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.

Clay mineralogical, geochemical and isotopic tracing of the evolution of the Woodleigh impact structure, Southern Carnarvon Basin, Western Australia

Chaotically structured diamictite from the inner ring syncline surrounding the central uplift of the Woodleigh impact structure contains shocked metamorphic and impact melt-rock fragments, largely derived from Ordovician and Devonian target sandstones. Coarse illite fractions (< 2 mu m) from the sandstones containing no K-feldspar yield K-Ar ages of around 400 Ma, whereas the K-Ar ages of authigenic clays of > 0.2 mu m fractions from the diamictite without smectite and K-feldspar cluster around 360 Ma, consistent with Rb-Sr data. Crystallisation of newly formed illite in the impact melt rock clasts and recrystallisation of earlier formed illite in the sandstone clasts preserved in the diamictite, are attributed to impact-induced hydrothermal processes in the Late Devonian. The illitic clays from the diamictite and from the sandstones have very similar trace element compositions, with significantly enriched incompatible lithophile elements, which increase in concentrations correlatively with those of the compatible ferromagnesian elements. The unusual trace element associations in the clays may be due to the involvement of hot gravity-driven basinal fluids that interacted with rocks of the Precambrian craton to the east of the study area, or with such material transported and reworked in the studied sedimentary succession.

Woodleigh, Southern Carnarvon Basin, Western Australia: history of discovery, Late Devonian age, and geophysical and morphometric evidence for a 120 km-diameter impact structure

The discovery of the Woodleigh impact structure, first identified by R. P. lasky, bears a number of parallels with that of the Chlcxulub impact structure of K-T boundary age, underpinning complications inherent in the study of buried impact structures by geophysical techniques and drilling. Questions raised in connection with the diameter of the Woodleigh impact structure reflect uncertainties in criteria used to define original crater sizes in eroded and buried impact structures as well as limits on the geological controls at Woodleigh. The truncation of the regional Ajona - Wandagee gravity ridges by the outer aureole of the Woodleigh structure, a superposed arcuate magnetic anomaly along the eastern part of the structure, seismic-reflection data indicating a central > 37 km-diameter dome, correlation of fault patterns between Woodleigh and less-deeply eroded impact structures (Ries crater, Chesapeake Bay), and morphometric estimates all indicate a final diameter of 120 km. At Woodleigh, pre-hydrothermal shock-induced melting and diaplectic transformations are heavily masked by pervasive alteration of the shocked gneisses to montmorillonite-dominated clays, accounting for the high MgO and low K2O of cryptocrystalline components. The possible contamination of sub-crater levels of the Woodlelgh impact structure by meteoritic components, suggested by high Ni, Co, Cr, Ni/ Co and Ni/Cr ratios, requires further siderophile element analyses of vein materials. Although stratigraphic age constraints on the impact event are broad (post-Middle Devonian to pre-Early Jurassic) high-temperature (200-250 degrees C) pervasive hydrothermal activity dated by K-Ar isotopes of illite - smectite indicates an age of 359 +/- 4 Ma. To date neither Late Devonian crater fill, nor impact ejecta fallout units have been identified, although metallic meteoritic ablation spherules of a similar age have been found in the Conning Basin.

Microchemistry and microstructures of hydrothermally altered shock-metamorphosed basement gneiss, Woodleigh impact structure, Southern Carnarvon Basin, Western Australia

Hydrothermally altered shock-metamorphosed gneisses consisting of relic igneous biotite-K-feldspor-Na-rich alkali feldspar - plagioclase - quartz assemblages ( accessory garnet, corundum, titanite, monazite, zircon), and showing extensive replacement by montmorillonite, illite, sericite, and to a lesser extent chlorite, calcite, epidote, zoisite and pyrite, occur in the basement core uplift of the Woodleigh impact structure, Western Australia. The rocks display extensive hydrothermal clay alteration, complicating identification of pre-hydrothermal and pre-impact textures and compositions. Analysis of quartz-hosted planar deformation features (PDFs) indicates a majority of indexed sets parallel to omega{10 (1) over bar3}, a lesser abundance of sets parallel to pi{10 (1) over bar2}, and some sets parallel to the basal plane (0001) and r,z {10 (1) over bar1}, consistent with pressures about or over 20 GPa. Feldspar-hosted FDFs form reticulate vein networks displaying checkerboard-like to irregular and serrated patterns attributable to preferential replacement of shock-damaged PDFs and/or perthitic twin lamella by clay minerals. The gneisses are pervaded by clay-dominated intergranular and intragranular veins of cryptocrystalline material that display marked departures from bulk-rock chemistry and from mineral compositions. XRD analysis identifies the cryptocrystalline components as illite - montmorillonite, illite and chlorite, while laser Raman analysis identifies high-fluorescence sub-micrometre clay assemblage, feldspar, quartz and minor mica. SEM/EDS-probe and laser-ICPMS analysis indicate low-K high-Mg clay mineral compositions consistent with montmorillonite. Quartz PDF-hosted cryptocrystalline laminae display distinct enrichments in Al, Mg, Ca and K. Altered intergranular veins and feldspar-hosted cryptocrystalline components show consistent enrichment in the relatively refractory elements (Al, Cc, Mg, Fe) and depletion in relatively volatile elements (Si, K, Na). The clay alteration retards determination whether clay-dominated vein networks represent altered shock-induced pseudotachylite veins, diaplectic zones and/or shock-damaged twin lamella, and/or result from purely mineralogical and chemical differentiation affected by hydrothermal fluids, Overall enrichment of the shocked gneiss and of the cryptocrystalline components in Mg and trace ferromagnesian elements (Ni, Cc, Cr) may be attributed alternatively to introduction of siderophile element-rich fluid from the projectile, or/and contamination of hydrothermal fluids by MgO from dolomites surrounding the basement uplift. High Ni/Co and Ni/Cr and anomalous DGE (platinum group elements) may support the former model.

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.

Clay mineralogical and isotopic (K-Ar, delta O-18, delta D) constraints on the evolution of the North Anatolian Fault Zone, Turkey

This study presents the first attempt to constrain the evolution of the North Anatolian Fault Zone (NAFZ) by age dating and isotope tracing of clay minerals formed during near-surface faulting. Extensive illitic clay mineralisation occurred along the NAFZ related to hydrothermal alteration of the fault gouges and pseudotachylytes. Samples representing the pre-fault protoliths outside the fault zone do not contain authigenic illitic clay minerals indicating that hydrothermal processes were confined to the areas within the fault zone. K-Ar age data indicate that the hydrothermal system and the associated illite authigenesis initiated at similar to 57 Ma. This process is interpreted to reflect the onset of significant strike-slip or transtensional faulting immediately after the continental collision related to the closure of the Neotethys Ocean. Following the initiation of the fault movements in the latest Paleocene-Early Eocene, displacements along the NAFZ have continued, with probably intensified fault activities at similar to 26 Ma and later than similar to 8 Ma. Oxygen isotope compositions of the illitic clays from different locations along the NAFZ are similar, with narrow ranges in delta O-18 values indicating clay precipitation from fluids with similar oxygen isotope compositions and crystallisation temperatures. The delta O-18 and delta D values of the calculated fluid isotopic composition (delta O-18=5.9 parts per thousand to 11.2 parts per thousand, delta D=-59 parts per thousand to -73 parts per thousand) are consistent with metamorphic and magmatic origin of fluids mobilised during active tectonism. The interpretation of the fluid flow history of the NAFZ is in agreement with that reported previously for some well-known large-scale high-angle fault zones, which similarly developed along collisional-type orogenic belts and are commonly associated with significant mesothermal ore mineralisation. (c) 2005 Elsevier B.V. All rights reserved.

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.

The manufacture and utilisation of architectural terracotta and faience.

The revival of terracotta and faience in British architecture was widespread, dramatic in its results and, for two decades, the subject of intense debate. However the materials have been frequently denigrated and more generally disregarded by both architects and historians. This study sets out to record and explain the rise and fall of interest in terracotta and faience, the extent and nature of the industry and the range of architectural usage in the Victorian, Edwardian and inter-war periods. The first two chapters record the faltering use of terracotta as an 'artificial stone', until the material gained its own identity, largely through the appreciation of Italian architecture. In the mid-Victorian period, terracotta will be seen to have become symbolic of the philosophy of the Victoria and Albert Museum and its Art School in attempting to reform both architecture and the decorative arts. The adoption of terracotta was furthered as much by industrial as aesthetic factors; three chapters examine how the exploitation of coal-measure clays, developments in the processes of manufacture, the changing motivation of industrialists and differing economics of production served to promote and then to hinder expansion and adaptation. The practical values of economy, durability and fire-resistance and the aesthetic potential, seen in terms of colour and decorative and sculptural modelling, became inter-related in the work of the architects who made extensive use of architectural ceramics. A correlation emerges between the free Gothic style, exemplified by the designs of Alfred Waterhouse and the use of red terracotta supplied from Ruabon, and between the eclectic Renaissance style and a buff material produced by different manufacturers.These patterns were modified as a result of the adoption of faience for facing external walls as well as interiors, and because of the new architectural requirements and tastes of the twentieth century. The general timidity in exploiting the scope for polychromatic decoration and the increasing opposition to architectural ceramics is contrasted with the most successful schemes produced for cinemas, chain-stores and factories. In the last chapter, those undertaken by the Hathern Station Brick and Terracotta Company between 1896 and 1939 are used as a case study; they confirm that manufacturers, architects and clients were all committed to creating a modern and yet decorative architecture, appropriate for new building types and that would appeal to and be comprehensible to the public.

The sedimentology and diagenesis of Lower Permian (Rotliegend) sediments: (onshore U.K. and southern North Sea). Available in 2 volumes.

The thesis provides a comparative study of both sedimentology and diagenesis of Lower Permian (Rotliegend) strata, onshore and offshore U.K. (Southern North Sea). Onshore formations studied include the Bridgnorth, Penrith and Hopeman Sandstone, and are dominated by aeolian facies, with lesser amounts of interbedded fluvial sediments. Aeolian and fluvial strata in onshore basins typically grade laterally into alluvial fan breccias at basin margins. Onshore basins represent proximal examples of Rotliegend desert sediments. The Leman Sandstone Formation of the Ravenspurn area in the Southern North Sea displays a variety of facies indicative of a distal sedimentological setting; Aeolian, fluvial, sabkha, and playa lake sediments all being present. "Sheet-like" geometry of stratigraphical units within the Leman Sandstone, and alternation of fluvial and aeolian deposition was climatically controlled. Major first order bounding surfaces are laterally extensive and were produced by lacustrine transgression and regression from the north-west. Diagenesis within Permian strata was studied using standard petrographic microscopy, scanning electron microscopy, cold cathodo-Iuminescence, X-ray diffraction clay analysis, X-ray fluorescence spectroscopy, fluid inclusion microthermometry, and K-Ar dating of illites. The diagenesis of Permian sediments within onshore basins is remarkably similar, and a paragenetic sequence of early haematite, illitic clays, feldspar, kaolinite, quartz and late calcite is observed. In the Leman Sandstone formation, authigenic mineralogy is complex and includes early quartz, sulphates and dolomite, chlorite, kaolinite, late quartz, illite and siderite. Primary lithological variation, facies type, and the interdigitation and location of facies within a basin are important initial controls upon diagenesis. Subsequently, burial history, structure, the timing of gas emplacement, and the nature of sediments within underlying formations may also exersize significant controls upon diagenesis within Rotliegend strata.