Magmas undergoing shear are prime examples of flows that involve the transport of solids and gases by a separate (silicate melt) carrier phase. Such flows are called multiphase, and have attracted much attention due to their important range of engineering applications. Where the volume fraction of the dispersed phase (crystals) is large, the influence of particles on the fluid motion becomes significant and must be taken into account in any explanation of the bulk behaviour of the mixture. For congested magma deforming well in excess of the dilute limit (particle concentrations >40% by volume), sudden changes in the effective or relative viscosity can be expected. The picture is complicated further by the fact that the melt phase is temperature- and shear-rate-dependent. In the absence of a constitutive law for the flow of congested magma under an applied force, it is far from clear which of the many hundreds of empirical formulae devised to predict the rheology of suspensions as the particle fraction increases with time are best suited. Some of the more commonly used expressions in geology and engineering are reviewed with an aim to home in on those variables key to an improved understanding of magma rheology. These include a temperature, compositional and shear-rate dependency of viscosity of the melt phase with the shear-rate dependency of the crystal (particle) packing arrangement. Building on previous formulations, a new expression for the effective (relative) viscosity of magma is proposed that gives users the option to define a packing fraction range as a function of shear stress. Comparison is drawn between processes (segregation, clustering, jamming), common in industrial slurries, and structures seen preserved in igneous rocks. An equivalence is made such that congested magma, viewed in purely mechanical terms as a high-temperature slurry, is an inherently nonequilibrium material where flow at large Pe´clet numbers may result in shear thinning and spontaneous development of layering.

Recent advances in ion microprobe instrumentation and techniques have enabled the mapping of C isotope ratios across the whole of a polished plate of a natural diamond from Guaniamo, Venezuela. The resultant map of C isotope variation closely matches the cathodoluminescence image of the growth structure of the diamond and, therefore, indicates an extremely limited scale of diffusion of C atoms sincethetimeof diamond formation. This result is compatible with thelimite d mobility of N atoms shown by theIaAB aggregation stateof thediamond. Inclusions in thediamond aree clogitic, in common with many Guaniamo diamonds with temperatures of formation of around 1200ºC. At such temperature the IaAB aggregation state indicates a mantle residence time on the order of 1 Ga. Such temperatures of formation and mantle residence times are common to many natural diamonds; thus the extremely limited diffusion of C isotopes shown by the mapping indicates that many diamonds will retain the C isotope compositions of their initial formation.

High-pressure-temperature (P-T) experiments were conducted in an attempt to determine the diffusion rates of C atoms in diamond, and the possibility of changes in the isotope compositions of diamond at high P-T in the Earth’s mantle. The starting material consisted of a polished plate of natural diamond (very largely 12C), which had been coated with 13C diamond by chemical-vapourdeposition to form a sharp interface between 12C and 13C diamond. Three experiments were performed at 1800, 2000 and 2300ºC, all at 7.7 GPa, for0.5 –20 h. Isotopic profiles obtained by ion microprobe before and after each experiment showed no evidence of relaxation of the sharp interface between 12C and 13C, and so diffusion must have been on a scale less than the ~32 nm depth resolution for this technique. Using 32 nm as the maximum length scale of diffusion across the interface, the maximum ln D (diffusion coefficient) values for the experiments were calculated to be in the range –38 to –42. Unlike previous experimental data, these results show that changes in the isotopic compositions of diamond on long time scales in the Earth’s upper mantle are unlikely. Furthermore, the results support empirical evidence from mapping of C isotope distributions in natural diamonds that C isotope compositions reflect diamond growth compositions.

Jurassic dykes of western Dronning Maud Land (Antarctica) form a minor component of the Karoo large igneous province. An extensive local dyke swarm intrudes Neoproterozoic gneisses and Jurassic syenite plutons on the margins of the Jutulstraumen palaeo rift in the Svedrupfjella region. The dykes were intruded in three distinct episodes (~204, ~176 and ~170 Ma). The 204 Ma dykes are overwhelminglylow-Ti, olivine tholeiites including some primitive (picritic) compositions (MgO >12 wt.%; Fe2O3 >12 wt.%; Cr >1000 ppm; Ni >600 ppm). This 204 Ma event precedes the main Karoo volcanic event by~25 Ma, so anycorrelations to the wider province are difficult to make. However, it mayrecord the earliest phase of rift activity along the Jutulstraumen. The 176 Ma dyke event is more intimately associated with the two syenite plutons. The dykes are alkaline (basanite/ tephrite) and were small-degree melts from an enriched, locallyderived source and underwent at least some degree of interaction with a syenitic contaminant. This ~176 Ma dyke event is widespread elsewhere in the Karoo (southern Africa and Dronning Maud Land). Later-stage (170 Ma) felsic (phonolite–comendite) dykes intrude the 176 Ma basanite–tephrite suite and represent the last phase of magmatic activityin the region.

The crystal structure of tedhadleyite, ideally Hg2+Hg101+O4l2(Cl,Br)2,triclinic, AĪ, a 7.0147(5), b 11.8508(7), c 12.5985(8) Å, α 115.583(5), β 82.575(2), γ 100.619(2)º, V 927.0(2) Å3, Z = 2,was solved by direct methods and refined to an R1 index of 4.5% for 2677 unique reflections. There are six symmetrically distinct Hg sites in tedhadleyite: Hg(1) is occupied by Hg2+ and Hg(2–6) are occupied by Hg+ that forms three [Hg–Hg]2+ dimers with Hg–Hg separations between 2.527 and 2.556 Å. These [Hg–Hg]2+ dimers have strong covalent bonds to O atoms,forming pseudo-linear O–Hg–Hg–O arrangements,and weak bonds to halogen and O atoms at high angles to the dimer axis. The [O–Hg–Hg-O] groups share anions to form four-membered square rings of composition [Hg8O4] that link along [100] via [O–Hg–Hg-O] groups and along [001] via [O–Hg–O] groups, forming rectangular rings of composition [Hg14O8]. The rings form a corrugated layer that interweaves with a symmetrically related layer whereby the [O–Hg(6)–Hg(6)–O] linking groups of one layer pass through the centres of the square [Hg8O4] rings of the other layer to form [Hg11O4] complex slabs parallel to (010) that link through Hg-I and Hg-Br,Cl bonds.

Steverustite, ideally Pb52+(OH)5[Cu+(S6+O3S2–)3](H2O)2, is a new supergene mineral from the Frongoch mine dump, Devils Bridge, Ceredigion, Wales. It generally forms fibrous fan-like bundles that occur in small cavities in quartz veins with other supergene species. Crystals are fibrous to acicular, elongated along [010], and are bounded by (h0l) faces too small to index reliably. It is transparent, colourless to white with a white streak, has a vitreous lustre, does not fluoresce under ultraviolet light and is brittle with a splintery fracture. The calculated density is 5.150 g/cm3, and the calculated mean refractive index is 1.94. The mineral is monoclinic, P21/n, a 12.5631(7), b 8.8963(5), c 18.0132(11) Å, β 96.459(1)º, V 2000.5(3) Å3, Z = 4, a:b:c = 1.41217:1:2.02480. The seven strongest lines in the X-ray powder diffraction pattern are as follows: d (Å), I, (h k l): 3.934, 10, (Ī14); 3.934, 8, (Ī11); 3.348, 7, (313); 6.211, 6, (200); 4.797, 6, (211); 3.026, 6, (314); 2.837, 5, (016). Chemical analysis by electron microprobe gave PbO 72.59, SO3 15.78, Cu2O 4.47, S2– 6.32, H2O 4.83, O=S2– –3.15, total 100.84 wt.% where the amount of H2O was determined by crystal-structure analysis. The resulting empirical formula is Pb4.992+Cu0.96+(S6+O3S2–)3.03(OH)4.88(H2O)1.67, based on O + OH + H2O + S2– = 18.67 a.p.f.u. (atoms per formula unit) with H2O = 1.67 a.p.f.u. (from crystal-structure solution and refinement).

The crystal structure of steverustite was solved by direct methods and refined to R1 = 2.7% for 3366 unique (Fo > 4σF) reflections. There are five distinct Pb2+ cations with coordination numbers from [8] to [11], all of which show stereoactive lone-pair behaviour and which form a strongly bonded cluster of composition [Pb5(OH)5]. There is one Cu+ cation triangularly coordinated by three S2– atoms that belong to three thiosulphate groups, forming a Cu+(S6+O3S2–)3 group. The [Pb5(OH)5] units and [Cu(S2O3)3] groups occur at the vertices of interpenetrating 36 nets to form layers of composition [Pb5(OH)5Cu(S2O3)3] parallel to (010) which are linked by weaker bonds. Examination of the stereochemistry of thiosulphate and thionate structures shows that the combination of <S–O> and S–S distances are distinct for these two types of structures.

The crystal structure of Ba2F2(S6+O3S2–), a natural thiosulphate weathering product of old smelting slags at the Surrender Mill, Yorkshire, England, UK, has been solved to R1 = 0.88% for 399 unique [Fo > 4α F] reflections and 0.91% for all 407 reflections. The compound is monoclinic, C2/m, a 15.3172(5), b 4.5898(1), c 4.6320(2) Å, β 101.449(1)º, V 319.17(2) Å3. The structure of Ba2F2(S6+O3S2–) consists of BaF2Ba layer fragments of the fluorite-type structure of frankdicksonite (BaF2) parallel to (100) alternating with layers of thiosulphate groups. The layer sequence in one unit cell is (S6+O3S2–)-BaF2Ba-(S6+O3S2–)-BaF2Ba. The structure resembles that of grandreefite, Pb2F2SO4.

A recent investigation of sphalerite from Akoluk deposit, Ordu, NE Turkey, revealed the possible presence of a new activator element in the sphalerite structure. The sample was studied under a reflected light microscope coupled with a cold-stage cathodoluminescence (CL) system which revealed a unique banding in the sphalerite. The same sample was subsequently examined using the backscattered electron and luminescence modes in an electron microscope, the results of which were later confirmed in terms of chemical composition by electron probe microanalyses (EPMA). Detailed evaluation of the EPMA data indicated the presence of a new CL activator element in the sphalerite structure. The data also indicate that Hg2+ in the sphalerite crystal structure substitutes for Zn in a simple manner and for Cd and Cu in a coupled manner. Spectral analysis indicated a bright yellow and orange-red blend (more like brown) CL colour with λmax centred at 580 nm, probably due to Cd and Mn ions, and relatively broad emission bands ranging from 525 to 690 nm with λmax centred at 580 and 700, due probably to Cu, Cd and Hg. This study reports that Hg in the sphalerite crystal lattice behaves as an activator and/or co-activator element resulting in emissions of CL colours that range from yellow with purple shades to shades of brown, based on their varying contents.

The nucleation and growth behaviour of the (Mn,Ca)CO3 solid solution from aqueous solutions in silica hydrogel were studied at 25ºC. In order to obtain different levels of supersaturation at nucleation, experiments were carried out in diffusion columns of different lengths. Zoning phenomena, compositional heterogeneity and morphological modifications of the crystals obtained were examined by electron microprobe and scanning electron microscopy and microanalyses. The large difference between the solubility of calcite (CaCO3) and rhodochrosite (MnCO3) implies a significant preferential partitioning of Mn towards the solid. The distribution of Mn2+ and Ca2+ ions between the aqueous and solid phase demonstrates that at elevated supersaturation, this preferential partitioning is softened. The morphologies of experimentally grown individuals show a clear dependence on the composition of the parent solution. Crystals obtained from aqueous solutions with large Mn contents exhibit a relatively sharp concentric zoning along the equatorial sections. On these bases, the roles of multiple kinetic and thermodynamic factors during nucleation and growth are also discussed. Finally, an X-ray diffraction analysis of the precipitates provided no evidence of the formation of the dolomite-type ordered kutnahorite [CaMn(CO3)2] in any of the experimentalsets.

The Palaeogene Eskdalemuir dyke, part of the Mull dyke swarm in the Southern Uplands of Scotland, is ~60 km long and up to 40 m thick. Its southern tip is 230 km from the inferred source on Mull. The dyke is composite, with tholeiitic basaltic margins and a vitreous central facies ranging from basaltic andesite to andesite in composition. Plagioclase and pyroxene phenocrysts and matrix crystals in the central facies show unusually large compositional ranges and complex textural relationships. Wholerock major and trace-element abundances show linear variations against MgO content, consistent with the rocks in the central facies having formed by mixing of basalt and rhyolite magmas. The rhyolite can be closely matched by rocks from the Mull centre. The mafic and silicic magmas were intruded from a compositionally zoned chamber beneath Mull, perhaps during collapse of the Centre 1 caldera. The lower-viscosity basaltic magma was emplaced before, but lubricated the lateral propagation of, the silicic magma, which mixed with the partially solidified basalt, the proportion of rhyolite increasing towards the dyke centre. The Eskdalemuir dyke represents an unusual, perhaps unique, example of a rhyolite magma being emplaced >200 km from its inferred source. The supposed correlative of the Eskdalemuir dyke north of the Southern Uplands Fault, the Dalraith-Linburn dyke, is not comagmatic with it.

The effect of cation vacancies upon the thermal expansion and crystal structure of a synthetic defect spinel with composition Mg0.4Al2.4☐0.2O4 was investigated by X-ray diffraction, in situ, at temperatures up to 1273 K. No evidence of symmetry violations from the Fd3m evenat the highest temperature were noted. The volume thermal expansion is markedly less than that of stoichiometric MgAl2O4 spinel, regardless of the degree of inversion. The u oxygen atomic coordinate remains constant throughout the temperature range investigated, with the M–O an dT–O bond lengths showing identical rates of expansivities. An analysis of the evolution of polyhedral volumes with temperature indicates that at 1273 K the octahedron inflates by 0.099 Å3 and the tetrahedron by 0.056 Å3. The expansion of the octahedron is significantly greater than in stoichiometric MgAl2O4 spinel, whereas the expansion of the tetrahedron is similar. The results demonstrate that an excess of Al in the spinel structure accompanied by the formation of cation vacancies strongly affect an important thermodynamic property, in this case, thermal expansion. Such an effect must be considered for those phases stable inthe Earth’s mantle where 4–5 wt.% Al2O3 is thought to be present.

Marbles and interlayered coesite-bearing eclogites near the village ofSanqingge in the Sulu ultrahighpressure (UHP) terrane ofeastern China were studied to estimate their P-T evolution. Using garnet, omphacite and phengite as geothermobarometers, the coesite eclogites are calculated to have experienced P-T conditions of3.4 –3.7 GPa and ~600ºC (stage I), followed by decompression and a slight temperature decrease to 2.7–3.2 GPa and 520–560ºC respectively (stage II) and later to 2.6–2.8 GPa and ~500ºC (stage III). No water influx affected the eclogites until reaching amphibolite facies conditions of 0.5–1.3 Gpa and 595–685ºC (stage IV). As we interpret the occasional appearance ofcalcite with magnesite relics in the core as a reaction ofUHP dolomite and magnesite with Ca-rich fluids at stage IV to form CaCO3, the calculated pressure for stage I could be the maximum pressure experienced by these rocks. Thus, the crustal material ofthe Sanqingge quarry, originally sedimentary carbonates (now marbles) and interstratified basic tuffs (now eclogites), has been buried to a depth of ≥ 120 km at ~600ºC. This burial occurred in a subduction setting along a very low geotherm of 5–6ºC/km. The exhumation possibly occurred in the environment ofa subduction channel.

Two Ca-Zr-Ti oxides, zirconolite CaZrTi2O7 and calzirtite Ca2Zr5Ti2O16, occur as minute interstitial crystals in skarn (forsterite-spinel-calcite, with rhythmic banding) ejecta from the 1631 eruption of Vesuvius. The substitutions in zirconolite observed here mainly include Nb-for-Ti (typical for zirconolites in alkaline magmatic surroundings) and (Th,U)-for-Ca, and produce a crystal-chemical formula Ca0.9–1Th0.04–0.12U0.04–0.10ZrTi1.36–1.61Nb0.09–0.22(Fe,Mg,Al)0.29–0.47O7. The skarn, which occurs in contact with a pyroxenite of magmatic origin, displays a mineralogical zoning with Zr-, Ti-, Nb- and (U,Th)-rich oxides (e.g. Nb-perovskite and zirconolite) close to the pyroxenite (<2 mm), whereas those oxides observed further from the pyroxenite (>1 cm) are richer still in Zr but (Ti, Nb, U, Th)-poor or free (e.g. calzirtite and baddeleyite ZrO2). Textural relationships between minerals provide evidence for a metasomatic development of the skarn at the expense of the pyroxenite, through drastic leaching of Na, K, Si, Fe. The same process is responsible for the zoning in the skarn (leaching of Fe, Si, Ti, Nb, U and Th), in which Zr was less mobilized than other HFSE. This process, related to the circulation of fluids equilibrated with carbonates, is responsible for those forsterite-spinel (± calcite) skarns which can be observed as remnants in a large part of the 1631 ejecta. Such endoskarns probably formed repeatedly during at least the last millennia of Vesuvius’ history, and existed prior to the emplacement at shallow depth of the 1631 magma whose chamber walls were different from the limestone/dolostone classically assumed to host the Vesuvius magmas (Fulignati et al., 2005).