In the copper deposit of Salobo 3A (Brazil), nontronite-like clay samples were found at the bottom of the weathering blanket. Samples were fractionated first by sedimentation and then by a HGMS method. From XRD data, it was found that the samples are essentially smectite with kaolinite in very small quantities. The average structural formula of the smectite, presented in the traditional manner, is:

Chemical analyses show that the smectite samples contain a population of clay particles whose chemistry ranges between a nontronite end-member and an Al-Mg beidellite end-member.

Spectroscopic studies by FTIR, Mössbauer, and ESR show that the three major octahedral cations (Al, Fe, Mg) are present in each octahedral sheet of the smectite, forming a solid solution, and that the chemical trends of the smectite clay detected at a “macroscopic” scale (associated clay particles) can also be observed at the unit cell scale.

This research aims to characterize the mineralogical and crystal-chemical purity of two samples of natural talc (BTT6, BTT7) from the occurrence ‘Ecole1’ in the deposit of Minzanzala, southwest Gabon. X-ray diffraction and modal-composition calculations demonstrated the presence of quartz and Al–Fe-bearing phases (kaolinite and/or chlorite and/or Al–Fe oxyhydroxides) as accessory minerals in both ores. In contrast, the chemical and spectroscopic characterization of the talc component revealed remarkable chemical purity expressed by very low Fe contents. According to these results, the talc of Minzanzala might be used as a filler in a wide range of industrial applications, such as in cosmetics, paints, polymers or ceramics.

This paper presents the results of an experimental study of the miscibility gap between trioctahedral and dioctahedral micas in the system K2O Li2O-MgO-FeO-Al2O3-SiO2-H2O-HF at 600°C under 2 kbar PH2O. The existence of this miscibility gap is known from previous experimental studies. The gap is large in the lithium-free system; its width reduces progressively with increasing Li content; for sufficient Li contents (Li > 0.6 atom per formula unit, based on 11 oxygens), a single Li-mica phase is obtained, intermediate between trioctahedral and dioctahedral micas. Any bulk composition located inside the miscibility gap gives an assemblage of two micas, one of the biotite-type and one of the muscovite-type. All the compositions located outside the gap, and, in particular, those belonging to the joins phlogopite-trilithionite and muscovite-zinnwaldite (or its magnesian equivalent) give a single mica phase, provided that the fluorine content is sufficient. The ratio Li/F ≈ 1 is a convenient suitable value. The types of micas and the evolutions of their compositions are well characterized by their interplanar distance d060. These experimental results allow the interpretation of most compositions of naturally occurring lithium micas, in the range 0 ⩽ Li ⩽ 1 a./f.u. Natural micas of biotite-type and muscovite-type are located on both sides of the miscibility gap and their compositions get closer with increasing Li content.

The petrographical, crystal-chemical and petrogenetical aspects of rutile rich in antimony (up to 33.75 wt.% Sb2O5; equal to 0.2 Sb5+ per O = 2) from St. Marcel-Praborna in the Aosta Valley, Italy, were re-examined. These compositions occur in two different petrographical environments (within the rock matrix or as microinclusions within Sb-rich titanite) in the manganese concentrations at this locality. The new data confirm our earlier hypothesis that two distinct petrogenetical/crystal-chemical processes both occurred: 1. Sb-metasomatism of pre-existing Sb-free rutile inclusions; and 2. creation of neoblastic Sb-rich rutile by the expulsion of Ti from pre-existing Sb-free titanite being metasomatized by Sb to form Sb-rich titanite. In the literature, Sb in minerals is variably considered as being trivalent and/or pentavalent. This work demonstrates that within rutile it is entirely Sb5+, substituting for Ti4+ by the following heterovalent cation exchange mechanism which is also the dominant one in the host Sb-rich titanite: 2 viR4+ = viR3+ + viR5+, where viR3+ = (Al,Cr,Mn,Fe)3+. A near-perfect correlation of ΣR5+vs. ΣR3+ (r > 0.98) is perturbed only by the presence of trace amounts of Ca2+, Sr2+ and Ba2+. Traces of Mn4+, Si4+ and/or (OH)− might also be present. These alkaline earth cations are the largest cations ever recorded in the rutile structure and are seemingly too large to occupy normal octahedral sites. The cation exchange mechanism involved might be that found in the ‘trirutile’ mineral group: 3 viR4+ = viR2+ + 2 viR5+. Alternatively these large divalent cations may be situated in the lozenge-shaped tunnels of the rutile structure, by analogy with other large cations occupying the wider subrectangular tunnels in the analogous cryptomelane/hollandite/priderite, romanéchite and todorokite mineral groups. This leads to a possible new cation exchange mechanism for the rutile structure: 2 viR4+ + tunelvacant = 2 viR3+ + tunnelR2+.

A multi-methodological study, based on electron microprobe analysis (in wavelength dispersive mode), single-crystal X-ray diffraction (XRD), transmission electron microscopy and single-crystal Fourier transform infrared spectroscopy was performed in order to describe the crystal chemistry of four leucite samples from different localities of the Roman Comagmatic Province (central Italy). All the crystals examined were found to be tetragonal (space group I41/a with a = 13.076–13.103 Å and c = 13.744–13.784 Å) and characterized by a complex twinning (merohedric twins: on the tetragonal planes (110) and (1̄10) with the two individuals having parallel crystallographic axes with a and b interchanged; pseudo-merohedric twins: on the tetragonal planes (101), (011), (1̄01), (01̄ 1), with the two individuals having parallel a (or b) axes and the remaining two axes not parallel). The chemical analyses show that all the samples contain minor Na and Fe. Infrared spectroscopy shows that all samples contain structurally bound water molecules, up to unexpectedly large amounts (~0.4 wt.%) for a nominally anhydrous mineral, suggesting that ‘analcime-like’ substitution (K to Na + H2O) occurs in the leucite samples investigated here. The detection limits of the ‘analcime-like’ substitution by singlecrystal XRD are also discussed.

Titanites rich in antimony (up to 12.59 wt.% Sb2O5; equal to 0.165 Sb5+ per Si4+ = 1.000) arc described for the first time. They coexist with various greenschist-facies minerals in three different petrographical environments in the manganese concentrations at St. Marcel-Praborna in the Aosta Valley, Italy. These titanites are chemically zoned, the Sb-richest parts generally occurring alongside grain boundaries, microfractures, pores or inclusions. Moderately-good positive correlations exist between the Sb, Al and Fe contents, with negative correlations of each of these elements with Ti. Cr has perturbed the Al and Fe contents since a better negative correlation with Ti is obtained with [Al + Cr + Mn + Fe]. The Sr, Ba, Mn and F contents are rather small and vary irregularly. Several crystal-chemical hypotheses are presented concerning the method of structural formula calculation and the valencies and site distributions of Sb and the companion additional minor elements. The favoured interpretation is to place: Sr2+, Ba2+, Mn2+, Fe2+ and possibly also Sb3+ in the viiCa2+ site; Sb5+, Cr3+, Al3+, Sb3+, Fe3+ and possibly also Mn3+ in the viTi4+ site; and Al3+ in the ivSi4+ site; this indicates the existence of a natural silicate containing not only both trivalent and pentavalent Sb, but also both valencies in the same site. The principal ionic substitution is believed to be: 2 viTi4+ = vi[Al3+ + Cr3+ + Mn3+ + Fe3+] + viSb5+ accompanied by a substantial minor proportion of: 2 viTi4+ = viSb3+ + viSb5, or possibly = 2 viSb4+ The data indicate a very late stage penetration of pre-existing titanites by mobilized Sb, Al, Cr, Mn, Fe, F and presumably also (OH) at this locality, whereas Sr and Ba were mobile at an earlier stage. Manganese, which existed in the sedimentary protoliths, did not enter the titanite structure in very significant quantities.

Twenty-four apatite (Ap) samples mainly from carbonatite and alkaline rocks were studied by electron microprobe, IR spectroscopy and X-ray powder diffraction. The crystal structures of six were refined using single crystal X-ray diffraction data to R = 1.7-2.5%. The generally high Si content of Ap from carbonatite and alkaline rock has been related to the presence of characteristic Si-O absorptions in IR spectra. Bands, whose intensities change with Si content, were observed at 520, 650, 930 and 1160 cm-1. The IR absorption features of v3 CO3 mode of Ap from carbonatite are different from those of v3 CO3 mode of Ap from sedimentary rock. This phenomenon is probably due to the different effects of F and OH on the CO3 substitution for PO4. The structural refinements yield more information on the CO3=PO4 substitution, which is now supported also by the geometrical evolution of the tetrahedron with increasing CO3 content: the tetrahedral size decreases and the angle distortion increases with C-content. It is likely that the triangular planar CO3 group is disordered on the four faces of PO43-tetrahedron. It was observed also that Ap from early-stage carbonatite is OH-dominant with considerable LREE, Si, CO3 and negligible Mn, Fe, Mg, K, S and C1 contents. They have high Sr/Mn, Si/S and C/S ratios.

The crystal chemistry of clinopyroxene, orthopyroxene and olivine from a crushed fragment of the H5 Zaoyang chondrite has been investigated by X-ray structure refinement and detailed microprobe analysis. The meteoritic pyroxenes have cell and polyhedral volumes which compare well with such data from terrestrial pyroxenes that typically crystallize at low-pressure. Fe2+ and Mg are rather disordered in M1 and M2 sites of clino- and orthopyroxenes; the closure temperatures of the exchange reaction are 600 and 512°C respectively, which is consistent with a reasonably fast cooling rate, estimated to be of the order of 1°C/day.

The closure temperature for the intercrystalline Ca-Mg exchange reaction for clino- and orthopyroxenes is 900°C as calculated from clino- and orthopyroxene intergrowth.

The cooling rates obtained from Fe2+-Mg intracrystalline partitioning suggest a cooling of the order of degrees per day at temperatures of 600–500°C due to a strong loss of heat by irradiation.

K-edge X-ray absorption spectra of Fe in garnet samples from the Ivrea-Verbano zone were collected using synchrotron radiation. From XANES analysis, the prevalent oxidation state of Fe has been determined as 2+ in all studied samples. Coordination numbers and Fe-O bond lengths derived from the EXAFS analysis are compatible with a dodecahedral environment of Fe atoms and seem to be nearly independent of the variable Fe/Ca ratio of the cations sharing the dodecahedral site in these garnets. This suggests that, since at least up to 0.5 Ca atoms p.f.u, no sensible deformation of the dodecahedron geometry is sensed by the Fe cations, iron might strongly compete with Ca atoms in controlling the entry of rare earth elements in the dodecahedral site of garnets falling within this compositional range. Comparison of the EXAFS results with the data from single crystal X-ray diffraction structure refinements indicates a first shell neighbour distance accuracy of ±0.02 Å, using theoretical EXAFS phases and amplitudes. The Debye-Waller factors derived from the EXAFS analysis indicate a higher degree of disorder on the four longer Fe-O bond distances, in comparsion with the other four shorter distances of the height-coordinated cation; this could be related to the nonrigid polyhedral behaviour of the dodecahedral site.

A wide range of natural K-, Na-, Ca- or (K + Li)-micas have been systematically examined by Raman spectrometry. The spectra are interpretable in terms of regular variations in peak positions and chemical parameters. Several vibrations give higher wavenumbers for Na-micas compared to K-micas, in accord with the smaller ionic size of Na+ than K+. The ≈195 cm-1 and ≈270 cm-1 peak wavenumbers and intensities vary as functions of the chemistry of the octahedral sites, i.e. the replacement of Mg2+ by Mn2+, Zn2+, Cr3+, Fe3+, Ti4+, and especially by Al3+, or by a vacancy, and the replacement of (OH)- by F-. The group of ≈700 cm-1 peaks vary in wavenumber and intensity with the replacement of Si by Al in the tetrahedra; distinct Si-O-Si and Si-O-Al vibrations can be recognized. Di- and tri-octahedral micas are distinguished on the basis of certain relative peak intensities which vary considerably with polarization direction, and of trends with increasing Al(iv), Al(vi) or Al(tot.). Calibration of these trends for the chemical analysis of mica microinclusions seems feasible once the uncertainties in the data set are resolved by the determination of further samples selected to highlight the effect of specific elements.

Two Mg-Al spinels (FAS1 and FAS2) in high-grade hornfels from the Toal de Mason skarn (Predazzo Monzoni, NE Italy) were investigated by means of single crystal X-ray diffraction and electron microprobe analysis in order to evaluate the last intra-crystalline closure temperature.

The evidence provided by crystal chemical data from the investigated spinels, compared with that for two other spinels from a websterite dyke and a chlorite schist (TS2 and SP78a, respectively) with similar chemical characteristics, yielded a new empirical geothermometer. This allowed estimation of intra-crystalline temperatures as low as c. 400°C and indicates that the closure temperature of FAS1 and FAS2 is c. 500°C i.e. 150–200°C lower than the spinel crystallisation temperature.

The crystal-chemical relationships occurring within a single grain of monazite-(Ce) from Vetralla, Vico Volcanic Complex, north of Rome, are outlined. The sample is from a miarolitic cavity in a holocrystalline ejectum consisting of K-feldspar plus minor plagioclase, mica and Fe-oxides, collected from a pyroclastic explosive level. The Gandolfi film (Cu-Kα radiation) can be indexed in space group P21/n with a = 6.816(4); b = 6.976(4); c = 6.471(3) Å; β = 103.63(3)°; V = 299.0(6) Å3. Electron-probe microanalyses plot within the field of monazite along the huttonite-monazite edge of the huttonite-monazite-brabantite triangle. Despite patchy and irregular zoning, the grain shows a clear enrichment towards pure monazite at the outer rim. A constant Th:Si ratio of 1:1 indicates the existence of a simple solid-solution between huttonite and monazite. The substitution can be written as Th4+ + Si4+ → REE3+ + P5+ without requiring any electrostatic compensation by divalent cations, or by anionic groups. The REE distribution pattern is compatible with that of monazites from syenitic rocks.

This paper reports the first in-situ finding of perrierite-(Ce) in Latium. The mineral occurs as brownish-red, transparent, well-developed, euhedral, prismatic crystals inside the miarolitic cavities of a holocrystalline ejectum from La Mola, Monti dell'Anguillara district, Sabatini volcanic complex.

The cell parameters (from Gandolfi film) are (in Å): a = 13.629(9), b = 5.727(1), c = 11.715(6), β(°) = 113.74(2), V(Å3) = 835.5(9). The crystal-chemical formula, based on microprobe analysis of one grain, is:

This perrierite is the most Zr-rich described so far. The entry of Zr in the C site of the structure is related to the substitution of large amounts of Ca in the A site, according to the charge balancing relationship:

The genesis of perrierite-(Ce) from La Mola is linked to late pneumatolitic-pegmatitic hypabyssal stages of the regional volcanic activity.

This paper presents the results of an experimental study of muscovite solid solutions in the system K2O-M2+O-Al2O3-SiO2-H2O-(HF), with M2+ = Mg2+ or Fe2+ in the temperature range 300-700°C under 2 kbar PH2O. Muscovite solid solutions can be described, in this system, as the result of two substitutions. One is the phengitic substitution (x), which preserves the pure dioctahedral character of the mica; the second is the biotitic substitution (y), which leads to trioctahedral micas and does not change the composition of the tetrahedral layer Si3Al. The general formula of muscovite in this system is K(Al2−x−2y∕3M2+x+y□1−y∕3)(Si3+xAl1−x)O10(OH,F)2. Both substitutions x and y are more extensive at lower temperatures. The extent of solid solution decreases drastically with increasing temperature.

For T > 600°C, the phengitic substitution (x) becomes negligible, but some biotitic substitution (y) persists. This unsymmetrical decrease of the solid solution of muscovite with increasing temperature is similar to that previously observed in phlogopite, the micas with a tetrahedral layer composition of Si3Al being the most stable. The behaviour of muscovite solid solutions in the ferrous system is qualitatively identical to that observed in the magnesian one, but the extent of solid solution is smaller than with Mg2+. Fluorine neither changes the size nor the shape of the solid solution fields but increases their stability by about 50°C.

A comparison of these experimental results with data on natural muscovites is presented. Most natural primary (magmatic) granitic muscovites lie very close to the muscovite end member, in agreement with their high-temperature origin. Low-temperature muscovites (300–400°C), typically muscovites from hydrothermally altered granitic rocks, can have high x and y values. The rate of the biotitic substitution y can reach 0.6, which corresponds to an octahedral occupancy of 2.2 atoms per formula unit (based on 11 oxygens), consistent with the experimental data.

The crystal structures of nine, and the chemical compositions of ten, natural samples of leucophanite, ideally NaCaBeSi2O6F, were investigated. The analysed samples display a large compositional variation with trace-element abundances >50,000 ppm, primarily due to rare earth elements (REE). Fromthese data, we propose a substitution scheme for the incorporation of REE for Ca, with additional Na substituting for Ca and the generation of vacancies to ensure charge balance. Compositional zonation was observed in some samples; this zonation correlates with variations in cathodoluminescence. The crystal structure of the nine analysed samples could all be refined in space group P212121. We found no evidence for a reduction of symmetry with increased trace-element concentration. Various twin combinations were observed and these seem related to crystallization conditions rather than structural or chemical factors.

Composite populations of monazite-group minerals of both metamorphic and metasomatic origin have been discovered in thin layers of granulite-facies metabasites interlayered with metapelites, located in the Val Strona di Omegna region of the Ivrea-Verbano Zone, Italy. In addition to monazite-(Ce), which is uncommonly poor in Th and is probably formed by incongruent dissolution of apatite, these populations include members of the monazite-huttonite series. The latter minerals contain between 13 and 30.1 mol.% ThSiO4 [= huttonitic monazite-(Ce)], and are known from only half a dozen other occurrences worldwide. We propose that breakdown of primary monazite-(Ce) in the metapelites during granulite-facies metamorphism mobilized Th and the REEs, which were then transported by high-grade metamorphic fluids into the metabasite layers to form the Th-rich minerals of the monazite-huttonite series.

The mineralogy and crystal chemistry of a new talc ore deposit situated at Thu Ngac commune, Thanh Son district, Phu Tho province, Vietnam, was investigated using X-ray fluorescence, electron microprobe, X-ray diffraction, Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance (29Si and 1H) and colorimetry.

Both chemical and crystal-chemical analyses showed that the talcs from the Phu Tho province are very pure because they contain few accessory minerals (chlorite, amphibole and goethite) and few substitutions of Si by Fe and Al in their crystal structure. The talc ore may well meet the standards required for a wide range of industrial applications.