A decade of research on clays that kill human pathogens, including antibiotic-resistant strains such as methicillin-resistant S. aureus (MRSA), has documented their common characteristics. Worldwide, ∼5% of clays tested to date are antibacterial when hydrated. Most antibacterial clays are from hydrothermally altered volcanics, where volcanogenic fluids produce minerals containing reduced metals. Ferruginous illite-smectite (I-S) is the most common clay mineral, although kaolins dominate some samples. Antibacterial clay mineral assemblages may contain other reduced Fe minerals (e.g. pyrite) that drive production of reactive oxygen species (H2O2, •OH, •O2−) and cause damage to cell membranes and intracellular proteins. Ion exchange can also cause loss of bacterial membrane-bound Ca2+, Mg2+ and PO43–.

Critically important is the role of clays in buffering the hydration water pH to conditions where Al and Fe are soluble. A nanometric particle size (<200 nm) is characteristic of antibacterial clays and may be a feature that promotes dissolution. Clay interlayers or the lumen of tubular clays may absorb reduced transition metals, protecting them from oxidation. When the clays are mixed with deionized water for medicinal applications, these metals are released and oxidized.

Different antibacterial clays exhibit different modes of action. The minerals may be a source of toxins, or by adsorption may deprive bacteria of essential nutrients. In the field, the pH and Eh (oxidation state) of the hydrated clay may help to identify potential antibacterial clays. If the pH is circum-neutral, toxic metals are not soluble. However, at pH < 5 or >9 many metals are soluble and the oxidation of transition metals increases the Eh of the suspension to >400 mV, leading to bacterial oxidation.

Understanding the antibacterial mechanism of natural clay may lead to design of new treatments for antibiotic-resistant bacteria, with potential applications in wound dressings, medical implants ( joint replacements, catheters), animal feed stocks, agricultural pathogens, and production of antibacterial building materials. This research exemplifies how ‘geomimicry’ (copying geochemical processes) may open new frontiers in science.

Glaucony is present in the Palaeocene sediments of the London Basin, from the Thanet Sand Formation to the gravel beds at the base of the Lower Mottled Beds of the Reading Formation. The Upnor Formation glaucony is a rare example of formation in warm, shallow, brackish water and this, combined with the ready availability of fresh material from boreholes, make this study important in developing our understanding of this mineral. Glaucony comprises up to 50% of the Upnor Formation, a grey to green sandstone, of variable thickness and composition, which was deposited in awarm, shallow, marine to estuarine environment, ∼55.6–56.2 Ma. Using morphological criteria, X-ray diffraction data and K+ abundance, the Upnor glaucony may be defined as evolved. The underlying shallow marine Thanet Sand contains <5% of nascent to slightly evolved glaucony. The rare earth element (REE) data for the Upnor Formation suggest more than one source for the sediment from which the Upnor glaucony formed, while the Thanet REE data are consistent with a large detrital clay component.

In the Upnor Formation, the large proportion of glaucony that occurs as granule fragments rather than whole granules, and the high-energy estuarine to shallow-marine environment of deposition, are indicative of reworking. The Upnor glaucony is inferred to be intraformationally reworked, rather than derived from the Thanet Sand Formation. The glaucony may have formed in sediments deposited away from the main estuarine channel, and been subsequently reworked into higher-energy sediments.Warm seas with freshwater mixing are more typically characteristic of verdine formation than of glaucony. The shallow, brackish environment of deposition suggests that there is not a clear distinction between the environmental requirements of verdine (or odinite) and glaucony (or glauconite), as is often proposed. The highly fractured, delicate nature of some granules indicates that they have experienced somematuration in situ, after reworking.

The oxygen and hydrogen isotopic compositions of Upnor Formation shark teeth and glaucony point to formation in low-salinity water at ∼23 ± 3°C, also consistent with formation in the Upnor Formation, rather than in a fully marine sediment and subsequent reworking. A higher than normal temperature of formation may have increased the rate of evolution of glaucony.

Our multidisciplinary study considers many of the factors relating to depositional environment that must be considered when glaucony-rich facies are encountered in comparable palaeo-environmental settings elsewhere in the geological record.

Natural aluminosilicates can contain Fe in tetrahedral or octahedral coordination. Amongst smectites, tetrahedral iron is known to occur in Fe-rich nontronites but few indications exist for the presence of tetrahedral Fe in smectites of the montmorillonite–beidellite series. A set of 38 different bentonites showed a correlation of tetrahedral charge and Fe content in their smectites. All materials with large tetrahedral charge were rich in Fe. This could be explained by a general tendency of Fe to enter the tetrahedral sheet. To investigate this correlation, nine materials were selected and investigated by Mössbauer, UV-Vis, Fe K pre-edge and EXAFS spectroscopy with respect to tetrahedral Fe (Fe[IV]). The latter two methods were at the detection limit but Mössbauer and UV-Vis spectroscopy provided consistent results indicating the significance of both methods in spite of some scatter caused by the overall small amount of tetrahedral Fe. The results indicate the absence of any relation between Fe content and tetrahedral Fe. Tetrahedral Fe can be present in Fe-poor smectites and absent in the case of Fe-rich materials. This means that Fe-rich montmorillonites have a larger tetrahedral charge which is not caused by Fe[IV] but by Al[IV]. A possible explanation for this indirect relation is based on: the coordination of Al3+ in the weathering/smectite-forming solutions determines the coordination in the precipitates; and the Al[IV/VI] ratio increases with increasing pH. The correlation could thus be explained if the pH of weathering solutions generally was higher in Fe-rich parent smectite rocks than in more acidic smectite parent rocks. The relation between tetrahedral charge and Fe content can probably be explained by different geochemical contexts throughout the formation of smectites which affect the coordination of dissolved Al.

The adsorption of C2H4 and H2 gases by bentonite from the Ünye region, Turkey both as raw (B) and as K+-, Li+-, Ag+- and Mg2+ -exchanged forms, was investigated using automated volumetric equipment and pressures up to 100 kPa at 273 K and 77 K, respectively. X-ray powder diffraction (XRD) and specific surface area measurement (BET) methods were employed to characterize the bentonite samples. The C2H4 and H2 gas adsorption capacities of the original and modified forms were in the ranges 1.817–0.201 mmol g−1 and 0.522–0.388 mmol g−1, respectively. The influence of salt modifications on the gas adsorption properties of bentonite is discussed.

The kinetics of dissolution of Amazonian metakaolin in hydrochloric acid (HCl) was studied using the ‘Shrinking Core Model’ for spherical and ‘flat plate’ particles of constant size. The Amazonian kaolin was calcined at 700°C for 2 h. The calcined samples (metakaolins) were leached in an HCl solution with 5% excess at 70, 80 and 95 ± 3°C for 3 h. Samples were collected every 15 min and subjected to Al analysis by the EDTA titrimetric method. Experimental data showed that the spherical morphology produced a better fit with respect to the regression coefficients. The activation energy of the reaction was 90.6 kJ/mol. The chemical process is a first-order leaching reaction. The results of the present study are consistent with those from previous research on this topic, which used HCl with an excess of >90%.

Ultramarine pigments were synthesized successfully from Na-A zeolite derived from kaolin waste. Na-A zeolite encapsulates the sulfur species formed and which act as chromophores, which circumvents their oxidation and the subsequent liberation of high levels of toxic gases during the reaction. Different Na-A zeolite matrices with various grain sizes (fine to coarse) were mixed with sulfur and sodium carbonate in various proportions to study the influence of these variables on the pigments’ colours and hues. After calcination at 500°C for 5 h, the products were characterized by X-ray diffraction, X-ray fluorescence and Raman spectroscopy and were classified by the Munsell system (colour and hue). Products with colour ranging from blue to green with various hues were obtained. Both colour and hue were affected by the amount of additives and by the particle size.

The effect of ulexite concentrator waste on the physical and mechanical properties and sintering behaviour of a standard floor tiles (FT) body fired at 1080°C was studied. The linear firing shrinkage, water absorption and fired bending strength of the floor tile/tiles were determined. X-ray diffraction analyses identified quartz, albite, mullite and hematite phases in the floor tiles containing 3 wt.% waste material. The FT body with the smallest water absorption (∼0.2%), the greatest bending strength (∼335 kgf/cm2) and the second greatest linear firing shrinkage values had optimal composition. In light of the excellent physical-mechanical properties and the results of the scanning electron microscopy-energy dispersive X-ray analyses, the authors determined that the sintering temperature of the FT body containing 3 wt.% ulexite concentrator waste was reduced by 100°C.

The Tremp–Isona basin (south-central Pyrenees, Lleida, Spain) shows maximum development of the Tremp Group (early Maastrichtian to late Paleocene) covering a wide geological record across the Cretaceous–Paleogene (K/Pg) boundary in continental facies. The mineralogy and geochemistry of lutites were used to assess the evolution of weathering from the Maastrichtian to the Eocene, and particularly for the red beds of the Lower Red and Upper Red Units (pre- and post-K/Pg, respectively). Chemical weathering decreased initially in the Maastrichtian (Gray Unit to Lower Red Unit), increasing subsequently from the Paleocene (Upper Red Unit) to Eocene units. ANOVA analysis of mineralogical compositions and cluster hierarchical analysis have been useful tools to select convenient lutites for assessment of weathering evolution by the chemical alteration index and by broadening of the 001 X-ray diffraction line of illite after ethylene glycol solvation. The lesser chemical weathering found in the Upper Red Unit (Danian) is interpreted in the context of relative warming and aridification, in climates of contrasting seasons and pronounced dry seasons.

In many countries, compacted bentonite is a candidate engineering barrier material for safe disposal of high-level radioactive waste. The Swedish Nuclear Fuel and Waste Management Company (SKB) set up an in situ experiment (the ABM project) to compare the stability of different bentonites under the conditions of exposure to an iron source and to elevated temperature (up to 130°C) at the Äspö Hard Rock Laboratory, Sweden. Results for the Japanese bentonite (Kunigel V1) are summarized in the present study.

Mineralogical investigation using X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) suggested no transformation of smectite or neoformed clay phases. However, a distinct change in exchangeable cations of smectite was indicated (i.e. from Na type to Fe type and/or Ca type) in the bentonite in the vicinity of the steel heater.

Measurements of hydraulic conductivity and swelling properties suggest that no significant changes occurred in the bentonite even in the vicinity of the steel heater. This is attributed to the limited portion of the bentonite affected by the iron–bentonite interactions and the incomplete ion-exchange reactions. The methylene blue cation exchange capacity and the determination of the exchangeable cations showed that the lateral distribution for these parameters was constant. However, the total exchangeable cation population has changed significantly compared to the initial sample.

The percolation of water through waste landfills produces leachates with high concentrations of which can generate -exchanged clays within geochemical barriers. These leachates also contain several volatile organic compounds (VOCs) which can interact with the clay barrier. The aim of the present study was to characterize the sorption of eight short-chain VOCs (acetonitrile, methyl tert-butyl ether, dichloromethane, benzene, phenol, ethanol, acetone and aniline) on -smectite, and to identify their sorption mechanisms. The samples treated were characterized by carbon and nitrogen elemental analysis, infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. For acetonitrile, methyl tert-butyl ether, dichloromethane and benzene, no sorption was detected. Phenol, ethanol and acetone were sorbed very weakly, through Van der Waals interactions. Aniline molecules were sorbed strongly on -smectite mainly with hydrogen bonds between aniline and interlayer water molecules. However, aniline sorption decreased the hydrophilic character of the -smectite, which may increase the permeability of the clay barrier.