Intrusive calcite-carbonatite ejecta (sovite) in the lowermost tephra layers of the Mt. Vulture alkaline mafic-ultramafic volcano (Upper Pleistocene), is the first intrusive carbonatite sample from southern Europe. The sovite is of coarse granularity and shows some textural and mineralogical layering. It is mainly formed of calcite (up to 3.5 wt.% MgO, and 0.53 wt.% SrO), less dolomite (average 18.2 wt.% MgO, and up to 2.1 wt.% SrO), spinel (60 wt.% Al2O3, 26.5 wt.% MgO, 10.7 wt.% FeO) and olivine (Fo99). Perovskite and apatite have been found only as microlites. Intergranular vugs are scattered throughout the rocks and small composite inclusions occur in calcite.

The mineral chemistry, high temperature melt inclusions, overall isotopic compositions, and the REE distribution are consistent with a primary igneous origin. Compared with world average sovite compositions, the Vulture sovite has lower LILE and HFSE but Rb, Sr, Th and U are high. The REE abundance is typical of carbonatites, having an LREE/HREE value of ∼100. The δ13C (−4.8% SMOW) is in the range for mantle-derived carbonatites. The 143Nd/144Nd (0.512648±15) and 87Sr/86Sr (0.705978±10) ratios show close similarity between the sovite and the Vulture alkaline mafic rocks. The sovite ejecta are interpreted as a crystallization product of carbonate ultramafic liquid. In common with many shallow-level carbonatites from other localities, the recrystallization of rather pure Mg-calcite, the presence of dissolution vugs and the depletion of some HFSE and the relatively high δ18O values, suggest that a secondary process, such as hydrothermal leaching, affected the rock.

Relics of HP-MT eclogitic assemblages related to the first metamorphic stage of the Hercynian orogeny in the Sierra de Guadarrama (Spanish Central System, SCS) are preserved as boudins of pre-Ordovician metabasites enclosed by felsic gneisses. Textures indicate a multi-stage metamorphic history starting in the MT eclogite facies (as deduced from the presence of omphacite and rutile included in garnet) and continuing through medium to low pressure granulite and retrograde amphibolite-greenschist facies. Thermobarometric calculations in the eclogitic paragenesis yield pressures of ∼14 kbar for temperatures in the range 725-775°C. Thermobarometry for the subsequent granulitic stage indicates a significant drop in pressure (P < 10 kbar) for similar temperatures of ∼750°C. Metabasites vary from gabbro to leucotonalites showing the typical Fe enrichment of the tholeiitic series. Chemical characteristics indicate a derivation from low-pressure crystallization of tholeiitic melts more enriched than typical MORB compositions. Their original location far from continental margins as evidenced by the absence of ophiolitic material in the area and their association with platform sediments suggests that eclogitization was related to intracontinental crustal subduction and thickening. The P-T conditions estimated in the metabasites for the first metamorphic stage are similar to ones deduced for the surrounding metasediments and suggest that the Hercynian crust could have reached a thickness of ∼70–80 km, which is more than the double the present thickness.

Structural data have been obtained on the cation surroundings in multi-component silicate and borosilicate glasses using chemically selective spectroscopic and scattering methods, such as extended X-ray absorption and neutron scattering with isotope substitution (NSIS). Transition elements such as Ni or Ti may occur in unusual 5-coordinated sites which coexist with other coordination numbers, depending on glass composition. Distribution of cationic sites in the glassy structure is responsible for unusual spectroscopic properties, as shown by Fe2+ Mössbauer spectroscopy. The environment of cations such as Zn, Zr or Mo, has been determined by EXAFS and discussed using the bond valence theory, which predicts the way to charge compensate the oxygen neighbours and which indicates the linkage of cationic sites with the silicate framework. Cation-cation correlations are given by NSIS up to ∼8 Á, indicating an extensive Medium Range Ordering (MRO) with corner- and edge-linked cationic polyhedra, for Ti and Ni-bearing glasses, respectively. This heterogeneous cationic distribution in glasses is consistent with the presence of two-dimensional domains in which cation mixing may occur, as shown in a Ca-Ni metasilicate glass. Three-dimensional domains have also been found by Ni-K edge EXAFS in the case of low alkali borate glasses, with a local structure which mimics some aspects of crystalline NiO. The presence of ordered cationic domains, clearly illustrated by Reverse Monte Carlo simulations helps to rationalize the physical properties of multi-component silicate glasses.

Many natural minerals and synthetic materials display twin microstructures resulting from displacive phase transitions. These microstructures may be removed temporarily from the sample by heating above the relevant transition temperature, though the twinning generally returns on subsequent cooling.

In anorthoclase, the spatial distributions of twins before and after brief annealing above TC are often identical. This property appears to be a common feature in many materials which undergo ferroelastic phase transitions, and is known as ‘twin memory’. The atomic mechanisms responsible for this twin memory may be investigated by studying the annealing regimes required to remove the memory effect; how long must a sample be annealed, and at what temperature, to induce ‘twin amnesia’.

High-resolution X-ray diffraction (XRD) has been used to investigate twin memory and twin amnesia in anorthoclase. In anorthoclase, the primary constraint on twin amnesia is thermodynamic, rather than kinetic. The critical temperature to induce amnesia correlates well with the top of the (Na, K) solvus in disordered alkali feldspar. For this reason, the proposed mechanism for twin memory involves the segregation of alkali cations in thin lamellae at the twin boundaries.

New Sr-Nd isotope data were obtained from Late Pleistocene carbonatite-kamafugite associations from the Umbria-Latium Ultra-Alkaline District of Italy (ULUD) with the aim of constraining their origin and possible mantle source(s). This is relevant to the origin and evolution of ultrapotassic (K/Na ≫2) and associated rocks generally, notably the occurrences from Ugandan kamafugites,Western Australian lamproites and South African orangeites. The selected ULUD samples yielded 87Sr/86Sr and 143Nd/144Nd ranging from 0.7100 to 0.7112 and from 0.5119 to 0.5121 respectively, similar to cratonic potassic volcanic rocks with higher Rb/Sr and lower Sm/Nd ratios than Bulk Earth. Silicate and carbonate fractions separated from melilitite are in isotopic equilibrium, supporting the view that they are cogenetic. The ULUD carbonatites yielded the highest radiogenic Sr so far reported for carbonatites. In contrast, sedimentary limestones from ULUD basement formations are lower in radiogenic Sr, i.e. 87Sr/86Sr = 0.70745–0.70735. The variation trend of ULUD isotopic compositions is similar to that reported for Ugandan kamafugites and Western Australian lamproites and overlaps the values for South African orangeites in the εSr-εNd diagram. A poor correlation between Sr/Nd and 87Sr/86Sr ratios in ULUD rocks is inconsistent with a mantle source generated by subduction-driven processes, while the negligible Sr and LREE in sedimentary limestones from the ULUD region fail to account for a hypothetical limestone assimilation process. The Nd model ages of 1.5–1.9 Ga have been inferred for a possible metasomatic event, allowing further radiogenic evolution of the source, a process which may have occurred in isolation until eruption time. While the origin of this component remains speculative, the Sr-Nd isotope trend is consistent with a simple mixing process involving an OIB-type mantle and a component with low εNd and high εSr.

We make the first report of fluid inclusion data from a black dolomite matrix breccia from the Irish orefield which confirm a relatively high-temperature hydrothermal origin. Breccia matrix dolomite formed from NaCl-dominated fluids with temperatures primarily in the range 150–220°C and salinities of 13–20 wt.% NaCl equivalent, comparable with inferred ore-stage fluids at the Silvermines, Tynagh, Lisheen and Navan deposits. The spread in salinity is considered to be due to mixing of a moderate salinity (~12 wt.%), higher temperature fluid, probably derived from the Lower Palaeozoic metasedimentary basement, with a low temperature brine. Non-stoichiometric, black dolomites are therefore considered to be a product of relatively high-temperature hydrothermal processes involving the principal orefluid in Ireland, and thus their occurrence is believed to be a prime exploration indicator.

Earlier, coarse white dolomite, texturally similar to regional dolomite cements commonly observed in the Irish Midlands, precipitated from fluids in the temperature range 140–200°C and salinities of 10.3–13.5 wt.% NaCl equivalent. This is comparable with the higher temperature, moderate salinity end-member inferred for the black dolomite. These data call into question a uniquely low-temperature burial origin for coarse white dolomite cements in Ireland. Paragenetically late low-Mg calcites were formed as a result of an influx of relatively low salinity fluids.

An experimental study of optical anomalies in solid solutions of alums in relation to their composition, growth temperatures and rates, and hydrodynamic regime was carried out. Theoretical analysis of the data showed that they can be understood in terms of a mechanism of kinetic ordering of the isomorphous atoms (the phenomenon of so-called ‘growth dissymmetrization’). A theoretical model is presented which is supported by data for a number of minerals and synthetic compounds, which are known for their optical anomalies due to growth dissymmetrization.

The known structure of a crystalline phase is almost always useful in investigating the unknown structure of the compositionally equivalent glass. For the local environment around elements like Si, B and P, the correspondence between site geometry and symmetry can be impressively close. Beyond near neighbours, any relationship becomes less obvious – at least in real-space data. Progress in understanding the medium-range structures of glasses has been painfully slow as a result. One essential clue is given by reciprocal-space features at low Q (scattering vector) in X-ray or neutron scattering data, which are clearly related to the medium-range structure. Interpretation of these features as ‘quasi-Bragg’ scattering allows direct comparison between the structures of the glass and equivalent crystalline phases. Applications of this method will be illustrated in borates and silicates, together with some chalcogenide glasses. Correspondence between low-Q features for these glasses and compositionally-equivalent crystals is qualitatively good. In some cases there is semi-quantitative agreement too. Thus the essential flavour of the medium-range structure of several typical glasses appears to be interpretable, rather easily.

Networks of interacting twin walls form hierarchical, mesoscopic structures in minerals. The typical thickness of transformation twins at T ≪ TC is ˜3 nm and increases at T → TC as . The internal structure of twin walls is derived to be chiral in systems with coupled order parameters. The effect of wall bending is discussed.

The crystal structure of chenevixite, Cu2M2(AsO4)2(OH)4 (where M = Fe3+ or Al), pseudo-orthorhombic, monoclinic, a = 5.7012(8), b = 5.1801(7), c = 29.265(2) Å, β = 89.99(1)°, V = 864.3(4) Å3, space group B1211, Z = 4, was solved by direct methods and refined by least-squares techniques to R = 8.4% and a goodness-of-fit (S) of 1.37 for 1176 unique observed (F≥4σF) reflections collected for a twinned microcrystal using graphite-monochromated Mo-Kα X-rays and a CCD area detector. Vertex- and edge-sharing arsenate tetrahedra, Alϕ6 octahedra, and Jahn-Teller-distorted Cu2+ϕ6 octahedra [ϕ: O2−;, (OH)−;] form a framework unique from those in Cu2+ oxysalt minerals. Chains of edge-sharing Cu2+ϕ6 octahedra, with Alϕ6 octahedra attached on opposing sides by the sharing of edges, are linked into layers parallel to (001) by sharing vertices with AsO4 tetrahedra, and the layers are linked to form a frameworkby the sharing of polyhedral elements between adjacent Alϕ6 octahedra, as well as between AsO4 tetrahedra and Alϕ6 octahedra.

The average compositions of menshikovite (Pd3Ni2As3) from the type locality (Lukkulaisvaara layered intrusion, Russian Karelia) and a Pd-Ni arsenide synthesized at 450°C, are very close. The observed ΣMetal:As ratio is close to 5:3, as in the case of previously described arsenides from the Stillwater and Two-Duck Lake intrusions. The compositions suggest that these unnamed Pd-Ni arsenides and the synthetic phase are in fact menshikovite.

The gold balance in an ore deposit where the ore is treated by cyanide is the sum of the ‘visible gold’ that is amenable to cyanidation and ‘visible gold’ and the ‘invisible gold’, which are not amenable to cyanidation. Petrographic analyses, electron and ion microprobe as well as scanning electron microscope studies of ore from the Golden Sunlight deposit, Montana, suggest that periods of relatively poor gold recoveries are primarily due to the presence of inclusions, <25 µm in size, of native gold, petzite, calaverite, buckhornite and krennerite. These are encapsulated in cyanide insoluble grains of pyrite, chalcopyrite and tennantite and are present in the tailings. This contribution probably accounts for 3–25% of the unrecoverable gold processed during the life of the mine. Minor amounts (6–7%) of ‘invisible gold’, as indicated by ion microprobe studies and the presence of up to 5% ‘visible gold’ in buckhornite, which is rare in nature, appears to account for the remainder of the gold budget.

Phase relations along the join bornite (Cu5FeS4)-digenite (Cu8.52Fe0.12S4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite-digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.

The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu5FeS4-Cu9S5. The thermal anomalies are correlated with structural phase transitions in componen phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu5FeS4 and T = 265°C. This temperature corresponds to that of the tricritical intermediate-high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.

A group of carbonate-rich tuffs are described from the Murumuli crater, Katwe-Kikorongo volcanic field, SW Uganda which contain abundant carbonatite pelletal lapilli, together with melilitite lapilli and a range of xenocrysts and lithic fragments including clinopyroxenites considered to be of mantle origin. The carbonatite lapilli consist essentially of Sr-bearing calcite and Mg-calcite which form quench-textured laths. The lapilli contain microphenocrysts of Ti-magnetite, perovskite, apatite, clinopyroxene, sanidine and altered prisms of melilite. A 7 cm long dolomite carbonatite bomb is described which displays a form typically assumed by lava clots erupted in a molten state. Chemical analyses of a tuff, the bomb and a range of minerals are presented. Carbonatite clearly played an important role in the Katwe-Kikorongo magmatism and it is suggested that carbonatite magma evolved from carbonate-bearing melilitite.

We present the results of an inelastic neutron scattering study of a crystalline polymorph of SiO2 (α-quartz), and a number of silicate glasses (pure silica, SiO2, and three glasses in the alkali series (K,Li)2Si2O5). We demonstrate the presence of the Boson peak in the inelastic spectra of the crystalline and amorphous materials and argue that it arises simply from the dispersion characteristics of transverse acoustic modes. Furthermore, we investigate the role of the lower-energy floppy modes in the inelastic spectra, and show that they are controlled by chemical effects.

Manganoan berthierine, sometimes only a few layers thick, is preserved interlayered with manganoan chlorite (chamosite) in small recrystallized patches in cherty metapelagites matamorphosed in the prehnite–pumpellyite facies at Meyers Pass, Torlesse Terrane, South Canterbury, New Zealand. The Mn occupies 11–12% of the octahedral sites, making this the most Mn–rich berthierine reported so far. The ratio (Fe+Mn)(Fe+Mn+Mg), 0.67–0.70, is at the lower end of those of previously reported occurrences, making these amongst the most Mg-rich berthierines known. Manganoan berthierine and interlayered manganoan chlorite also make up ~11–13% of the cryptocrystalline groundmass in which the berthierine is believed to have crystallized under early diagenetic conditions near a deep-ocean–sediment interface. The occurrence of berthierine in the recrystallized patches lends support to the possibility of a stability field at the temperature of prehnite-pumpellyite facies recrystallization in association with chlorite of similar but not identical composition.

Examples of apparent exsolution lamellae and lenticular blebs of chalcopyrite in pyrrhotite are described in orthopyroxene-bearing granulite facies rocks from two, oxidized (log10fO2 = −14 to −11), widely separated, well characterized high grade terranes: the Bamble Sector, SE Norway (795°C, 7.5 kbar) and the Shevaroy Hills Massif, Tamil Nadu, S India (750°C, 7.5 kbar). These exsolution features only occur in isolated pyrrhotite grains and not in integral pyrrhotite-pyrite-chalcopyrite-magnetite grain clusters which essentially represent an oxidation equilibrium. Reintegration of these chalcopyrite exsolution features back into the pyrrhotite host indicate Cu contents ranging from 1 to 5 wt.% in good agreement with experimental observations which indicate that pyrrhotite can take up to 7 wt.% Cu at temperatures above 800°C at pressures of ∼1 bar. This suggests that under high grade conditions these chalcopyrite exsolution features were in solid solution with pyrrhotite. Whether Cu stabilizes pyrrhotite at higher oxygen fugacities or these chalcopyrite-pyrrhotite grains represent a metastable phase is uncertain. One possibility is that the isolated pyrrhotite grains with chalcopyrite lamellae could represent grains that were preferentially not exposed to infiltrating fluids, which oxidized the pyrrhotites in other areas of the sample. A second possibility is that either these grains had enough Cu to stabilize them during pervasive infiltration of oxidizing fluids or that they represent a metastable phase with respect to the overall oxygen fugacity of the sample. The two conclusions that can be drawn from these observations are, firstly, that it is possible for pyrrhotite and chalcopyrite to form a limited solid solution at granulite facies temperatures and pressures under relatively high oxidizing conditions, i.e. 1.5 log units above fayalite-magnetite-quartz, at 800°C and 8 kbar. Secondly, this limited solid solution should have some bearing on the stability of pyrrhotite with respect to co-existing magnetite and pyrite as a function of the oxidation state of the rock, be it inherited or fluid induced.

Phase relations in the S-poor portions of the dry condensed Pt-Ir-Fe-S system were determined at 1000° and 1100°C with a particular emphasis on delineation of the solid solubility fields of the Pt-Ir-Fe alloys. At both temperatures, a broad field of γ(Ir,Fe,Pt) alloy coexists with γ-(Pt,Fe), Pt3Fe and PtFe which dissolve respectively at least 5.1, 29.3 and 24.0 at.% Ir at 1100°C (2.2, 23.6 and ≤17.2 at.% Ir at 1000°C). Gaps between the nearly Ir-free Pt-Fe alloys γ(Pt,Fe), Pt3Fe s.s., PtFe s.s. and γ(Fe,Pt) were estimated as 20–23 at.%, 40–42 at.% and 54.2–~57 at.% Fe at 1100°C (18–23, 39.5–42.5 and 59–62 at.% Fe at 1000°C). The first gap agrees with data from natural phases by Cabri et al. (1996). The Fe-rich sulphide melt dissolves only traces of Pt and Ir; Fe1–xS dissolves up to 5.8 at.% Ir at 1100°C and 3.4 at.% Ir at 1000°C. These solubilities and the compositions of coexisting alloys (before low-temperature exsolution) may serve as geothermometers. The S-rich melt dissolves up to 8.2 at.% Pt and 2.5 at.% Ir (measured on a solidified melt) at 1100°C. The Fe-Ir thiospinel dissolves up to 2.2 at.% Pt (for the composition Fe21.6Ir18.9Pt2.2S57.3 at 1100°C). The 25–28 at.% Fe portions of Pt3Fe with <10 at.% Ir partake in all important sulphide (± melt)-alloy assemblages (with PtS, Ir2S3, pyrrhotite, S-rich melt and thiospinel). Therefore, their use in recognizing distinct natural assemblages of genetic importance is of limited value.

Ion probe data for zircons from tuffs within the Llfynant flags (Arenig) and the Serw Formation (lower Llanvirn) of north Wales have been revised using better statistical methods for separating detrital ages, making allowance for recently-found variability in radiogenic 206Pb/238U in the reference zircon SL13, and testing the sensitivity of the ages to the secondary ion discrimination slope. The revised ages are options of 469.2 ± 2.1 (σ) or 472.9 ± 2.9 Ma for the Llfynant flags dependent on mixture modelling, and 465.3 ± 1.4 Ma for the Serw Formation. All ages are within error of previous SHRIMP results and the Serw age now has the same numerical value as a previous MSID age for the same sample. It is shown that an MSID age of 483 ± 0.5 Ma with interpreted Pb loss for a late Tremadoc bentonite is dependent on the correction for common Pb, and that a slightly more radiogenic choice for the common Pb composition places nearly all data on Concordia. The latter would indicate that the bentonite might contain two zircon populations: inherited grains at 482 Ma and tuff magmatic grains at 473 Ma, which is more compatible with the SHRIMP Arenig result. Interpretations of other MSID zircon ages from the Ordovician are also sensitive to choice of common Pb, and raise the likelihood that many multigrain ages might be too old owing to admixture with slightly older inherited zircon. A supposed 1–2% technical bias of SHRIMP 206Pb/238U ages relative to MSID is refuted.

The monoclinic structural distortion in lead phosphate and lead arsenate is correlated with the ferroelastic phase transition R3̄m → C2/c and R3̄m → P21/c respectively. The resulting domain patterns in the mixed compounds depend on their chemical composition. The intersection of ferroelastic W domain walls with the (100) surface of lead phosphate-arsenate mixed crystals has been imaged using tapping mode atomic force microscopy. Dilution of the strain leads to characteristic surface deformations which deviate from those in pure lead phosphate. In high twinned lead phosphate-arsenate, X-ray diffraction (XRD) was used to show renormalization effects and scattering phenomena stemming from the twin walls. The wall trajectory was found to be independent of chemical variations using transmission electron microscopy.