The design of nanostructured materials based on natural components, such as clay minerals, offers new solutions to biomedical challenges such as more efficient and storage-stable vaccines. Clay-lipid hybrid materials have proved useful as adjuvants in influenza vaccines and with a possible projection to leishmaniasis vaccines and other pathogens. Self-assembly of phospholipid molecules on the surface of microfibrous sepiolite and lamellar Mg/Al layered double hydroxide renders a biocompatible lipid bilayer membrane that ensures non-degrading immobilization of proteins and other biological species including viral particles and DNA (deoxyribonucleic acid). Immunization tests in mice showed the superior immunogenicity of a clay-lipid-supported virus compared to a commercial aluminium hydroxide adjuvant.

Newly discovered K-bentonite beds, interstratified with limestones/dolomitic limestones of the Upper Devonian–Lower Carboniferous Yılanlı Formation, are exposed in the northwestern Black Sea region of Turkey, around Zonguldak and Bartın. K-bentonite samples collected from four different locations: the Gavurpınarı and Yılanlı Burnu quarries from the Bartın area, the Çimşir Çukurları quarry from the Şapça area, and the Güdüllü and Gökgöl highway tunnel section near Zonguldak city were investigated using optical microscopy, X-ray diffraction and inductively coupled plasma mass spectrometry in order to reveal their mineralogical and geochemical characteristics and understand their origin and evolution. The K-bentonites occur at different levels in the Yılanlı Formation as 2–40 cm-thick, greenish to yellowish beds cropping out several hundred metres along strike. Preliminary biostratigraphic data suggest that the protoliths of the Bartın (Gavurpınarı and Yılanlı Burnu) and Güdüllü K-bentonites were deposited at around the boundary between the Frasnian and Famennian, whereas those in the Şapça and Gökgöl sections are slightly younger (Devonian–Carboniferous boundary interval). The lithofacies types of the host carbonate rocks suggest an ‘epeiric’ shallow carbonate platform environment. Illite and mixed-layer illite-smectite were the major clay minerals in the K-bentonites. The K-bentonites from the Bartın area display a high degree of illitization and consist mainly of illite indicating high-grade diagenesis, whereas illite-smectite-rich samples from the Şapca and Gökgöl tunnel locations reflect relatively lower diagenetic conditions. According to their geochemical compositions, two groups of K-bentonites were distinguished, one with alkali basalt (Bartın area and Güdüllü locations) and one with trachyte affinities (Gökgöl tunnel and Şapça locations). Geochemical fingerprinting of K-bentonites by trace and rare earth element (REE) data suggest that tephras with alkali basalt composition have been derived by a source formed in a ‘continental back-arc’ setting, whereas the source of K-bentonites with trachytic precursors is related to ‘continental within-plate rifting’. An evaluation of the global Late Devonian and Devonian–Carboniferous volcanism suggests that the bentonite precursors may be related to late-Variscan magmatism in Laurussia.

Greece is a major bentonite producer, with Milos Island being one of the largest bentonite mining centres in the world. In addition to the bentonite deposits which are well known, various other occurrences exist in the islands of Chios and Samos, Eastern Aegean and in some areas of Thrace, in NE Greece. These bentonites are associated with volcanic activity and their age ranges from Lower Oligocene in Thrace, to Lower–Middle Miocene in Chios and to Upper Miocene in Samos. Although some of these materials have been utilized since ancient times (e.g. the Samian Earth), these bentonites have been mined only at a local scale. In this study the first data on the mineralogical and geochemical characteristics of these bentonites are presented.

The Samos bentonites of UpperMiocene age are medium–lowgrade (40–70% smectite) and crop out in the SE margin of the Karlovasi Basin formed at the expense of acidic pyroclastic flows mainly in a subaeriallacustrine environment. They consist mainly of Ca-rich medium–high-charge montmorillonite, opal-CT and sanidine with minor quartz and locallymordenite. The Chios bentonites of Lower–MiddleMiocene agewere formed at the expense of trachyandesitic tuffs in a lacustrine environment in the Neogene Basin at theSEpart of the island. They consist mainly of Ca,Mg-rich high-charge montmorillonite (33–75%), similar to the SAz-1, and opal-CT, minor plagioclase, chlorite, plagioclase, carbonates and traces of talc and serpentine. In Thrace, LowerOligocene pyroclastic flows, tuffs and lavas of acidic-intermediate compositionwere altered to zeolites and bentonites in the sedimentary basins of the Feres-Pefka, Skaloma and Sappes areas. The parent pyroclastic rockswere altered to Ca-rich and in places,Na-rich, dioctahedralmontmorillonite or Fe-rich beidellite (Sappes area) and with minor opal-CT,mordenite, quartz, plagioclase and, in places, illite. The bentonites are medium–high grade (50–58% smectite in Feres-Pefka, 74–86% in Skaloma and 29–40% in Sappes).

The bentonites havemoderate cation exchange capacity andmoderate/lowswelling index and viscosity and they are not suitable for the drilling and foundry industries. However, preliminary results show that after processing, most of the depositsmight be utilized in high added-value applications such as bleaching earths or in the synthesis of clay-based polymer nanocomposites.

The objective of the DOPAS international project is to design a sealing-plug system for deep geological repository (DGR) use, to provide detailed plans for the design of such plugs, to test the characteristics of the materials to be used and the construction technology and to install four experimental in situ plugs. The Czech experimental pressure and sealing-plug (EPSP) experiment is being conducted in a rock environment consisting of granitoids at the Josef Regional Underground Research Centre. The concept of the experiment is based primarily on the use of materials and technology available in the Czech Republic and the principal aim is to demonstrate the technical viability and functioning of a pressure-resistant plug located in a future DGR. The completion of the EPSP experiment will contribute towards both the demonstration of how sealing-plug systems behave under real underground conditions and the long-term safety of a future DGR in the Czech Republic.

The distribution of octahedral cations in the two component layers of a 7 Å–14 Å interstratified mineral with a bulk chemical composition (Fe4.122+Mg0.07Mn0.01Al1.69□0.11)(Si2.56Al1.44) O10(OH)8 was investigated using high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) in combination with the image simulations. In the 14 Å component layers, comparison between the observed and simulated images revealed that the M4 sites of the interlayer sheets were occupied preferentially by Al together with a small amount of Fe; the other M1, M2 and M3 sites were occupied by dominant Fe and residual Al in equal proportions. Two types of octahedral sheets with disordered and ordered cation distributions were recognized in the 7 Å component layers. The two types of sheets were similar to the octahedral sheet of the 2:1 layer and the interlayer sheet in the 14 Å layer above, respectively. Irregular vertical stacking and lateral contact of the different component layers in structure and chemistry characterized the interstratification, which may be caused by rapid precipitation and accretion of the component layers in hydrothermal environments.

The advantages and limits of empirical, semi-empirical and thermodynamic methods devoted to the estimation of chlorite-formation temperature are discussed briefly. The results of semiempirical and thermodynamic approaches with different assumptions regarding the redox state of iron in chlorite are compared for a large set of natural data covering a range of pressure conditions from a few hundred bars to 18 kbar and temperature from 100 to 500°C. The T-XFe3+ evolution estimated using the thermodynamic approach of Vidal et al. (2005) shows a systematic increase in XFe3+ with decreasing temperature, which is compatible with the decrease in aO2 buffered by magnetite- or hematite-chlorite equilibrium. This trend as well as the observed increase in vacancies in chlorite with decreasing temperature is interpreted as the incorporation of Fe3+-sudoite. The standard-state properties of this endmember have been derived to reproduce the observed T-aO2-XFe3+ evolutions. It can be used to estimate T-aO2-XFe3 values with a Chl-Qtz-H2O multi-equilibrium approach. When combining our results with those of other studies published recently, it appears that thermodynamic approaches and mapping techniques developed for metamorphic rocks can be used to discuss the conditions of formation of very low-grade rocks where kinetics is much more sluggish than in metamorphic rocks. This requires use of appropriate analytical tools and techniques with a spatial resolution of a few hundred nanometres.

Tosudite, a regularly interstratified chlorite-smectite, crystallizes as an alteration mineral of several preexisting Al-bearing silicates (feldspars, kaolin minerals, chlorites) present in arkosic sandstones hosted in uranium deposits in Niger. X-ray diffraction patterns show a sharp superstructure at 29–29.6 Å for an air-dried state and a peak at 30.8–31.6 Å following ethylene glycol solvation. The 060 reflection at 1.507–1.509 Å indicates an overall dioctahedral character, and the very low coefficient of variation of the d00l reflections for the solvated mineral (0.03–0.13) permits validation of the regular interstratification justifying its identification as tosudite. Microprobe analysis allowed specification of the component layers of this mixed-layer mineral. The chlorite is a di-trioctahedral type analogous to sudoite (Si3Al4Mg2(OH)8), and the smectite component is a low-charge montmorillonite type Tosudite is characterized by large Al2O3 and MgO contents and small Fe content; its composition corresponds approximately to the formula where octahedral occupancy is ∼7. Scanning electron microscope (SEM) observations show that tosudite is closely associated with some uranium minerals: tosudite crystallization occurred during a late alteration event which post-dates burial diagenesis and during which uranium was remobilized by Mg-rich oxidizing fluids.

Chlorite (C)-corrensite (Co)-smectite (S) seriesminerals occur as vein constituents in the two epithermal ore veins, the Chuetsu and Shuetsu veins of the Todoroki Au-Ag deposit. The characteristics of the C–Co–S seriesminerals indicate that the clays may be products of direct precipitation from hydrothermal fluids and subsequent mineralogical transformations during and/or after vein formation. The minerals from the Chuetsu vein are characterized by ‘monomineralic’ corrensite showing an extensive distribution throughout the vein, and trioctahedral smectite occurring locally. The Shuetsu vein minerals are characterized by C-Co series minerals which can be divided into three different types: a I type including discrete chlorite with minor amounts of S layers, a II type comprising interstratified C/Co and discrete chlorite, and a III type characterized by segregation structures of C and Co layers. The C-Co series minerals show slightly different spatial distributions in the Shuetsu vein. Different epithermal environments during the vein formations and possible kinetic effects may have played a role in the formation and conversion of Co-C series at the Shuetsu vein and S-Co series at the Chuetsu vein.

A compilation of Fe3+-bearing chlorite analyses is used: (1) to investigate the Alfree di-trioctahedral (AFDT) substitution 2Fe3+ +□= 3(Mg,Fe2+) in chlorite; and (2) to estimate the composition of a ferri-sudoite end-member (Si3Al)[(Fe2+,Mg)2□Al]O10(OH)8 within the chlorite solid-solution domain. According to our observations, up to two Fe3+ cations might be allocated in the M2-M3 chlorite sites by the substitution AFDT, which does not involve Al. These unexpected observations were made possible by the development of μXANES techniques allowing in situ measurements of XFe3+ (Fe3+/(Fe2+ + Fe3+)) in heterogeneous chlorite. Although further studies are required to confirm the crystallographic position of Fe3+ and refine its ionic/ magnetic behaviour in chlorite, this development creates opportunities for developing new geothermometers.

The MH-2B borehole, a part of Project HOTSPOT, was drilled to a depth of 1821 m in late Cenozoic basalts, hyaloclastites and interbedded lake sediments, on the Mountain Home Air Force Base in southern Idaho, USA. Drillers encountered hot water (145°C) under artesian pressure at 1745 m in a narrow zone of highly fractured rock associated with a major sub-surface fault. X-ray diffraction (XRD) analysis identified corrensite (with and without smectite) between 1700 and 1800 m, but only smectite above 1700 m and below 1800 m. This corrensite horizon contains a relatively narrow zone of fracturing and hot artesian water near its centre but for the most part occurs in relatively massive basalt flows. No evidence was found for randomly interstratified chlorite-smectite.

The intercalation of Tb(III) into layered magadiite is achieved by three-step ion exchanges with H+/Na+, TBA+ (tetra-n-butylammonium ions)/H+ and Tb(EDTA)3+/TBA+. Various techniques, including powder X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), thermogravimetric and differential thermogravimetry (TG-DTG), Fourier transform infrared (FTIR) spectroscopy, and photoluminescent spectroscopy (PL), were employed to characterize the Tb-intercalated magadiites. The XRD results revealed that the basal spacing of the Tb-intercalated magadiites was obviously larger than that of the Na-magadiite, confirming the intercalation. The IR spectra showed no bands attributable to EDTA in the Tb-intercalated magadiites, indicating that the EDTA has broken away from Tb(III)-ETDA complexes during ion exchange. Moreover, the basal spacing of Tb-intercalated magadiite tends to increase slightly with the increase in water content in the Tb-intercalated magadiite. The PL spectra show weak emissions, attributed to 5D4-7FJ (J = 3, 4, 5, 6) transitions of Tb3+.