Cementitious materials and their alkaline pore fluids can change the structure of bentonite used as a raw material for road embankments or concrete storage of garbage cans. This study investigated the alteration of montmorillonite-rich bentonite from northeast Morocco (Trebia deposit, Nador) in alkaline media rich in Ca2+, Mg2+, Na+, or K+. Specimens based on raw bentonite mixed with variable proportions of oxides (CaO, MgO) or hydroxides (NaOH, KOH) and water were prepared and aged for 28 days. Mineralogical composition by X-ray diffraction (XRD) was determined on raw bentonite and specimens to follow phase changes. Chemical composition and thermal characteristics were determined for raw bentonite and specimens by Fourier-transform infrared spectroscopy (FT-IR) and thermogravimetric/differential thermal analysis (TGA/DTA). Microstructural evolution and alteration of the external surface of bentonite were evaluated using scanning electron microscopy coupled with energy dispersive X-ray (SEM/EDX) analysis. XRD results of bentonite-CaO mixture demonstrated the formation of gels (e.g. C-S-H) and calcite. When the amount of CaO added increased, excess portlandite and the precipitation of calcite in the outer surface of bentonite occurred, stopping pozzolanic reaction and consequently decreasing the compressive strength of specimens. On the other hand, the addition of MgO allowed the formation of brucite. Sodalite and cancrinite were neoformed with the addition of 32 wt.% NaOH after 28 days of hydration. The addition of hydroxides (NaOH or KOH) to bentonite did not reveal any setting due to the absence of the formation of cementitious phases.

The present work shows the results of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and thermal analysis of untreated (RMnt) and acid-treated red mud (RMa), a bauxite ore-processing waste, exchanged with Pb2+, Cd2+, and Zn2+ cations. These studies were performed in order to investigate the changes in the sorbent structure caused by the exchange with metals of different ionic radii.

The XRD pattern of RMnt, analyzed according to the Rietveld method, showed a mixture of eight different phases. However, just three phases made up 78 wt.% of the RMnt: cancrinite (33 wt.%), hematite (29 wt.%), and sodalite (16 wt.%). X-ray diffraction patterns of RMnt exchanged with Pb2+ and Cd2+ cations revealed two additional phases, namely hydrocerussite [Pb3(CO3)2(OH)2 (10 wt.%))] and octavite [CdCO3 (8 wt.%)].

These two phases probably originated from the carbonate precipitation processes which were due to the decarbonation of cancrinite. Hydrocerussite and octavite were not found in the case of acid-treated red mud samples.

In the FTIR spectra, the introduction of cations caused a distinct shift to higher wavenumbers in the peak at ∼1100 cm−1, which is attributed to the asymmetric stretch of Si-O-Al. This effect may be associated with the Pb2+, Cd2+, and Zn2+ adsorbed by the red muds which caused a deformation of the initial structure.

Thermal analysis data of the red mud samples were obtained by thermogravimetric/differential thermogravimetric analysis, and these methods were employed to evaluate the desorption behavior of water and to clarify the thermal stability of the chemical phases of the different red mud samples. The loss of metal-bound water in the red mud samples was found to depend on the size of non-framework cations and water loss consistently followed the order: Zn2+>Cd2+>Pb2+.

Caustic nuclear wastes have leaked from tanks at the US Department of Energy’s Hanford site in Washington State (USA) causing hundreds of thousands of gallons of waste fluids to migrate into the underlying sediments. In this study, four simulant tank waste (STW) solutions, which are high in NaOH (1.4 and 2.8 mol/kg), NaNO3 (3.7 mol/kg) and NaAlO2 (0.125 and 0.25 mol/kg), were prepared and reacted with reference kaolinite KGa-1 and KGa-2 at 50 and 80°C for up to 2 months. The structure and morphology of the resulting products were characterized using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. The products were also examined for cation exchange and Cs+ sorption as a function of ionic strength and types of cations in the background solutions. Cancrinite and sodalite were the only new minerals observed in all of the conditions tested in this experiment. Two major chemical processes were involved in the reactions: dissolution of kaolinite and precipitation of cancrinite and sodalite. Increasing NaOH concentration and temperature, and decreasing NaAlO2 concentration increased the transformation rate. Both cancrinite and sodalite appeared stable thermodynamically under the experimental conditions. The newly formed feldspathoids were vulnerable to acid attack and pronounced dissolution occurred at pH below 5.5. Cancrinite and sodalite can incorporate NaNO3 ion pairs in their cages or channels. Sodium in cancrinite and sodalite was readily exchangeable by K+, but less easily by Cs+ or Ca2+. The feldspathoid products sorb nearly an order of magnitude more Cs+ than the unaltered kaolinite. The Cs adsorption is reduced by competing cations in the background solutions. At low ionic strength (0.01 M NaNO3 or 0.005 M Ca(NO3)2), Ca2+ was more competitive than Na+. When the concentration of the background solution was increased 10 times, Na+ was more competitive than Ca2+.

The Mount Mather Creek sodalite-bearing carbohydrothermal breccia dyke is located ~35 km northwest of Golden, British Columbia, Canada, within the Foreland Belt on the eastern side of the Mississippian-to-Devonian British Columbia Alkaline Province. The dyke occurs in situ on the western side of the Mount Mather Creek gully, cropping out over a distance of ~80 m with a thickness of up to 10 m, intruding a syncline of Middle and Upper Cambrian Chancellor Group carbonate rocks. To date, no parental alkaline complex has been found adjacent or proximal to the dyke. The breccia dyke is flow-banded and matrix-supported and consists of host rock clasts, medium- to coarse-grained, anhedral-to-poikilitic carbonate-rich syenite segregations that occur as veins and pods, and fine-grained banded sodalite plus carbonate fragments in a carbonate-rich matrix. The sodalite-carbonate segregations consist dominantly of sodalite, ferroan dolomite, calcite and microcline, with an extensive suite of trace minerals enriched in rare earth elements (REE), Na, Ba and Sr, including albite, analcime, ancylite-(Ce), chabazite-Na, fluorapatite, baryte, barytocalcite, cancrinite, galena, goethite, gonnardite, harmotome, edingtonite, a potentially new Mg-bearing edingtonite-like mineral, natrolite, nordstrandite, pyrite, quintinite and sphalerite. Alteration of the primary silicate–carbonate assemblage has resulted in a secondary assemblage of hydrothermal or carbohydrothermal REE–Ba–Sr–Na phases including albite, analcime, cancrinite, gonnardite and nordstrandite after sodalite, together with complex intergrowths of ancylite-(Ce), barytocalcite, edingtonite, and a potentially-new Mg-bearing edingtonite-like mineral. Remobilisation of Ba and Sr from barytocalcite resulted in crystallisation of late-stage baryte and Sr-rich calcite. Mount Mather Creek is only the fifth Canadian occurrence of the Ba-zeolite, edingtonite, and the second Canadian occurrence of the rare layered double hydroxide quintinite. The Mount Mather Creek breccia is a carbohydrothermal deposit, the product of a low temperature (<450°C), highly evolved, alkaline, SiO2-undersaturated, Na–Ba–REE–Cl-rich, residual carbonated silicate melt whose parental origins remain unknown.

Crystallographic distortions in the alternating aluminium and silicon tetrahedral framework of sodalite (Na8Al6Si6O24Cl2), and beryllium and silicon in helvine (Mn8Be6Si6O24S2), (framework designated SOD) are described in terms of a set of condensed normal mode amplitudes and phases derived from an ideal tetrahedron of a theoretical aristotype phase. For a sodalite-structured hettotype phase in space group $P{\overline 4} 3n$, these normal modes transform as the irreducible representations A1, E(α) and T1(z) of point-group ${\overline 4} 3m$, where to a good approximation A1 acts as a pure breathing mode, E(α) as a polyhedral distortive mode and T1(z) as a rigid unit rotation about the unique ${\overline 4}$ axis of the T-site under consideration. Parameterisation of the mode amplitudes in terms of low-order polynomials as a function of thermodynamic variable permits the crystal structure of sodalite-structured phases to be accurately interpolated at intermediate values of the thermodynamic variable. Published data for the high-temperature behaviour of sodalite have been re-analysed in terms of mode amplitudes which accurately reproduce the temperature dependence of the bond lengths, bond angles and the Al–O–Si inter-polyhedral angle. Full expressions for these derived structural parameters in terms of mode amplitudes and the lattice parameter are tabulated and agree with experimental results to within one estimated standard deviation of the experimental parameter. The potential for mode decomposition in lower symmetry SOD framework crystal structures is illustrated by deriving an aristotype structure for tugtupite (Na8Al2Be2Si8O24Cl2) at room temperature in space group $I{\overline 4}$.

A unique hybrid natrocarbonatite, collected from the new ash cone of the volcano Oldoinyo Lengai. Tanzania in July 2008, consists of phenocrysts of nyerereite and gregoryite together with xenocrysts of clinopyroxene, nepheline and Ti-andradite set in a groundmass of cuspidine, sodalite, ferroan manganoan monticellite, K-Fe sulphide and manganoan titanian magnetite and gregoryite. The xenocrysts were not in equilibrium with the melt which formed their current host, as clinopyroxenes and Ti-andradite are mantled by cuspidine, and nepheline by sodalite and phlogopite—potassian kinoshitalite solid solutions. A microxenolith of ijolite exhibits similar reaction phenomena. The minerals of the xenocryst suite have similar compositions to plutonic ijolites found at Oldoinyo Lengai, and are thus considered to be derived by the fragmentation of such material in a previously contaminated natrocarbonatite melt. The latter, which has cuspidine, sodalite and monticellite as primary liquidus phases, is considered to have been formed by the complete assimilation of ijolitic material in a natrocarbonatite magma at depth in the volcano conduit. The occurrence of trace amounts of cuspidine, Fe-Mn-monticellite, K-Fe sulphide and Mn-Ti-spinel in recently erupted natrocarbonatites is ascribed to similar, but less extensive, assimilation of silicate material prior to their eruption.

This paper reports an infrared spectroscopic study of a set of sodalite-group minerals. The specimens have been identified using a combination of X-ray diffraction and microchemical analysis. As expected, the Si/Al ratio is ~1; the extra framework cation content is characterized by a well-defined Na ⇌ (Ca+K) substitution. The lattice parameters of the studied samples range from sodalite (sample LM11) with a = 8.889(2) Å, to haüyne (sample HR3S) with a = 9.1265(2) Å. The specimens, having the SO2– group as a dominant anion, show a clear correlation between the a cell edge and the K content. Singlecrystal FTIR spectroscopy shows that haüyne and nosean typically contain enclathrated CO2 molecules, inadditionto H2O and minor carbonate, while sodalite is virtually CO2-free. Detailed microspectrometric mappings show a non-homogeneous distribution of volatile constituents across the crystals, which may be related to the presence of fractures in the crystals. Because of such zoning, a relatively wide variation is observed when calibrating extinction coefficients on the basis of a bulk analytical method such as CHN elemental analysis.

The incorporation of pertechnetate (TcO4–) into feldspathoids produced by alkaline alteration of aluminosilicate clays may offer a potential treatment route for 99Tc-containing groundwater and liquors. Kaolinite was aged in NaOH to determine the effect of base concentration, temperature, and solution composition on mineral transformation and pertechnetate uptake. In all reactions, increased temperature and NaOH concentration increased the rate of kaolinite transformation to feldspathoid phases. In reactions containing only NaOH, sodalite was the dominant alteration product; however, small amounts (6–15%) of cancrinite also formed. In experiments containing NaOH/Cl and NaOH/NO3 mixtures, sodalite and nitrate cancrinite were crystallized (at 70°C), with no reaction intermediates. The addition of SO42– crystallized sulfatic sodalite at 40 and 50°C, but at higher temperatures (60 and 70°C) sulfatic sodalite transforms to vishnevite (sulfatic cancrinite). In experiments where a pertechnetate tracer was added (at ∼1.5 μmol l–1), only 3–5% of the 99Tc was incorporated into the feldspathoid phases. This suggests that the larger pertechnetate anion was unable to compete as favourably for the internal vacancies with the smaller OH–, NO3–, SO42– or Cl– anions in solution, making this method likely to be unsuitable for groundwater treatment.

Kaolin wastes from the Capim and Jari regions (Brazil) were used to produce sodalite under the same conditions used in the Bayer process, in order to control its formation when necessary. Of the two kaolin source materials, the kaolinite from the Jari region was more reactive in the synthesis of sodalite, which is attributed to the low degree of structural order of this clay mineral which increased its reactivity. At a temperature of 150°C and with a Na/Al ratio of 2, although the kaolinite did not react completely, sodalitewas the primary reaction product. An increase in the temperature to 200°C provoked the complete reaction of the kaolinite only for the products in which carbonate and sulfate were used. With a Na/Al ratio >2 and for both of the temperatures, the kaolinite reacted completely to form sodalite.

The title compound, ∣Na6Li1.6K0.4Cl2∣[Al6Si6O24]‐SOD, is similar to sodalite proper, but the introduction of Li and K into the structure creates a reduction in unit-cell volume and additional collapse of the framework tetrahedra. Refinement of an X-ray powder diffraction pattern of a multiphase material yielded for sodalite a lattice parameter of 0.88427 (2) nm, an Al–O–Si bond angle of 137.9(3°), and Al–O and Si–O bond lengths of 0.1730(5) nm and 0.1620(5) nm, respectively. The angle of the unique Al–O–Si bond corresponds well with the 138° obtained by 29Si solid-state magic-angle-spinning nuclear magnetic resonance spectroscopy. This characterization is important since the compound constitutes an essential part of a radioactive waste form intended for a high-level waste repository.

A natural sodalite from the geological site Alkaline Complex of Floresta Azul, Bahia, Brazil, has been characterized by electron microprobe, infrared spectroscopy, and powder high-resolution X-ray diffraction techniques. The mineral is an aluminosilicate framework, formed by cages called sodalite unity. Although the sample is natural, the chemical analysis reveals that it is indeed the end member sodalite sensu strictu, Na8[Si6Al6O24]Cl2. Infrared spectroscopy shows Si, Al tetrahedral-oxygen stretching nonsymmetric mode, stretching symmetric mode, and bending modes. Indexing of the experimental X-ray diffraction pattern led to cubic space group P-43n, and unit-cell parameters: a=8.8767(7) Å, Dx=2.301 g cm−3, and V=699.46(1) Å3. X-ray diffraction data are reported. Rietveld refinement was also performed, and the confidence factors are Rp=0.079, Rwp=0.118, and χ2=2.19. The structure of the minerals of sodalite group holds four different tetrahedra: AlO4, ClNa4, Na(ClO3), and SiO4, with Al, Cl, Na, and Si located at the center of each tetrahedron.