Mössbauer spectroscopy is the technique of recoil-free resonant emission and absorption of gamma rays. It has the advantage of being oblivious to all elements except the one under survey. In the case of materials formed on the earth’s surface, such as soils and clays, the only propitious element is Fe. Iron is the fourth most abundant element in the Earth’s crust, it is essential for life, and almost all environmental materials contain at least some Fe. It is also fortuitous that 57Fe Mössbauer spectroscopy is among the most straightforward to operate. 57Fe Mössbauer spectroscopy thus allows the characterization of iron speciation, and thereby of environmental conditions, over a wide range of concentrations, making it an extremely effective environmental probe.

Straightforward as it may seem, Mössbauer spectroscopy nevertheless has many pitfalls. Besides problems arising from the basic physics, complications can arise among other causes from imperfect crystallinity (small particle size), non-stoichiometry, interparticle effects and isomorphous substitutions.

In this paper a succinct review of the basic principles of Mössbauer spectroscopy is presented, followed by examples of Mössbauer spectra of minerals that are common constituents of clays and soils, and by more complex cases of soils, clays and fired clays.

A grafted polymer (P(MMA-MAh)-PEGME)) was synthesized by reacting poly(ethylene glycol) monomethyl ether (PEGME) with copolymer of poly(methyl methacrylate-maleic anhydride) (P(MMA-MAh)and end-capping the residual carboxylic acid with methanol. Natural rectorite (REC) was made organophilic by modification with the surfactant dodecyl benzyl dimethyl ammonium chloride. The organoclay was termed OREC and was used as a filler additive to modify gel polymer electrolytes (GPEs) which consisted of the grafted polymer (used as a polymer matrix), propylene carbonate (PC) as a plasticizer and LiClO4 as a lithium ion producer.

The temperature dependence of the ionic conductivity of the GPEs agreed well with the VTF (Vogel-Tamman-Fulcher) relation. 5 phr doses of OREC resulted in the highest ionic conductivity. Using OREC also considerably improved the plasticizer retention levels. As a consequence of OREC occupation of the free volume space in the polymer matrix of GPEs, the bulk resistance of the GPEs was reduced and the glass transition temperature (Tg) increased. From the present research, it can be concluded that the incorporation of PEGME into the copolymer of P(MMA-MAh) produced a great improvement in ionic conductivity, plasticizer retention capability and movement of carrier charge of Li+.

Extensive drying of smectites can cause the interlayer space to break down (collapse). This can affect the properties of bentonites as geotechnical barriers of HLRW (highly radioactive waste) repositories. If and to what extent the collapse occurs depends strongly on the type of interlayer cation. In particular K is known to lead to ready dehydration, in contrast to Ca and Mg. In the present study, various bentonites and one illite/smectite clay were dried/heated at 90ºC for 1.5 a and in a different experiment at 120ºC for 4.5 a and investigated with respect to mineralogical and geochemical changes of the smectite.

Smectite alteration after extensive drying was restricted to changes of the exchangeable cations. The CEC decreased by 9% (90ºC test) and 14% (120ºC test). A slight decrease of exchangeable Na+ was observed following the 90ºC test. No significant further decrease was observed after the 120ºC test. In contrast, the larger cation exchange capacity (CEC) decrease after the 120ºC test could be explained by increased Ca/Mg fixation. A possible mechanism for the observations is presented.

This study focuses on the main factors determining the apparent porosity of porous bioceramics prepared using small organic foam spheres as the pore-making reagent, in order to determine the best technical parameters for preparing porous bioceramics. In every experiment, only one of these factors (the time of heating, the sintering temperature, the mass ratio between small organic foam spheres and beta-tricalcium phosphate (β-TCP) powder, and the rate of the temperature rise) was changed, while the others were kept constant. In each case the apparent porosity was tested and the relation between the specific variable and apparent porosity was observed. Finally, the optimum technical parameters were deduced. The apparent porosity shows an inverse linear relation to the time of heating and the sintering temperature, and is approximately proportional to the mass ratio between the small organic foam spheres and the β-TCP powder and the rate of temperature rise. These factors have important influences on the apparent porosity. The optimum conditions were: heating time (soak time) 120 min, sintering temperature 850ºC, mass ratio 0.25, and a rate of temperature increase of 120ºC h–1.

In the western High Atlas basin, the evolution of the clay assemblage of the Upper Jurassic–Cretaceous sedimentary series is controlled by palaeogeographic changes of the basin and by burial diagenesis.The effects of burial are expressed by an increase in the proportions of illite and chlorite with depth, a decrease of expandability of smectite minerals and by a decrease in the Kübler Index.Kaolinite is preserved at greater depths than smectite, but also tends to diminish in abundance. TEM observations show that idiomorphic pseudo-hexagonal crystals of illite increase in size and abundance downwards, especially in the sandy levels.In the Agadir section, the main change in the clay mineral evolution related to late diagenesis occurs at the Mid-Albian, corresponding to a burial depth of about 1800 m; in the Essaouira section it occurs at the Lower Tithonian at a burial depth of about 2100 m.Considering the different geothermal gradient between Agadir (36ºC km–1) and Essaouira (27ºC km–1), the disappearance of smectite occurs at the same temperature in these two sites (60 to 65ºC).

We have determined the adsorption of RNA components (adenine, cytosine, uracil, ribose and phosphate) by Mg2+-exchanged montmorillonite. The isotherms for adenine, cytosine and uracil were of the C-type, the amount adsorbed increasing linearly with the equilibrium solute concentration. All three nucleic acid bases were apparently adsorbed by coordination to Mg2+ ions through a water bridge. Very little ribose was adsorbed by Mg-exchanged montmorillonite. The isotherm for phosphate was of the L-type. The plateau value of about 0.012 mmol g–1 indicated that phosphate adsorbed on the edge surface of montmorillonite. At comparable solute concentrations, adsorption decreased in the order adenine > cytosine > uracil. This observation reflects differences in basicity, size, and aqueous solubility among the three compounds.

A clay from the Mediterranean area classified as natural bleaching earth was comprehensively characterized and the quantitative phase content was determined. Morphology and surface characteristics were determined by environmental scanning electron microscopy (ESEM) and nitrogen adsorption. The BET surface area was >200 m2 g–1 and the average mesopore diameter was >10 nm. Thus the clay is suitable for bioseparation of larger proteins. X-ray diffraction (XRD), X-ray fluorescence (XRF), cation exchange capacity (CEC), layer charge measurement and simultaneous thermal analysis (STA) were used for mineralogical characterization. Determination of the phase content by Rietveld analysis was possible only after Sr2+ saturation, while Rietveld analysis of XRD patterns from Na+-saturated clay resulted in a strong overestimation of the amorphous content and masking of the sepiolite. The clay consists of sepiolite, dioctahedral smectite with high layer charge and low stack height, X-ray amorphous matter (probably mainly SiO2) and accessory feldspars.

Sodium montmorillonite (MMT) was organically modified with hexadecyltrimethyl-ammonium ions and subsequently treated with dichlorosilanes and water, aimed at in situ silane condensation polymerization and modification of clay platelets by polysiloxane coatings. Dimethyldichlorosilane, methylphenyldichlorosilane, and diphenyldichlorosilane were used to produce three siloxane-modified organoclays. The structure and morphology of the clay materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric studies (TG) and scanning electron microscopy (SEM). XRD results showed that the silanes were effectively polymerized in the clay galleries, forming a nanocomposite of intercalated particles. A fraction of the siloxane formed is bonded to the clay surface by covalent siloxane bonds. Strong structural differences in both morphology and thermal stability of the materials may occur when changing methyl or phenyl groups in the siloxane structure. The formation mechanism of these intercalated nanocomposite particles is considered. Finally, these modified clays were incorporated in an olefin polymer and morphological analyses using transmission electron microscope (TEM) images were carried out.

Plate-like α-Al2O3 particles are used to reinforce metal or ceramics to improve their mechanical properties. Here, we have demonstrated the production of alumina platelets using kaolin as a raw material in a sodium sulphate flux. When kaolin was sintered using Na2SO4 flux, the main phase formed in samples sintered at 900ºC was mullite, but alumina was produced at 1000ºC. Sintering at 1200ºC led to alumina and sodium aluminosilicate, with little of the mullite phase present. Plate-like α-Al2O3 particles were observed in samples sintered at 1200ºC, with diameters ranging from 1.5 to 4.5 µm and thicknesses from 0.05 to 0.1 µm. This production method is economically feasible because the raw materials have a low cost and the sintering temperature is low.

Selected samples of large cavity filling and vein-type fibrous zeolites from Eocene volcanic rocks in the Kahrizak region, northern Iran, have been studied for their mineralogical and chemical characteristics. X-ray powder diffraction and electron microprobe analyses confirmed the presence of natrolite, mesolite and scolecite with compositions of [Na14.922Ca0.202K0.015Ba0.002] [Al15.697Si24.267O80]·nH2O, [Ca15.714Na14.224][Al46.431Si73.398O240]·nH2O and [Ca7.804Na0.142K0.024 Ba0.012Mg0.006][Al15.320Si24.437O80]·nH2O, respectively. In addition, examination of textural relationships in thin sections and back-scattered electron images reveals a paragenetic order in which the Ca-rich zeolites crystallized first. It is most probable that the fibrous zeolites of Kahrizak were formed during two pulses of hydrothermal activity in the area. Scolecite and mesolite were precipitated from Ca-rich solution, whereas the second stage Na-rich, low-temperature fluid crystallized natrolite and reacted with Ca-species.