The hydroxyl orientations in 31 dioctahedral and trioctahedral 2:1 phyllosilicate structures have been determined by electrostatic energy calculations. These structures included micas, brittle micas, and other related minerals exhibiting ordered as well as disordered cation distributions. The dioctahedral micas and brittle micas were examined with and without the interlayer cation. A range of orientations from 1.3° to 183.3° (the angle ρ between the O-H and (001) measured with respect to the M1 site) were found. The orientations for the dioctahedral structures represent a continuum of values whereas the trioctahedral species exhibit two possible orientations separated by an energy barrier. One orientation is near 90° the other is near 180°. The latter orientation results from a concentration of charge on the interlayer (IC) and tetrahedral (T) sites at the expense of the octahedral (M) sites. A multiple regression analysis of all 31 structures, using as predictors the a and b cell parameters, d001, and the charges for T, IC, M1, and M2 sites, was performed. This analysis indicated that the important factors are the charges for IC, T, and M2 sites. When treated as a separate group, one finds the same factors for the dioctahedral structures. The trioctahedral orientations are determined by the charge on the M2 site and the amount of tetrahedral rotation. Using these two predictor equations, the value of ρ can be estimated with a standard deviation of 4.7° and 2.9° for the dioctahedral and trioctahedral cases, respectively.

Iron phyllosilicates with 1:1 and 2:1 layer structures were prepared from silicic acid, ferrous sulfate and sodium hydroxide. Hydrothermal treatment at 100–200°C of a reaction mixture with an initial Fe/Si ratio of 1.5 gave the 2:1 iron phyllosilicate, whereas a Fe/Si ratio of 2.25 gave the 1:1 phyllosilicate. The 57Fe Mössbauer spectroscopy showed that 60% of the iron in the 1:1 phyllosilicate is ferrous, versus only 3% in the 2:1 phyllosilicate. The values of quadrupole coupling showed that the iron-oxygen tetrahedra and octahedra in the 2:1 phyllosilicate were more deformed than those in the 1:1 phyllosilicate.

The chemical composition of hydrothermal chlorite was determined by means of more than 200 electron microprobe analyses (EMPA) in almost all of the 70 chlorite-bearing samples taken from 5 boreholes in a study of the active geothermal system of Los Humeros, Mexico. Bulk rock composition of 6 different volcanic lithologies, as well as available in situ temperatures and chemical compositions of chlorite, were analyzed by principal component analysis (PCA) in order to test the dependence of chlorite composition on physicochemical parameters. The results show that chlorite minerals display a wide range of chemical compositions in this hydrothermal system that reflect the particular conditions of crystallization episodes: The Na + K + 2Ca values are low (from 0 to 0.6) and they show no correlation patterns with octahedral vacancies (¤) in chlorite, indicating that compositional variations are not due to the intergrowth of smectite and/or illite. The octahedral occupancy of most chlorite is relatively high (from 11.3 to 11.95), especially that from a high-temperature range, as is the case of metamorphic chlorite. The octahedral occupancy seems not to be related to other chemical variables of chlorite from the G3, G4 and G5 lithologic units, suggesting that the lack of complete occupancy is not dependent on “contamination” by other silicates (such as quartz). Cationic substitution in tetrahedral sites in chlorite is small and via a Tschermak exchange (MgVISiIV ↔ AlVIAlIV). To preserve a charge balance in the structure, an octahedral substitution of R2+ by Al3+ accompanies the Tschermak exchange. The chemical composition of hydrothermal chlorite is very similar to that of metamorphic chlorite but slightly different from equivalent phases found in diagenetic environments. In hydrothermal chlorite the SiVI, AlVI and ¤ decrease, whereas the AlIV and Fe2+ contents increase with the degree of alteration and depth, the same way as in chlorite formed in diagenetic high-temperature environments. The ferrous iron content, in general, increases with depth and temperature; however, whole-rock chemistry affects the iron distribution in chlorite of Los Humeros. Changes in the oxygen fugacity of fluids at depth also affect the iron distribution in chlorite, XFe = Fe/(Fe + Mg), which ranges from 0.30 to 0.38 in oxidizing conditions and from 0.39 to 0.60 in reducing conditions. Finally, the chemical composition of chlorite in Los Humeros appears to change with temperature, but the correlations of ¤ and AlIV with temperature are more variable than in another nearby active geothermal system located in Los Azufres, Mexico. This implies that geothermometers based on chlorite composition and empirically calibrated in some geothermal systems cannot be generalized and it is necessary to consider other physicochemical variables.

Smectites are one of the most important groups of phyllosilicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature (<100°C), (2) under moderate hydrothermal conditions (100–1000°C, pressures to several kbars), (3) under extreme hydrothermal conditions (>1000°C or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrothermal conditions are the most numerous and the most successful in terms of smectite yield and phase-purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The presence of Mg2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temperatures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under-and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody-namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.

Some aspects of the crystal structure of illite are not understood properly yet, in spite of its abundance and significance as a component of soils, sediments, and low-grade metamorphic rocks. The present study aimed to explore the role of hydronium cations in the interlayer space of illite in a theoreticalexperimental approach in order to clarify previous controversial reports. The infrared spectroscopy of this mineral has been studied experimentally and by means of atomistic calculations at the quantum mechanical level. The tetrahedral charge is critical for the stability of the hydronium cations, the presence of which has probably been underestimated in previous studies. In the present study, computational studies have shown that the hydronium cations in aqueous solutions are likely to be intercalated in the interlayer space of illite, exchanging for K cations. During the drying process these cations are stabilized by hydrogen bonds in the interlayer space of illite.

Accidental discharges of the hazardous nuclear fission products 137Cs+ and 90Sr2+ into the environment, such as during the Fukushima Dai-ichi nuclear accident, have occurred repeatedly throughout the ‘nuclear age.’ Numerous studies of the fate and transport of 137Cs+ and 90Sr2+ in soils and sediments have demonstrated their strong and selective binding to phyllosilicate clay minerals, primarily by means of cation exchange into interlayer sites. The locally concentrated amounts of these radioactive beta-emitters that can be found in these host minerals raise important questions regarding the long-term interplay and durability of radioisotope—clay associations, which is not well known. The present study goes beyond the usual short-term focus to address the permanence of radioisotope retention in clay minerals, by developing a general theoretical understanding of their resistance to the creation of defects. The present study reports ab initio molecular dynamics (AIMD) calculations of the threshold displacement energy (TDE) of each symmetry-unique atomic species comprising the unit cell of model vermiculite. The TDE values determined are material specific, radiation independent, and can be used to estimate the probability of Frenkel-pair creation by direct electron—ion collision, as could be induced by the passage of a high-energy electron emitted during the beta-decay of 137Cs, 90Sr, and daughter 90Y. For 137Cs and 90Sr, the calculated probability is ~36%, while for 90Y the probability is much greater at ~89%. The long-term retention picture that emerges is that decay will progressively alter the clay interlayer structure and charge, probably leading to delamination of the clay, and re-release of residual parent isotopes. Further work examining the effect of Frenkel defect accumulation on the binding energy of parent and daughter radionuclides in the interlayer is thus justified and potentially important for accurate long-term forecasting of radionuclide transport in the environment.

We used high-resolution X-ray texture goniometry to quantify changes in the mm-scale orientation of phyllosilicate minerals in a suite of Paleogene mudstones from the Podhale Basin in southern Poland. The sample set covers an estimated range of burial depths between 2.4 and 7.0 km, corresponding to a temperature range of 60–160°C. Although mechanical compaction has reduced porosities to ∼10% in the shallowest samples, the phyllosilicate fabric is only modestly aligned. Coarser-grained (>10 µm) detrital chlorite and mica appear to be more strongly aligned with (001) parallel to bedding, suggesting their deposition as single grains rather than as isotropic flocs or aggregates. From 2.4 to 4.6 km, R0 illite-smectite with 40–50% illite layers changes to R1 illite-smectite with 70–80%) illite layers. At the same time kaolinite is lost and diagenetic chlorite is formed. The mineralogical changes are accompanied by a strong increase in the alignment of illite-smectite, chlorite, and detrital illite, parallel to bedding and normal to the presumed principal effective stress. We propose that the development of a more aligned I-S fabric results from the dissolution of smectite and the growth of illite with (001) normal to the maximum effective stress. Water released by illitization may act as a lubricant for the rotation of all platy minerals into nanoporosity transiently formed by the illitization reaction. At greater depths and temperatures, further illitization is inhibited through the exhaustion of K-feldspar. After the cessation of illitization, a further 2.4 km of burial only results in a small increase in phyllosilicate alignment. At such small values for porosity and pore size, increasing stress does not substantially reorient phyllosilicates in the absence of mineralogical change.

Over several decades, a wealth of literature has been devoted to correlations between the chemistries of phyllosilicates and their crystallographic unit-cell parameter values. The c parameter is currently used because of its relation to the layer-to-layer distance, characteristic of the various families of phyllosilicates. The b parameter is also of interest because it allows measurement of the layer lateral dimensions and inherent structural adjustments. This unit-cell distance can be extracted from X-ray diffraction traces from the (06ℓ;33ℓ) diffraction region and by attributing the main diffraction peak observed to a 060 reflection, leading to the relationship b = 6.d(060). The aim of this paper is to revisit the relationships between the b value (or equivalent) of the phyllosilicate (i.e. TO, TOT and TOTO) or hydroxide (i.e. hydroxide, oxyhydroxide and layered double hydroxide) families and the layer chemistry based on a mean ionic radius R of octahedral cations, calculated as $R = \mathop \sum \nolimits_{i = 1}^n ( {r_i.x_i} )$, where ri is the ionic radius of the octahedral cation i and xi is its molar fraction over n types of octahedral cations ($\mathop \sum \nolimits_{i = 1}^n ( {x_i} ) = 1$). The data were collected from the literature and involved both natural and synthetic samples with both dioctahedral and trioctahedral structures of the octahedral sheet. The results showed that b values can be linked strongly to R, leading to suitable linear regressions for all of the studied structures. All correlations were found to be applicable irrespective of the di- or trioctahedral nature of the octahedral sheet, and these are discussed in light of (1) the lateral dimension of the octahedral sheet and (2) the dimensional misfit between the tetrahedral and octahedral sheets. For hydroxide families, all data can be gathered on a single b vs R correlation line, and the dimensional properties of the octahedral sheet can be interpreted simply based on an oxygen–cation–oxygen mean distance. For TO structures, two general b vs R correlation trends were reported, and these were assigned to two adjustment mechanisms corresponding to distinct types of tetrahedral and octahedral distortions. For the mica TOT family, two main trends were also reported, whereas the use of the synthetic mica series allowed us to demonstrate that the obtained scattering of data was mainly driven by the presence of multiple limited solid solutions. Such chemical complexity was also noted for smectites, especially regarding the tetrahedral composition and associated variability in layer charge. This variability made it difficult to propose a general regression correlating b to R values for smectites, although the regression obtained for neutral TOT layers can apply as a first-order relation. Finally, a single general b vs R correlation was obtained for chlorites, and the observed slope of the regression was interpreted according to the role played by the isolated hydroxide sheet on the evolution of the lateral dimension of the structures.

A new phyllosilicate mineral, lipuite (IMA2014-085), has been discovered from the N'Chwaning III mine, Kalahari Manganese Fields, Northern Cape Province, Republic of South Africa. It occurs as platy, tabular, or granular crystals and veined agglomerate in association with Mn-bearing sugilite, taniajacoite, pectolite, richterite, norrishite and namansilite. Lipuite is dark red–brown with vitreous lustre, red streak, an estimated Mohs hardness of 5 and the measured density is 2.83(3) g/cm3. It is biaxial (+) and characterised by bright red to dark red colour in thin section with measured refractive indices in white light: α = 1.635(1), β = 1.653(1), γ = 1.670(1) and 2V = 86(2)°. The Raman spectra of lipuite are composed of over 21 bands at 109, 146, 162, 183, 206, 244, 288, 342, 362, 455, 496, 520, 552, 613, 669, 886, 930, 971, 1097, 3487 and 3540 cm–1. The empirical formula from microprobe analyses is (based on total number of cations = 27.5 and structural refinement): K1.12Na8.16(Mn4.77Fe0.07)Σ4.84Mg0.44[Si11.97O30(OH)4](PO4)0.94O2(OH)2·4H2O. The idealised formula is: KNa8Mn3+5Mg0.5[Si12O30(OH)4](PO4)O2(OH)2·4H2O.

Lipuite is orthorhombic, space group Pnnm, a = 9.080(3), b = 12.222(3), c = 17.093(5) Å, V = 1897.0(9) Å3 and Z = 2. The strongest powder X-ray diffraction peaks [d, Å (I) (hkl)] are: 9.965(40)(011), 2.938(33)(310), 2.895(100)(311), 2.777(38)(224), 2.713(53)(320), 2.483(32)(126), 2.086(35)(046) and 1.534(40)(446). The crystal structure of lipuite is characterised by sheets of SiO4 tetrahedra that are linked together along [010] by K+, Na+, Mn3+, Mg2+ and P5+ cations, as well as hydrogen bonds. These tetrahedral sheets consist of 14-membered rings of SiO4 tetrahedra that zigzag along [100]. The two independent Mn3+ cations are both octahedrally coordinated. They form five-membered, edge-shared octahedral clusters between the SiO4 tetrahedral sheets. Lipuite represents a rather unique structure type and its silicate tetrahedral sheets can be considered a derivative of the silicate sheets in mica.

The crystal structure of burckhardite from the type locality, Moctezuma, Sonora, Mexico, has been refined to R1 = 0.0362 and wR2 = 0.0370 for 215 reflections with I > 2σ(I). Burckhardtite is trigonal, space group P1m, with the unit-cell parameters a = 5.2566(5) Å , c = 13.0221(10) Å , V = 311.62(5) Å3 and Z = 1 for the ideal formula unit Pb2(Fe3+Te6+)[AlSi3O8]O6. There is no long-range order of (Fe3+, Te6+) or (Al3+, Si4+). New microprobe data were used to estimate site scattering factors, and Raman spectroscopic data showed no evidence of O–H stretching bands. Burckhardtite is not closely related to the micas, as supposed previously, but is a double-sheet silicate in which the aluminosilicate anion resembles that of minerals such as cymrite and kampfite. The [(Fe3+Te6+)O6]3– part of the structure is not bonded directly to the aluminosilicate layer, but forms a discrete anionic phyllotellurate layer that alternates with the [AlSi3O8]– double sheets. Similar phyllotellurate layers are known from several synthetic phases. In burckhardtite, Pb2+ cations intercalate between phyllosilicate and phyllotellurate layers, forming a Pb2[FeTeO6] module that is topologically similar to a slab of the structure of rosiaite, Pb[Sb2O6]. The crystal symmetry, structure, classification as a double-sheet silicate and chemical formula, including the determination of the 6+ valence of Te and absence of essential H2O, are all new findings for the mineral.

A description of the new mineral innsbruckite, Mn33(Si2O5)14(OH)38, a hydrous manganese phyllosilicate found in Tyrol, Austria is given. The crystal structure was determined by singlecrystal synchrotron radiation diffraction experiments at the X06DA beamline at the Swiss Light Source (Paul Scherrer Institute, Villigen, Switzerland). The space group is Cm and lattice parameters are a = 17.2760(19), b = 35.957(5), c = 7.2560(8) Å , β = 91.359(7)º, V = 4506.1(10) Å3, Z = 2. Innsbruckite belongs to the group of modulated 1:1 layer silicates and is chemically and structurally quite closely related to bementite, Mn7(Si2O5)3(OH)8. The chemical analysis revealed a close to ideal composition with only minor amounts of Al, Fe and Mg. Using Liebau’s nomenclature for silicate classification the silicate anion can be described as an unbranched siebener single layer. Innsbruckite shows a complex topology of the silicate sheet, exhibiting 4-, 5-, 6- and 8-membered rings. The silicate sheet is fully characterized using vertex symbols, and its topology is compared to those in other complex sheet silicates. Furthermore, the structural investigation is complemented with Raman spectroscopic studies.

This study examined basal peak irrationalities according to boundary conditions of the hectorite basal diffraction unit (BDU), which were recognized as the total assembly of 2:1 phyllosilicate layer plus interlayer material. The hectorite basal profiles were computer-simulated using the three kinds of BDU settings identified from the middle of octahedral sheets in the nearest neighbor (centrosymmetric model), the middle of interlayers in the nearest neighbor (centrosymmetric model), and a basal oxygen plane to the margin of interlayer in contact with the next phyllosilicate layer (non-centrosymmetric model). In the results of simulations, irrationality and asymmetry of the hectorite basal peaks relied straightforwardly on the BDU scattering modulations for the non-Bragg angles containing information on the synergic scattering events of phyllosilicate layer and interlayer material. Among the concerned BDU boundaries, the non-centrosymmetric model more effectively represented the real hectorite profile than the two previously reported centrosymmetric models.