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 application of natural fertilizer mixtures that improve nutrient retention ability of soils has attracted considerable attention in recent years. In addition to rock phosphate (RP), the basic components of these mixtures are zeolites modified with selected cations, such as the ammonium ion. The NH4-zeolite serves as a carrier of nutrients as well as a soil conditioner, and it promotes the RP dissolution in all soil types. The purpose of the present work was to prepare costeffective NH4-zeolite supplement, using 32 full factorial experimental designs, with concentration of modifier and processing time as variables. Saturation processes were carried out on two types of natural zeolites, K- clinoptilolite (K-Cp) and Ca-clinoptilolite (Ca-Cp). The Response Surface Method (RSM) was applied for evaluation of cation exchange, suggesting an effective NH4+ modification of natural zeolite at lower quantities of modifier than commonly found in other studies on the topic. Using Principal Component Analysis (PCA), differences between samples relative to the process variables were clearly outlined and correlated with concentrations of the exchanged cations. The best results were obtained for the K-Cp type modified with 1.5 M solution of ammonium sulfate (at a Cp/NH4+ stochiometric ratio 1:7.5) for all three processing intervals. By optimizing the modification process parameters, an experimental design of partially saturated NH4-Cp supplement that has the potential to supply all major plant nutrients was proposed.

This paper addresses the mineralogy, geochemistry, and genesis of palygorskite and associated calcretes in the Kırşehir region. In this area, the Quaternary calcretes are present within and/or on lacustrine mudstones of the Kızılırmak Formation (Late Miocene-Pliocene). The calcretes occur in the form of nodules, tubes, fracture-infills, and hard laminated crusts (hardpans). Calcrete samples are predominantly composed of calcite associated with smectite, quartz, feldspar, and minor palygorskite. The lacustrine mudstone samples consist mainly of smectite and palygorskite with minor calcite, quartz, feldspar, illite, kaolinite and amorphous material. Petrographic studies revealed that the calcrete samples are predominantly micrites that were partially converted to microsparites by recrystallization. Scanning and transmission electron microscopy images indicate that palygorskite fibres formed authigenically on and between calcite rhombs in the calcrete samples and at the edges of smectite flakes of host rocks adjacent to the calcretes. The oxygen and hydrogen stable isotope values of the calcite suggest that it precipitated from meteoric water under arid or seasonally arid climatic conditions. Calcite precipitation occurred in the vadose zone, as evidenced by desiccation cracks and vadose pisolites. The enrichment of Rb+Ba±Sr and Light Rare Earth Elements (LREE) relative to Heavy Rare Earth Elements (HREE)with a distinct negative Eu anomaly are responses to the fractionation of volcanogenic feldspar and hornblende under the influence of meteoric water. The palygorskite associated with calcretes was precipitated from alkaline water rich in Si, Al and Fe and low in Mg. The palygorskite precipitation occurred at increased temperatures, characterising the advanced stage of calcrete formation which lowers the Ca content in the soil water. The required chemical elements for palygorskite and calcite were most likely derived from the dissolution of smectitic clays, ignimbrites and carbonate minerals.

Although investigation of the hydraulic conductivity behaviour of zeolite-bentonite mixtures (ZBMs) has been a topic of interest for researchers recently, the influence of compaction water content on the hydraulic conductivity of ZBMs has not been studied so far. This study discusses the hydraulic conductivities of ZBMs and compares the results with those of sand-bentonite mixtures (SBMs). The hydraulic conductivities of SBMs were unaffected by compaction water content and bentonite content, but the hydraulic conductivities of ZBMs were substantially different in mixtures containing 10% and 20% bentonite. The hydraulic conductivity of 10% ZBM (i.e. containing 10% bentonite and 90% wt. zeolite) gradually decreased as the water content increased to optimum water content and then it tended to decrease rapidly when the water content exceeded the optimum. In contrast, the hydraulic conductivity of 20% ZBM sharply decreased at the early stages of compaction water content (i.e. on the dry side of optimum water content) and levelled off when the water content was at the optimum water content. However, there is at least one order of magnitude difference between the hydraulic conductivities of ZBMs and SBMs, supporting the zeolite network model as suggested in previous works.

The aspect ratios of common clay minerals have been determined from conductometric titrations. The sample set comprises 11 Na-saturated bentonites, 16 smectites with different interlayer cations, three illites/muscovites and two talc dominated specimens. It is shown that the aspect ratios of smectites saturated with divalent cations are lower than those of the same smectite saturated with a monovalent cation. This observation is discussed in terms of the number of smectite layers making up a particle.

The purpose of this study was to determine whether a bentonite from the Gafsa deposit (western Tunisia) could be used to remove the Foron Blue 291 (FB) azo dye from wastewater. Batch adsorption and desorption experiments were conducted using untreated and purified bentonite and the influence of contact time, pH, adsorbent mass and temperature of the dye solution on the adsorption of FB was evaluated. Kinetic and isotherm data were fitted using two non-linear kinetic and two non-linear isotherm equations. In addition, the fits were evaluated using the coefficient of determination (R2) and the RMSE. The percentage of dye removal increased with increasing amount of adsorbent until total discolouration was achieved. The adsorption isotherms followed the Langmuir model, with the purified bentonite having a higher adsorption capacity than the raw material due to its higher specific surface area. In addition, the FB molecules were removed from the liquid medium by physical adsorption. Batch desorption experiments were conducted to study the desorption kinetics and the characteristics of the desorption isotherms as well as to quantify the portion of the FB (by mass) that was irreversibly fixed on the solid. Overall, the desorption kinetics were similar to the adsorption kinetics, which indicated that the adsorption-desorption process of azo dye is non-singular; irreversibility occurred that was underlined by an observed thermodynamic index of irreversibility (TII) of 0.69–0.94. The desorption isotherms of the FB depended on the mass of the FB that was initially adsorbed on the bentonite sample, suggesting hysteresis. The amount of irreversibly retained FB was between 46 and 68% of the initial adsorbed mass.

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.

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.