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.

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.

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

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.

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.

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.

A brief review is given of the ways in which the local structure in glass can influence the microstructure that supports ionic transport. This in turn contributes to the co-operative nature of ion dynamics and ways in which this underpins the ‘mixed alkali effect’ are discussed. Glass microstructure too is expected to affect glass fracture as well as the chemistry of glass surfaces. In melts, though, these restrictions appear to vanish as the rigidity of intermediate range order is lost.

The structure of amorphous silica has frequently been compared with its crystalline counterparts in an attempt to understand the glass structure beyond short-range correlations. This paper presents results from neutron total scattering measurements of several polymorphs of silica and shows how these can be used to make a direct, quantitative comparison of amorphous and crystalline forms. It is found that the glass is similar to HP-tridymite and β-cristobalite, both dynamically-disordered crystalline phases of silica, but only out to distances ∼7.5 Å, beyond which the structures diverge. This is too small to validate a microcrystallite theory of glass structure. It is the average 180° Si–O–Si linkage in these two crystalline phases which gives them the flexibility for their instantaneous disordered structure to resemble the quenched (static) glass structure.

The Cnoc Rhaonastil minor dolerite intrusion on Islay, NW Scotland represents a single body of alkali olivine basalt magma which differentiated in situ, from leucodolerite, through teschenite to minor nepheline syenite. The syenites occur as isolated nests and pegmatitic schlieren within the leucodolerite, and schlieren of gabbroic pegmatite also occur at the margin of the teschenite. The differentiated rocks contain pyroxene, amphibole and biotite of variable compositions which reflect both primary fractionation processes and late-stage deuteric alteration and reaction.Mafic phases within the gabbroic pegmatite, teschenite and syenite are typically rimmed and speckled with biotite, the composition of which is controlled by the local environment of crystallization. The nepheline syenites contain primary ferro-kaersutite which, where in contact with interstitial patches, has been altered to arfvedsonite, which occasionally contains up to 1.2 wt.% ZrO2. The occurrence of Zr-arfvedsonite (and of Zr-aegirine) in interstitial patches suggests that variably trace element-enriched domains existed within the residual melts on very small scales.

Garnet pyroxenite xenoliths from the Delegate nephelinitic breccia pipes, New South Wales, Australia, contain relict garnets (py40 alm39 gr21) which are replaced by dark kelyphitic rims resulting from garnet breakdown. The kelyphite is composed of a lamellar intergrowth of secondary minerals, in which the lamellae are <1 μm in width. Analyses by SEM and ICPMS reveal that the kelyphite has an identical bulk chemical composition to the primary garnet. Kelyphitic rims on garnet are well known from xenoliths and xenocrysts in kimberlite pipes and from tectonically-uplifted mafic and ultramafic rocks in some metamorphic terranes. Orthopyroxene occurs in metamorphic kelyphites and it has been assumed that orthopyroxene is also the breakdown product of garnet transported in basic-ultrabasic magmas. However, TEM study of Delegate kelyphite shows that the ultrafine lamellae do not contain orthopyroxene but are instead composed of magnesian clinoferrosilite (En45Fs55), and lesser ferroan spinel and anorthite. The clinoferrosilite is probably the inversion product of initially-formed magnesian protoferrosilite. The breakdown reaction is believed to result from a sudden change to lower temperature and pressure conditions when the xenoliths were transported in the Delegate magma from ∼40 km depth to the surface.

In the 1944 Vesuvius eruption, the shallow magma chamber was disrupted during the highly energetic explosive phases. Abundant cognate xenoliths such as subvolcanic fergusites and cumulates, hornfels, skarns and rare marbles occur in tephra deposits.

Mineral chemistry, melt inclusions in minerals and glassy matrix compositions show that fergusites (highly crystalline rocks made of leucite, clinopyroxene, plagioclase, olivine, apatite, oxides and glass) do not correspond to melt compositions but result from combined sidewall accumulation of crystals, formed from K-tephriphonolitic magma resident in the chamber, and in situ crystallization of the intercumulus melt. Very low H2O contents in the intercumulus glass are revealed by FTIR and apatite composition. Whole rock compositions are essentially determined by the bulk mineral assemblages.

Glass–bearing fergusites constitute the outer shell of the magma chamber consisting of a highly viscous crystal mush with a melt content in the range 20–50 wt.%. The leucite/(clinopyroxene+olivine) modal ratio, varies with the extraction order of magmas from the chamber, decreasing upwards in the stratigraphic sequence. This reflects a vertical mineralogical zonation of the crystal mush. These data contribute to the interpretation of the subvolcanic low–pressure crystallization processes at the magma chamber sidewalls affecting alkaline potassic magmas.

Thermal reduction in wolframite (composition: Fe1-xMnxWO4 (0.08<x<0.87)) from different deposits in Argentina, was analysed using a temperature-programmed reduction (TPR) technique. X-ray powder diffraction analysis (XRPD), vibrational spectroscopy (IR and Raman), scanning electron microscopy (SEM) and electron microprobe analysis (EDAX) were used to assess the relationship between reactivity degree in a reducing atmosphere (H2 10% – N2 90%) and chemical composition of wolframite.Similar studies were carried out with other related minerals, especially the ones found in natural deposits as alteration or association products. Stability of the solid solution serial members is correlated with redox properties of divalent cations.

In the Yichun granite complex (SE China), columbite group minerals, microlite and cassiterite are the main Nb, Ta, Sn-bearing minerals. They are mainly concentrated in the uppermost albite-lepidolite granite. Rutile is the only Nb, Ta-bearing phase in the geochemically primitive muscovite-zinnwaldite granite. The chemical evolution of the columbite group minerals (the most abundant and commonly zoned Nb, Ta-bearing minerals) indicates a complex crystallization history of the host granites with: (1) fractional crystallization at depth, reflected by a strong increase of Mn/(Mn+Fe) ratios with a moderate increase of Ta/(Ta+Nb) ratios from the muscovite-zinnwaldite granite to the Li-mica granite and then the most fractionated topaz-lepidolite granite; and (2) emplacement of successive magma batches corresponding to the different units of the granite complex with progressive crystallization of each unit, mainly reflected by a strong increase of Ta/(Ta+Nb) ratios with moderate variation of Mn/(Mn+Fe) ratios during the growth of the zoned crystals. The data are compared with those from the RMG of Ezzirari (Morocco), Montebras, Beauvoir and Chèdeville (France).

The Pandé massif is a small (4.9×63.4 km) subvolcanic complex of the Cameroon Line striking W – E and intrudes a Panafrican granite basement. It comprises a syenite-granite suite, where coarse- to finegrained syenites are predominant and the granites are the product of residual melt after syenite crystallization, and two volcanic (trachyte-rhyolite and trachyte) sequences. Amphibole and pyroxene are the dominant mafic silicates, the first occurring mainly in rhyolites and coarse- to medium-grained syenites, and the second, principally in all syenites, trachytes and granites. Rare biotite flakes are encountered in the coarse-grained or alkaline syenites and fayalite rimmed with oxides occurs in trachyte from the first volcanic sequence (T1). Apatite and zircon are common accessories, whereas some titanite occurs in the medium-grained syenites. The plutonic rocks are drusy, intrude the first volcanic sequence but pre-date the second (T2).

All the mafic minerals are Fe-rich. Detailed studies of amphibole and pyroxene show that their compositions define relatively limited trends, amphibole varying from ferro-richterite to arfvedsonite and pyroxenes along the acmite-hedenbergite join of the Ac-Hd-Di diagram, in both the intrusive suite and volcanic rocks. Where the two minerals coexist, pyroxene crystallized subsequent to amphibole, a situation generally found in late-stage or subsolidus aegirines. The overlap in plutonic and volcanic pyroxene trends suggests their crystallization from magmas of the same composition. However, the presence of quartz and fayalite in T1 and of pure aegirine in T2 and the occurrence of Zr-bearing aegirine (NaZr0.5Fe0.52+Si2O6) in the early crystallizing alkaline syenites evolving towards pure aegirine from medium- to fine-grained quartz syenites and granites, are consistent with changes in oxygen fugacities during magmatic differentiation. Two stages are distinguished: fO2 increasingly decreased from T1 to alkaline syenite emplacement (from 10−16 to 10−24 bracketed by WM and QFM buffers) where a disequilibrium, probably caused by water dissociation with volatile loss (H2) during magma degassing, favoured crystallization of Zr-bearing aegirine; a decrease in amphibole proportions towards medium-grained quartz syenites and an increase in fO2 from the medium-grained quartz syenites to granites and T2 sequence.

The Mg-poor nature of all the mafic silicates, subsolidus origin of amphiboles, crystallization of pyroxene subsequent to amphibole and subsolidus trends defined by pyroxenes are compatible with the parental magma having itself been a late-stage derivative magma, e.g. the last product of an alkaline melt from which the voluminous Mayo Darlé granite bodies crystallized.

Mineralogical, geochemical and fluid inclusion investigations of a representative suite of fissure vein mineralizations in the Rheinisches Schiefergebirge, NW Germany indicate a link to the latest stage of the Variscan orogenic evolution. Model P-T-conditions during initiation of fibrous fissure vein quartz growth are in the range 370–420°C at 0.2–0.7 kbar. The dataset suggests significant fluid cooling during evolution of the vein systems. Minimum temperatures at the end of fibrous quartz growth lie in the range 140–190°C, with conductive heat transfer and heat consumption during interaction with wallrock believed to be the main mechanisms responsible. Wallrock alteration is characterized by leaching and mobilization of most of the dominant vein components (quartz, albite, apatite), notably Si, Na and P. The principal stage of vein formation is, on the basis of available data, believed to relate to a process of intra-formational redistribution or lateral secretion. However, part of those elements deposited both in wallrock and fissure veins were probably supplied directly by the external fluid. Rates of fissure opening and material deposition were in equilibrium during the principal growth stage of fibrous quartz. However, this situation evolved due to a slowing down of material supply and deposition coupled with an increased rate of fissure opening to produce open fissures and formation of idiomorphic quartz crystals within them. Deposition depths were in the range of 0.6–2.1 km, appreciably lower than estimations of overburden. We believe therefore that formation of the fissure vein systems took place along the retrograde late–orogenic exhumation path, in a transitional stage between Variscan collision and a late- to post-orogenic extensional regime. Fluid composition characteristics also strongly suggest a relationship to the latest stages of the Variscan mineralization cycle in which low–salinity brines dominate. Development of fissure vein systems during the latest stages of continental collision, identified here from the Variscan orogeny, can be considered analogous with similar phenomena in the Alpine orogenic belt.

The isothermal equation of state (EoS) of phase E, Mg1.96(7)Fe0.072(5)Si1.04(5)H3.7(8)O6, has been determined using high-pressure single-crystal X-ray diffraction. A third-order Birch Murnaghan EoS fit to pressue-volume data collected from room pressure and temperature to 6.7 GPa reveals that phase E has the lowest bulk modulus, KT = 92.9(7) GPa, and highest pressure derivative of the bulk modulus, K' = 7.3(2), for any dense hydrous magnesium silicate (DHMS) yet measured. A parameterized third-order Birch-Murnaghan EoS was also fit to the unit-cell parameters which display significant curvature with increasing pressure. This analysis shows that the c-axis (Kc = 89.1(10) GPa) is 6% more compressible than the a-axis (Ka = 94.8(6) GPa), with little of the anisotropy commonly observed in other layered structures. The high K' is indicative of the similarity to layers of the brucite structure. The introduction of interlayer cation polyhedra to the structure serves to reduce both the anisotropy, by reducing the compressibility perpendicular to the sheets, and the ability to shear, by increasing the coherence between layers.

The crystal structure of the high-pressure phase-II of cristobalite has been solved by neutron diffraction (space group P21/c, a = 8.3780(11) Å, b = 4.6018(6) Å, c = 9.0568(13) Å, β = 124.949(7)°, at P = 3.5 GPa). This phase corresponds to a distortion of the high-temperature cubic β-phase, rather than of the ambient temperature and pressure tetragonal α-phase.