Analytical solutions of linear finite- and small-strain one-dimensional consolidation

Analytical solutions are presented for linear finite-strain one-dimensional consolidation of initially unconsolidated soil layers with surcharge loading for both one- and two-way drainage. These solutions complement earlier solutions for initially unconsolidated soil layers without surcharge and initially normally consolidated soil layers with surcharge. Small-strain solutions for the consolidation of initially unconsolidated soil layers with surcharge loading are also presented, and the relationship between the earlier solutions for initially unconsolidated soil without surcharge and the corresponding small-strain solutions, which was not addressed in the earlier work, is clarified. The new solutions for initially unconsolidated soil with surcharge loading can be applied to the analysis of low stress consolidation tests and to the partial validation of numerical solutions of non-linear finite-strain consolidation. They also clarify a formerly perplexing aspect of finite-strain solution charts first noted in numerical solutions. Copyright (C) 2004 John Wiley Sons, Ltd.

Visoelastic studies on thermoplastic polyurethane nanocomposites using a nano-hardness tester

The viscoelastic behaviour of a range of polyurethane thermoplastic elastomer montmorillonite nanocomposites has been studied using a nanohardness tester. For softer Shore hardness 80A materials, the introduction of the organo-clay increased the creep strain obtained while the nano-indentor was held at constant load. The increase in creep strain was greatest for materials containing an organo-clay modified with a more hydrophilic quaternary alkylammonium surfactant and with higher loadings of the hydrophilic organo-clay. This suggested the effect might be due to a plasticising effect of the excess surfactant. For the harder Shore hardness 55D materials, the addition of the organo-clays produced only a small decrease in the creep strain, probably due to the interconnected hard domains in this material.

Flow field analysis of some mixing and conveying screw element regions, within a closely intermeshing, co-rotating twin-screw extruder.

Grafting of antioxidants and other modifiers onto polymers by reactive extrusion, has been performed successfully by the Polymer Processing and Performance Group at Aston University. Traditionally the optimum conditions for the grafting process have been established within a Brabender internal mixer. Transfer of this batch process to a continuous processor, such as an extruder, has, typically, been empirical. To have more confidence in the success of direct transfer of the process requires knowledge of, and comparison between, residence times, mixing intensities, shear rates and flow regimes in the internal mixer and in the continuous processor.The continuous processor chosen for the current work in the closely intermeshing, co-rotating twin-screw extruder (CICo-TSE). CICo-TSEs contain screw elements that convey material with a self-wiping action and are widely used for polymer compounding and blending. Of the different mixing modules contained within the CICo-TSE, the trilobal elements, which impose intensive mixing, and the mixing discs, which impose extensive mixing, are of importance when establishing the intensity of mixing. In this thesis, the flow patterns within the various regions of the single-flighted conveying screw elements and within both the trilobal element and mixing disc zones of a Betol BTS40 CICo-TSE, have been modelled using the computational fluid dynamics package Polyflow. A major obstacle encountered when solving the flow problem within all of these sets of elements, arises from both the complex geometry and the time-dependent flow boundaries as the elements rotate about their fixed axes. Simulation of the time dependent boundaries was overcome by selecting a number of sequential 2D and 3D geometries, used to represent partial mixing cycles. The flow fields were simulated using the ideal rheological properties of polypropylene and characterised in terms of velocity vectors, shear stresses generated and a parameter known as the mixing efficiency. The majority of the large 3D simulations were performed on the Cray J90 supercomputer situated at the Rutherford-Appleton laboratories, with pre- and postprocessing operations achieved via a Silicon Graphics Indy workstation. A mechanical model was constructed consisting of various CICo-TSE elements rotating within a transparent outer barrel. A technique has been developed using coloured viscous clays whereby the flow patterns and mixing characteristics within the CICo-TSE may be visualised. In order to test and verify the simulated predictions, the patterns observed within the mechanical model were compared with the flow patterns predicted by the computational model. The flow patterns within the single-flighted conveying screw elements in particular, showed good agreement between the experimental and simulated results.

Chemical and physical characterization of clay bodies

Suitable methods for the assessment of the effect of freeze-thaw action upon ceramic tiles have been determined. The results obtained have been shown to be reproducible with some work in this area still warranted. The analysis of Whichford Potteries clays via a variety of analytical techniques has shown them to be a complex mix of both clay and non-clay minerals. 57Fe Mössbauer spectroscopy has highlighted the presence of both small and large particleα-Fe203, removable via acid washing. 19F MAS NMR has demonstrated that the raw Whichford Pottery clays examined have negligible fluorine content. This is unlikely to be detrimental to ceramic wares during the heating process. A unique technique was used for the identification of fluorine in solid-state systems. The exchange of various cations into Wyoming Bentonite clay by microwave methodology did not show the appearance of five co-ordinate aluminium when examined by 27Al MAS NMR. The appearance of Qo silicate was linked to an increase in the amount of tetrahedrally bound aluminium in the silicate framework. This is formed as a result of the heating process. The analysis of two Chinese clays and two Chinese clay raw materials has highlighted a possible link between the two. These have also been shown to be a mix of both clay and non-clay minerals. Layered double hydroxides formed by conventional and microwave methods exhibited interesting characteristics. The main differences between the samples examined were not found to be solely attributable to the differences between microwave and conventional methods but more attributable to different experimental conditions used.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Studies in clay chemistry

A study of clay chemistry has been approached with three aims: - to modify the conducting properties by intercalation of tetrathiafulvalene, - to study the electrochemistry of redox-active coordination compounds immobilised on clay coated electrodes, and - to study the role of clays as reagents in inorganic glass forming reactions using mainly solid-state magic-angle-spinning NMR. TTF was intercalated by smectites containing different interlayer and lattice cations. Evidence from ESR and 57Fe Mossbauer indicated charge-transfer from TTF to structural iron in natural montmorillonite, and to interlayer Cu2+ in Cu2+ exchanged laponite. No charge transfer was observed for laponite (Na+ form) itself. Ion exchange of TTF3(BF4)2 with laponite was found to proceed quantitatively. The intercalated species were believed to be (TTF)2+ dimers. Conductivity data showed an order of magnitude increase for the intercalated clays. The mechanism is thought to be ionic rather than CT as Na+ laponite showed a similar enhancement in conductivity. Mechanically robust colloidal clay films were prepared on platinum electrodes. After immersion in solutions containing redox active complexes [Co(bpy)3]3+ and [Cr(bpy)3]3+, the films became electroactive when a potential was applied. Cyclic voltammograms obtained for both complexes were found to be of the diffusion controlled type. For [Co(bpy)3]3+ immobilised on clay coated electrodes, a one-step oxidation and four-step reduction wave was observed corresponding to a one electron stepwise reversible reduction of Co(III), through Co(II), Co(I), Co(O) to Co(I) oxidation state. For [Cr(bpy)3]3+ the electrochemistry was complicated by the presence of additional waves corresponding to the dissociation of [Cr(bpy)3]3+ into the diaquo complex. ESR and diffuse reflectance data supported such a mechanism. 29Si, 27Al and 23Na MAS NMR spectroscopy, supported by powder XRD and FTIR, was used to probe the role of clays as reagents in glass forming reactions. 29Si MAS NMR was found to be a very sensitive technique for identifying the presence and relative abundance of crystalline and non-crystalline phases. In thermal reactions of laponite formation of new mineral phases such as forsterite, akermanite, sillimanite and diopside were detected. The relative abundance of each phase was dependent on thermal history, chemical nature and concentration of the modifier oxide present. In continuing work, the effect of selected oxides on the glass forming reactions of a model feldspar composition was investigated using solid state NMR alone. Addition of network modifying oxides generally produced less negative 29Si chemical shifts and larger linewidths corresponding to a wider distribution of Si-O-Si bond angles and lengths, and a dominant aluminosilicate phase with a less polymerised structure than the starting material. 29Si linewidths and 27Al chemical shifts were respectively correlated with cationic potential and Lewis acidity of the oxide cations. Anomalous Al(4) chemical shifts were thought to be due to precipitation of aluminate phases rather than a breakdown in Lowenstein's aluminium avoidance principle.

Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.