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This study aims to understand the causes of anomalous pore fluid pressures within sedimentary sequences of an active tectonic basin through well log analysis, pressure data evaluation and thermo-hydro-geomechanical modelling. The study focuses on the East Coast Basin (ECB), New Zealand, an active convergent margin, where anomalously high pore pressures have been encountered in deep-water systems at burial depths as shallow as 200 m. A regional investigation including analysis of the Cretaceous to Holocene tectono-stratigraphy and diagenetic histories of the ECB, was combined with seismic and well log interpretation to understand the structural and sedimentation history of the ECB, and thus the main factors that were likely to contribute to overpressure generation/dissipation and porosity loss. 1D hydro-geomechanical models were then built to undertake a parametric study to investigate the effect on porosity and pore pressure evolution of different sedimentation and erosion rates, hiatus periods, different erosion thicknesses, and tectonic compression. The parametric models show that high overpressures can be preserved during rapid erosion events due to the relatively small timeframe for pore pressure dissipation, depending on sediment permeability. Furthermore, only recent erosion events are relevant to the present-day overpressure. In addition, high levels of tectonic compression (12.5 %) applied in recent events can produce both high pore pressure values and significant porosity reduction if the sedimentary column was undercompacted prior to the tectonic compression. Learnings from the parametric studies were used as a starting point to understand controls on the pore pressure and porosity in the Opoutama-1 well, located on the onshore area of the ECB. Results from the Opoutama-1 well show that the high pore pressure registered at shallow depths (< 1 km) in this well is significantly driven by tectonic compression as a result of high subduction rates (presently 48 mm/yr). Disequilibrium compaction also contributed to overpressure generation due to high sedimentation rates (up to ~3000 m/Ma). However, much of the disequilibrium compaction-related overpressure was dissipated during uplift, hiatus, and erosion. Where overpressure is preserved, it is related to thick (up to 1 km) mudstone packages deposited during the Cretaceous to Holocene, thin low permeable layers of limestones deposited during the Miocene to Pliocene and marl intervals with high content of smectite.

Upper Jurassic Fulmar Formation sandstones from the Fulmar Field in the Central North Sea are buried to 3.2 km and 128 °C but contain only 3.7 ± 1.7% (1σ) quartz cement, substantially less than volumes predicted by models based on temperature-related quartz precipitation kinetics. Oxygen isotope microanalysis of quartz overgrowths suggests that only limited cementation occurred at temperatures above 110 °C. We suggest that the anomalously low volumes of quartz cement are most readily explained by the effective stress history of the Fulmar Formation. Regional pore pressure analysis strongly suggests that pore fluid pressures in the Fulmar Formation decreased substantially in the last

Shale gas is an important hydrocarbon resource in a global context. It has had a significant impact on energy resources in the US, but the worldwide development of this methane resource requires further research to increase the understanding of the relationship of shale structural characteristics to methane storage capacity. In this study a range of gas adsorption, microscopic, mercury injection capillary pressure porosimetry and pycnometry techniques were used to characterize the full range of porosity in a series of shales of different thermal maturity. Supercritical methane adsorption methods for shale under conditions which simulate geological conditions (up to 473 K and 15 MPa) were developed. These methods were used to measure the methane adsorption isotherms of Posidonia shales where the kerogen maturity ranged from immature, through oil window, to gas window. Subcritical methane and carbon dioxide adsorption studies were used for determining pore structure characteristics of the shales. Mercury injection capillary pressure porosimetry was used to characterize the meso and macro porosity of shales. The sum of the CO2sorption pore volume at 195 K and mercury injection capillary pressure pore volumes (1093–5.6 nm) were equal to the corresponding total pore volume (

This paper investigates the nano to core-scale geomechanical properties of a maturity series of organic-rich, calcareous shales buried to 100-180°C, with a focus on: (a) the mechanical properties of organic matter; (b) the elastic response and anisotropy of the shale composite at micro and core scale; and (c) the creep response. Atomic force microscopy was used to target kerogen at nanoscale resolution, and it was found that the elastic stiffness increased with thermal maturity from 5.8 GPa in an immature sample to 11.3 GPa in a mature sample. Nanoindentation testing of the shale matrix showed that diagenesis is a key factor in determining the bulk elasticity, with increasingly intense carbonate cementation at higher thermal maturities contributing to a stiffer response. A multiscale model was formulated to upscale the elastic properties from nanoscale solid clay minerals to a microcracked composite at core scale, with good predictions of the micro and core-scale stiffness in comparison to indentation and triaxial results. A negative correlation was found between the creep modulus and clay/kerogen content, with greater creep displacement observed in nanoindentation tests in the immature clay- and kerogen-rich sample compared to samples of higher thermal maturity.

Muds deposited in large-scale epicontinental seaways provide deep insights into palaeoclimates, biogeochemical cycles, sedimentation processes, and organic carbon burial during exceptionally warm periods throughout the Phanerozoic. Temporal changes can be monitored at single locations but the key, larger-scale oceanographical and related biogeochemical processes are likely to be more clearly revealed by comparisons between individual sub-basins within seaways. Here, we compare inorganic geochemical records from the Jurassic (upper Pectinatites wheatleyensis to lower Pectinatites pectinatus ammonite zones) of the Swanworth Quarry 1 Core from the Wessex Basin (Dorset, UK) to time-equivalent records from the Ebberston 87 Core in the Cleveland Basin (Yorkshire, UK), 400 km apart. Our synthesis shows that while the Dorset sediments were deposited in an energetically more dynamic setting than the Yorkshire sediments, the overarching climatic and oceanographical processes responsible for variations in organic carbon enrichment and sedimentation, were similar. Intervals of coeval organic carbon-rich sedimentation occurred in both basins, and a particulate shuttle was intermittently active in both basins. Consistent with recent climate simulations, we conclude that tropical climate conditions, associated with enhanced nutrient supply, were key drivers of sedimentation between the Jurassic Wessex and Cleveland Basins.

Mudstones exert a fundamental control on the flow of both aqueous and non‐aqueous fluids in sedimentary basins. Predicting their flow and storage properties requires an understanding of pore size and connectivity, yet there are very few quantitative descriptions of pore systems of mineralogically and texturally well‐characterised mudstones. We use a combination of electron microscopy, mercury injection capillary pressure porosimetry, and CO2 sorption methods to generate a quantitative description of the size distribution, connectivity, and evolution of pore systems in a sequence of Posidonia Shale mudstones buried to 100‐180 °C. We place the pore data into a detailed mineralogical, petrographical and textural context to show that the nature and evolution of porosity and pore systems can be described in terms of associations with clay‐rich, microfossil‐rich and organic matter‐rich domains, common to many mudstones. Pore size distributions are described by power laws and pore systems are well connected across the full nanometer‐micrometer spectrum of pore sizes. However, connected networks occur primarily through pores < 10 nm radius, with typically 20‐40% of total porosity associated with pores with radii < ca. 3 nm, within both organic matter and the clay matrix. Clay‐rich, microfossil‐rich and organic matter‐rich domains have distinct pore size distributions which evolve in very different ways with increasing thermal maturity. We suggest that the flow of aqueous and non‐aqueous fluids depends not only on the overall connectivity of pores but also the larger‐scale connectivity and wetting state of clay‐rich, microfossil‐rich and organic matter‐rich domains.

International audience; Fine-grained sedimentary successions contain the most detailed record of past environmental conditions. High-resolution analyses of these successions yield important insights into sedimentary composition and depositional processes and are, therefore, required to contextualise and interpret geochemical data which are commonly used as palaeoclimate proxies. The Kimmeridge Clay Formation (KCF) is a 500 m-thick mudstone succession deposited throughout the North Sea in the Late Jurassic and records environmental conditions through this time. Here, we present petrographic analyses (on 36 thin sections) on a 50 m section of a KCF core from the Cleveland Basin (Yorkshire, UK) to investigate controls on sedimentation in this region during the Tithonian, Late Jurassic. Facies descriptions demonstrate that deposition took place in a hydrodynamically variable environment in which the sediment origins, sediment dispersal mechanisms, and redox conditions fluctuated on the scale of thousands of years. Petrographic analyses show that the sediment comprises marine (algal macerals, calcareous fossils), detrital (quartz, clay, feldspar), and diagenetic (dolomite and authigenic kaolinite) components and that several sediment dispersal mechanisms influenced deposition and facilitated both the supply and preservation of terrestrial and marine organic material. This work provides a framework for the interpretation of geochemical palaeoclimate proxies and reinforces the importance of looking at the rock when interpreting whole-rock geochemical data.

We present a geochemical dataset which helps unravel the complex set of processes by which light alkanes are sourced, charged, mixed, leaked and altered in the Plio-Pleistocene Nile Delta. Thermogenic gas derives from a sub-Messinian source and mixes with microbial, hydrogenotrophic, methane-rich gas in the Plio-Pleistocene section. There is strong isotopic evidence for both microbial generation and microbial degradation of ethane and propane, but these signals are only recorded where the rates of biological processes outstrip the rate of thermogenic charge. High resolution gas geochemistry profiles through four, 500–1100 m sequences of mixed channel, channel levee, mass flow deposits and hemipelagites shed light on migration and leakage pathways. We see limited geochemical evidence for migration along or across faults which cross-cut mud-rich sequences. Lateral migration along sands/silts delivers gas to structural highs, where leakage occurs vertically along focussed pathways through heterogeneous mud-rich sediments. We propose that in situ generation of microbial gas within mud-rich sequences facilitates percolation of migrating gases that replenishes C2+ components and sustains the biodegradation pathway in syntrophic microbial communities. High resolution changes in gas composition suggest an unequilibrated system which is being actively charged. In some structures, rates of charge and of microbial alteration of gas are broadly similar; in others, rates of charge exceed rates of microbial alteration. Our results have important implications for the understanding of both basin-wide fluid flow and the ecology of the deep biosphere.

The potential development of shale gas has brought with it several concerns about environmental impacts, these include: induced seismicity, air pollution, and groundwater contamination. During hydraulic fracturing for shale gas, large volumes of oxic and acidic water are injected into the gas-bearing formations. The injected fluids contain a range of additives and will mix and react with the in-situ groundwater and shale rock with the potential to drive water-rock interactions; release metal contaminants; alter the permeability of the bedrock; with each of these affecting the transport and recovery of water, hydrocarbons, and contamination. The purpose of this study is to understand the geochemical processes and inorganic metals release during hydraulic fracturing to assess the potential contribution of fluid-rock interaction for the composition of produced waters and alteration of shale mechanical properties. The study has: i) Statistically analysed the chemical composition of hydraulic fracturing in USGS dataset to create prior distributions for the prediction of the salinity and chemical composition of flowback fluids in the UK. ii) Statistically analysed the composition and controls on geothermal waters in the UK. Deep geothermal waters are an analogue for the in-situ groundwater composition with which injected fracking fluids will react and mix.iii) Both sources of information have assisted in the design of the high pressure, high temperature experiments that will simulate the fracking fluid processesiv) Undertaken sequential extraction of target shales to understand the data from existing batch experiments undertaker Future work will include isotope proxy and mineralogical texture studies to predict flowback fluid composition and the post-frack condition of the shale.

We present coupled, critical state, geomechanical-fluid flow simulations of the evolution of a fold-and-thrust belt in NW Borneo. Our modelling is the first to include the effects of both syntectonic sedimentation and transient pore pressure on the development of a fold-and-thrust belt. The present-day structure predicted by the model contains the key first order structural features observed in the field in terms of thrust fault and anticline architectures. Stress predictions in the sediments show two compressive zones aligned with the shortening direction located at the thrust front and back limb. Between the compressive zones, near to the axial plane of the anticline, the modelled stress field represents an extensional regime. The predicted overpressure distribution is strongly influenced by tectonic compaction, with the maximum values located in the two laterally compressive regions. We compared the results at three notional well locations with their corresponding uniaxial strain models: the 2D thrust model predicted porosities which are as much as 7.5% lower at 2.5 km depth and overpressures which are up to 6.4 MPa higher at 3 km depth. These results show that one-dimensional methods are not sufficient to model the evolution of pore pressure and porosity in contractional settings. Finally, we performed a drained simulation during which pore pressures were kept hydrostatic. The predicted geological structures differ substantially from those of the coupled simulation, with no thrust faulting. These results demonstrate that pore pressure is a key control on structural development.

Shallow-buried fluvial mudstones are of great significance as potential top seals for natural gas accumulations in the Zhanhua depression. Four samples were chosen to represent the range of fine-grained microfacies, from clay-rich to silt-rich to cemented, and mercury injection capillary pressure (MICP) porosimetry is combined with Scanning Electron Microscopy (SEM) to characterize microstructure and pore systems quantitatively. The nature of the pore systems that allow capillary breakthrough and thus leakage, were also estimated. Pore areas inferred from SEM data, obtained from representative elementary areas (REAs), follow a similar power law distribution to bulk sample MICP within a specific range, indicating that pores with areas larger than 103 nm2 are well connected. In samples without carbonate cement, pores within the clay matrix are larger in coarser-grained, siltier samples, and there are more pores at the edges of non-clay minerals; this results from force chains of large grains shouldering more effective stress. With increasing silt content, SEM-visible porosity increases and the contribution of pores between non-clay minerals grows significantly, while the contribution of pores within clay matrix reduces. In more clay-rich samples, capillary breakthrough is estimated to occur in pores associated with the clay matrix; in siltier samples, breakthrough will occur at lower entry pressures associated with larger interparticle pores. Carbonate cements play a key role in reducing pore space in some siltier samples by partially filling interparticle pores at (a) the interfaces between clay and non-clay minerals, and (b) pores between non-clay minerals areas larger than 106 nm2. By filling larger pores, capillary breakthrough in carbonate-cemented samples occurs at relative high entry pressures through pores in the clay matrix. However, carbonate cements, generally less than 20%, are not sufficient to enable silt-rich mudstones to become effective barriers. Clay content is the most critical control on mudstone seal capacity.

Determination of the mechanical response of shales through experimental procedures is a practical challenge due to their heterogeneity and the practical difficulties of retrieving good-quality core samples. Here, we investigate the possibility of using multiscale homogenisation techniques to predict the macroscopic mechanical response of shales based on quantitative mineralogical descriptions. We use the novel PeakForce Quantitative Nanomechanical Mapping technique to generate high-resolution mechanical images of shales, allowing the response of porous clay, organic matter, and mineral inclusions to be measured at the nanoscale. These observations support some of the assumptions previously made in the use of homogenisation methods to estimate the elastic properties of shale and also earlier estimates of the mechanical properties of organic matter. We evaluate the applicability of homogenisation techniques against measured elastic responses of organic-rich shales, partly from published data and also from new indentation tests carried out in this work. Comparison of experimental values of the elastic constants of shale samples with those predicted by homogenisation methods showed that almost all predictions were within the standard deviation of experimental data. This suggests that the homogenisation approach is a useful way of estimating the elastic and mechanical properties of shales in situations where conventional rock mechanics test data cannot be measured.

At low temperatures, siliciclastic mudstones compact mechanically. Above 70 °C, where the smectite-to-illite transformation dominates clay diagenesis, they also compact chemically, provided that excess pore water can escape. There are two prevailing conceptual models for the compaction of siliciclastic mudstones at higher temperatures, above ∼100 °C. One holds that precipitation of minerals during diagenesis cements the mudstones such that mechanical compaction no longer occurs even if the mudstones can drain freely. According to the other model, diagenetically altered mudstones continue to compact mechanically in response to increasing effective stress. We found that wireline-log and pressure data from Cretaceous mudstones at Haltenbanken are consistent with ongoing mechanical compaction accompanying chemical compaction up to at least 130 °C. We suggest that mechanical compaction continues because grain contacts in siliciclastic mudstones following smectite-to-illite transformation are still mostly between clay grains.

The Kimmeridge Clay Formation (KCF) is a laterally extensive, total organic carbon-rich succession deposited throughout Northwest Europe during the Kimmeridgian–Tithonian (Late Jurassic). Here we present a petrographic and geochemical dataset for a 40 metre-thick section of a well-preserved drill core recovering thermally-immature deposits of the KCF in the Cleveland Basin (Yorkshire, UK), covering an interval of approximately 800 kyr. The new data are discussed in the context of depositional processes, sediment source and supply, transport and dispersal mechanisms, water column redox conditions, and basin restriction. Armstrong et al. (2016) recently postulated that an expanded Hadley Cell, with an intensified but alternating hydrological cycle, heavily influenced sedimentation and total organic carbon (TOC) enrichment, through promoting the primary productivity and organic matter burial, in the UK sectors of the Boreal Seaway. Consistent with such climate boundary conditions, petrographic observations, total organic carbon and carbonate contents, and major and trace element data presented here indicate that the KCF of the Cleveland Basin was deposited in the distal part of the Laurasian Seaway. Depositional conditions alternated between three states that produced a distinct cyclicity in the lithological and geochemical records: lower variability mudstone intervals (LVMIs) which comprise of clay-rich mudstone, TOC-rich sedimentation, and carbonate-rich sedimentation. The lower variability mudstone intervals dominate the studied interval but are punctuated by three ~ 2–4 m thick intervals of alternating TOC-rich and carbonate-rich sedimentation (here termed higher variability mudstone intervals, HVMIs). During the lower variability mudstone intervals, conditions were quiescent with oxic to sub-oxic bottom water conditions. During the higher variability mudstone intervals, highly dynamic conditions resulted in repeated switching of the redox system in a way similar to the modern deep basins of the Baltic Sea. During carbonate-rich sedimentation, oxic conditions prevailed, most likely due to elevated depositional energies at the seafloor by current/wave action. During TOC-rich sedimentation, anoxic-euxinic conditions led to an enrichment of redox sensitive/sulphide forming trace metals at the seafloor and a preservation of organic matter, and an active Mn-Fe particulate shuttle delivered redox sensitive/sulphide forming trace metals to the seafloor. In addition, based on TOC–S–Fe relationships, organic matter sulphurisation appears to have increased organic material preservation in about half of the analysed samples throughout the core, while the remaining samples were either dominated by excess Fe input into the system or experienced pyrite oxidation and sulphur loss during oxygenation events. New Hg/TOC data do not provide evidence of increased volcanism during this time, consistent with previous work. Set in the context of recent climate modelling, our study provides a comprehensive example of the dynamic climate-driven depositional and redox conditions that can control TOC and metal accumulations in the distal part of a shallow epicontinental sea, and is therefore key to understanding the formation of similar deposits throughout Earth's history.

Expanded successions of marine black shale provide important proxy records to test climatic teleconnections across ocean basins and paleo-latitudes. The causal and generic relationships controlling the timing, composition, and internal variability of marine organic carbon (OC)-rich shale over large distances and during variable global climate states are, however, far from understood but relevant for hydrocarbon generation potential. Despite detailed documentation of the processes operating in individual ocean settings and under specific climatic conditions, it remains a challenge to present a unifying concept that explains the generic and far field interconnections between climate zones and ocean basins at multiple temporal and spatial scales. Progress towards such a unifying model has been made for the Cretaceous Atlantic providing an important step forward to simulate the location and internal heterogeneity of black shale formation more reliably, especially for areas where limited field data exist due to harsh or remote conditions, such as the Mesozoic Arctic. In this study we combine new, high resolution geochemical and sedimentological records from the Jurassic boreal seaway, where widespread deposition of the Jurassic Kimmeridge Clay Formation (KFC) is well documented with large scale climate and biogeochemical modelling, placing the seaway into a global climatic context.

Summary The effective exploitation of unconventional shale hydrocarbon resources requires the robust geomechanical characterisation of the reservoir. However, there is still a paucity of mechanical data on well-characterised shale, partly due to the technical and economic difficulties in obtaining high quality core for laboratory testing. Here, we present the results of a study which combines PeakForce Quantitative Nanomechanical Mapping and nanoidentation testing on three shales from the Posidonia of NW Germany, covering a range of thermal maturities. PF-QNM is used to determine the mechanical properties of individual organic, clay mineral and other phases, including their anisotropy. Estimates of bulk elastic and viscoelastic parameters are determined through use of high load instrumented indentation testing. These data form the building blocks for the estimation of the geomechanical properties of shales at larger scales, as a function of mineralogy and organic matter type and content.

Temperature-controlled precipitation kinetics has become the overwhelmingly dominant hypothesis for the control of quartz cementation in sandstones. Here, we integrate quantitative petrographic data, high spatial resolution oxygen isotope analyses of quartz cement, basin modelling and a kinetic model for quartz precipitation to suggest that the supply of silica from stress-sensitive intergranular pressure dissolution at grain contacts is in fact a key control on quartz cementation in sandstones. We present data from highly overpressured sandstones in which, despite the current burial temperature of 190 °C, quartz cement occurs in low amounts (4.6 ± 1.2% of bulk volume). In situ oxygen isotope data across quartz overgrowths suggest that cementation occurred over 100 Ma and a temperature range of 80–150 °C, during which time high fluid overpressures resulted in consistently low vertical effective stress. We argue that the very low amounts of quartz cement can only be explained by the low vertical effective stress which occurred throughout the burial history and which restricted silica supply as a result of a low rate of intergranular pressure dissolution at grain contacts.

Homogenisation techniques have been successfully used to estimate the mechanical response of synthetic composite materials, due to their ability to relate the macroscopic mechanical response to the material microstructure. The adoption of these mean-field techniques in geo-composites such as shales is attractive, partly because of the practical difficulties associated with the experimental characterisation of these highly heterogeneous materials. In this paper, numerical modelling has been undertaken to investigate the applicability of homogenisation methods in predicting the macroscopic, elastic response of clayey rocks. The rocks are considered as two-level composites consisting of a porous clay matrix at the first level and a matrix-inclusion morphology at the second level. The simulated microstructures ranged from a simple system of one inclusion/void embedded in a matrix to complex, random microstructures. The effectiveness and limitations of the different homogenisation schemes were demonstrated through a comparative evaluation of the macroscopic elastic response, illustrating the appropriate schemes for upscaling the microstructure of shales. Based on the numerical simulations and existing experimental observations, a randomly distributed pore system for the micro-structure of porous clay matrix has been proposed which can be used for the subsequent development and validation of shale constitutive models. Finally, the homogenisation techniques were used to predict the experimental measurements of elastic response of shale core samples. The developed methodology is proved to be a valuable tool for verifying the accuracy and performance of the homogenisation techniques.

Image analysis is widely used to quantify porosity because, in addition to porosity, it can provide quantitative pore system information, such as pore sizes and shapes. Despite its wide use, no standard image analysis workflow exists. When employing image analysis, a workflow must be developed and evaluated to understand the methodological pitfalls and assumptions to enable accurate quantification of total porosity. This study presents an image analysis workflow that is used to quantify total porosity in a range of carbonate lithofacies. This study uses stitched BSE-SEM photomicrographs to construct greyscale pore system images, which are systematically thresholded to produce binary images composed of a pore phase and a rock phase. The ratio of the area of the pore phase to the total area of the pore system image defines the total porosity. Image analysis total porosity is compared with total porosity quantified by standard porosimetry techniques (He-porosimetry and mercury injection capillary pressure (MICP) porosimetry) to understand the systematics of the workflow. The impact of carbonate textures on image analysis porosity quantification is also assessed.A comparison between image analysis, He-porosimetry and MICP total porosity indicates that the image analysis workflow used in this study can accurately quantify or underestimate total porosity depending on the lithofacies textures and pore systems. The porosity of wackestone lithofacies tends to be significantly underestimated (i.e. greater than 10%) by image analysis, whereas packstone, grainstone, rudstone and floatstone lithofacies tend to be accurately estimated or slightly underestimated (i.e. 5% or less) by image analysis. The underestimation of image analysis porosity in the wackestone lithofacies is correlated to the quantity of matrix pore types and is thought to be caused by incomplete imaging of microporosity and by unrepresentative fields of view. Image analysis porosity, which is calculated from 2D areas, is comparable with 3D porosity volumes in lithofacies that lack or are weakly microporous; in such lithofacies, image analysis is assumed to be accurately measuring other 2D parameters, including pore sizes and shapes. Image analysis accurately quantifies or underestimates porosity (?) in carbonates.The estimation of ? depends on the lithofacies texture and the pore system.? is significantly underestimated in wackestones.This underestimation is caused by micro-? and unrepresentative fields of view.? is accurately quantified or slightly underestimated in lithofacies lacking micro-?.

We present quantitative petrographic data, high spatial resolution oxygen isotope analyses of quartz cement, basin modelling and a kinetic model for quartz precipitation for two Paleocene-Eocene Wilcox Group sandstones from Texas and two Jurassic Fulmar Formation sandstones from the Central North Sea. At each location, one sandstone has been buried to ca. 145 °C and one to ca. 185 °C. A key difference between the Wilcox and Fulmar burial histories is that the Wilcox sandstones are currently at higher vertical effective stresses and, from basin modelling studies, have been subjected to generally higher vertical effective stresses through their burial history. The amounts of quartz cement in the Wilcox sandstones are between 12 and 18%, and between 2 and 6% in the Fulmar sandstones. High-spatial-resolution oxygen isotope data obtained from the quartz cements suggest temperature ranges for quartz precipitation from 60 to 80 °C to values approaching maximum burial temperature. Factors such as grain coatings or the timing of petroleum emplacement cannot explain the differences in the amounts of quartz cement. Petrographic data show that most of the silica for quartz cement can be derived from intergranular pressure dissolution. Although the sample set is small, we interpret the results to suggest that the differences in quartz cementation in Fulmar and Wilcox sandstones can be explained better by differences in their vertical effective stress history than their temperature history; in this case, the supply of silica rather than the precipitation of quartz becomes an important control on the rate and extent of cementation.

Robust geomechanical characterisation of shale reservoirs is necessary for safe and economic resource exploitation but there is still a lack of mechanical data on well-characterised shale, partly due to the difficulties of obtaining high quality core samples for laboratory testing. The composition of shale also presents challenges when attempting to constrain the mechanical response. Multi-scale homogenisation techniques have recently been used to predict the macroscopic behaviour of shales based on quantitative mineralogical descriptions. However, there is a considerable amount of uncertainty associated with some key inputs into these homogenisation schemes. In particular, the organic matter of shale encompasses a range of scales, from nanometre to micrometre-size material, and its mechanical properties are not well understood. Here, PeakForce Quantitative Nanomechanical Mapping (PF-QNM), a recently developed form of atomic force microscopy (AFM), is combined with nanoindentation testing to characterise the mechanical response of the organic matter and clay phases of Posidonia shale from north-west Germany. The nanoscale testing revealed a clear peak in the histograms of the reduced elastic modulus, which can be attributed to kerogen in the shale matrix. Upscaling of the mechanical properties through homogenisation showed a reasonable prediction when compared with experimental data, including capturing the inherent anisotropy of the shale response. The influence of factors such as the volume fraction of silt inclusions and the applicability of different homogenisation formulations warrant further investigation.

Calcite cementation and dolomitization are key diagenetic processes in many sedimentary systems. Unravelling detailed histories and timescales of cementation and replacement is, however, often compromised by the limited spatial resolution of many analytical techniques; in some cases multiple grains are co-analyzed so that diagenetic histories are blurred and reaction periods are difficult to establish. In this study we have used 10-micrometer-resolution, in situ secondary ion mass spectrometry to determine the oxygen isotope composition of 197 individual, 10-50-micrometer-size crystals of dolomite and calcite from six samples in a single core of Upper Devonian Middle Bakken Member siltstones and sandstones, the major tight oil formation of the Williston Basin, USA. This amount of data places important constraints on the range of temperatures and times that carbonate cementation and replacement occurred. Petrographic data show that microcrystalline calcite cement is an early phase, and combined with mineralogical data suggest that much of the dolomite replaces calcite. Over spatial scales of less than a centimeter, analyses of individual calcite crystals have a range of 5‰ for 18O in the group of crystals, and for the group of individual dolomite crystals, 10‰. These sub-centimeter ranges are as great as those observed in previous studies of carbonate cements sampled over many meters and remind us that previous low-resolution studies may have inadvertently analyzed mixed phases. There is no relationship between dolomite texture and isotopic composition at this spatial scale; microscale backscattered electron imagery and scanning electron microscopy cathodoluminescence zoning is seen, but cannot be resolved with a 10 micrometer spot size. Assuming, since it is an early cement, that calcite precipitated from seawater (δ18O = -1.5‰), it formed at ca. 15-40°C, mainly at the lower temperatures. Present-day formation waters in Devonian rocks in this region have oxygen isotope compositions of 7-8‰ VSMOW. Using these values as a likely dolomitizing fluid, we suggest that dolomitization occurred continuously between 40 and 140°C over 150 – 200 million years, most likely in a fluid with a high Mg/Ca ratio resulting from gypsum formation in local evaporites. We suggest that this exceptionally low rate of dolomitization was controlled by the low rate of supply of Mg in a very sluggish flow regime; dolomitization is incomplete because of a limited supply of Mg.

Well-characterized samples from the Podhale Basin, southern Poland, formed the basis for exploring and illuminating subtle diagenetic changes to a mudstone toward the upper end of the diagenetic window, prior to metamorphism.Transmission electron microscopy (TEM) performed on dispersed grains and ion-beam thinned preparations, selected area diffraction patterns,and chemistry by TEM-EDS (energy dispersive spectra) augmented mineralogy and fabric data. The deepest samples show no change in their percent illite in illite-smectite (I-S), yet I-S–phase octahedral Fe3+ and Al3+ are statistically different between samples. A decrease in the Fe3+ concentration in the octahedral sheet correlates with an increase in I-S fabric intensity and apparent crystallinity. The D-statistic from the Kolmogorov-Smirnov test on TEM- EDS data describes statistical differences in the I-S chemistry. Previous work on these samples showed a significant increase in the preferred orientation of the I-S phase across the smectite to illite transition and a significant slowdown in the rate of development of preferred orientation beyond the termination of smectite illitization. Lattice fringe images describe an I-S morphology that coalesces into larger and tighter packets with increasing burial temperature and a decrease in I-S packet contact angle, yet some evidence for smectite collapse structures is retained. The deepest sample shows the thickest, most coherent I-S packets. We propose that the deepest samples in the Podhale Basin describe the precursor stage in phyllosilicate fabric preferred orientation increase from diagenesis into metamorphism, where continued evolution of crystallite packets and associated crystallinity create higher I-S fabric intensities as the structural formulae of I-S approach an end-member composition.

An inter-laboratory study of high-pressure gas sorption measurements on two carbonaceous shales has been conducted in order to assess the reproducibility of the sorption isotherms and identify possible sources of error. The measurements were carried out by seven international research laboratories using either in-house or commercial sorption equipment (manometric and gravimetric methods). Excess sorption isotherms for methane, carbon dioxide and ethane were measured at 65 °C and at pressures up to 25 MPa on two organic-rich shales in the dry state. The samples used in this study were taken from immature Posidonia shale (Germany) and over-mature Upper Chokier Formation (Belgium). Their total organic carbon (TOC) contents were 15.1% and 4.4% , respectively, and their vitrinite reflectance (VRr) values 0.5% and 2.0%. The objective of this study was to assess the reproducibility of sorption isotherms among laboratories each following their own measurement and data reduction procedures. All labs were asked to follow a predefined sample drying procedure prior to measurement in order to minimize any effects related to moisture. The reproducibility of the methane excess sorption isotherms was better for the high-maturity shale (within 0.02–0.03 mmol/g) than for the low-maturity sample (up to 0.1 mmol/g), similar to observations in earlier inter-laboratory studies on coals. The reproducibility for CO2 and C2H6 sorption isotherms was satisfactory at pressures below 5 MPa, however, the results deviate considerably at higher pressures. Anomalies in the shape of the excess sorption isotherms were observed for CO2 and C2H6 and these are explained as being due to high sensitivity of gas density to temperature and pressure close to the critical point as well as from a limited measurement accuracy and possibly uncertainty in the equation of state (EoS). The low sorption capacity of carbonaceous shales (as compared to coals and activated carbons) sets very high demands on the accuracy of pressure and temperature measurement and precise temperature control. Furthermore, the sample treatment, measurement and data reduction procedures must be optimized in order to achieve satisfactory inter-laboratory consistency and accuracy. Systematic errors must be minimized first by calibrating the pressure and temperature sensors to high-quality standards. Blank sorption measurements with a non-sorbing sample (e.g. stainless steel) can be used to identify and quantitatively account for measuring artifacts resulting from unknown residual systematic errors or from the limited accuracy of the EoS. The possible sources of error causing the observed discrepancies are discussed.

Evaluating the timing and origin of quartz cement is central to understanding how porosity is lost in sandstones during burial. Kinetic models of quartz cementation have been calibrated using large–scale datasets but have never been tested at the microscopic level at which cement forms. Here, we use high-precision, in situ oxygen isotope analyses on sandstone from the Jurassic Ness Formation from the North Sea to reveal the growth history of single quartz overgrowths to a resolution of 2 µm. Measured δ18O(cement) range from +28 to +20‰ V-SMOW in early to late cement and are consistent with quartz cementation models that propose the bulk of quartz precipitates as a continuous process beginning at 60–70 °C. Quantitative X-ray Diffraction analyses and clay mineralogical analysis of interbedded shales are inconsistent with a silica source from shale, implying that silica for the cement is sourced internally to the sand. These isotope data are broadly consistent with predictive, conceptual quartz cementation models and provide a critical link from micron-scale measurements to basin-scale predictions and observations.

Porous rocks in the subsurface are now used for carbon capture and storage (CCS), to help ameliorate the effects of greenhouse gas emissions. These porous reservoir rocks require a caprock to retain the CO 2 . It is important to characterize caprock quality and its stability in the presence of elevated partial pressures of CO 2 . Lower Triassic sandstones are common in the UK and NW Europe and are being considered for future CCS projects. The caprock to these sandstones is the Middle and Upper Triassic Mercia Mudstone Group. We have studied the Mercia Mudstone using mineralogy, petrology and mercury injection porosimetry to assess its caprock quality. Detrital minerals are dominated by quartz, K-feldspar, illite and chlorite; diagenetic pore-filling minerals are dominated by calcite, dolomite and gypsum. In samples with abundant clay minerals, there are only small quantities of pore-filling diagenetic cements. Porosity is broadly uniform for both clay-rich and clay-poor samples. The cleaner (clay-poor) samples had their initial pore spaces filled with early diagenetic pore-filling carbonates and gypsum. Despite the broadly uniform porosity, mean pore throat diameter displays a strong inverse correlation with clay content whereas threshold capillary entry pressure shows a strong positive correlation with clay content. The more clay-rich samples represent much better caprock than the coarser-grained samples that contain abundant pore-filling cement. The samples could support potential column heights of supercritical CO 2 between 70 and 540 m and have calculated permeabilities between 10 −20 and 10 −19 m 2 ; leakage would occur only on geological time scales, assuming that these samples are representative of the whole caprock. Because caprock quality correlates with illite content and illite will be relatively immune to elevated partial pressures of CO 2 , the Mercia Mudstone probably represents a durable caprock for future Lower Triassic sandstone CCS projects.

Most of the methods currently used for pore pressure prediction in sedimentary basins assume one-dimensional compaction based on relationships between vertical effective stress and porosity. These methods may be inaccurate in complex tectonic regimes where stress tensors are variable. Modelling approaches for compaction adopted within the geotechnical field account for both the full three-dimensional stress tensor and the stress history. In this paper a coupled geomechanical-fluid flow model is used, along with an advanced version of the Cam-Clay constitutive model, to investigate stress, pore pressure and porosity in a Gulf of Mexico style mini-basin bounded by salt subjected to lateral deformation. The modelled structure consists of two depocentres separated by a salt diapir. 20% of horizontal shortening synchronous to basin sedimentation is imposed. An additional model accounting solely for the overpressure generated due to 1D disequilibrium compaction is also defined. The predicted deformation regime in the two depocentres of the mini-basin is one of tectonic lateral compression, in which the horizontal effective stress is higher than the vertical effective stress. In contrast, sediments above the central salt diapir show lateral extension and tectonic vertical compaction due to the rise of the diapir. Compared to the 1D model, the horizontal shortening in the mini-basin increases the predicted present-day overpressure by 50%, from 20 MPa to 30 MPa. The porosities predicted by the mini-basin models are used to perform 1D, porosity-based pore pressure predictions. The 1D method underestimated overpressure by up to 6 MPa at 3400 m depth (26% of the total overpressure) in the well located at the basin depocentre and up to 3 MPa at 1900 m depth (34% of the total overpressure) in the well located above the salt diapir. The results show how 2D/3D methods are required to accurately predict overpressure in regions in which tectonic stresses are important.

We present an interpretational framework for the analysis of a diverse set of geological structures that breach sealing sequences and allow fluids to flow vertically or subvertically across the seal. In so doing, they act as seal bypass systems (SBS). We define SBS as seismically resolvable geological features embedded within sealing sequences that promote cross-stratal fluid migration and allow fluids to bypass the pore network. If such bypass systems exist within a given seal sequence, then predictions of sealing capacity based exclusively on the flow properties (capillary entry pressure and hydraulic conductivity) of the bulk rock can potentially be negated by the capacity of the bypass system to breach the grain and pore network. We present a range of examples of SBS affecting contrasting types of sealing sequences using three-dimensional (3-D) seismic data. These examples show direct evidence of highly focused vertical or subvertical fluid flow from subsurface reservoirs up through the seal sequence, with leakage internally at higher levels or to the surface as seeps. We classify SBS into three main groups based on seismic interpretational criteria: (1) fault related, (2) intrusion related, and (3) pipe related. We show how each group exhibits different modes of behavior with different scaling relationships between flux and dimensions and different short- and long-term impacts on seal behavior. Copyright ©2007. The American Association of Petroleum Geologists. All rights reserved.

Pore pressure prediction in shales is typically addressed using 1D compaction methods. However, this approach is only valid in basins where disequilibrium compaction is the dominant overpressure generation mechanism. For basins subjected to tectonic deformation, the predictions made by 1D methods are likely to be deficient due to the impact of lateral stresses on compaction and overpressure generation. In this research, we use a coupled fluid flow-geomechanical approach that accounts for the full 3D stress tensor to model the mechanical compaction of mudstones where tectonic regimes are significant. We use a 2D plain strain column to investigate the effect of different factors of basin burial and tectonic histories on stress, porosity and overpressure. From the different cases analysed the models predicted an increase in overpressure of up to 16 MPa at 3.5 km dept and a porosity loss of up to 6 porosity units due to the tectonic deformation.

Clay mineral diagenesis has a considerable effect on the physical properties of siliciclastic mudstones. The dominant clay mineral reaction, the conversion of smectite to illite, involves a series of dissolution and reprecipitation reactions which results in a significant change in the orientation of the whole clay fabric; not only smectite-illite but also kaolinite and chlorite. We have found clear evidence for chemically enhanced compaction (porosity loss/sediment volume reduction) associated with illitization of smectite in Lower Cretaceous mudstones at Halten Terrace, offshore mid-Norway from measured physical, textural, and mineralogical properties, and from log responses. We also see continuing compaction of diagenetically mature, illitized mudstones with increasing effective stress in the Central Malay Basin. These results are evidence that tends to refute the stress-independent chemical compaction model for diagenetically altered mudstones at temperatures above ~100C. Compaction in these diagenetically-altered mudrocks appears to be driven mainly by mechanical processes, although porosity loss is enhanced by small-scale fabric destabilization as a result of clay diagenesis.

Low and high resolution petrographic studies have been combined with mineralogical, TOC, RockEval and porosity data to investigate controls on the evolution of porosity in stratigraphically equivalent immature, oil-window and gas-window samples from the Lower Toarcian Posidonia Shale formation. A series of 26 samples from three boreholes (Wickensen, Harderode and Haddessen) in the Hils syncline was investigated. The main primary components of the shales are microfossiferous calcite (30–50%), clay minerals (20–30%) and Type II organic matter (TOC = 7–15%, HI = 630–720 mg/gC in immature samples). Characteristic sub-centimetric light and dark lamination reflects rapid changes in the relative supply of these components. Total porosities decrease from 10 to 14% at Ro = 0.5% to 3–5% at Ro = 0.9% and then increase to 9–12% at Ro = 1.45%. These maturity-related porosity changes can be explained by (a) the primary composition of the shales, (b) carbonate diagenesis, (c) compaction and (d) the maturation, micro-migration, local trapping and gasification of heterogeneous organic phases. Calcite undergoes dissolution and reprecipitation reactions throughout the maturation sequence. Pores quantifiable in SEM (>ca. 50 nm) account for 14–25% of total porosity. At Ro = 0.5%, SEM-visible macropores1 are associated mainly with biogenic calcite. At this maturity, clays and organic matter are not visibly porous but nevertheless hold most of the shale porosity. Porosity loss into the oil window reflects (a) compaction, (b) carbonate cementation and (c) perhaps the swelling of kerogen by retained oil. In addition, porosity is occluded by a range of bituminous phases, especially in microfossil macropores and microfractures. In the gas window, mineral-hosted porosity is still the primary form of macroporosity, most commonly observed at the organic-inorganic interface. Increasing porosity into the gas window also coincides with the formation of isolated, spongy and complex meso- and macropores within organic particles, related to thermal cracking and gas generation. This intraorganic porosity is highly heterogeneous: point-counted macroporosity of individual organic particles ranges from 0 to 40%, with 65% of organic particles containing no macropores. We suggest that this reflects the physicochemical heterogeneity of the organic phases plus the variable mechanical protection afforded by the mineral matrix to allow macroporosity to be retained. The development of organic macroporosity cannot alone account for the porosity increase observed from oil to gas window; major contributions also come from the increased volume of organic micro- and meso-porosity, and perhaps by kerogen shrinkage.

Grains within siliciclastic muds are deposited either as flocs, in which grains are generally ,10 mm, or as single grains: “sortable silt,” generally .10 mm. When clay-size (,2 mm diameter) particles form .30% of mudstones, pore-size distributions are controlled mainly by the interaction of phyllosilicates; these materials are ‘matrix-supported.’ Pores associated with clay-size particles are typically ,20 nm, even at shallow burial. When clay-size particles comprise ,30% of the grain-size distribution, a second, much larger pore system is observed, controlled by the amount and size of sortable silt; these mudstones are ‘framework-supported.’ Compaction of these silt-rich materials occurs mainly by the loss of the largest pores, but large pores still exist up to high effective stresses in the absence of chemical compaction. Mercury injection porosimetry (MIP) gives information about pore-throat size and pore connectivity and thus provides useful data with which to estimate permeability. Models based on generally flat pore shapes can estimate the permeability of homogenous mudstones to+a factor of 3 of the true value, but cannot be used for heterogeneous, laminated mudstones, which exhibit highly anisotropic permeabilities. As MIP gives information about pore throats and microscopy gives information about pore bodies, the two techniques generate different results. Both are required, along with other techniques such as small-angle neutron scattering and low-pressure gas sorption, in order to fully appreciate the complexity of mudstone pore systems.

How the micro-scale fabric of clay-rich mudstone evolves during consolidation in early burial is critical to how they are interpreted in the deeper portions of sedimentary basins. Core samples from the Integrated Ocean Drilling Program Expedition 308, Ursa Basin, Gulf of Mexico, covering seafloor to 600 meters below sea floor (mbsf) are ideal for studying the micro-scale fabric of mudstones. Mudstones of consistent composition and grain size decrease in porosity from 80% at the seafloor to 37% at 600 mbsf .Argon-ion milling produces flat surfaces to image this pore evolution over a vertical effective stress range of 0.25 (71 mbsf) to 4.05 MPa (597 mbsf). With increasing burial, pores become elongated, mean pore size decreases, and there is preferential loss of the largest pores. There is a small increase in clay mineral preferred orientation as recorded by high resolution X-ray goniometry with burial.

Understanding the impact of faults on fluid flow in the subsurface is important for the extraction of oil, gas and groundwater as well as the geological storage of waste products. We address two problems present in current industry-standard workflows for fault seal analysis that may lead to fault rocks not being represented adequately in computational fluid flow models. Firstly, fluid flow properties of fault rocks are often measured only for small-scale faults with throws not exceeding a few centimetres. Large seismic-scale faults (throws >20 m) are likely to act as baffles or conduits to flow but they are seldom recovered from subsurface cores and consequently fault rock data for them is sparse. Secondly, experimental two-phase fluid flow data is lacking for fault rocks and, consequently, uncertainties exist when modelling flow across faults in the presence of two or more immiscible phases. We present a data set encompassing both single- and two-phase fluid flow properties of fault and host rocks from the 90-Fathom fault and its damage zone at Cullercoats Bay, NE England. Measurements were made on low-throw single and zones of deformation bands as well as on slip-surface cataclasites present along the ∼120 m throw main fault. Samples were analysed using SEM and X-ray tomography prior to petrophysical measurements. We show that single deformation bands, deformation band zones and slip-surface cataclasites exhibit dissimilar single- and two-phase fluid flow properties. This is due to grain-size reduction being more pronounced in slip-surface cataclasites and changes in microstructure being fault-parallel for deformation bands but mostly fault-perpendicular for slip-surface cataclasites. A trend of fault rocks with low absolute permeabilities exhibiting lower relative permeabilities than more permeable rocks at the same capillary pressure is evident.

The Holywell Shale is part of the Carboniferous Bowland Shale Formation, identified as the main potential shale gas system in the UK. Here, we report geochemical and petrographic data from five outcrops of the Lower and Upper Holywell Shale across northeast Wales. At outcrop, the Holywell Shale is immature to early oil mature and has total organic carbon (TOC) values ranging between 0.1 and 10.3 wt %, with a mean of 1.9 wt %. Carbon isotope data clearly differentiate terrestrial and marine organic matter and show that both occur throughout the Holywell, with terrestrial sources (Type III/IV) dominating the Upper Holywell and marine sources dominating the Lower Holywell (Type II/III). Trace element data indicate that bottom waters were oxygenated, resulting in poorly preserved organic matter, supported by C/N and HI data. A range of silt- and clay-rich lithofacies occur, which show no relationship to either the amount or type of organic matter. We interpret the data in terms of a mixed supply of terrestrial and marine organic matter to marine depositional environments in which there was sufficient hydrodynamic energy to transport fine-grained sediment as bed load. The resulting mudstones exhibit a range of sedimentary textures with millimetre- to centimetre-scale silt–clay bed forms which show almost no relationship to organic matter type and amount. The small-scale variability and heterogeneity of both organofacies and lithofacies means that the reservoir quality of the Holywell Shale is inherently difficult to predict.

Mudstone is the most abundant sedimentary rock and variously acts as sources, seals, and shale gas reservoirs in petroleum systems. Many important physicochemical properties of mudstones are strongly influenced by the mineralogy and size of deposited grains, and by diagenetic changes (precompaction and postcompaction); these are commonly predictable. The diverse composition of mudstones reflects input and hydrodynamic segregation of detrital materials to basins, primary production within basins, and diagenetic processes (both precipitation and dissolution) in the sediment. High-magnification observations both in modern and ancient sediments demonstrate that mudstones are texturally and mineralogically heterogeneous; this variability is not always readily apparent. Although some mud is indeed deposited by suspension settling out of low-energy buoyant plumes, textural analyses reveal that it is commonly dispersed by a combination of waves, gravity-driven processes, and unidirectional currents driven variously by storms and tides. Such dispersal mechanisms mean that muddy successions are typically organized into packages that can be interpreted using sequence stratigraphy. Early bioturbation homogenizes mud, whereas early chemical diagenesis can result in highly cemented zones developing, especially at stratal surfaces. The nature of deeper burial diagenesis, which involves compaction, mineral dissolution, recrystallization, mineral reorientation and lithification, and petroleum generation, is preconditioned by depositional and early diagenetic characteristics of the mud. Although the petrophysical properties of homogeneous mudstones are reasonably well known, the quantitative implications of heterogeneity for petroleum expulsion, retention, petroleum migration, seal capacity, acoustic anisotropy, and identification of shale gas reservoir sweet spots are essentially unexplored. Future work should seek to redress this position.

Wilcox Group mudstones have been mechanically and geochemically transformed over a temperature range of 20–200 °C. Our research controlled for provenance and age by sampling from five wells, parallel to the paleodepositional axis, all within the Houston delta system. Across the sampled depths, mudstone porosity has been reduced from ∼25 to

A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (177 mg L(-1)) and aluminium (85 mg L(-1)) and to increase pH (3.2) and alkalinity (or =0 mg L(-1) CaCO(3) eq). Secondary objectives were to decrease zinc (2.8 mg L(-1)), manganese (20.5 mg L(-1)) and sulfate (2120 mg L(-1)). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO(4)(2)(-). Alkalinity (74%) and pH (95% as H(+)) were increased. Area adjusted removal rates (Fe=1.49+/-0.66 g d(-1) m(-2); acidity=6.7+/-4.9 g d(-1) m(-2)) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.

The relationship between permeability and porosity for fine-grained clastic sediments (“mudstones”) is a key constitutive equation for modelling subsurface fluid flow and is fundamental to the quantification of a range of geological processes. For a given porosity, mudstone permeability varies over a range of 2–5 orders of magnitude. We show here that much of the range can be explained by variations in lithology, which we define simply and pragmatically by clay content (mass fraction of particles less than 2 microns in diameter). Using clay content as the quantitative lithology descriptor, we have used a dataset (clay content range of 12–97%; porosity range of 0.04–0.78; six orders of magnitude permeability range) comprising 376 data points to derive a new bedding perpendicular permeability (K, m2) – void ratio (e = porosity/(1-porosity)) relationship as a function of clay content (CF): ln ( K ) = − 69.59 − 26.79 ⋅ C F + 44.07 ⋅ C F 0.5 + ( − 53.61 − 80.03 ⋅ C F + 132.78 ⋅ C F 0.5 ) ⋅ ⅇ + ( 86.61 + 81.91 ⋅ C F − 163.61 ⋅ C F 0.5 ) ⋅ ⅇ 0.5 The coefficient of regression (r2) = 0.93. At a given porosity, the inclusion of the quantitative lithological descriptor, clay content reduces the predicted range of permeability from 2 to 5 orders of magnitude to one order.

Fine-grained siliciclastic lithologies commonly act as sealing caprocks to both petroleum fields and host reservoirs for carbon capture (CO2 sequestration) projects. Fine-grained lithologies are thus of great importance in controlling fluid flow and storage in the subsurface. However, fine-grained rocks are rarely characterised in terms of primary sedimentary characteristics, diagenesis and how these relate to their flow properties (i.e. sealing or caprock quality). Seventeen samples from Lower Carboniferous estuarine caprock to a gas field (also to be used as a carbon capture site), have been analysed using a range of petrological and petrophysical techniques. The rock unit that represents the caprock to this gas field was found to be predominantly silt grade with porosity values as low as 1.8%. In these rocks, caprock quality (porosity) is controlled by intrinsic and extrinsic factors linked to primary mineralogy and diagenetic processes. Depositional mineralogy was dominated by quartz, detrital mica, detrital clay (likely Fe-rich 7A clay and illite–smectite) with minor feldspar and oxide phases. Diagenetic processes included compaction, minor feldspar dissolution and kaolinite growth and the more important processes of chlorite, siderite and quartz cementation, as well as the likely transformation of smectite into illite. Caprock quality is controlled by the primary quantity of illite-muscovite in the sediment and also by the localised extent of chlorite and quartz cementation. Deposition in an estuarine environment led to highly heterogeneous distribution of primary and diagenetic minerals, and thus caprock quality, between and within the samples.

article i nfo High-resolution X-ray texture goniometry (HRXTG) has been used to quantify the alignment (anisotropy) of phyllosilicate minerals in a series of diagenetically altered mudstone samples from the deep subsurface of the Texas Gulf Coast and the northern North Sea. The sampled formations have undergone a simple burial history with no overprint of tectonic deformation that may have influenced the phyllosilicate orientation. Observations have been made in two constrained temperature windows 148-150 °C (North Sea data) and 169-210 °C (Texas Gulf Coast) wherein less than 20% smectite remains in the mixed layer phase illite- smectite. Quantitative X-ray powder diffraction (XRPD) shows quartz (which is dominantly detrital) and phyllosilicate content having an inverse relationship. Quantified illite-smectite fabric intensity (phyllosi- licate alignments) ranges from low alignment values of 2.42 m.r.d. (multiples of a random distribution) to high alignment values 6.75 m.r.d. and chlorite+kaolinite ranges from 1.80 to 6.46 m.r.d. We propose that the broad range of phyllosilicate fabric intensity observed reflects the range of quartz/phyllosilicate ratios that are the imprint of depositional setting, bedform truncation, and initial grain size. Detrital quartz acts to disrupt fabric intensity by being non-platy, producing areas sheltered from effective stress ('pressure shadows'), and acting as a matrix support. There is no evidence that bioturbation is a significant control on phyllosilicate alignment in these quartz/phyllosilicate mixtures. These findings have important implications for the role of grain-scale alignment on seismic anisotropy in mudstone systems. Fabric intensity in post- diagenetic samples can be predicted from (1) quartz content and (2) total clay content where

The results are reported of a geochemical study of sediment cores and surface waters taken over an annual cycle from the compost-based constructed wetland at Quaking Houses, NE England. The wetland was built to treat acidic and metalliferous waters emanating from colliery spoil. The influent waters contain up to 10 mM SO 4 2 - , total Fe around 100 μM, and a mean pH of 6.2. The organic-rich sediments sustain a coupled redox cycle of Fe and S which occurs throughout the year but which is more intense in the summer months. Throughout the sediments, reduction of Fe(III) and SO 4 2 - apparently occur within the same macroscopic volume of sediment, along with oxidation of sulfide and Fe(III). In the top 2 cm of the sediment, pore water Fe concentrations reach a maximum of ∼1 mM in the presence of high concentrations of Fe oxides and the occurrence of SO 4 reduction. Partial re-oxidation of sulfide is indicated by the presence of significant elemental S. Total Fe in the surface 10 cm has a mean value of 7–9% of sediment dry weight, of which sulfide–Fe represents 7–12% and reactive amorphous Fe 20–45%; around 90% of the solid phase sedimentary Fe occurs as oxides or oxyhydroxides. It is suggested that the downwards diffusion of dissolved Fe from the near-surface maximum is sustained by the precipitation of Fe oxides as a result of radial O 2 loss from roots in the dense rhizosphere. Pore water pH is between 7.2 and 7.8 and alkalinity increases downwards, coupled to microbial SO 4 and Fe reduction. Transport processes occurring at and across the sediment–water interface are sufficiently rapid in the ∼20 h residence time of the waters to: (a) remove 70–90% of influent Fe and 15–25% of influent SO 4 into surface sediments and (b) increase both the pH and alkalinity of effluent waters. Coupling of the Fe and S cycles is fundamental to effective remediation in terms of both alkalinity generation and the retention of metals.