Mg-silicate minerals (e.g., stevensite, kerolite, talc, sepiolite) play an important role in the construction of facies models in lacustrine and peri-marine environments because they are sensitive to changes in solution chemistry. However, the response of Mg-silicate mineralogy to changing aqueous chemistry is only broadly understood because the mechanisms underpinning the coprecipitation of Mg2+ and SiO2(aq) from surface water, and subsequent Mg-silicate crystallization, are unclear. Here we describe the results of experiments designed to systematically examine the effects of pH, Mg/Si and salinity of the parent solution on the nature of initially precipitated products. Structural interrogation of the products with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal analysis (TGA/DTA) allow comparison of synthetic products with naturally occurring crystalline counterparts. In general, Mg2+ and SiO2(aq) co-precipitation and nucleation of Mg-silicate layer structures first involves the rapid formation of 2:1 layers with trioctahedral occupancy and a mean coherent X-ray scattering domain between 1–2 unit cells with respect to the c axis. Well defined but diffuse hk reflections indicate two-dimensional growth, turbostratic stacking and highly variable interlayer hydration. Diffuse reflectance FTIR shows numerous structural similarities with stevensite, kerolite and sepiolite. However, TGA/DTA analysis indicates the presence of variable kerolite/stevensite interstratification not readily detectable through XRD analyses, as well as a significant degree of surface and interlayer hydration (e.g. 15–20 wt.%).

We observe a number of clear trends in the products with respect to solution chemistry. For example, at low salinity, kerolite-like products dominate at high Mg/Si and high pH, whereas sepiolite-like products are formed at lower pH and lower Mg/Si. At high salinity and high Mg/Si, stevensite-like products are favoured at high pH and kerolite-like products dominate at lower pH, whereas a decrease in Mg/Si of the solution leads to sepiolite-like products at low pH and only stevensite-like products at high pH. Higher pH leads to an increase in octahedral vacancies which favour stevensite-like products; this may result from a higher rate of two-dimensional tetrahedral sheet expansion relative to the octahedral sheet, as inferred from studies of silica oligomerization and brucite growth kinetics.

Together, our results indicate that the neoformation of Mg-rich silicates from solution may often begin with the rapid nucleation of hydrated 2:1 layers. Subsequent dehydration leads to progressive layer stacking order and could occur in response to wetting/drying cycles, prolonged exposure to high salinity solutions, or burial and heating. The surface and interlayer water associated with these products is undoubtedly an important source of diagenetic water in Mg-silicate-bearing successions, and the chemistry of this water upon later diagenesis should be a focus of future investigation.

An understanding of the nature and scales of diagenetic variability within organic-rich mudstones is critical to the accurate assessment of shale-gas reservoir properties, as well as for elucidating chemical evolution pathways within mudstones. Here we integrate field observations with thin section descriptions (optical and electron optical techniques) and mineralogical data for the Blackhawk Member time-equivalent Mancos Shale in Book Cliffs, Utah, to determine the impacts of early and burial diagenesis on this mudstone succession.

The detrital assemblage in the Mancos Shale comprises quartz-silt, feldspar, clay minerals, dolomite and organic matter (TOC of 1 to 2.5%). Biogenic silica is negligible. Field mapping reveals laterally continuous (km scale), ferroan dolomite cemented units up to 0.3 m thick, are present. These cemented units cap both coarsening-upward units (1 to 3 m thick), and stacked successions of coarsening-upward units (5 to 15 m thick). These upward-coarsening sediment packages, capped by dolomite cemented strata, correlate to bedsets and parasequences in updip settings. Pervasive cementation in these dolomite-cemented units is likely to have occurred prior to compaction as a result of bacterially mediated respiratory processes. Cementation at these levels is particularly evident because cement precipitation occurred during breaks in sediment accumulation below marine flooding surfaces. The abundance of dolomite cements highlights the importance of macroscopic-scale diagenetic carbonate mobility in these mudstones.

In addition to carbonate-cements, diagenetic alteration and precipitation of quartz and alumina-silicate minerals are also important in these mudstones. Kaolinite is present both in uncompacted test of organisms and as vein fills in septarian concretions. Kaolinite precipitation is interpreted to have occurred prior to significant compaction and indicates that both silicon and aluminium were mobile during early diagenesis. We interpret the abundance of early diagenetic kaolinite cement to be the result of Al-mobilization by organic acids generated during organic matter oxidation reactions, with the Al sourced from poorly crystalline detrital aluminium oxides and clay minerals. There is also indirect evidence for burial diagenetic kaolinitization of feldspar grains. Quartz cement takes the form of quartz overgrowths and microcrystalline quartz crystals. Textures and CL spectra for the quartz microcrystalline cement suggests that recrystallization of biogenic silica (opal-A) was likely to have been an important source for quartz cements, although smectite-to-illite transformation may have contributed some. These mineral phases highlight that microscopic-scale diagenetic mobility of silica is important, even within mudstones lacking obvious sources of biogenic silica and is likely to be an important processes in a wide range of mudstones.

Detrital, volcanic and diagenetic origins have been used to explain the smectite clay assemblage that characterizes the Upper Cretaceous Chalk of Europe. To further the understanding of how clays of different origins may have converged to this characteristic clay mineral assemblage a new approach is put forward for their investigation. This is based upon (1) the correlation that exists between the trace element and stable isotope geochemistry of the calcite cements preserved within Chalk brachiopods and the various diagenetic phases of early lithification and cementation recognized in the Chalk, and (2) an understanding of the process of late diagenetic cementation that has caused regional differences in the hardness of the Chalk. It is suggested that each phase of lithification and associated calcite cementation may preserve the different clay assemblages at various stages in their convergence to the characteristic Chalk smectite assemblage.

The nature of the alteration of basaltic, andesitic and rhyolitic glass of Holocene and Pleistocene age and their physical and chemical environments have been investigated in the ash layers within the cryogenic soils associated with the volcanoes in the central depression of Kamchatka. One of the main factors controlling the alteration of the volcanic glass is their initial chemistry with those of andesitic (SiO2 = 53–65 wt.%) and basaltic (SiO2 < 53 wt.%) compositions being characterized by the presence of allophane, whereas volcanic glass of rhyolitic composition (SiO2>65 wt.%) are characterized by opal. Variations in the age of eruption of individual ashes, the amount and nature of the soil water, the depth of the active annual freeze-thawing layer, the thermal conductivity of the weathering soils, do not play a controlling role in the type of weathering products of the ashes but may affect their rates of alteration.

To a mineralogist, minerals are defined primarily by their crystal structure and chemical composition. Many minerals of industrial importance retain this identity in their final application. For the producer and end user, the physical properties of these industrial mineral products such as size and shape distribution, refractive index, density, hardness, refractoriness and colour are of primary importance, since it is the combination of these, together with its surface chemistry, which gives the mineral its functionality. As a result, minerals which are very different in structure and origin but have many similar physical properties, such as kaolin and calcium carbonate, are often used in very similar roles and in similar applications.

Examples of mineral use in diverse applications such as paper, paints and coatings, polymers and films show how the physical properties of different minerals are exploited and engineered to provide optical, mechanical and rheological performance and to minimise cost. Industrial mineral producers have been manipulating these properties for many decades and continue to do so in search of improved performance and new applications. As new high performance materials become more commonplace, the challenge is to find new ways of transforming minerals to provide the necessary functionality for them.

The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato, berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.

This paper describes a study of the hydraulic reactions between metakaolin (MK) and air lime using electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance spectroscopy (NMR). Tests were carried out at 20, 25 and 30°C on lime-MK pastes with 10:1 w/w ratio. Tests over 28 days allowed identification of relevant changes in the EIS signals and characterization of pastes using thermal analysis (TGA/DSC), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP) and uni-axial compressive tests. Tests over shorter periods of time (up to 42 h) allowed more detailed studies of the hydraulic phases formed at the very beginning of the reactions.

Results of thermal analyses demonstrate formation of hydraulic compounds such as CSH, C4AH13 and C3ASH6 and show their evolution over time. MIP analysis demonstrates changes in pore size distribution related to the formation and trasformation of hydraulic phases. Variations of impedance response with time are shown to be associated with reaction kinetics. Changes in the NMR signal within the first 42 h of reaction are shown to be associated with the dissolution of calcium hydroxide in the pore solution. Overall, this paper demonstrates the importance of NMR in the study of hydraulic reactions in lime based materials and the ability of EIS to detect the formation of hydraulic compounds and the end of the calcium hydroxide dissolution process.

The instability of shales in drilled formations leads to serious operational problems with major economic consequences for petroleum exploration and production. It is generally agreed that the nature of the clay minerals in shale formations is a primary causative factor leading to their instability, although the exact mechanism involved is more debateable. Currently, the principal cause of shale instability is considered to be volume expansion following the osmotic swelling of Nasmectite. However, illitic and kaolinitic shales may also be unstable, so that interlayer expansion cannot therefore be considered as a universal causative mechanism of shale instability. This review considers alternative scenarios of shale instability where the major clay minerals are smectite, illite, mixed-layer illite-smectite (I/S) and kaolinite respectively. The influence of interacting factors that relate to shale clay mineralogy such as texture, structure and fabric are discussed, as are the pore size distribution and the nature of water in clays and shales and how these change with increasing depth of burial. It is found from the literature that the thickness of the diffuse double layer (DDL) of the aqueous solutions associated with the charged external surfaces of clay minerals is probably of the same order or even thicker than the sizes of a significant proportion of the pores found in shales. In these circumstances, overlap of the DDLs associated with exposed outer surfaces of clay minerals on opposing sides of micropores (<2 nm in diameter) and mesopores (2–50 nm in diameter) in a lithostatically compressed shale would bring about electrostatic repulsion and lead to increased pore/ hydration pressure in smectitic, illitic and even kaolinitic shales. This pressure would be inhibited by the use of more concentrated K-based fluids which effectively shrink the thickness of the DDL towards the clay mineral surfaces in the pore walls. The use of soluble polymers would also encapsulate these clay mineral surfaces and so inhibit their hydration. In this scenario, the locus of action with respect to shale instability and its inhibition is moved from the interlamellar space of the smectitic clays to the charged external surfaces of the various clay minerals bounding the walls of the shale pores.

Nanometre-sized illite-type crystals extracted from mixed-layer illite-smectite of cored bentonite beds from the East Slovak Basin were studied to investigate timing, duration and physical/chemical conditions of their nucleation and growth. The study includes application of the results to an evaluation of the regional extent of illitization. Close to salt-bearing formations, the nanometric particles underwent a more intense illitization, of identical duration, but with changing oxygen and hydrogen isotope characteristics of the parental brines.

A comparison of the stratigraphic ages of the bentonite beds with the K-Ar ages of the authigenic crystals shows that illitization started during the Middle-Miocene Serravalian (Lower Sarmatian) subsidence that lasted from 17 to 11.5 Ma. Duration of illitization was bracketed between 14.5 and 9.0 Ma, with further episodes until recently at 0 Ma, depending on the geographic location of the host beds. The calculated subsidence rate varies from less than 300 m/Ma to more than 500 m/Ma and the thermal gradient ranges from ~60°C/km to less than 50°C/km. The K-Ar ages of the nanometric illite point to either short-duration illitization when the onset was soon after sedimentation, or long-duration when the onset was significantly later after sedimentation. The illite δ18O varies little with increasing crystal size, whereas the δD changes significantly. In most samples the crystallization temperature determined by different criteria did not change significantly during crystal growth, but the oxygen and hydrogen isotopic compositions of the interacting fluids varied depending on sample location, immediate environment, timing and duration of illitization.

The stable isotope composition of illite in bentonite beds with reduced fluid-rock ratios gives insight into the fluid-temperature regime of sedimentary basins through identifying local processes rather than wide-scale ones. Illitization is episodic with variable duration along different crystallization pathways, and to various extents in low-porosity, low-permeability bentonite beds. Depending on local conditions, illitization may vary even within apparently homogeneous beds. This contrasts with the situation for porous aquifers having large-scale fluid connectivity.

The influence of individual clay minerals on formation damage of reservoir sandstones is reviewed, mainly through the mechanism of fine particle dispersion and migration leading to the accumulation and blockage of pore throats and significant reduction of permeability. The minerals discussed belong to the smectite, kaolinite, illite and chlorite groups respectively. These minerals usually occur in an aggregate form in reservoir sandstones and the physicochemical properties of these aggregates are reviewed in order to reach a better understanding of the factors that lead to their dispersion in aqueous pore fluids. Particularly significant properties include the surface charge on both basal and edge faces of the clay minerals and how this varies with pH, external surface area of both swelling and non-swelling clays, porosity and pore size distribution in the micro- and meso-pore size range and overall aggregate morphology. For non-swelling clays, and perhaps even for swelling clays, dispersion is thought to be initiated at the micro- or meso-pore level, where the interaction between the pore solution and the charged clay surfaces exposed on adjacent sides of slit- or wedge-shaped pores brings about expansion of the diffuse double electric layer (DDL) and an increase in hydration pressure. Such expansion occurs only in dilute electrolyte solutions in contrast to the effect of concentrated solutions which would shrink the thickness of the DDL and so inhibit dispersion. Stable dispersions are formed, particularly where the solution pH exceeds the isoelectric pH of the mineral, which is often at alkali pH values, so that both basal face and edge surfaces are negatively charged and the particles repel each other. The osmotic swelling of smectitic clays to a gel-like form, so effectively blocking pores in situ, is often invoked as an explanation of formation damage in reservoir sandstones. Such swelling certainly occurs in dilute aqueous solutions under earth surface conditions but it is uncertain that stable smectitic gels could form at the temperatures and pressures associated with deeply buried reservoir sandstones.

It has been previously reported that late diagenetic fibrous illite, separated out from oilfield sandstones for dating by the K-Ar method, has systematically shown an increasing K-content with burial depth in the UK northern and central North Sea. This is surprising as fibrous illite is believed to form rapidly, in response to a geological event such as oil charging, and to retain its composition during subsequent burial. If the composition of the illite is related to present-day conditions, rather than the conditions of initial formation, then argon loss may have occurred, making K-Ar ages of questionable validity. Variations in crystal chemistry of the illite and their fundamental particle size and shape (length/width) distribution suggest alteration of the illite from the time of formation. The extent to which K-Ar ages of illite might need to be re-interpreted as a result of this post-formation alteration is not quantifiable at present; however there is evidence to suggest that the ages may be interpreted in terms of burial models involving both crystal nucleation and growth, and that a high proportion of Ar within the crystals may be retained during post-growth recrystallization.

The Cambridge Diagenesis Conferences (1981–1998) were set up to act as a conduit for the interchange of clay mineral expertise between universities and research institutes on one hand, and the hydrocarbon industry on the other. At the time, oil companies were dealing with the development of the North Sea Oil Province which was turning out to be a natural laboratory for the fundamental study of authigenic clay minerals and their relationship to lithofacies, burial, overpressure, reservoir quality and hydrocarbon emplacement. This symbiosis between industry and academia flourished for nearly two decades. Each conference was followed by a special issue of Clay Minerals dealing with topics relevant to, or discussed at the particular meeting. By the late 1990s the North Sea had become a mature province and the major oil companies were looking to other parts of the world to replenish their reserves.

Geochemical analysis of acid-insoluble residues derived from white chalks and marl seams of Campanian age from Sussex, UK, has been undertaken. All display a broadly similar <2 μm mineralogical composition consisting of smectite or smectite-rich illite-smectite with subordinate illite and minor amounts of talc. Plots of K2O/Al2O3 and TiO2/Al2O3 indicate that most marl seams have an acid-insoluble residue composition which is slightly different to that of the over- and underlying white chalk, implying that marl seams are primary sedimentary features not formed through white chalk dissolution. On the basis of a negative Eu anomaly and trace element geochemistry one marl seam, the Old Nore Marl, is considered to be volcanically derived and best classified as a bentonite; it is considered to correlate with the bentonite M1 of the north German succession.

Many safety functions required of the compacted bentonite buffer in the KBS-3 concept rely on processes influenced by the composition of the pore water. Important safety-relevant processes are related to the bentonite buffer, e.g. swelling, precipitation and dissolution reactions, and transport of water, colloids and ions. One of the methods used in analysing pore water in compacted bentonite is the ‘squeezing technique’. Various possible artefacts which can occur during squeezing, such as mixing of different pore-water types, dissolution of accessory minerals and cation exchange, need special attention.

The present work describes the methodology for studying the composition of the non-interlamellar pore water by combining squeezing methods, chemical analyses, microstructure measurements and geochemical modelling. Four different maximum pressures were used to squeeze the compacted bentonite pore water. The origin of the pore water was studied by analysing the bentonite microstructure both before and after squeezing using SAXS and NMR, the cation exchange and dissolution reactions were studied by chemical analyses and geochemical modelling.

The pore-water yield increased from 32 to 48 wt.% from the initial amount of porewater in the samples when the maximum squeezing pressure was increased from 60 MPa to 120 MPa. About 35 wt.% of the water collected originated from the interlamellar (IL) pores. The ratio between IL and non-IL pore waters as well as the composition of the squeezed porewater was constant in the squeezing-pressure range used. The results of microstructural measurements by SAXS were in perfect agreement with previous studies (e.g. Muurinen & Carlsson, 2013). The dissolving accessory minerals have an effect on the ratio of the cations in the squeezed solution while the migration of anions in bentonite seems to be diffusion limited. According to geochemical modelling the chloride concentration of the non-IL pore water in compacted bentonite before squeezing was 0.34 Mgreater than in the squeezed pore water due to the mixing of two main water types.

Anisotropy and compositional and structural heterogeneity in clays are causes of considerable deviations from homogeneous diffusion, in particular in terms of direction-dependent transport rates and preferred transport zones. Conventional diffusion experiments, in which the sample is treated as a homogeneous black box in a concentration gradient, are interminable and insensitive to spatial effects. In contrast, tomographic imaging methods are capable of both reducing the amount of observation time required and revealing space-dependent features of the diffusion process.

In the present study, positron-emission-tomography (PET) was applied as the most sensitive quantitative spatiotemporal tomographic modality for direct observation of positron-emitting radiotracers in opaque media at reasonable resolution (1 mm) on a laboratory scale (100 mm).

Geoscientific applications of PET, or GeoPET, have revealed anisotropic and heterogeneous effects in diffusion experiments that have been conducted on Opalinus clay samples of different sizes, as well as on other rock types. Applying the Comsol Optimization Module to 2D-image sections of the PET tomograms, effective parameter values were derived, thereby quantifying the anisotropic diffusion.

Organoclays are sorbent materials prepared from clays by exchanging inorganic with organic cations. Their properties depend on the loading and conformational structure of the organic cations, but little information is available about the surface structures of organoclays. In this work, X-ray photoelectron spectroscopy (XPS) and classical molecular dynamics (MD) simulations are combined to characterize the external interface of an organoclay prepared from hexadecylpyridinium (HDPy+) and bentonite. The XPS survey spectra show well the varying elemental composition of the surface with increasing amount of surfactant, showing a decreasing contribution of clay-derived elements with increasing organic coverage. The high-resolution C 1s XPS spectra depict sensitively the surface arrangement of the surfactant. In combination with MD simulations, the results implied a monolayer coating for low surfactant coverage and a disordered bilayer arrangement at high surfactant uptakes. Molecular dynamics simulations showed that for very high cation uptake a quasi-paraffin-like configuration is also possible. The combination of experimental and modelling methods yielded congruent information on the molecular-scale arrangement of organic cations at the organoclay surfaces and the controlling mechanisms.

Alteration of cement–bentonite interfaces and accompanying changes in diffusivity of tritiated water (HTO) was investigated experimentally using intact, hardened cement-paste specimens. The alteration by carbonate solution was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼70 ± 7%of the initial value after a 180-day period. Another alteration in contact with compacted bentonite was accompanied by mineralogical changes at the interface and a decrease in the HTO diffusivity to ∼71 ± 10% of the initial value after a 600-day period. The changes in the diffusivity were considerably less than those observed for mixed specimens of ground, granulated hardened cement paste and bentonite where the diffusivity decreased to 20% of the initial value over 180 days. The results were extrapolated to 15 y under simple assumptions and showed good agreement with those observed in the cement–argillite interface at Tournemire URL (France). Such an explanation enhances confidence in the assessment of the alteration of cement-bentonite systems and might be a basis for using the data and models obtained in the long-term assessment of radioactive waste disposal.

Up until about 2005, the main application of halloysites had been as an alternative raw material to kaolinite for ceramics. Since then, however, there has been an exponential increase in studies aimed at applications of halloysite nanotubes, now widely referred to as HNTs. The readily available and relatively cheap nanotubular forms of halloysite have potential uses in nanocomposites with polymers, as carriers for active agents, e.g. in medicine, agriculture, cosmetics and environmental remediation, as well as in nanotemplating, as supports for catalyst immobilization and as heterogeneous catalysts.

Molecular cluster models, developed for an exfoliated kaolinite, provide a structural description comparable to that of periodic slab models for a fraction of the computational cost. These models include both the octahedral and the tetrahedral sheets of kaolinite. The first-generation model (G1) contains the inner and outer coordination sphere of the Al- and Si-honeycombs as the preferred sites for adsorption of small organic molecules. Since no experimental information is available to date at the atomic level for exfoliated kaolinite, we carried out a systematic density functional theory evaluation for establishing the most reasonable coordinates of the ions and groups. The results of molecular cluster and periodic calculations were utilized for evaluating semi-empirical Hamiltonians on larger models. Using a PM7 Hamiltonian, the structure of cluster models containing 1 + 6 (second generation) and 1 + 6 + 12 (third generation) Al- and Si-honeycombs which are out of reach for ab initio calculations, were determined. These molecular slab models offer a structural platform for adsorption, intercalation and delamination studies.