TiO2/stevensite nanocomposite photocatalysts were synthesized by a solvothermal method using TiCl3/HCl as reactants and the stevensite clay mineral extract as support. The prepared photocatalyst samples were then characterized using various techniques such as X-ray diffraction (XRD), Infrared spectroscopy (IR) and Transmission Electron Microscopy (TEM). The Points of Zero Charge (PZC) of the various samples were evaluated by titration of the non-modified and the Ti-modified clay aqueous dispersions, with cationic surfactant solutions. The photocatalytic activity of the resulting nanocomposites samples were evaluated for the removal of Orange G (OG) from aqueous solution as a model dye pollutant. The data indicate that the formation of Na+-stevensite by the TiO2 particles leads to TiO2/stevensite nanocomposites having higher specific surface areas and mesopore volumes, and lower PZC values. Further, the photocatalytic activity was greater for the TiO2/stevensite nanocomposites having the greatest Ti amount, as compared to a pure TiO2 sample, and increased with the increase of the TiO2 content in the TiO2/stevensite nanocomposites.

Organo-bentonites were prepared using a bentonite and an aqueous cetyltrimethylammonium hydroxide solution. The ratio of the surfactant (in mmoles) to the cation exchange capacity varied from 0.5 to 20, with 20 being the highest ratio ever reported in the literature. At high surfactant to cation exchange capacity ratios, the interlayer spacing increased to 3.75 nm due to the formation of a paraffin-type bilayer of surfactant cations, which was shown to be mainly in gauche conformations using solid state 13C CP/NMR. When the exchange reaction was carried out in a methanol-water mixture, the expansion of the organo-bentonites depended on the concentration of methanol (% by volume). The decomposition temperatures of the organic cations depended on the basal spacing of the organo-bentonites, and in situ X-ray diffraction revealed that the basal spacing of our organo-bentonites was stable up to 210°C. Above this temperature, the basal spacing shrunk to 1.47 nm due to decomposition of the surfactants.

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.

The purpose of this paper is to determine the effect of NaF and firing temperature on the dielectric properties (dielectric constant and dielectric loss) of talc, which is used in the electrical and electronic industries as a circuit element. A detailed characterization of the samples was made by XRD, FTIR, SEM and TG-DTG methods. Dielectric measurements were performed in the frequency range from 1 MHz to 80 MHz at room temperature. The dielectric constant value increased with an increase in firing temperature due to the removal of polarizable compounds from the talc structure. The higher dielectric constant values were obtained by addition of NaF. The dielectric loss of NaF doped talc decreased with the increase of firing temperature and increased with the increase of the amount of NaF.

Seven commercial cosmetic clays having different colour (white, green, pink and red) available in pharmacies and herbalists’ shops in the Greek market have been examined for their trace element concentrations (Ag, As, Ba, Be, Cd, Ce, Co, Cr, Cs, Cu, Ga, Hf, Hg, La, Mo, Ni, Pb, Rb, Sb, Sc, Se, Sr, Tl, V, Y, Zn and Zr). According to EC Regulation 1223/2009 the presence of As, Be, Cd, Cr, Hg, Ni, P, Pb, Sb, Se, Te, Tl, Zr and their compounds is prohibited in cosmetics. The most abundant trace elements in the white clays were P (330 μg/g), Pb (220 μg/g) and Zr (11 μg/g) and for the green clays were P (1250 μg/g), As (43 μg/g), Cr (31 μg/g), Pb (30 μg/g) and Ni (23 μg/g). Red and pink clays had lower concentrations of these elements than their white and green counterparts. The green clays are three times enriched in As and the kaolinite-rich white clays are nine times enriched in Pb compared to the Average Shale. The main mineral phase in the white clays is either kaolinite or calcite, in green clays smectite, in pink clay kaolinite and talc and in red clays it is vermiculite. The specific activities of 238U, 226Ra, 228Ra, 228Th and 40K were determined by γ-ray spectroscopy. The kaolinite-rich white clays are more enriched in 238U-series radionuclides (238U and 226Ra) than the smectitic green clays. In contrast, the green clays were more enriched in 232Th-series radionuclides (228Ra and 228Th) and 40K than the white clays.

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.

The Mamil Choique halloysite deposits of Patagonia, Argentina, contain randomly distributed green clay inclusions and patches within the halloysite mass. Halloysite has been formed from the thorough alteration of rhyolitic to dacitic ash fall tuffs and ignimbrites of the Huitrera Formation, Eocene age, under ambient conditions. The smectites present in the clay inclusions have been determined as ferruginous beidellites with variables amounts of Fe3+ in octahedral sites. The weathering activity that caused the formation of halloysite was also responsible for the genesis of the iron-bearing clay minerals, the formation of which was controlled mainly by permeability. Textural variations within the rock indicate favourable local geochemical environments for the formation of the green clay minerals.

In the present study, changes of iron content, brightness, particle size, mineralogy and paramagnetic properties of kaolins before and after superconducting high gradient magnetic separation (SHGMS) were investigated. The Fe2O3 contents of the feed decreased by 56% after 3.5T SHGMS with 1# steel wool, but higher magnetic intensity to 5.5T did not remove additional iron. The ISO brightness of the kaolin sample after SHGMS was improved from 56.9% to 76.7%. The D50 value of the magnetic rejects was 35% larger compared to the feed. Large particles might block the micro-pores in the steel wool matrix. Compared to the feed, the dark or red impurities significantly decreased in the non-magnetic product. Paramagnetic species in the kaolin sample were sensitive to SHGMS. The resonances at g = ~2.0 and g = 4.0 decreased significantly in the concentrate compared to the feed in the ESR spectra. Iron components in the non-magnetic product were more likely to be non-paramagnetic. The results are useful for understanding the SHGMS in kaolin treatment, and might be a guide for optimizing process parameters.

Silylated kaolinites were synthesized at 80°C without the use of inert gas protection. The method presented started with mechanical grinding of kaolinite, followed by grafting with 3- aminopropyltriethoxysilane (APTES). The mechanical grinding treatment destroyed the ordered sheets of kaolinite, formed fine fragments and generated broken bonds (undercoordinated metal ions). These broken bonds served as new sites for the condensation with APTES. Fourier transform infrared spectroscopy (FTIR) confirmed the existence of −CH2 from APTES. 29Si cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy (29Si CP/MAS NMR) showed that the principal bonding mechanism between APTES and kaolinite fitted a tridentate silylation model (T3) with a chemical shift at −66.7 ppm. The silane loadings of the silylated samples were estimated from the mass loss obtained by TG-DTG curves. The results showed that the 6-hour ground kaolinite could be grafted with the most APTES (7.0%) using cyclohexane as solvent. The loaded amount of APTES in the silylated samples obtained in different solvents decreased in the order as: nonpolar solvent > polar solvent with low dielectric constant (toluene) > polar solvent with high dielectric constant (ethanol).

This study examines the effect of German camomile (Matricaria camomilla L.) cultivation on the weathering of minerals present in the clay fraction of five different soil series modified or not unmodified (control) with cattle manure. A factorial experiment was performed in a randomized complete block design (RCBD) with three replications. At harvest time the rhizosphere soil was separated from bulk soil and the mineralogy was examined by X-ray diffraction (XRD). Trioctahedral chlorite transformed to hydroxy-interlayer vermiculite (HIV), while kaolinite disappeared. The presence of HIV was identified by an increase in the intensity ratio of the 1.0 and 1.4 nm peaks after Na-citrate pretreatment and K-saturation. It is suggested that Al3+ is released during dissolution of kaolinite and subsequently enters into the interlayer sheet of chlorite, and consequently the brucite layer disappears. This was verified by a significant Mg2+ increase in the soil solution in three out of five experiments at harvest time compared to pre-planting. The pots amended with manure showed the same changes as the pots without manure. The results of this study may explain the presence of unexpected clay minerals in regions with unsuitable conditions for their formation.

Clays are commonly used as liners in urban landfills. However, the reactive processes with landfill leachates, and in particular the role of accessory minerals is poorly known. The aim of this work is to evaluate the diffusion of a synthetic urban landfill leachate through compacted natural smectite-illitic clays containing carbonates and sulfates and to predict the functioning of the clay liner for different minor mineral proportions. The leachate, characterized by acidic pH conditions and high organic matter content, is a typical aqueous solution formed in the acetogenic phase of organic matter degradation in urban landfill areas. Medium-scale (11 cm) laboratory diffusion tests were performed over 77 days. Chloride diffusion coefficients, porosity changes, cation exchange constants and the sulfate reduction rate were quantitatively assessed by means of reactive transport modelling. The exchange capacity of the clays is responsible for NH4+ retention. However, the presence or absence of gypsum in the initial clay rock controls the functioning of the liner. Gypsum dissolution ensures a high sulfate concentration in the porewater and enhances the acetate consumption via sulfate reduction. Gypsum dissolution and the concomitant calcite precipitation do not significantly alter the porosity of the clay rock.

In order to improve the optical properties and enhance the stability of Zn1–xCdxS nanoparticles, which are important optoelectrical materials, the ternary Zn1–xCdxS nanoparticles were enclosed in a layered octosilicate by a three-step process, namely (i) protonation of Naoctosilicate, (ii) ion-exchange in order to introduce Zn and Cd ions into the interlayer space, and (iii) addition of S2– to form Zn1–xCdxS particles in the interlayer space of the octosilicate. The basal spacing (~10 Å) of the final ZnCdS-Oct-n (n = 1, 2, 3, 4) composites noticeably increased in comparison with that of the precursor H-Oct (7.5 Å). This may be attributed to the incorporation of larger size Zn1–xCdxS particles into the interlayer space of H-Oct. The UV-visible spectra of the composites suggested that the transmission band-edges gradually shifted to low energy with increasing molar ratio of Cd/Zn. Moreover, the transmission band-edges of the composites are between those of layered Octosilicate, ZnS, and CdS. TEM observation confirmed that the size of Zn1–xCdxS nanoparticles enclosed in the layered silicate was about ~3–5 nm.

Mudstones and claystones from the southern marginal area of the European Upper Triassic, midcontinental Keuper basin (Silesia, southern Poland) were investigated using XRD, organic and inorganic geochemistry, SEM, K-Ar of illite-smectite, AFT, and stable isotopes of O and C in carbonates in order to unravel the consequent phases of the geological history of these rocks, known for abundant fossils of land vertebrates, and in particular to evaluate the diagenetic overprint on the mineral composition. The detected and quantified mineral assemblage consists of quartz, calcite, dolomite, Ca-dolomite, illite, mixed-layer illite-smectite, and kaolinite as major components, plus feldspars, hematite, pyrite, chlorite, anatase, siderite, goethite as minor components. Palygorskite, gypsum, jarosite and apatite were identified in places.

The K-Ar dates document a post-sedimentary thermal event, 164 Ma or younger, which resulted in partial illitization of smectite and kaolinite. The maximum palaeotemperatures were estimated from illite-smectite as ∼125°C. Apatite fission track data support this conclusion, indicating a 200–160 Ma age range of the maximum temperatures close to 120°C, followed by a prolonged period of elevated temperatures. These conclusions agree well with the available data on the Mesozoic thermal event, which yielded Pb-Zn deposits in the area. Organic maturity indicators suggest the maximum palaeotemperatures <110°C.

Palygorskite was identified as authigenic by crystal morphology (TEM), and calcite by its accumulation in soil layers and by its isotopic composition evolving with time, in accordance with the sedimentary and/or climatic changes. Dolomite isotopic composition indicates more saline (concentrated) waters. Palygorskite signals a rapid local change of sedimentary conditions, correlated with algal blooms. This assemblage of authigenic minerals indicates an arid climate and the location at the transition from a distal alluvial fan to mudflat.

Fe-rich smectite, kaolinite, and hematite were products of chemical weathering on the surrounding lands and are therefore mostly detrital components of the investigated rocks. Kaolinite crystal morphology and ordering indicates a short transport distance. Hematite also crystallized in situ, in the soil horizons. A large variation in kaolinite/2:1 minerals ratio reflects hydraulic sorting, except of the Rhaetian, where it probably signals a climatic change, i.e. a shift in the weathering pattern towards kaolinite, correlated with the disappearance of hematite. Quartz, 2M1 illite, and minor feldspars and Mg-chlorite were interpreted as detrital minerals. The documented sedimentation pattern indicates that in more central parts of the Keuper playa system, where an intense authigenesis of the trioctahedral clays (chlorite, swelling chlorite, corrensite, sepiolite) took place, illite and smectite were the dominant detrital clay minerals.

Cr/Nb and Cr/Ti ratios were found as the best chemostratigraphic tools, allowing for the correlation of all investigated profiles. A stable decrease of these ratios up the investigated sedimentary sequence is interpreted as reflecting changes in the provenance pattern from more basic to more acidic rocks.

Trachyandesite rocks, occurring over an area of about 1 km2 in the southwest part of Limnos Island, Greece, are altered mainly to halloysite. The samples were collected and analysed by polarizing microscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and chemical analysis. The alteration of plagioclase to halloysite follows seven discrete stages that are described in detail. The geochemical evaluation of the data shows enrichment of the light REE (LREE) over heavy REE (HREE) as expressed by the (La/Yb)n ratio. The ΣLREE range from 206.44 to 272.30, while the sum of HREE varies from 11.01 to 26.26. The (La/Yb)n ratio ranges from 9.72 to 27.64. Fractionation among LREE expressed as (La/Sm)n and between middle REE (MREE) and HREE is shown as (Tb/Yb)n ratios. The most altered rocks close to the fault zone have high (Tb/Yb)n ratios and low (La/Sm)n and Eu/Eu* ratios. Although mineralogy and clay mineral textures indicate hydrothermal genesis of halloysite, the geochemical data are not conclusive due to a secondary weathering effect.

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 Maastrichtian-Palaeogene series of the Western High Atlas and Meseta Basins in Morocco are particularly rich in palygorskite. The present work is aimed at clarifying the genesis of palygorskite from the interbedded facies and gaining an understanding of their relationships with the depositional environment. The mineralogical characteristics of palygorskite from these series were studied by X-ray diffraction (XRD) and electron microscopy (SEM/TEM). The palygorskite content and microstructure show large geographical and stratigraphical variations in the deposits studied. The palygorskite occurrence is directly related to palaeobathymetry, since it is the dominant clay mineral in shallow marine and restricted environments. According to the morphology of palygorskite crystallites, four types of textures were distinguished. These types of palygorskite are polygenetic, formed by chemical precipitation, by the recrystallization of smectite clays or reworked by wind or water from sub-aerial environments. The difference between the two studied sub-basins with respect to palygorskite occurrence is attributed to the palaeomorphology of the hinterlands, to the tectonic differentiation and to the physical-chemical conditions of seawater.

The composition, morphology and crystal order of clay minerals in silt-sized sediments carried in suspensions from 25 major rivers across tropical southern Africa have been studied by X-ray diffractometry and scanning and transmission electron microscopy. Our goal was to determine the spatial variability of clay-mineral associations in diverse geological settings, and in climatic conditions ranging from humid Angola and Zambia to hyperarid Namibia and the Kalahari. Specific attention was paid to the micromorphology and chemical composition of smectite particles. The relative abundance of smectites, illite/mica, kaolinite and chlorite enabled identification of regions characterized by different physical and chemical processes: (1) negligible chemical weathering is documented in Namibia, where river muds mostly contain illite/mica or smectite derived from Damara metasedimentary or Etendeka volcanic rocks; (2) kaolinite documenting intense weathering, reaches a maximum in the Okavango, Kwando and Upper Zambezi, sourced in subequatorial Angola and Zambia; (3) suspended-load muds in the Limpopo and middle Zambezi catchments display intermediate features, with varied assemblages and smectite compositions reflecting diverse parent lithologies. Clay mineralogy and chemical composition are confirmed as a most effective tool to unravel present and past climatic conditions on a continental scale.

An Early Pliocene sedimentary succession in the Yenidoğan area, Sivrihisar, Turkey, consists of sepiolite, stevensite, kerolite, dolomite and magnesite. The geology, mineralogy and geochemistry of the succession was examined by extensive field work along several trenches and a representative measured section, followed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal, and chemical analyses.

Structurally, two distinct forms of sepiolites were distinguished by XRD: (a) well crystallized sepiolite with a 110 reflection at 12.07–12.3 Å , and (b) poorly crystallized sepiolite in which the 110 reflection occurs at 12.7–13.0 Å (denoted as sepiolite-13Å ). Differences in crystal chemistry, thermal and morphological properties of these forms, the vibrational spectra and XRD characterization of the related phyllosilicates were also documented.

Stevensite, kerolite and sepiolite were formed by direct precipitation from alkaline lake water rich in Mg and Si. Sepiolite-13Å was probably formed by transformation from precursor smectite via dissolution-precipitation, more likely during early diagenesis. Environmental conditions such as ion concentration, salinity and variations in pH may have controlled the formation of the phyllosilicates.

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.

Kaolinite- and halloysite-potassium acetate complexes were synthesized by cogrinding with solid potassium acetate (mechanochemical intercalation). The efficiency of mechanochemical intercalation was compared to the intercalation in solution and by homogenization. The effects of ageing and grinding parameters (grinding time, sample:grinding body mass ratio (SGMR), rotational speed) and the humidity on the intercalation were studied. The degree of intercalation increased exponentially with ageing of the samples prepared by mechanochemical and homogenization techniques. For the mechanochemical and homogenization techniques the required amount of potassium acetate per gram of kaolin (∼0.4 g/g) was two orders of magnitude lower than that for the solution intercalation (78.6 g/g). The highest degree of intercalation (86%) and the lowest structural deformation were achieved by the mechanochemical method (¼ h of co-grinding with 1:2 SGMR at 300 rpm), followed by 16 h ageing at 57% relative humidity.