A one-day meeting was held in the Department of Earth Sciences, University of Cambridge, on the theme of the ‘Structure and Dynamics of Silicate Glasses and Melts’. The meeting was sponsored by the Mineral Physics group of the Mineralogical Society, and was attended by ∼80 people. The objective of the meeting was to bring together experts from the glass community with members of the mineralogical community who are interested in glasses and melts. The scope of the talks considered structural details over length scales from nearest-neighbour coordinations up to 1–2 nm, and dynamics in both the slow relaxational and fast vibrational ranges. The talks also covered both experimental (particularly neutron scattering and NMR) and computer simulation methods.

The meeting was organized into three groups of themes, namely structure and dynamics in glasses, structure and dynamics in melts, and vibrational dynamics in glasses.

One of the major goals of mineral science is attaining an understanding of the atomic-scale mechanisms and dynamics of minerals that control their structural transformations as a function of pressure, temperature or chemical composition in the natural environment. Examples of research programmes that sail under this heading include those devoted to observing and modelling the role of phase transformations on controlling mineral microstructures, ordering, elasticity, transport, premelting and exsolution. The geological relevance and intrinsic importance (as being representative of specific properties or thermodynamic/ kinetic behaviour) of mineral transformations has long been appreciated. It prompted the recent initiation of a network on Mineral Transformations (http://www.esc.cam.ac.uk/mintrans/) under the European Union TMR Programme. In response to this development, a special session on Mineral Transformations was held at the EUG congress in Strasbourg last year.

We present experimental data for the Pm3m-I4/mcm phase transitions in the perovskite crystals KMn1-xCaxF3 and SrTiO3. Comparison of calorimetric data (latent heat and specific heat) with order parameter data (measured with X-ray rocking methods) indicates that these transitions follow mean-field behaviour, and may be described using Landau potentials where the free energy expansion includes terms up to Q6. This potential is characteristic of transitions close to the tricritical point. Comparison of the behaviour of SrTiO3 and KMnF3 indicates that KMnF3 is closer to the tricritical point; a small amount of substitution of Ca for Mn causes the transition to cross the tricritical point from first order to second order behaviour.

Reinvestigation of the top 25 m of the 165 m thick Shiant Isles Main Sill requires reinterpretation of its internal structure, especially of the last unit emplaced – the granular olivine picro-dolerite. New mineral analyses allow re-assessment of the magmatic processes involved in the intrusion and differentiation of this classic multiple sill. C-shaped vertical mineral composition profiles, which occur in olivine-rich, alkaline basaltic sills, reflect reaction between phenocrysts and variable composition liquids. A case is made for vertical migration of interstitial liquids within and across the boundaries of intrusive units, for the mixing of such liquids from adjacent units, and for their influence on mineral chemistry on both sides of the interface.

Synthesis of large zeolite A and X crystals by a modified Charnell’s method led to the formation of twinned zeolite NaA crystals, overgrowth of NaX onto NaA and co-crystallization of another phase analysed by electron microprobe as a Na aluminosilicate but not yet identified. Single crystals of NaA have a perfect cubic habit with a 100 μm edge. Twinned crystals of NaA are of the same size and correspond to an intergrowth of two cubes like that found in twinned fluorite crystals. NaX single crystals are octahedral, 220 μm along the [100] direction. Based on the difference in morphology of A and X crystals, epitaxial growth of NaX zeolite on NaA was also clearly identified by scanning electron micrographs. The object of this contribution is to provide topological and structural information on the twinning and epitaxy.

We apply the Rigid Unit Mode model, which was initially developed for crystalline silicates, to the study of the flexibility of silica glass. Using a density-of-states approach we show that silica glass has the same flexibility against infinitesimal displacements of crystalline phases. Molecular dynamics simulations also show that parts of the silica structure are able to undergo large spontaneous changes through reorientations of the SiO4 tetrahedra with no energy cost.

In situ high temperature single crystal X-ray diffraction (XRD) experiments have been performed on a chemically quasi-ideal omphacite sample up to 1000°C. The lattice parameters were studied as a function of temperature, and their thermal expansion coefficients determined. The b and c cell edges show discontinuities as a function of temperature which are interpreted here in terms of intracrystalline cation diffusion processes. Structure refinements have been carried out using data collected at room temperature, at 800°C and at ambient conditions after cooling. The structural behaviour as a function of temperature of chemically quasi-ideal omphacites is compared with those of jadeite and diopside.

Kyono et al. (1999) have synthesized a thallium leucite. They have drawn conclusions from this relating to cation mobilities. Attention is drawn to alternative explanations and related to extensive previous work.

Serpentinized ultramafic rocks recovered from beneath the southern Iberia Abyssal Plain (Ocean Drilling Programme Leg 173) provide the first record of fractal carbonate replacement patterns in a serpentinite. The patterns are expressed as microscopic branching aggregates (clusters) of aragonite disseminated throughout the serpentinites. Aragonite growth was the final mineralization event. The aragonite diminishes rapidly in quantity from an essential to a trace component of the serpentinite over a distance of ∼40 m from a normal fault. Decreasing abundance of aragonite away from the normal fault links the growth of the carbonate to the multistage hydrothermal mineralization associated with the fault.

Aragonite clusters are concentrated in picrolite, where they are interwoven with colloid-sized chrysotile, and show fractal growth habits. Areas adjacent to the clusters are sites of Mg enrichment of the serpentine medium relative to aragonite-free picrolite. It is interpreted that the aragonite clusters result from incursions of reactive seawater solutions through fine-scale pore structures in and around the fault in response to pressure gradients emanating from active tectonism. Cluster growth is interpreted to be a percolation phenomenon and provides a novel source of information on the nature of fine-scale reactive fluid flow, pore-space connectivity, and carbonate replacement processes in serpentinites.

In this paper the Late Pleistocene carbonatite-melilitite association (CMA) of Italy is evaluated in terms of the Plio-Quaternary extensional structures in the crust and mantle lithosphere. In particular, we briefly discuss the geometry and stress field of the host geological structures, the tectonic control on the eruptive style, the thickness and composition of the lithosphere. Some implications for a passive rift geodynamic environment are also considered.

Recent experimental and theoretical studies provide new insight into the variety of high-pressure transformations in minerals that comprise the Earth’s deep mantle and core. Representative examples of reconstructive, displacive, electronic and magnetic transformations studied by new diamond-anvil cell techniques are examined. Despite reports for various transitions in (Mg,Fe)SiO3-perovskite, the stability field of the orthorhombic phase expands relative to magnesiowüstite + SiO2 with increasing pressure and temperature. The partitioning of Fe and Mg between Mg-rich silicate perovskite magnesiowüstite depends strongly on pressure, temperature, bulk Fe/Mg ratio, and ferric iron content. The soft-mode transition in SiO2 from the rutile- to CaCl2-type structure, originally documented by X-ray powder diffraction, Raman scattering, and first-principles theory has been explored in detail by single crystal diffraction, and transitions to higher-pressure forms have been examined. The effect of H on the transformations of various nominally anhydrous phases and transitions in dense hydrous Mg-silicates are also examined. New studies of the phase diagram of FeO include the transition to rhombohedral and higher-pressure NiAs polymorphs, and provide prototypical examples of coupled structural, electronic, and magnetic transitions. High-spin/low-spin transitions in FeO have been examined by high-resolution X-ray emission spectroscopy to 150 GPa, and the results are compared with similar studies of Fe2O3 and FeS. Finally, laser-heating studies to above 150 GPa and 2500K show that (hcp) ε-Fe has a large P-T stability field. Radial XRD measurements carried out at room temperature to 220 GPa have constrained the elasticity, rheology and sound velocities of ε-Fe at core pressures.

The effects of ion irradiation in the ABO4-type compounds were compared by performing experiments on four materials that include the most common crystal structures (monazite vs. zircon) and chemical compositions (phosphates vs. silicates) for these phases. Pure synthetic single crystals of ZrSiO4, monoclinic ThSiO4, LaPO4 and ScPO4 were irradiated using 800 keV Kr+ ions. Radiation damage accumulation was monitored as a function of temperature in situ in a transmission electron microscope. The activation energies for recrystallization during irradiation were calculated to be 3.1–3.3 eV for the orthosilicates but only 1.0–1.5 eV for the isostructural orthophosphates. For the ion-beam-irradiated samples, the critical temperature, above which the recrystallization processes are faster than damage accumulation and amorphization cannot be induced, is >700°C for ZrSiO4 but it is only 35°C for LaPO4. At temperatures above 600°C, zircon decomposed during irradiation into its component oxides (i.e. crystalline ZrO2 plus amorphous SiO2). The data are evaluated with respect to the proposed use of the orthophosphates and orthosilicates as host materials for the stabilization and disposal of high-level nuclear waste. The results show that zircon with 10 wt.% Pu would have to be maintained at temperatures in excess of 300°C in order to prevent it from becoming completely amorphous. In contrast, a similar analysis for the orthophosphates implies that monazite-based waste forms would not become amorphous or undergo a phase decomposition.

Phengite 3T (Dora-Maira massif, Italian western Alps), with chemical composition K0.96Na0.01Al1.44Mg0.56(Si3.59 Al0.41)O10(OH)2 has been investigated using powder neutron diffraction, at the ILL (Institut Laue-Langevin) Facility, on the D2B diffractometer. Data sets were collected at 293 and 873 K, and the present results are compared with those obtained previously using the time-of-flight (TOF) technique, on the same compound. In the octahedral sheet, Al tends to order into the M2 site, in accordance with the measurements mentioned above, whereas the Al/Si tetrahedral ordering we observe (i.e. Si fully into T1 site) is at variance with that determined previously. These discrepancies are ascribed to the presence of talc impurities in the sample used previously (∼6 wt.%), which affected the results obtained.

Dissolved water has significant effects on the physical and chemical properties of silicate melts. Some of the different approaches towards understanding these effects are reviewed here. Spectroscopic measurements on hydrous glasses quenched from melts provide good models for the structure of the melts at the glass transition temperature (Tg). Such measurements suggest that the mechanism of dissolution of water in silicate melts varies strongly with the bulk composition. In particular framework aluminosilicate compositions seem to have very different dissolution mechanisms from Al-free compositions. The water speciation reactions are temperature dependent, with some of the molecular water which is present in glasses at room temperature being converted to hydroxyl at high temperatures. This conversion probably occurs only above Tg. Data on the kinetics of the speciation reaction and the dynamics of microscopic processes in hydrous silicate melts are also discussed. Finally some important aims of future work on hydrous silicate melts are suggested

At the abandoned pyrite mine at Genna Luas (Sardinia, Italy), melanterite is the most environmentally important secondary phase associated with pyrite oxidation. A complete cycle, including formation on pyrite surface, dissolution in water, precipitation from water and subsequent alteration, can be observed. The oxidation of pyrite to melanterite is related mainly to the ‘intrinsic’ features of the Genna Luas pyrite, such as its cryptocrystalline pseudo-colloidal texture. During melanterite formation on pyrite there is transient storage of Fe2+, SO42- and acidity. This is controlled mainly by wetting-drying seasonal cycles. Laboratory experiments have shown that the simple dissolution of melanterite is an acidity-generating process which affects the geochemistry of water and, indirectly, contributes to the supply of the Fe3+ required for the aqueous oxidation of pyrite. According to this geochemical model, the interaction between rainwaters and ground pyritic materials accumulated in heaps generates hyperacidic saline waters (pH = 0.6; TDS = 300 g/l) with very high SO42+ contents (203 g/l), Fe2+ contents (73 g/l), Zn contents (11 g/l), and numerous potentially toxic elements. Melanterite precipitates from these waters (SIMelanterite = 0.15, calculated using PHRQPITZ software), giving rise to attractive emerald green crystal aggregates which, when exposed to air, alter to a fine white powder composed mainly of melanterite, and minor amounts of rozenite and szomolnokite.

We present petrographic and mineralogical data for 21 mantle xenoliths (12 lherzolites, 8 wehrlites and 1 composite) selected from a suite of more than 70 samples collected from the Monticchio Formation, Mt. Vulture volcano, southern Italy. The xenoliths are rounded, coarse- to porphyroclastic-textured, and very fresh, with the following equilibrated mineral assemblages; olivine (Fo90–92), orthopyroxene (∼En89, Wo2.0), clinopyroxene (Mg90–92, 3–6% Al2O3, 1–1.5% Cr2O3), and chrome-spinel (14–20% MgO, ∼30–40% Cr2O3). Many xenoliths contain partial melt glasses and accessory sulphide (pentlandite) Some contain primary mica (phlogopite with ∼4% FeO, 1.8% Cr2O3, 1.4–2.8% TiO2) with slightly zoned rims (Fe-, Ti-, Al-enriched). One contains relics of garnet (pyrope; Mg84). Secondary veins in several xenoliths contain carbonate with significant Sr levels (∼0.5–1.0% SrO), occasional apatite and scarce melanite, all typical of carbonatites and presumably related to the host magma (melilitite/carbonatite). Although amphibole is a common megacryst in the same volcanic units, no primary amphibole was found in the xenoliths themselves. Calculated pressures and temperatures using a range of geothermometers/barometers give values of 14–22 kbar and 1050–1150°C. In particular, the En-Sp and Di-Sp thermo/barometers (Mercier, 1980) show a good positive correlation between P and T. The Monticchio xenoliths lie on the high-T side of an ‘oceanic’ geotherm. The xenolith geotherm is hotter than general heat flow values in this region at the current day (50 mWm−2) but it compares well with the high-pressure end of a typical alkaline continental rift.

Four distinct associations of graphite have been identified in the low-pressure, high-temperature belt of the Sierra de Aracena (SW Spain). Syngenetic occurrences include: (1) stratiform graphite mineralization within a calc-silicate series; (2) disseminated graphite within a terrigenous sequence; and (3) ‘restitic’ graphite within anatectic tonalites and their enclaves. Epigenetic graphite occurs as (4) veins cross-cutting mafic granulites.

Graphite in all types of occurrences is highly crystalline, with the c parameter close to 6.70 Å. Such c values correspond to temperatures of formation of ∼800°C. The thermal properties of graphite are also typical of well-ordered graphite and provide DTA exothermic maxima ranging from 810 to 858°C depending on the mode of occurrence. The differences among the temperatures of formation estimated by graphite geothermometry, the position of the exothermic maximum in the DTA curves, and petrologic geothermometers are discussed in terms of the applicability of graphite geothermometry to granulite-facies rocks. Carbon isotope analysis yields δ13C values in the range from −31.6 to −21.4% for syngenetic graphite of types I, II and III attributable to biogenically-derived carbon. The heavier signatures for graphite in vein occurrences (δ13C= −17.7 to −18.3%) with respect to syngenetic graphites suggest that isotopically heavy carbonic species were incorporated into the metamorphic fluids (probably as a consequence of decarbonation reactions of the calc-silicate rocks) from which graphite precipitated into the veins. These fluids were strongly channelled through structural pathways.

The crystal structure of strontian potassicrichterite (Mg4.871Fe0.1263+ Mn0.052)Σ5.049(Na1.425Ca0.348Sr0.297)σ2.07K0.873Si8.048O22(OH)2.15 – an unusual amphibole containing up to 3.7 wt.% SrO from the Murun alkaline massif, Eastern Siberia has been refined from X-ray powder diffraction data in monoclinic space group C2/m, with a = 10.0325(1) Å, b = 17.977(1) Å, c = 5.2698(1) Å, and β = 104.70(1)°. According to Mössbauer spectroscopy, nearly all iron occurs as Fe3+ in octahedral coordination. Rietveld refinement shows the Fe3+ to be ordered onto the M(2) site. Sr is completely ordered onto M(4).

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.