New analyses are given of granites from 23 intrusions in Scotland, Ireland, and the Isle of Man. Together with existing analyses, these were used to measure the regional variation in composition of Caledonian granites by means of trend surface analysis. An explanation of the variation is presented that involves the production of magma by melting in the crust, at a depth determined by the geothermal gradient.

At any set of thermodynamic conditions a mineral will have some well defined equilibrium crystal structure. However, this structure can be locally disturbed by crystal defects, such as domain walls or solute atoms. This distorted structure will only affect a finite volume within the crystal, but the need to retain continuity within the crystal means that this volume must be non-zero. This means, for example, that the boundary between two domains will include a transition zone from one domain's crystal structure to that of the other domain. Thick twin domain walls can be studied quantitatively, by measuring the intensity of diffuse diffraction between pairs of twin-related Bragg peaks. In alkali feldspar (Or30) at room temperature, these walls are approximately 25 Å thick. Similarly, a single solute atom in a mineral will only affect a small region within a crystal. As a result, chemical mixing will only occur in a substitutional solid solution once there is significant overlap between the strain fields around individual solute atoms. This causes the ‘plateau effect’, where the properties of a phase transition are independent of composition. In alkali feldspar, this plateau extends from albite to 2% Or, which corresponds to a strain field radius of 10 Å.

These phenomena can be modelled using Ginzburg-Landau theory, which predicts that the range of these strain fields will increase as the temperature is raised to Tc. This has been confirmed by measuring the thickness of twin walls as a function of temperature.

Synchrotron X-ray diffraction (XRD) is a powerful technique to study in situ and in real-time the structural and kinetic processes of pressure-induced phase transformations. This paper presents the experimental set-up developed at beamline ID27 of the ESRF to perform time-resolved angle dispersive XRD in the Paris-Edinburgh cell. It provides a practical guide for the acquisition of isobaric-isothermal kinetic data and the construction of transformation-time plots. The interpretation of experimental data in terms of reaction mechanisms and transformation rates is supported by an overview of the kinetic theory of solid-solid transformations, with each step of data processing illustrated by experimental results of relevance to the geosciences. Reaction kinetics may be affected by several factors such as the sample microstructure, impurities or differential stress. Further high-pressure kinetic studies should investigate the influence of such processes, in order to acquire kinetic information more akin to natural or technological processes.

Using type material from the Österby pegmatite in Dalarna, Sweden, the chemical composition and structural parameters of thalénite-(Y) [ideally Y3Si3O10(OH)] were examined by wavelength dispersive spectroscopy electron microprobe (WDS EMP) analysis and single-crystal X-ray diffraction. High contrast back-scatter electron images of the Österby material show at least two generations of thalénite-(Y). The formula of the primary thalénite-(Y) normalized to 11 anions is (Y2.58Dy0.11Yb0.09Gd0.06Er0.06Ho0.02Sm0.02Tb0.02Lu0.02Nd0.01Tm0.01)Σ3.00Si3.01O10F0.97OH0.03. The secondary thalénite-(Y), replacing the primary material, is weakly enhanced in Y and depleted in the lightest and the heaviest rare-earth elements, yielding the formula (Y2.63Dy0.12Yb0.06Gd0.06Er0.05Ho0.02Sm0.02Tb0.02Tm0.01Nd0.01Lu0.01)Σ3.00Si3.01O10F0.98OH0.02. Structural data for thalénite-(Y) from Österby clearly indicate the monoclinic space group P21/n, with a = 7.3464(4), b = 11.1726(5), c = 10.4180(5) Å, β = 97.318(4)°, V = 848.13(7) Å3, Z = 4, which is consistent with previous investigations. The structure was refined from single-crystal X-ray diffraction data to R1 = 0.0371 for 1503 unique observed reflections, and the final chemical composition obtained from the refinement, (Y2.64Dy0.36)Σ3.00F0.987[Si3O10], Z = 4, is in good agreement with the empirical formula resulting from electron microprobe (EMP) analysis. Both techniques reveal a strong dominance of F over OH, which means that the type material actually corresponds to the fluorine analogue. Moreover, new EMP analyses of samples of thalénite-(Y) from an additional seven localities (Åskagen and Reunavare in Sweden; White Cloud and Snow Flake in Colorado, USA; the Guy Hazel claim in Arizona, USA; Suishoyama and Souri in Japan) clearly show the prevalence of F over OH as well. Based on these observations, the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association has recommended a redefinition of the chemical composition of thalénite-(Y) to represent the F-dominant species with the ideal formula Y3Si3O10F, as it has historical priority. Consequently, the later described fluorthalénite-(Y) has to be discredited.

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.

Several uncommon phosphate minerals including tarbuttite, parahopeite, scholzite, and collinsite occur in near-surface gossans at the Reaphook Hill zinc prospect. Electron-probe microanalyses of the tarbuttite and scholzite compare well with published analyses of specimens of these minerals from the type localities in Zambia and Bavaria respectively. However, microanalyses of the parahopeite are significantly different from published analyses of parahopeite, and suggest that it may be one member of an isomorphous series in which six-coordinated Zn can be replaced by other cations, including Fe, Mg, and Mn. Furthermore, crystals of the Reaphook Hill parahopeite are compositionally zoned with their centres enriched in Fe and Mn relative to the margins, which are enriched in Mg.

Zincian collinsite occurs at Reaphook Hill as concentric crusts composed of very fine grained radially oriented plates. Electron-probe microanalyses of this material are significantly different from published analyses of collinsite from the type locality in British Columbia: Zn instead of Fe occupies the divalent cation sites; this material may be part of an isomorphous series that includes fairfieldite. Microanalyses also indicate that the Reaphook Hill collinsite crusts are compositionally zoned such that Zn:Mg ratios vary from the base to the outer edges of the crusts. This zoning is interpreted as the result of variation in the availability of Zn and Mg during growth. Zoning of similar type, but due to variation in the Fe: Mg ratio, was observed in concentric crusts of collinsite from the type locality in British Columbia.

Dokuchaevite, ideally Cu8O2(VO4)3Cl3, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Dokuchaevite occurs on the crusts of various copper sulfate exhalative minerals (such as kamchatkite and euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P$\bar{1}$, a = 6.332(3), b = 8.204(4), c = 15.562(8) Å, α = 90.498(8), β = 97.173(7), γ = 90.896(13)°, V = 801.9(7) Å3 and R1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (d, Å (I)(hkl): (15.4396)(18)(00$\bar{1}$), (7.2762)(27)(0$\bar{1}$1), (5.5957)(43)(012), (4.8571)(33)($\bar{1}\bar{1}$1), (3.1929) (29)(023), (2.7915)(30)(202), (2.5645)(21)(032), (2.5220)(100)(1$\bar{3}$0), (2.4906)(18)(130) and (2.3267)(71)(2$\bar{2}$2). The chemical composition determined by electron-microprobe analysis is (wt.%): CuO 60.87, ZnO 0.50, FeO 0.36, V2O5 19.85, As2O5 6.96, SO3 0.44, MoO3 1.41, SiO2 0.20, P2O5 0.22, Cl 10.66, –O = Cl2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions per formula unit is (Cu7.72Zn0.06Fe0.05)Σ7.83(V2.20As0.61Mo0.10S0.06P0.03Si0.03)Σ3.03O13.96Cl3.04.

The crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate the remarkable diversity of Cu2+ mixed-ligand coordination environments. The crystal structure of dokuchaevite is based on OCu4 tetrahedra that share common corners thus forming [O2Cu6]8+ single chains. Two of the eight symmetrically independent copper atoms do not form Cu–O bonds with additional oxygen atoms, and thus are not part of the OCu4 tetrahedra, but provide the three-dimensional integrity of the [O2Cu6]8+ chains into a framework. TO4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu2[Cu6O2](VO4)3Cl3.

Blue-coloured gem-quality spinel from Nigeria was analysed by wet chemical methods (using atomic absorption spectrophotometry) and investigated by X-ray diffraction. The results showed it to be gahnite (unit cell dimension a=8.091±0.003 Å) containing 36.7% ZnO, 3.58% FeO, and 0.12% MgO. The spinel has an RI of 1.79 and density between 4.4 and 4.59. Broadening of the n[111] XRD reflections indicates a measure of compositional heterogeneity. The gahnite analyses were compared with compositions of zinc spinels from other parts of the world. The analyses cluster into two distinct groups, Mg-rich spinels of metamorphic origin and Mg-poor spinels (including the Nigerian gahnite) with igneous affinities. Diadochy seems to operate within the zinc spinel structure between (Zn + Mn) and (Fe + Mg).

The structures of bustamite and the poly-types of wollastonite are shown to be derived from variations in the stacking sequence of a single type of structural unit. This structural unit is a column of unit cells of wollastonite along the b-axis and is bounded by (100) and (001) planes (P1̄ cell); these units may be stacked together along [100] and [001] with either zero displacement between successive units, or a relative displacement of 1/2[010]. Regular stacking sequences give rise to the ordered structures of wollastonite polytypes and of bustamite, while the transformations between these structures proceed by the propagation of line defects with Burgers vectors of 1/2[010] which thus change the stacking sequence of the structural units.

Field gamma-ray spectrometry is a rapid and effective quantitative method of mapping variations of radioelements within igneous intrusions. A field procedure for radioelement mapping demonstrates the value of the method to studies of late-stage magmatic processes during the emplacement of granite intrusions and the determination of their present-day heat productivities. Methods and problems of instrument calibration using both natural and artificial sources are discussed. Calibration based on neutron activation analysis of samples from natural outcrops achieves results comparable with those obtained using artificial sources and has the advantage that it relates directly to field conditions; furthermore it enables secular disequilibrium in the uranium and thorium decay series to be recognized.

The crystal structure of chloroxiphite, Pb3CuO2(OH)2Cl2, from Merehead Quarry (monoclinic, P21/m, a = 6.6972(8), b = 5.7538(5), c = 10.4686(14) Å,β = 97.747(10)°, V = 399.72(8) Å3) has been refined to R1 = 0.041. The structure contains three symmetrically unique Pb sites and one Cu site. The strong distortion of the Pb2+ coordination polyhedra is due to the stereoactivity of the s2 lone electron pairs on the Pb2+ cations. The Cu-site is coordinated by four OH- groups to form an almost planar Cu(OH)4 square that is complemented by two apical Cl– anions, forming an elongated [Cu(OH)4Cl2] octahedron. Because of the large size and variability of coordination polyhedra around Pb2+ cations and the strength of the Me–O bonds in comparison to the Me–Cl bonds (Me = metal), it is convenient to describe the structure of chloroxiphite in terms of oxocentred OPb4 tetrahedra. The O1 atom is tetrahedrally coordinated by four Pb2+ cations forming relatively short and strong O–Pb bonds. The OPb4 tetrahedra link together via common edges to form [O2Pb3]2+ double chains. The difference between chloroxiphite and other natural oxyhalides is the presence of Cu2+ cations which form an independent structural unit that links to units formed by OPb4 tetrahedra. In this sense, chloroxiphite can be considered as a modular structure consisting of both strong cation- and anion-centred units.

The high-temperature (HT) behaviour of kyanite (Al2SiO5) was investigated by in situ neutron powder diffraction up to 1200°C. Within the investigated T range, no phase transition was observed. The axial and volume thermal expansion coefficient (αj = lj-1(𝜕1j/𝜕T), αv = V-1 (𝜕V/𝜕T)), calculated by weighted linear regression through the data points, are: αa = 5.5(2) x 10-5, αb= 5.9(2) x 10-5, αc = 5.18(8) xl0-5, αv = 7.4(1) x 10-3 “C-1, with αa:αb:αc = 1.06:1.14:1. All three angles of the kyanite lattice show a slight decrease with T, with 𝜕α/𝜕T = -2(2) x 10-5, 𝜕β/𝜕T = -4(1) x 10-5, 𝜕γ/𝜕T = –10(2) x 10-5%C. The magnitudes of the principal Lagrangian unit-strain coefficients (ε1,ε2, ε3) and the orientations of the thermal strain-ellipsoids, between the ambient temperature and each measured T, were calculated. The magnitude and the orientation of all the three unit-strain coefficients are almost maintained constant with T. At T-To = 1177°C , ε^a = 76(2)°, ε^b = 70(2)°, ε^c = 38(3)°, ε2^a = 49(3)°, ε2^b = 66(3)°, ε2^c = 127(4)°, ε3^a = 135(3)°, ε3^b = 31(3)°, ε3^c = 91(2)° with ε1:ε2:ε3 = 1.57:1.29:1. The structural refinements, performed at 23, 600, 650, 700, 750, 800, 900, 950, 1050 and 1200°C allowed the description of the structural evolution and the main T-induced deformation mechanisms, which are mainly represented by the polyhedral distortions of the AlO6 octahedra.

New occurrences of hibbingite, γ-Fe2(OH)3Cl, have been found associated with platinum-group minerals in the Noril'sk Complex, and with the Korshunovskoye iron ores of the southern Siberian platform. The Norils'k grains, which are up to 0. 6 mm in diameter, are associated with the platinumgroup minerals froodite, cabriite, urvantsevite and with native silver in massive pentlandite–cubanite– chalcopyrite ore. The Korshunovskoye iron ore sample in which hibbingite was found is composed of fine-grained magnetite ore associated with halite. Hibbingite, hematite and silver grains are found in cavities in halite; the reddish-brown hibbingite grains usually occur as encrustations in the cavities. The size of hibbingite and hematite grains is up to 100 µm.

Hibbingite from the Noril'sk Complex contains a significant kempite (Mn2(OH)3Cl) component; in some cases it contains over 50 mol. % Mn. These data suggest that at least a partial solid solution series exists between hibbingite and kempite. All known occurrences of hibbingite represent paragenetically late mineral assemblages. In the case of the Korshunovskoye deposits, the occurrences are associated with highly concentrated hydrothermal brines derived from the Lower Paleozoic saline sediments of the Siberian Platform cover.

The crystal structure of mosandrite, ideally Na2Ca4REETi(Si2O7)2OF3, a = 7.4184(8), b = 5.6789(6), c = 18.873(2) Å, β = 101.410(2)°, V = 779.35(5) Å3, space group P21/c, Z = 2, Dcalc = 3.363 g.cm-3, from the type locality, Låven (Skådön), Langesundsfjorden, Larvik, Vestfold, Norway, has been refined to Ri = 6.33% on the basis of 1113 unique reflections F°≥4σF. Electron microprobe analysis gave the empirical formula Na1.99(Ca3.93Sr0.02)Σ3.95(Ce0.41La0.16Nd0.13Pr0.04Sm0.02Dy0.01Y0.13)Σ0.90 (Ti0.864+Nb0.08Zr0.05)Σ0.99(Si207)2(F1.20O0.80)Σ2.00F2, Z = 2, calculated on the basis of 18 (O + F) a.p.f.u.. The crystal structure of mosandrite is a framework of TS (titanium silicate) blocks. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). The TS block in mosandrite exhibits linkage and stereochemistry typical for Group I (Ti = 1 a.p.f.u.) Ti-disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to the trans edges of a Na polyhedron of the O sheet. The O sheet cations give Na(NaCa)Ti (4 a.p.f.u.). The TS blocks link via common vertices of (Si2O7) groups and common vertices and edges of Ca-dominant MH and Ap polyhedra. Two adjacent TS blocks are related by the glide plane cy. Composition and topology of the TS block in mosandrite and rinkite are identical. The crystal structure of mosandrite from the type locality is topologically and chemically identical to that of rinkite from the type locality of Kangerdluarssuk, Greenland.

The new durangite-group mineral arsenatrotitanite, ideally NaTiO(AsO4), was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with orthoclase, tenorite, hematite, johillerite, bradaczekite, badalovite, calciojohillerite, arsmirandite, tilasite, svabite, cassiterite, pseudobrookite, rutile, sylvite, halite, aphthitalite, langbeinite and anhydrite. Arsenatrotitanite occurs as prismatic, tabular, lamellar or acicular crystals up to 0.3 mm × 0.8 mm × 2 mm. They are separated or combined in open-work aggregates up to 2 mm across or interrupted crusts up to 2 mm × 5 mm in area and up to 0.3 mm thick. Arsenatrotitanite is transparent, brownish red to pale pinkish-reddish or almost colourless, with vitreous lustre. It is brittle and the Mohs’ hardness is ~5½. Cleavage is perfect on {110} and the fracture is stepped. Dcalc is 3.950 g cm–3. Arsenatrotitanite is optically biaxial (+), α = 1.825(5), β = 1.847(6), γ = 1.896(6) (589 nm) and 2Vmeas. = 70(5)°. Chemical composition (wt.%, electron-microprobe) is: Na2O 12.26, CaO 3.10, Al2O3 4.39, Fe2O3 9.57, TiO2 17.11, SnO2 1.03, As2O5 50.17, F 3.29, O = F –2.39, total 99.53. The empirical formula based on 5 (O + F) apfu is (Na0.91Ca0.13)Σ1.04(Ti0.49Fe3+0.27Al0.20Sn0.02)Σ0.98(As1.00O4.00)(O0.60F0.40). Arsenatrotitanite is monoclinic, C2/c, a = 6.6979(3), b = 8.7630(3), c = 7.1976(3) Å, β = 114.805(5)°, V = 383.48(3) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 4.845(89)($\bar{1} {11}}$), 3.631(36)(021), 3.431(48)(111), 3.300(100)($\bar{1} {12}}$), 3.036(100)(200), 2.627(91)(130) and 2.615(57)(022). The crystal structure was solved from single-crystal XRD data with R = 1.76%. Arsenatrotitanite belongs to the titanite/durangite structure type. It is named as an arsenate of sodium (natrium in Latin) and titanium isostructural with titanite.

Cesanite, Ca1+xNa4−x(SO4)3(OH)x · (1 − x) H2O, is hexagonal, space group P63/m, a = 9.446(1) and c = 6.895(1) Å, Z = 2. The crystal structure refinement, carried out by utilizing 457 independent reflections (final R = 0.021), shows that cesanite is isotypic to hydroxyapatite. The P atom of apatite is completely replaced in cesanite by an S atom; the two independent Ca sites of apatite are occupied respectively by Na and Na + Ca, the charge balance being by partial substitution of H2O for OH− although the occupancy of the (H2O,OH−) sites is not complete. The relationship between the water vacancies and the structural features of the (Ca,Na) polyhedron is discussed. A new general formula for the apatite-wilkeite-ellestadite series is proposed.

Cathodoluminescence, produced by electronic bombardment in the microprobe, can serve to indicate the nature and distribution of elements present in amounts below the normal detection limit of the probe. This is illustrated by a study of specimens of blende from various localities.

Two mixites from Boss Tweed Mine, Tintic District, Juab County, Utah and Tin Stope, Majuba Hill, Pershing County, Nevada, USA, were analysed by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis and by Raman spectroscopy. The SEM images show the mixite crystals to be elongated fibres up to 200 μm long and 2 μm wide. Detailed images of the mixite crystals show the mineral to be composed of bundles of fibres. The EDX analyses depend on the crystal studied, though the Majuba mixite gave analyses which matched the formula BiCu6(AsO4)3(OH)6.3H2O. Raman bands observed in the 880–910 cm−1 and 867–870 cm−1 regions are assigned to the AsO-stretching vibrations of (HAsO4)2− and (H2AsO4)− units, whilst bands at 803 and 833 cm−1 are assigned to the stretching vibrations of uncomplexed (AsO4)3- units. Intense bands observed at 473.7 and 475.4 cm−1 are assigned to the v4 bending mode of AsO4 units. Bands observed at 386.5, 395.3 and 423.1 cm−1 are assigned to the v2 bending modes of the HAsO4 (434 and 400 cm−1) and the AsO4 groups (324 cm−1). Raman spectroscopy lends itself to the identification of minerals on host matrices and is especially useful for the identification of mixites.

Stable perovskite and metastable post-perovskite NaCoF3 were deformed in pure-shear geometry in a deformation-DIA press with radiographic monitoring of the sample strain. In isothermal experiments where there was no transformation, post-perovskite was found to be 5 times weaker than perovskite. In temperature-ramping experiments where post-perovskite transformed to perovskite during the deformation experiment the initial post-perovskite sample was 5–10 times weaker than perovskite under comparable conditions and their strengths converged during the transformation, being equal on completion of the transformation. These results confirm recent findings which show that postperovskite is weaker than perovskite, regardless of the prior history of the sample.

Hydroxycalciomicrolite, Ca1.5Ta2O6(OH) is a new microlite-group mineral found in the Volta Grande pegmatite, Nazareno, Minas Gerais, Brazil. It occurs as isolated octahedral and as a combination of octahedral and rhombic dodecahedral crystals, up to1.5 mm in size. The crystals are yellow and translucent, with a white streak and vitreous to resinous lustre. The mineral is brittle, with a Mohs hardness of 5–6. Cleavage is not observed and fracture is conchoidal. The calculated density is 6.176 g cm–3. Hydroxycalciomicroliteis isotropic, ncalc. = 2.010. The infrared and Raman spectra exhibit bands due to O–H stretching vibrations. The chemical composition determined from electron microprobe analysis (n = 13) is (wt.%): Na2O 0.36(8), CaO 15.64(13), SnO2 0.26(3),Nb2O5 2.82(30), Ta2O5 78.39(22), MnO 0.12(2), F 0.72(12) and H2O 1.30 (from the crystal structure data), O = F –0.30, total 99.31(32), yielding an empirical formula, (Ca1.48Na0.06Mn0.01)∑1.55(Ta1.88Nb0.11Sn0.01)∑2.00O6.00[(OH)0.76F0.20O0.04].Hydroxycalciomicrolite is cubic, with unit-cell parameters a = 10.4205(1) Å, V = 1131.53(2) Å3 and Z = 8. It represents a pyrochlore supergroup, microlite-group mineral exhibiting P4332 symmetry, instead of Fd3m. Thereduction in symmetry is due to long-range ordering of Ca and vacancies on the A sites. This is the first example of such ordering in a natural pyrochlore, although it is known from synthetic compounds. This result is promising because it suggests that other species with P4332or lower-symmetry space group can be discovered and characterized.