Intermediate compositions along the bornite–digenite join exsolve during quenching from above-solvus temperatures. This involves vacancy clustering and cation ordering processes, and is facilitated by fast cation diffusion rates in the presence of a large (10–25%) metal vacancy population. Samples of six different compositions across the bornite–Cu9S5 join, synthesised from component elements in sealed quartz capsules, were water-quenched from 600°C and analysed using high-resolution neutron powder diffraction (HRPD). Time-of-flight spectra measured at room temperature showed all intermediate compositions had exsolved into mixtures of bornite and low digenite with a 5.0a superstructure. No evidence for the presence of any other phase was found. Variations in the lattice parameters of the exsolved bornite phase were observed for different bulk compositions across the join, and ascribed to variations in the degree of order. Bornite exsolved from digenite-rich compositions may not be fully ordered due to the much lower solvus temperatures at the Cu-rich end of the solid solution. As only slight differences were observed between the diffraction patterns of a visibly exsolved and a rapidly quenched sample of the same bulk composition, the formation of optically-visible exsolution lamellae on {100} is ascribed to a process of coalescence of sub-microscopic domains initially formed during the quenching process. The rapid kinetics of exsolution at geologically low temperatures, explains the lack of authenticated natural occurrences of intermediate compositions in the solid solution in nature, and the limited degree of stoichiometric variation observed in end-members.

Wooldridgeite, ideally Na2(P2O7)2(H2O)10, orthorhombic, a = 11.938(1), b = 32.854(2), c = 11.017(1) Å , V = 4321.2(8) Å3, a:b:c = 0.3634:1:0.3353, space group Fdd2, Z = 8, is a new mineral from Judkins Quarry, Nuneaton, Warwickshire, England. Associated minerals are calcite, chalcopyrite, bornite and baryte. It occurs as equant crystals forming rhombic dipyramids; no twinning was observed. It is transparent blue-green with a very pale-blue streak, a vitreous lustre, and does not fluoresce under long- or short-wave ultraviolet light. Wooldridgeite has a Mohs hardness of 2–3, is brittle with an irregular fracture, and has no cleavage. The calculated density is 2.279 g/cm3. In transmitted light, wooldridgeite is colourless, non-pleochroic, and shows no dispersion. It is biaxial negative with α = 1.508(1), β = 1.511(1), γ = 1.517(1), 2V(meas.) = 76.2(5), 2V(calc.) = 71(10)8, X = b, Y = c, Z = a. The strongest five reflections in the X-ray powder diffraction pattern are [d(Å), (I), (hkl)]: 8.23(30)(040), 6.52(100)(131), 4.05(40)(260), 3.255(40)(262); 2.924(40)(371). Electron-microprobe analysis of wooldridgeite gave P2O5 39.37, CuO 20.24, MgO 0.24, CaO 7.73, Na2O 8.33, K2O 0.17, H2O(calc.) 24.72, sum 100.80 wt.%; the corresponding unit formula (based on 24 anions) is (Na1.96K0.03)Ca1.00(Cu1.85Mg0.04)P4.04O14(H2O)10 where the H2O groups were assigned from knowledge of the crystal structure; the infrared absorption spectrum also indicates the presence of H2O in the structure. The mineral is named for James Wooldridge (1923–1995), a fervent amateur mineral collector who discovered this mineral.

The structure of antimonian dussertite, (AsO4)2(OH,H2O)6, has been refined in space group R3̄m with a 7.410(3), c 17.484(4) Å, Z = 3, to R = 3.2 % and Rw = 3.7 % using 377 observed reflections with I ≥ 3 σ(I). The structure is of the alunite-type and consists of sheets of corner-sharing (Fe3+,Sb5+)O6 octahedra parallel to (0001). The substitution of Sb5+ for Fe3+, and not for As5+, is unambiguously demonstrated not only by the structure refinement but also by electron microprobe analyses and crystal-chemical considerations. The icosahedrally coordinated Ba cations occupy cavities between pairs of octahedral sheets and are surrounded by six O atoms from the AsO4 tetrahedra and six O atoms from the (Fe3+,Sb5+)O6 octahedra. The mean bond lengths for the various coordination polyhedra are As-O 1.684(3) Å, (Fe,Sb)-O 2.004(1) Å, and Ba-O 2.872(2) Å. A hydrogen-bonding network is modelled using bond-valence calculations. The dussertite sample investigated is the first member of the crandallite group found to contain substantial Sb.

The current definition of samarskite-group minerals suggests that ishikawaite is a uranium rich variety of samarskite whereas calciosamarskite is a calcium rich variety of samarskite. Because these minerals are chemically complex, usually completely metamict, and pervasively altered, their crystal chemistry and structure are poorly understood. Warner and Ewing (1993) proposed that samarskite is an A3+B5+O4 mineral with an atomic arrangement related to α-PbO2. X-ray diffraction analyses of the recrystallized type specimen of ishikawaite and the Ca-rich samarskite reveal that they have the same structure as samarskite-(Y) recrystallized at high temperatures. Electron microprobe analyses show that the only significant difference between samarskite-(Y), ishikawaite, and calciosamarskite lies in the occupancy of the A-site. The A-site of samarskite-(Y) is dominated by Y+REE whereas the A-site of ishikawaite is dominantly U+Th and calciosamarskite is dominantly Ca. Additionally, a comparison of these data to those of Warner and Ewing (1993) show that in several cases Fe2+ or Fe3+ are dominant in the A-site. We propose that the name samarskite-(REE+Y) should be used when one of these elements is dominant and that the mineral be named with the most abundant of these elements as a suffix. The name ishikawaite should be used only when U+Th are dominant and the name calciosamarskite should only be used when Ca is the dominant cation at the A-site. Finally, because of the inability to quantify the valence state of iron in these minerals, the exact nature of the valence state of iron in these minerals could not be determined in this study.

The Coire Dhuinnid fault zone contains emerald green chromian illite-ankerite-quartz rocks that are similar in appearance to the fuchsite(or mariposite)-carbonate-quartz parageneses that are commonplace in Archaean greenstone belts but which are rather rare in Phanerozoic rocks. The chromian illite contains 2.3 wt.% Cr2O3, low K2O (7.1–7.6 wt.%) and high H2O+ (5.7 wt.%), and it is a 1M polytype with ≤10% of an illite/smectite interstratification indicative of a formation temperature of c. 175–200°C. The host rocks contain high concentrations of Ni and Cr, and show low concentrations of Ti, Nb, Y and Zr, suggesting a former primitive mafic protolith (boninitic magma?); they are considered to be retrograde remnants of Lewisian rocks. The latter, and the associated rocks of the Moine Series, have been affected by CO2 metasomatism that was accompanied by the addition of Ca(+Sr), Fe and Mg, and by the removal of Na from, and the addition of H2O to the Moine metasediments. Radiogenic isotope studies of mineral separates and whole rock from sample no. 43 yielded ages of 483±2 Ma (Ar-Ar dating on Cr illite), 413±12 Ma (K-Ar dating on Cr illite), and 322±9 Ma (Rb-Sr dating on minerals and whole rock); the significance of this discrepant pattern is discussed.

Several K-Fe sulphide minerals have been described from natrocarbonatite lavas erupted from the Tanzanian volcano Oldoinyo Lengai but uncertainty remains about their exact identity. They do not appear to be any of the established K-Fe sulphides according to Dawson et al. (1995) and Mitchell (1997). Here, we describe yet another variant which is a Mn- and F-bearing variety of rasvumite. It appears to have formed by reaction of Fe alabandite grains with natrocarbonatite magma and occurs as minute rims on the alabandite. Its formula is: (K0.94Na0.06)(Fe1.91Mn0.13Ca0.01Sr0.01)(S2.06F0.24Cl0.04).

A major disadvantage of the electron microprobe is its inability to determine Li, which may make up an essential component in micaceous minerals. Correct classification of micas and proper calculation of their formulae require alternative methods. One of these is the indirect estimation of the lithium concentration by empirical approaches based on element correlations. Relationships between Li2O and SiO2 have long been used for this purpose; however, they are valid only for a limited range of mica compositions (i.e. Li-rich, Mg-poor varieties).

In this paper we report the results from a renewed study of the correlation between Li2O and MgO contents in trioctahedral micas. It is demonstrated that the relations between both oxides are strongly dependent upon the geological environment in which the mica was formed. It is necessary to distinguish a ‘normal group’, which comprises micas from ‘common’ S- and I-type magmatic rocks and most metamorphic rocks , a ‘low Li-Mg group’, to which belong Fe-rich micas from non-alkaline rocks of A-type affinity, and a ‘high Li-Mg group’ which includes micas from either peraluminous or peralkaline igneous rocks and Mg-enriched wall-rocks. These wall rocks supplied additional magnesium to the mica-forming environment. We offer empirical expressions relating Li2O and MgO contents for these three types which, in many cases, allow a sufficiently good estimation of the lithium content in trioctahedral micas of widely varying compositions.

Thallium leucite, TlAlSi2O6, has been synthesized at 450°C for 7 days, under ambient conditions, by the transformation of dehydrated analcime NaAlSi2O6 in the presence of excess TlCl. This substitution of Tl for Na leads to confirmation of a thallium-leucite pseudomorph after analcime. Their optical properties, X-ray powder diffraction patterns, electron microprobe analysis, infrared spectra, and X-ray photoelectron spectroscopy have characterized the synthetic Tl-leucites. The IR spectra show that the mid-IR modes T-O stretching and T-O-T bending vibrations for TlAlSi2O6 are more resemblant of those for analcime than for leucite, KAlSi2O6. This resemblance implies that Tl cation enters the W-site rather than the S-site in the analcime structure: Na (S) + H2O (W) ⇋ □ + K (leucite) ⇋ □ + Tl (Tl- leucite), where □ represents an S-site vacancy. The mechanism of this substitution is supported by the crystal chemical constraints: inasmuch as the S-site is smaller than the W-site, Tl+ cations being larger than Na+ plainly prefer the latter site to the former. One inference from the binding energy for Tl+ by XPS is that Tl+ occupies the extra-framework site in synthetic leucite pseudomorph, rather than the smaller tetrahedral site. The difference in Al/Si disordering between analcime and leucite and the nonstoichiometry due to the solid solution of the □Si3O6 component into the leucite structure may provide a fundamental insight into understanding why TlAlSi2O6 deviates from the trend defined by K-, Rb- and CsAlSi2O6 leucite series on the a-c parameter diagram, inasmuch as these three cations in the leucite structure occupy the W-sites. Finally, synthesis of TlAlSi2O6 leucite has an implication for the existence of other polymorphs due to different degrees of Al/Si disordering, except for high- and low-temperature leucites already known: natural leucites crystallized directly through igneous processes are different from those formed by substitution of K for Na in analcimes.

In this paper we present new petrological and geochemical data for two peraluminous granite batholiths (Nisa Alburquerque and Jalama batholiths) representative of the ‘Araya-type’ granites of the Central-Iberian Zone. Both granites are composite with several facies (monzogranites and leucogranites) that can be grouped into two main granite units: the external units and central units. Intrusive relationships and lack of geochemical coherence between the central and external units indicate that they are not comagmatic but represent different pulses. The central units of both batholiths are petrologically and geochemically different. On the other hand, external units show a lot of similarities and are the main object of this study. The main characteristics of the external granites can be interpreted in terms of an incomplete fractional crystallization process of early mineral phases (plg + Kf + bt) which probably took place at the level of emplacement. Other possible mechanisms of magmatic differentiation (magma mixing, restite unmixing, sequential melting) can be discarded based on field, petrography and geochemical data. We propose that the ‘Araya-type’ granites are formed by the intrusion of distinct magma pulses (central and external). Further evolution within each pulse can be due to incomplete fractional crystallization possibly taking place at the emplacement level.

Chloritoid with significant Mg-Fe zoning occurs as lath-shaped porphyroblasts and as clusters of subradiating crystals in the Triassic Verrucano metapsammite (quartz + muscovite + chlorite + chloritoid ± kyanite) of the Massa Unit, Alpi Apuane. Two main types of chloritoid zoning profiles were found. The first type is characterised by gradual increase in Mg from core to rim of the porphyroblasts. In the second type the Mg content is constant from the core to the inner rim, but sharply decreases in the outer rim. Both types of zoning have been interpreted as the result of prograde growth during the Alpine metamorphism. The temperature, estimated using the chlorite-chloritoid thermometer, ranges from 467 to 560°C.

In the Apuane Alps (AA) metamorphic core complex, syn-metamorphic mineral deposits are mainly restricted to extensional shear zones in the Lower Plate Palaeozoic basement. By contrast, the extension structures at upper levels, such as the detachment fault, that are typically the seat of fluid circulation and mineralization in other core complexes, are barren in the AA. Extension veins hosted by the Jurassic Carrara marbles are among the few examples of (minor) mineralization located in the upper levels of the AA core complex. Calcite–dolomite geothermometry and fluid inclusion data suggest that the mineralizing process in these veins began under pressure (P)-temperature (T) conditions close to the metamorphic peak (about 400°C, 3 kbar). Progressive cooling and mixing between metamorphic and late stage meteoric fluids were probably responsible for most of the mineral deposition. Batches of relatively saline fluids presumably resulted from interaction with evaporitic levels located along the detachment fault. In agreement with previous estimates, fluid inclusion constraints on the P—T synmetamorphic path of the AA suggest a relatively rapid cooling of the core complex as a result of uplift. However, the maximum estimated geothermal gradient (about 35°C/km) is considerably lower than in other core complexes, where large-scale hydrothermal circulation was associated with extension and uplift. Hence, in the AA, fluid circulation at shallow levels and mixing among fluids of different origin were not favoured, thus precluding the formation of mineral deposits along major extensional structures.

Titanite occurs in the groundmass of a holocrystalline volcanic ejectum collected in the pyroclastic rocks of the Vico Volcanic complex at Tre Croci, near Viterbo, Italy. The host rock is composed of abundant K-feldspar and minor plagioclase, biotite, clinopyroxene and a feldspathoid (sodalite). Titanite is typically associated with zirconolite, biotite and Fe-oxides. It has a medium Al content (Al2O3 + Fe2O3 = 4–6 wt.%) and contains significant amounts of Zr and LREE, with a chondrite- normalised REE pattern similar to those of titanites from other alkaline rocks. Titanite has been corroded by fluids probably rich in dissolved F and P during a late alteration stage, with evidence for some remobilization and redistribution of the REE and actinide elements.

The ignimbrites of the northeast Niğde area, which are subdivided into the Lower, Middle and Upper ignimbrites on the basis of their compositional and stratigraphical characteristics, display textural variations from the base to the top. A large proportion of these ignimbrites have been altered and recrystallized by the processes of compaction, welding and devitrification, and as a result of volatile movement. The alteration and recrystallization processes include four stages: hydration, glassy and spherulitic stages accompanied by vapour-phase crystallisation. In the early phases of devitrification, detailed shard shapes are easily recognisable with the scanning electron microscope, but as alteration proceeds clarity of detail disappears because compaction results in collapse of the structure of the rock. Spherulitic and vapour-phase crystallisation usually involves the growth of alkali feldspar and cristobalite. These later stages are more common in the Upper Ignimbrite than the Middle and Lower ignimbrites.