Sepiolite is a fibrous clay mineral and consists of 2:1 silicate blocks connected at the corners and separated by tunnels (channels on external surfaces) that extend in the direction of fiber length. The tunnels, 3.7 Å × 610.6 Å in cross-section, are responsible for the incorporation of organic and inorganic compounds. The present study aimed to examine the capacity of twelve different organic molecules, such as pyridine, indigo, methylene blue, and quaternary amines, to gain access to the tunnels of sepiolite using quantum chemistry techniques. The interaction energy computations performed at the B97-D/TZVP level showed that all of the considered organic molecules tend to access the tunnels of sepiolite if external water molecules are absent. This finding is in agreement with experimental studies that included pyridine, indigo, 2,2-bipyridyl, and methylene blue. Interestingly, 2,6-dimethyl pyridine preferred to remain in a tunnel rather than an external channel of the sepiolite.

Polycyclic aromatic hydrocarbons (PAHs) are a large class of organic compounds which are commonly mentioned and have been shown to be highly carcinogenic and to persist in the environment for many years. An inexpensive remediation method has yet to be found, so the current study was undertaken to test the use of sepiolite, a fibrous clay mineral, as a potentially inexpensive and effective solid-phase adsorbent for sequestering PAHs. Pyrene was chosen as a model PAH due to the specific volatility, miscibility, and relatively soluble properties of the compound. A sepiolite of Turkish origin was then investigated to explore its potential to adsorb hydrophobic organic compounds from aqueous solution. The microstructure and morphology of the sepiolite were characterized using elemental analysis, X-ray diffractometry (XRD), Fourier-transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FE-SEM), and specific surface area from N2 adsorption isotherms. The pyrene adsorption isotherms were closely fitted to the Langmuir model and the coefficients of determination (RP2) were higher than 0.999. The results indicated that the high affinity of pyrene for sepiolite surfaces was dominated by the structural channels and the large number of Si-OH groups located on the basal surfaces. The intracrystalline interactions of pyrene with the sepiolite were, however, more favorable than pyrene interactions with sepiolite surface Si-OH groups, which can react directly with pyrene to form true covalent bonds (chemical interactions). Finally, the FE-SEM images initially revealed that, after sepiolite was loaded with adsorbed pyrene, a fairly straight and rigid arrangement of fibers occurred due to the aggregation of laths to form rods and the increased amounts of adsorbed pyrene.

The performance of bentonite barriers for high level radioactive waste (HLRW) disposal is currently being tested in various real-and up-scale disposal tests. One of the disposal tests, the ABM test (ABM = alternative buffer material), was conducted by SKB (Svensk Kärnbränslehantering) as a mediumscale experiment at the Äspö hard rock laboratory in Sweden. The present study deals with the second parcel (ABM-II), which was retrieved after 6.5 years with 2.5 years of water saturation and 3–4 years of heating up to 141°C. Nine different bentonites and two marine clays were tested to investigate the performance. The aim of the study was to provide a detailed characterization of the mineralogical and chemical changes that took place in ABM-II, compare the findings with ABM-I (the first of the six test parcels), and try to draw some general conclusions concerning the use of bentonites in such geotechnical barriers. The ABM-II test parcel revealed a set of reactions that a HLRW bentonite might undergo. The most prominent reaction was the rather complete exchange of cations, which was discussed in a second part to this publication (II — cation exchange; Dohrmann and Kaufhold, 2017). The corrosion of the Fe in metal canisters was observed, but no discrete corrosion product was identified. At the interface of bentonite and the metal canister, the formation of smectite-type trioctahedral clay minerals was observed. In contrast to the ABM-I test, anhydrite was present in many of the bentonite blocks of the ABM-II test. In most concepts used for HLRW disposal in crystalline rocks, a temperature below 100°C at the canister surface was applied to avoid boiling. In the ABM-II test, boiling of water was possibly observed. Throughout the experiment, a pressure/water loss was recorded in the upper part of the geotechnical barrier and water was added to maintain pressure in the bentonite. As a result of evaporation, NaCl crusts might have formed and the barrier was partly disintegrated. These results demonstrated that a reasonable assumption is that no boiling of water occurs in disposal concepts in which a pressure loss can occur.

A more controllable method to synthesize particular zeolites from geopolymers is needed in order to effectively use these materials in industrial applications. In the present study, a well-crystallized zeolite P1 was synthesized from a metakaolin-based geopolymer (SiO2/Al2O3=3.2) using a hydrothermal method. The products obtained by hydrothermal treatment were identified using X-ray diffraction (XRD), scanning electron microscopy (SEM), and specific surface areas. The XRD patterns and SEM micrographs indicated that the structure and morphology of zeolite P1 could be controlled by the NaOH solution concentration, hydrothermal temperature, and the hydrothermal treatment time. The crystalline structure of the prepared zeolite P1 was refined using the Rietveld method and the crystal structure parameters were as follows: a = 10.01 Å, b = 10.01 Å and c = 10.03 Å. The optimal hydrothermal conditions to form zeolite P1 were 24 h at a hydrothermal temperature of 100°C and 2.0 M NaOH solution. Moreover, the synthesized zeolite P1 had a specific surface area of 36.56 m2/g.

The removal of Co2+, Ni2+, and Pb2+ from aqueous solutions using a modified zeolite was investigated because of the need to eliminate toxic contaminants from wastewaters. In the present study the ways in which equilibrium, thermodynamics, and kinetics parameters affected the removal of heavy metals were evaluated and compared. An Iranian clinoptilolite with a Si/Al ratio of 6.5 was used as an adsorbent. In order to increase the adsorption capacity of the adsorbent, it was converted to a manganese oxide-coated zeolite (MOCZeo) using various Mn solutions. The initial concentration of metals, pH, contact time, and temperature were the variables studied and optimal conditions were established. The maximum amount of Co2+, Ni2+, AND Pb2+ adsorption on MOCZeo was ascertained. A thermodynamics study, using ΔG, ΔH, and ΔS state functions showed that adsorption of Pb2+ was more spontaneous than that of Co2+, Ni2+ ions. The adsorption of these ions on MOCZeo was an endothermic reaction. Investigation of the adsorption models revealed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed both the Langmuir and Freundlich models. Kinetics studies showed that the adsorption of Pb2+, Co2+, and Ni2+ on MOCZeo followed the pseudo-second order kinetics model with a high correlation coefficient.